U.S. patent application number 16/376096 was filed with the patent office on 2019-08-01 for methods for production of aromatic dicarboxylic acids and derivatives thereof.
The applicant listed for this patent is Novomer, Inc.. Invention is credited to Jay J. Farmer, Sadesh H. Sookraj.
Application Number | 20190233360 16/376096 |
Document ID | / |
Family ID | 57144364 |
Filed Date | 2019-08-01 |
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United States Patent
Application |
20190233360 |
Kind Code |
A1 |
Farmer; Jay J. ; et
al. |
August 1, 2019 |
Methods for Production of Aromatic Dicarboxylic Acids and
Derivatives Thereof
Abstract
Provided are methods for the production of phthalic acid (PA),
isophthalic acid (IP A), terephthalic acid (TP A), and derivatives
thereof. The methods are based on the addition of beta
propiolactone to furfural or a derivative thereof. Provided are
cost effective routes to biobased IP A and derivatives thereof,
including terephthalic acid.
Inventors: |
Farmer; Jay J.; (Ithaca,
NY) ; Sookraj; Sadesh H.; (Cambridge, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Novomer, Inc. |
Boston |
MA |
US |
|
|
Family ID: |
57144364 |
Appl. No.: |
16/376096 |
Filed: |
April 5, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15809612 |
Nov 10, 2017 |
10252969 |
|
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PCT/US16/29020 |
Apr 22, 2016 |
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16376096 |
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62151589 |
Apr 23, 2015 |
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62187326 |
Jul 1, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 67/39 20130101;
C07D 493/08 20130101; C07C 63/26 20130101; C07C 67/34 20130101;
C07C 51/235 20130101; C07C 51/353 20130101; C07C 51/235 20130101;
C07C 63/24 20130101; C08G 63/181 20130101; C07C 51/235 20130101;
C07C 67/39 20130101; C07C 69/82 20130101; C07C 67/34 20130101; C07C
69/82 20130101; C07C 63/16 20130101; C07C 63/26 20130101; C07C
51/353 20130101; C07C 63/26 20130101; C07C 63/24 20130101; C07C
69/80 20130101 |
International
Class: |
C07C 51/235 20060101
C07C051/235; C07D 493/08 20060101 C07D493/08; C07C 67/39 20060101
C07C067/39; C07C 67/34 20060101 C07C067/34; C07C 51/353 20060101
C07C051/353; C07C 63/24 20060101 C07C063/24; C07C 63/26 20060101
C07C063/26; C07C 63/16 20060101 C07C063/16; C07C 69/82 20060101
C07C069/82 |
Claims
1. A method for the production of a compound of formula:
##STR00186## the method comprising the step of oxidizing a compound
of formula: ##STR00187## wherein each R.sup.z is selected from the
group consisting of: --H, R.sup.y, optionally substituted
C.sub.1-20 aliphatic, and optionally substituted aryl; and R.sup.y
is hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms selected from
the group consisting of nitrogen, oxygen, and sulfur; 4- to
7-membered heterocyclic having 1-2 heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group.
2. The method of claim 1, wherein each R.sup.z is --H.
3. The method of claim 1, wherein each R.sup.z is --CH3.
4. The method of claim 1, wherein the compound of formula:
##STR00188## is produced by reaction of furfural with a compound
having a formula: ##STR00189##
5. A method for the production of a compound of formula:
##STR00190## the method comprising the steps of reacting furfural
with beta propiolactone and oxidizing the resulting adduct, where
each R.sup.z is selected from the group consisting of: hydrogen, or
an optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms selected from the group
consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms selected from the group
consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group.
6. The method of claim 5, wherein each R.sup.z is --H.
7. The method of claim 5, wherein each R.sup.z is --CH3.
8. A method for the production of a compound of formula:
##STR00191## the method comprising the steps of reacting furfural
with beta propiolactone and oxidizing the resulting adduct, where
each R.sup.z is selected from the group consisting of: hydrogen, or
an optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms selected from the group
consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms selected from the group
consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group.
9. The method of claim 8, wherein each R.sup.z is --H.
10. The method of claim 8, wherein each R.sup.z is --CH3.
11. An isophthalic acid composition produced via cycloaddition
reaction of furfural with an alpha beta unsaturated carboxylic
acid, wherein the isophthalic acid is at least partially derived
from a biobased feedstock.
12. The isophthalic acid composition of claim 11, wherein carbon
atoms one through five as shown in the formula: ##STR00192## are
derived from biobased furfural.
13. An isophthalic acid composition produced via reaction of
furfural with beta propiolactone, wherein the isophthalic acid is
at least partially derived from a biobased feedstock.
14. The isophthalic acid composition of claim 13, wherein carbon
atoms one through five as shown in the formula: ##STR00193## are
derived from biobased furfural.
15. The isophthalic acid composition of claim 11, wherein carbon
atoms six through eight as shown in the formula: ##STR00194## are
derived from a biobased alpha beta unsaturated acid.
16. The isophthalic acid composition of claim 13, wherein carbon
atoms six through eight as shown in the formula: ##STR00195## are
derived from a biobased beta propiolactone.
17. A biobased polymer composition derived from an isophthalic acid
composition of claim 11.
18. The biobased polymer composition of claim 17, wherein the
polymer comprises polyethylene isophthalate (PIT).
19. The biobased polymer composition of claim 18, wherein the
polyethylene isophthalate further comprises biobased ethylene
glycol.
20. A method for the production of biobased phthalic acid or an
ester thereof, comprising: a. reacting ethylene oxide with carbon
monoxide to provide a product selected from beta propiolactone,
acrylic acid and acrylate ester; b. reacting the product of step
(a) with furfural to provide a Diels Alder adduct; and c. oxidizing
the Diels Alder adduct of step (b) to provide a product selected
from phthalic acid and phthalate ester.
21. The method of claim 20, wherein at least one of the ethylene
oxide, the carbon monoxide or the furfural is biobased.
22. A method for the production of biobased isophthalic acid or an
ester thereof, comprising: a. reacting ethylene oxide with carbon
monoxide to provide a product selected from beta propiolactone,
acrylic acid and acrylate ester; b. reacting the product of step
(a) with furfural to provide a Diels Alder adduct; and c. oxidizing
the Diels Alder adduct of step (b) to provide a product selected
from isophthalic acid and isophthalate ester.
23. The method of claim 22, wherein at least one of the ethylene
oxide, the carbon monoxide or the furfural is biobased.
24. A method, comprising: feeding a first reaction zone with
furfural and a compound of formula: ##STR00196## wherein R.sup.y is
hydrogen, or an optionally substituted moiety selected from the
group consisting of acyl; arylalkyl; 6- to 10-membered aryl;
C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms selected from the group consisting of nitrogen, oxygen,
and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms selected from
the group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group, to provide a first product stream comprising a
first product of formula: ##STR00197## feeding the first product
stream to an oxidizing reaction zone where the first product is
contacted with air to form a second product stream comprising a
second product having formula: ##STR00198## wherein each R.sup.z is
selected from the group consisting of --H, R.sup.y, optionally
substituted C.sub.1-20 aliphatic, and optionally substituted aryl;
and continuously feeding the second product stream to a
rearrangement reaction zone where the second product is converted
to a compound of formula: ##STR00199##
25. The method of claim 24 wherein R.sup.y is --H.
26. The method of claim 24 wherein R.sup.y is C.sub.1-20
aliphatic.
27. The method of claim 24 wherein each R.sup.z is --H.
28. The method of claim 24 wherein each R.sup.z is --CH.sub.3.
29. A method, comprising: feeding a first reaction zone with
furfural and beta propiolactone, and an alcohol of formula
HOR.sup.y, to provide a first product stream comprising a first
product having formula: ##STR00200## wherein R.sup.y is hydrogen,
or an optionally substituted moiety selected from the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms selected from
the group consisting of nitrogen, oxygen, and sulfur; 4- to
7-membered heterocyclic having 1-2 heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group; and; feeding the first product stream to an
oxidizing reaction zone where the first product is contacted with
air to form a second product stream comprising a second product
having formula: ##STR00201## wherein each R.sup.z is selected from
the group consisting of --H, R.sup.y, optionally substituted
C.sub.1-20 aliphatic, and optionally substituted aryl; and feeding
the second product stream to a rearrangement reaction zone where
the second product is converted to a compound of formula:
##STR00202##
30. The method of claim 29, wherein R.sup.y is --H.
31. The method of claim 29, wherein R.sup.y is C.sub.1-20
aliphatic.
32. The method of claim 29, wherein each R.sup.z is --H.
33. The method of claim 29, wherein each R.sup.z is --CH.sub.3.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 15/809,612, filed Nov. 10, 2017, which is a
national stage of International Application No. PCT/US16/029,020,
filed Apr. 22, 2016, which claims the benefit of U.S. Provisional
Patent Application No. 62/151,589, filed Apr. 23, 2015, and U.S.
Provisional Patent App. No. 62/187,326, filed Jul. 1, 2015, all of
which are incorporated herein by reference in their entireties.
FIELD
[0002] The present disclosure relates generally to the production
of aromatic dicarboxylic acid compounds and derivatives thereof,
and more specifically to the production of phthalic acid (PA),
isophthalic acid (IP A), and terephthalic acid (TP A) and their
esters and derivatives.
BACKGROUND
[0003] Phthalic acid (PA), Isophthalic acid (IP A), and
Terephthalic acid (TP A) and their esters and derivatives are
important precursors for the synthesis of polyesters and other
useful materials.
##STR00001##
[0004] The largest use of IP A and TP A at present is production of
high performance polyamide and polyester polymers. For example, TP
A is used to produce polyethylene terephthalate (PET) which is used
extensively in consumer goods packaging, most prominently in the
now ubiquitous clear plastic water bottles. IP A is also used to
make polyesters as well as high performance polyamides. PA is an
important precursor to plasticizers used in a range of polymers.
Together PA, IP A, and TP A are produced on the scale of many
millions of tons per year scale by oxidation of xylenes which are
obtained from petroleum distillates.
[0005] There is strong demand from consumers and consumer goods
companies for sustainable alternatives to petroleum-based plastics
for packaging applications. Indeed, Coca Cola.RTM. and others have
recently introduced PET containing biobased monoethylene glycol
(MEG). Beverage bottles made from this PET are branded as the
"Plant Bottle.TM." and have been well received in the marketplace.
Unfortunately, since about 70% of the mass (and 8 out of every 10
carbon atoms) in PET derives from terephthalic and isophthalic
acids, replacing petroleum-sourced MEG with biobased material
yields PET that is only about 30% biobased. There is huge interest
in biobased IP A and TP A to enable fully biobased PET production,
but to date no economically feasible biobased processes exist.
BRIEF SUMMARY
[0006] In one aspect, provided are methods for producing phthalic
acid (PA) and isophthalic acid (IP A) and derivatives thereof. In
some embodiments, the methods are based on the reaction of beta
propiolactone (BPL) with furfural or a derivative thereof to
provide a cyclohexene intermediate as shown in the general scheme
below. Furfural derivatives may include, for example, furfural
compounds with a protected aldehyde, such as the acetal compounds
described herein.
##STR00002##
[0007] The resulting adducts have all eight carbon atoms connected
as needed for PA and IP A production. Oxidation and dehydration of
the adducts (either tandemly or in a series of operations) provides
phthalic and/or isophthalic acid (or esters or other derivatives
thereof). Since furfural is already produced on the scale of
millions of tons per year from biobased feedstocks, the methods
described herein provide an efficient and practical way to make
biobased PA and IP A. Additionally, the methods described herein
provide attractive new routes to biobased TP A.
[0008] The renewable content of the diacids produced can be further
increased by utilizing a biobased alpha beta unsaturated carboxylic
acid. For example, the renewable content of the diacids produced
can be further increased by utilizing biobased BPL. BPL can be
obtained by carbonylation of ethylene oxide, which in turn is
readily available from bio-sourced ethanol. As such, the present
methods provide a practical and cost-effective route to 100%
renewable IP A and TP A.
[0009] In another aspect, provided are processes for producing PA
and/or IP A based on the reaction of furfural (or derivatives
thereof) with BPL. In certain embodiments, the methods described
herein operate in a continuous flow format. In certain embodiments,
the methods include continuously passing a mixture of furfural (or
a derivative thereof) and beta propiolactone through a heated
reaction zone, optionally in the presence of solvent, catalysts, or
co-reactants.
[0010] In certain embodiments, subsequent oxidation of the addition
product of furfural with the BPL is performed in a continuous flow
format. In certain embodiments, two or more reactions selected from
the group consisting of: dehydration to remove the bridgehead
oxygen, dehydration of the cyclohexene ring to an aryl ring,
oxidation of the aldehyde to a carboxylic acid, and esterification
or saponification of one or both carboxyl groups of the final
product occur without isolation of intermediate products. In
certain embodiments, cycloaddition of the furfural (or a derivative
thereof) and BPL occurs in a first fixed bed reactor and the
effluent from the reactor is fed to a second reactor where the
product is heated under dehydrative conditions to effect
aromatization of the addition product.
[0011] In another aspect, provided are processes for producing PA
and/or IP A that are integrated with an ethylene oxide-based
process for BPL production. In certain embodiments, the ethylene
oxide-based process produces BPL continuously and a stream from
that process is fed to a continuous reactor where it is contacted
with furfural. In certain embodiments, the resulting product is fed
to an aromatization reactor where it is converted to an aromatic
diacid (or mixture of diacids). In certain embodiments, the process
includes a rearrangement reactor for conversion to phthalic acid
and/or isophthalic acid to terephthalic acid.
[0012] In certain embodiments, provided are integrated processes
for the production of phthalic and/or isophthalic and/or
terephthalic acids from ethylene oxide and furfural, one or both of
which may be biobased:
##STR00003##
[0013] In another aspect, provided are compounds having the
formula:
##STR00004##
wherein Z is as defined below and described in the classes and
subclasses herein.
[0014] In a further aspect, provided are aromatic diacid
compositions. In certain embodiments, provided are isophthalic
and/or terephthalic acid compositions characterized in that they
contain or are derived from IP A that is produced by cycloaddition
of an alpha-beta unsaturated acid or ester to furfural or a
derivative thereof. In certain embodiments, the aromatic diacid
compositions are characterized in that five of the eight carbon
atoms in the IP A (and/or TP A) are derived from biobased furfural.
In certain embodiments, provided aromatic diacid compositions are
characterized in that three of the eight carbon atoms in the IP A
(and/or TP A) are derived from a biobased alpha beta unsaturated
acid (or a derivative of such a biobased acid). In certain
embodiments where the alpha beta unsaturated acid is derived from
ethylene oxide and carbon monoxide, one, two or three of the carbon
atoms in the alpha beta unsaturated acid may be derived from
biobased feedstocks. By extension, aromatic diacid compositions
provided herein may contain various degrees of bio content: for
example only one biobased carbon atom (e.g. bio CO is combined with
fossil-based EO to produce acrylic acid which is combined with
non-biobased furfural), two biobased carbon atoms (e.g. biobased
ethylene oxide is combined with fossil-based CO to make acrylic
acid which is combined with non-biosourced furfural), three
biobased carbon atoms (e.g., biobased acrylic acid is combined with
non-biosourced furfural), five biobased carbon atoms (bio furfural
is combined with fossil-derived acrylic acid), six biobased carbon
atoms (bio furfural is combined with acrylic acid derived from
biosourced CO and fossil-derived EO), seven biobased carbon atoms
(e.g. bio furfural is combined with acrylic acid derived from
biosourced EO and fossil-derived CO), or eight biobased carbon
atoms (bio furfural plus bio acrylic acid). This is a unique
property of the processes described herein and enables an IP A
(and/or TP A) producer to offer customers a range of price points
and bio-content. In a related aspect, provided are PET compositions
with varying biocontent derivable by combining the IP A and/or TP A
compositions described with biosourced or fossil-based monoethylene
glycol (MEG).
[0015] In another aspect, provided are processes for producing IP A
based on the cycloaddition of furfural (or derivatives thereof)
with acrylic acid (or derivatives thereof). In certain embodiments,
the processes operate in a continuous flow format. In certain
embodiments, the process includes continuously passing a mixture of
furfural (or a derivative thereof) and an alpha beta unsaturated
acid over a bed of solid catalyst where the catalyst promotes the
Diels Alder cycloaddition reaction of these two chemicals. In
certain embodiments, the oxidation of the cycloaddition product of
furfural with the alpha beta unsaturated acid is performed in a
continuous flow format. In certain embodiments, two or more
reactions selected from the group consisting of: dehydration to
remove the bridgehead oxygen, dehydration of the cyclohexene ring
to an aryl ring, oxidation of the aldehyde to a carboxylic acid,
and esterification or saponification of one or both carboxyl groups
of the final product occur without isolation of intermediate
products. In certain embodiments, cycloaddition of the furfural and
alpha beta unsaturated acid (or derivative) occurs in a first fixed
bed reactor (the Diels Alder reactor) and the effluent from the
Diels Alder reactor is fed to a second reactor where the product is
heated under oxidative conditions to effect aromatization of the
cycloaddition product.
[0016] In another aspect, provided are processes for producing IP A
that are integrated with an ethylene oxide-based process for
acrylic acid production. In certain embodiments, the ethylene
oxide-based process produces beta propiolactone (BPL) as an
intermediate. In certain embodiments, the resulting isophthalic
acid is further converted to terephthalic acid. In certain
embodiments, the conversion to terephthalic acid is a continuous
process fed from the continuous oxidative aromatization
reactor.
[0017] In certain embodiments, provided are integrated processes
for the production of isophthalic and/or terephthalic acid from
ethylene oxide and furfural, one or both of which may be
biobased:
##STR00005##
BRIEF DESCRIPTION OF THE FIGURES
[0018] The present application can be best understood by reference
to the following description taken in conjunction with the
accompanying figures, in which like parts may be referred to by
like numerals.
[0019] FIG. 1 depicts an exemplary process to produce compounds of
Formulae IV and V from furfural and beta propiolactone.
[0020] FIG. 2A depicts exemplary process to produce compounds of
Formulae IV and V from furfural and alpha beta unsaturated
acids.
[0021] FIG. 2B depicts exemplary process to produce compounds of
Formula V from furfural and alpha beta unsaturated acids.
[0022] FIG. 3A depicts an exemplary process to produce compounds of
Formulae II and IIb from furfural and an alcohol.
[0023] FIG. 3B depicts an exemplary process to produce
4-formyl-7oxabicyclo[2.2.1]hept-5-ene-2-carboxylic acid from
furfural and an alcohol.
[0024] FIG. 3C depicts an exemplary processes to produce a compound
of Formula I' from furfural.
[0025] FIG. 4A depicts an exemplary process to produce a compound
of Formula IV from an acetal compound and beta propiolactone.
[0026] FIG. 4B depicts an exemplary process to produce a compound
of Formula IV from an acetal compound and an alpha beta unsaturated
acid or ester.
DEFINITIONS
[0027] Definitions of specific functional groups and chemical terms
are described in more detail below. The chemical elements are
identified in accordance with the Periodic Table of the Elements,
CAS version, Handbook of Chemistry and Physics, 75.sup.th Ed.,
inside cover, and specific functional groups are generally defined
as described therein. Additionally, general principles of organic
chemistry, as well as specific functional moieties and reactivity,
are described in Organic Chemistry, Thomas Sorrell, University
Science Books, Sausalito, 1999; Smith and March March's Advanced
Organic Chemistry, 5.sup.th Edition, John Wiley & Sons, Inc.,
New York, 2001; Larock, Comprehensive Organic Transformations, VCH
Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods
of Organic Synthesis, 3.sup.rd Edition, Cambridge University Press,
Cambridge, 1987.
[0028] Certain compounds described herein can comprise one or more
asymmetric centers, and thus can exist in various stereoisomeric
forms, e.g., enantiomers and/or diastereomers. Thus, compounds and
compositions thereof may be in the form of an individual
enantiomer, diastereomer or geometric isomer, or may be in the form
of a mixture of stereoisomers. In certain embodiments, the
compounds described herein are enantiopure compounds. In certain
other embodiments, mixtures of enantiomers or diastereomers are
provided.
[0029] Furthermore, certain compounds as described herein may have
one or more double bonds that can exist as either a Z or E isomer,
unless otherwise indicated. In some variation, the compounds are
individual isomers substantially free of other isomers and
alternatively, as mixtures of various isomers, e.g., racemic
mixtures of enantiomers. In addition to the above-mentioned
compounds per se, provided are compositions comprising one or more
compounds.
[0030] As used herein, the term "isomers" includes any and all
geometric isomers and stereoisomers. For example, "isomers" include
cis- and trans-isomers, E- and Z-isomers, R- and S-enantiomers,
diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof,
and other mixtures thereof, as falling within the scope of the
description herein. For instance, a compound may, in some
embodiments, be provided substantially free of one or more
corresponding stereoisomers, and may also be referred to as
"stereochemically enriched".
[0031] Where a particular enantiomer is preferred, it may, in some
embodiments be provided substantially free of the opposite
enantiomer, and may also be referred to as "optically enriched."
"Optically enriched," as used herein, means that the compound is
made up of a significantly greater proportion of one enantiomer. In
certain embodiments the compound is made up of at least about 90%
by weight of an enantiomer. In some embodiments, the compound is
made up of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%,
or 99.9% by weight of an enantiomer. In some embodiments the
enantiomeric excess of provided compounds is at least about 90%,
95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In some
embodiments, enantiomers may be isolated from racemic mixtures by
any method known to those skilled in the art, including chiral high
pressure liquid chromatography (HPLC) and the formation and
crystallization of chiral salts or prepared by asymmetric
syntheses. See, for example, Jacques, et al., Enantiomers,
Racemates and Resolutions (Wiley Interscience, New York, 1981);
Wilen, S. H., et al., Tetrahedron 33:2725 (1977); Eliel, E. L.
Stereochemistry of Carbon Compounds (McGraw-Hill, N Y, 1962);
Wilen, S. H. Tables of Resolving Agents and Optical Resolutions p.
268 (E. L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, Ind.
1972).
[0032] The terms "halo" and "halogen" as used herein refer to an
atom selected from fluorine (fluoro, --F), chlorine (chloro, --Cl),
bromine (bromo, --Br), and iodine (iodo, --I).
[0033] The term "aliphatic" or "aliphatic group", as used herein,
denotes a hydrocarbon moiety that may be straight-chain (i.e.,
unbranched), branched, or cyclic (including fused, bridging, and
spiro-fused polycyclic) and may be completely saturated or may
contain one or more units of unsaturation, but which is not
aromatic. In some variations, the aliphatic group is unbranched or
branched. In other variations, the aliphatic group is cyclic.
Unless otherwise specified, in some variations, aliphatic groups
contain 1-30 carbon atoms. In certain embodiments, aliphatic groups
contain 1-12 carbon atoms. In certain embodiments, aliphatic groups
contain 1-8 carbon atoms. In certain embodiments, aliphatic groups
contain 1-6 carbon atoms. In some embodiments, aliphatic groups
contain 1-5 carbon atoms, in some embodiments, aliphatic groups
contain 1-4 carbon atoms, in yet other embodiments aliphatic groups
contain 1-3 carbon atoms, and in yet other embodiments, aliphatic
groups contain 1-2 carbon atoms. Suitable aliphatic groups include,
for example, linear or branched, alkyl, alkenyl, and alkynyl
groups, and hybrids thereof such as (cycloalkyl)alkyl,
(cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
[0034] The term "heteroaliphatic", as used herein, refers to
aliphatic groups wherein one or more carbon atoms are independently
replaced by one or more atoms selected from the group consisting of
oxygen, sulfur, nitrogen, phosphorus, or boron. In certain
embodiments, one or two carbon atoms are independently replaced by
one or more of oxygen, sulfur, nitrogen, or phosphorus.
Heteroaliphatic groups may be substituted or unsubstituted,
branched or unbranched, cyclic or acyclic, and include
"heterocycle," "heterocyclyl," "heterocycloaliphatic," or
"heterocyclic" groups. In some variations, the heteroaliphatic
group is branched or unbranched. In other variations, the
heteroaliphatic group is cyclic. In yet other variations, the
heteroaliphatic group is acyclic.
[0035] The term "epoxide", as used herein, refers to a substituted
or unsubstituted oxirane. Substituted oxiranes include, for
example, monosubstituted oxiranes, disubstituted oxiranes,
trisubstituted oxiranes, and tetrasubstituted oxiranes. Such
epoxides may be further optionally substituted as defined herein.
In certain embodiments, epoxides comprise a single oxirane moiety.
In certain embodiments, epoxides comprise two or more oxirane
moieties.
[0036] The term "glycidyl", as used herein, refers to an oxirane
substituted with a hydroxyl methyl group or a derivative thereof.
The term glycidyl as used herein includes moieties having
additional substitution on one or more of the carbon atoms of the
oxirane ring or on the methylene group of the hydroxymethyl moiety,
such substitution may include, for example, alkyl groups, halogen
atoms, and aryl groups. The terms glycidyl ester, glycidyl
acrylate, glycidyl ether etc. denote substitution at the oxygen
atom of the above-mentioned hydroxymethyl group, i.e. that oxygen
atom is bonded to an acyl group, an acrylate group, or an alkyl
group, respectively.
[0037] The term "acrylate" or "acrylates", as used herein, refers
to any acyl group having a vinyl group adjacent to the acyl
carbonyl. The terms encompass mono-, di- and tri-substituted vinyl
groups. Acrylates may include, for example, acrylate, methacrylate,
ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate, and
senecioate.
[0038] The term "polymer", as used herein, refers to a molecule
comprising multiple repeating units. In some variations, the
polymer is a molecule of high relative molecular mass, the
structure of which comprises the multiple repetition of units
derived, actually or conceptually, from molecules of low relative
molecular mass. In certain embodiments, a polymer is comprised of
only one monomer species (e.g., polyethylene oxide). In certain
embodiments, the polymer is a copolymer, terpolymer, heteropolymer,
block copolymer, or tapered heteropolymer of one or more epoxides.
In one variation, the polymer may be a copolymer, terpolymer,
heteropolymer, block copolymer, or tapered heteropolymer of two or
more monomers.
[0039] The term "unsaturated", as used herein, means that a moiety
has one or more double or triple bonds.
[0040] The terms "cycloaliphatic", "carbocycle", or "carbocyclic",
used alone or as part of a larger moiety, refer to a saturated or
partially unsaturated cyclic aliphatic monocyclic, bicyclic, or
polycyclic ring systems, as described herein, having from 3 to 12
members, wherein the aliphatic ring system is optionally
substituted as defined above and described herein. Cycloaliphatic
groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl,
cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl. In
some embodiments, the cycloalkyl has 3-6 carbons. The terms
"cycloaliphatic", "carbocycle" or "carbocyclic" also include
aliphatic rings that are fused to one or more aromatic or
nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl,
where the radical or point of attachment is on the aliphatic ring.
In some embodiments, a carbocyclic groups is bicyclic. In some
embodiments, a carbocyclic group is tricyclic. In some embodiments,
a carbocyclic group is polycyclic.
[0041] The term "alkyl", as used herein, refers to a saturated
hydrocarbon radical. In some variations, the alkyl group is a
saturated, straight- or branched-chain hydrocarbon radicals derived
from an aliphatic moiety containing between one and six carbon
atoms by removal of a single hydrogen atom. Unless otherwise
specified, in some variations, alkyl groups contain 1-12 carbon
atoms. In certain embodiments, alkyl groups contain 1-8 carbon
atoms. In certain embodiments, alkyl groups contain 1-6 carbon
atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms,
in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet
other embodiments, alkyl groups contain 1-3 carbon atoms, and in
yet other embodiments alkyl groups contain 1-2 carbon atoms. Alkyl
radicals may include, for example, methyl, ethyl, n-propyl,
isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl,
tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl,
n-octyl, n-decyl, n-undecyl, and dodecyl.
[0042] The term "alkenyl", as used herein, denotes a monovalent
group having at least one carbon-carbon double bond. In some
variations, the alkenyl group is a monovalent group derived from a
straight- or branched-chain aliphatic moiety having at least one
carbon-carbon double bond by the removal of a single hydrogen atom.
Unless otherwise specified, in some variations, alkenyl groups
contain 2-12 carbon atoms. In certain embodiments, alkenyl groups
contain 2-8 carbon atoms. In certain embodiments, alkenyl groups
contain 2-6 carbon atoms. In some embodiments, alkenyl groups
contain 2-5 carbon atoms, in some embodiments, alkenyl groups
contain 2-4 carbon atoms, in yet other embodiments alkenyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkenyl
groups contain 2 carbon atoms. Alkenyl groups include, for example,
ethenyl, propenyl, butenyl, and 1-methyl-2-buten-1-yl.
[0043] The term "alkynyl", as used herein, refers to a monovalent
group having at least one carbon-carbon triple bond. In some
variations, the alkynyl group is a monovalent group derived from a
straight- or branched-chain aliphatic moiety having at least one
carbon-carbon triple bond by the removal of a single hydrogen atom.
Unless otherwise specified, in some variations, alkynyl groups
contain 2-12 carbon atoms. In certain embodiments, alkynyl groups
contain 2-8 carbon atoms. In certain embodiments, alkynyl groups
contain 2-6 carbon atoms. In some embodiments, alkynyl groups
contain 2-5 carbon atoms, in some embodiments, alkynyl groups
contain 2-4 carbon atoms, in yet other embodiments alkynyl groups
contain 2-3 carbon atoms, and in yet other embodiments alkynyl
groups contain 2 carbon atoms. Representative alkynyl groups
include, for example, ethynyl, 2-propynyl (propargyl), and
1-propynyl.
[0044] The term "carbocycle" and "carbocyclic ring", as used
herein, refer to monocyclic and polycyclic moieties wherein the
rings contain only carbon atoms. Unless otherwise specified,
carbocycles may be saturated, partially unsaturated or aromatic,
and contain 3 to 20 carbon atoms. Representative carbocyles
include, for example, cyclopropane, cyclobutane, cyclopentane,
cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl,
cyclohexene, naphthalene, and spiro[4.5]decane.
[0045] The term "aryl", used alone or as part of a larger moiety as
in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic
and polycyclic ring systems having a total of five to 20 ring
members, wherein at least one ring in the system is aromatic and
wherein each ring in the system contains three to twelve ring
members. The term "aryl" may be used interchangeably with the term
"aryl ring". In certain embodiments, "aryl" refers to an aromatic
ring system which includes, for example, phenyl, naphthyl, and
anthracyl, which may bear one or more substituents. Also included
within the scope of the term "aryl", as it is used herein, is a
group in which an aromatic ring is fused to one or more additional
rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl,
phenanthridinyl, and tetrahydronaphthyl.
[0046] The terms "heteroaryl" and "heteroar-", used alone or as
part of a larger moiety, e.g., "heteroaralkyl", or
"heteroaralkoxy", refer to groups having 5 to 14 ring atoms,
preferably 5, 6, 9 or 10 ring atoms; having 6, 10, or 14 pi (.pi.)
electrons shared in a cyclic array; and having, in addition to
carbon atoms, from one to five heteroatoms. The term "heteroatom"
refers to nitrogen, oxygen, or sulfur, and includes any oxidized
form of nitrogen or sulfur, and any quaternized form of a basic
nitrogen. Heteroaryl groups include, for example, thienyl, furanyl,
pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl,
isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl,
pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl,
naphthyridinyl, benzofuranyl and pteridinyl. The terms "heteroaryl"
and "heteroar-", as used herein, also include groups in which a
heteroaromatic ring is fused to one or more aryl, cycloaliphatic,
or heterocyclyl rings, where the radical or point of attachment is
on the heteroaromatic ring. Examples include indolyl, isoindolyl,
benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl,
benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl,
phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,
carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,
tetrahydroquinolinyl, tetrahydroisoquinolinyl, and
pyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be
monocyclic or bicyclic. The term "heteroaryl" may be used
interchangeably with the terms "heteroaryl ring", "heteroaryl
group", or "heteroaromatic", any of which terms include rings that
are optionally substituted. The term "heteroaralkyl" refers to an
alkyl group substituted by a heteroaryl, wherein the alkyl and
heteroaryl portions independently are optionally substituted.
[0047] As used herein, the terms "heterocycle", "heterocyclyl",
"heterocyclic radical", and "heterocyclic ring" are used
interchangeably and may be saturated or partially unsaturated, and
have, in addition to carbon atoms, one or more, preferably one to
four, heteroatoms, as defined above. In some variations, the
heterocyclic group is a stable 5- to 7-membered monocyclic or 7- to
14-membered bicyclic heterocyclic moiety that is either saturated
or partially unsaturated, and having, in addition to carbon atoms,
one or more, preferably one to four, heteroatoms, as defined above.
When used in reference to a ring atom of a heterocycle, the term
"nitrogen" includes a substituted nitrogen. As an example, in a
saturated or partially unsaturated ring having 0-3 heteroatoms
selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as
in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or .sup.+NR
(as in N-substituted pyrrolidinyl).
[0048] A heterocyclic ring can be attached to its pendant group at
any heteroatom or carbon atom that results in a stable structure
and any of the ring atoms can be optionally substituted. Examples
of such saturated or partially unsaturated heterocyclic radicals
include, for example, tetrahydrofuranyl, tetrahydrothienyl,
pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl,
tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl,
oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl,
oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms
"heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic
group", "heterocyclic moiety", and "heterocyclic radical", are used
interchangeably herein, and also include groups in which a
heterocyclyl ring is fused to one or more aryl, heteroaryl, or
cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl,
phenanthridinyl, or tetrahydroquinolinyl, where the radical or
point of attachment is on the heterocyclyl ring. A heterocyclyl
group may be mono- or bicyclic. The term "heterocyclylalkyl" refers
to an alkyl group substituted by a heterocyclyl, wherein the alkyl
and heterocyclyl portions independently are optionally
substituted.
[0049] As used herein, the term "partially unsaturated" refers to a
ring moiety that includes at least one double or triple bond. The
term "partially unsaturated" is intended to encompass rings having
multiple sites of unsaturation, but is not intended to include aryl
or heteroaryl moieties, as herein defined.
[0050] As described herein, compounds described herein may contain
"optionally substituted" moieties. In general, the term
"substituted", whether preceded by the term "optionally" or not,
means that one or more hydrogens of the designated moiety are
replaced with a suitable substituent. Unless otherwise indicated,
an "optionally substituted" group may have a suitable substituent
at each substitutable position of the group, and when more than one
position in any given structure may be substituted with more than
one substituent selected from a specified group, the substituent
may be either the same or different at every position. Combinations
of substituents envisioned are preferably those that result in the
formation of stable or chemically feasible compounds. The term
"stable", as used herein, refers to compounds that are not
substantially altered when subjected to conditions to allow for
their production, detection, and, in certain embodiments, their
recovery, purification, and use for one or more of the purposes
disclosed herein.
[0051] In some chemical structures herein, substituents are shown
attached to a bond which crosses a bond in a ring of the depicted
molecule. This means that one or more of the substituents may be
attached to the ring at any available position (usually in place of
a hydrogen atom of the parent structure). In cases where an atom of
a ring so substituted has two substitutable positions, two groups
may be present on the same ring atom. When more than one
substituent is present, each is defined independently of the
others, and each may have a different structure. In cases where the
substituent shown crossing a bond of the ring is --R, this has the
same meaning as if the ring were said to be "optionally
substituted" as described in the preceding paragraph.
[0052] Suitable monovalent substituents on a substitutable carbon
atom of an "optionally substituted" group are independently
halogen; --(CH.sub.2).sub.0-4R.sup..smallcircle.;
--(CH.sub.2).sub.0-4OR.sup..smallcircle.;
--O--(CH.sub.2).sub.0-4C(O)OR; --(CH.sub.2).sub.0-4CH(OR).sub.2;
--(CH.sub.2).sub.0-4SR.sup..smallcircle.; --(CH.sub.2).sub.0-4Ph,
which may be substituted with R.sup..smallcircle.;
--(CH.sub.2).sub.0-4O(CH.sub.2).sub.0-1Ph which may be substituted
with R.sup..smallcircle.; --CH.dbd.CHPh, which may be substituted
with R.sup..smallcircle.; --NO.sub.2; --CN; --N.sub.3;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)R.sup..smallcircle.;
--N(R)C(S)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)NR.sup..smallcircle..sub.2;
--N(R.sup..smallcircle.)C(S)NR.sup..smallcircle..sub.2;
--(CH.sub.2).sub.0-4N(R.sup..smallcircle.)C(O)OR.sup..smallcircle.;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)R.sup..smallcircle.;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)NR.sup..smallcircle..su-
b.2;
--N(R.sup..smallcircle.)N(R.sup..smallcircle.)C(O)OR.sup..smallcircle-
.; --(CH.sub.2).sub.0-4C(O)R.sup..smallcircle.;
--C(S)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)OR.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-4C(O)SR.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)OSiR.sup..smallcircle.;
--(CH.sub.2).sub.0-4C(O)R.sup..smallcircle.;
--OC(O)(CH.sub.2).sub.0-4SR--, SC(S)SR.sup..smallcircle.;
--(CH.sub.2).sub.0-4SC(O)R; --(CH.sub.2).sub.0-4C(O)NR.sub.2;
--C(S)NR.sup..smallcircle..sub.2; --C(S)SRO;
--SC(S)SR.sup..smallcircle.,
--(CH.sub.2).sub.0-4OC(O)NR.sup..smallcircle..sub.2;
--C(O)N(OR.sup..smallcircle.)R.sup..smallcircle.;
--C(O)C(O)R.sup..smallcircle.;
--C(O)CH.sub.2C(O)R.sup..smallcircle.;
--C(NOR.sup..smallcircle.)R.sup..smallcircle.;
--(CH.sub.2).sub.0-4SSR.sup..smallcircle.;
--(CH.sub.2).sub.0-4S(O).sub.2R.sup..smallcircle.;
--(CH.sub.2).sub.0-4S(O).sub.2OR.sup..smallcircle.;
--(CH.sub.2).sub.0-4OS(O).sub.2R.sup..smallcircle.;
--S(O).sub.2NR.sup..smallcircle..sub.2;
--(CH.sub.2).sub.4S(O)R.sup..smallcircle.;
--N(R.sup..smallcircle.)S(O).sub.2NR.sup..smallcircle..sub.2;
--N(R)S(O)R.sup..smallcircle.; --N(OR.sup..smallcircle.)R;
--C(NH)NR.sup..smallcircle..sub.2; --P(O).sub.2R;
--P(O)R.sup..smallcircle..sub.2; --OP(O)R.sup..smallcircle..sub.2;
--OP(O)(OR.sup..smallcircle.).sub.2; SiR.sup..smallcircle..sub.3;
--(C.sub.1-4 straight or branched
alkylene)O--N(R.sup..smallcircle.).sub.2; or --(C.sub.1-4 straight
or branched alkylene)C(O)O--N(R.sup..smallcircle.).sub.2, wherein
each R.sup..smallcircle. may be substituted as defined below and is
independently hydrogen, C.sub.1-8 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur, or, notwithstanding the
definition above, two independent occurrences of
R.sup..smallcircle., taken together with their intervening atom(s),
form a 3-12-membered saturated, partially unsaturated, or aryl
mono- or polycyclic ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur, which may be
substituted as defined below.
[0053] Suitable monovalent substituents on R.sup..smallcircle. (or
the ring formed by taking two independent occurrences of
R.sup..smallcircle. together with their intervening atoms), are
independently halogen, --(CH.sub.2).sub.0-2R.sup..cndot.,
-(haloR.sup..cndot.), --(CH.sub.2).sub.0-2OH,
--(CH.sub.2).sub.0-2OR.sup..cndot.,
--(CH.sub.2).sub.0-2CH(OR.sup..cndot.).sub.2;
--O(haloR.sup..cndot.), --CN, --N.sub.3,
--(CH.sub.2).sub.0-2C(O)R.sup..cndot., --(CH.sub.2).sub.0-2C(O)OH,
--(CH.sub.2).sub.0-2C(O)OR.sup..cndot.,
--(CH.sub.2).sub.0-4C(O)N(R.sup..smallcircle.).sub.2;
--(CH.sub.2).sub.0-2SR.sup..cndot., --(CH.sub.2).sub.0-2SH,
--(CH.sub.2).sub.0-2NH.sub.2, --(CH.sub.2).sub.0-2NH.sub.2,
--(CH.sub.2).sub.0-2 NHR.sup..cndot.,
--(CH.sub.2).sub.0-2NR.sup..cndot..sub.2, --NO.sub.2,
--SiR.sup..cndot..sub.3, --OSiR.sup..cndot..sub.3,
--C(O)SR.sup..cndot., --(C.sub.1-4 straight or branched
alkylene)C(O)OR.sup..cndot., or --SSR.sup..cndot. wherein each
R.sup..cndot. is unsubstituted or where preceded by "halo" is
substituted only with one or more halogens, and is independently
selected from C.sub.1-4 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur. Suitable divalent
substituents on a saturated carbon atom of R.sup..smallcircle.
include .dbd.O and .dbd.S.
[0054] Suitable divalent substituents on a saturated carbon atom of
an "optionally substituted" group include the following: .dbd.O,
.dbd.S, .dbd.NNR*.sub.2, .dbd.NNHC(O)R*, .dbd.NNHC(O)OR*,
.dbd.NNHS(O).sub.2R, .dbd.NR*, .dbd.NOR*,
--O(C(R*.sub.2)).sub.2-3O--, or --S(C(R*.sub.2)).sub.2-3S--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur. Suitable divalent
substituents that are bound to vicinal substitutable carbons of an
"optionally substituted" group include: --O(CR*.sub.2).sub.2-3O--,
wherein each independent occurrence of R* is selected from
hydrogen, C.sub.1-6 aliphatic which may be substituted as defined
below, or an unsubstituted 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur.
[0055] Suitable substituents on the aliphatic group of R* include
halogen, --R.sup..cndot., -(haloR.sup..cndot.), --OH,
--OR.sup..cndot., --O(haloR.sup..cndot.), --CN, --C(O)OH,
--C(O)OR.sup..cndot., --NH.sub.2, --NHR.sup..cndot.,
--NR.sup..cndot..sub.2, or --NO.sub.2, wherein each R.sup..cndot.
is unsubstituted or where preceded by "halo" is substituted only
with one or more halogens, and is independently C.sub.1-4
aliphatic, --CH.sub.2Ph, --O(CH.sub.2).sub.0-1Ph, or a 5-6-membered
saturated, partially unsaturated, or aryl ring having 0-4
heteroatoms independently selected from nitrogen, oxygen, and
sulfur.
[0056] Suitable substituents on a substitutable nitrogen of an
"optionally substituted" group include --R.sup..dagger.,
--NR.sup..dagger..sub.2, --C(O)R.sup..dagger.,
--C(O)OR.sup..dagger., --C(O)C(O)R.sup..dagger.,
--C(O)CH.sub.2C(O)R.sup..dagger., --S(O).sub.2R.sup..dagger.,
--S(O).sub.2NR.sup..dagger..sub.2, --C(S)NR.sup..dagger..sub.2,
--C(NH)NR.sup..dagger..sub.2, or
--N(R.sup..dagger.)S(O).sub.2R.sup..dagger.; wherein each
R.sup..dagger. is independently hydrogen, C.sub.1-6 aliphatic which
may be substituted as defined below, unsubstituted --OPh, or an
unsubstituted 5-6-membered saturated, partially unsaturated, or
aryl ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, and sulfur, or, notwithstanding the definition
above, two independent occurrences of R.sup..dagger., taken
together with their intervening atom(s) form an unsubstituted
3-12-membered saturated, partially unsaturated, or aryl mono- or
bicyclic ring having 0-4 heteroatoms independently selected from
nitrogen, oxygen, and sulfur.
[0057] Suitable substituents on the aliphatic group of
R.sup..dagger. are independently halogen, --R.sup..cndot.,
-(haloR.sup..cndot.), --OH, --OR.sup..cndot.,
--O(haloR.sup..cndot.), --CN, --C(O)OH, --C(O)OR.sup..cndot.,
--NH.sub.2, --NHR.sup..cndot., --NR.sup..cndot..sub.2, or
--NO.sub.2, wherein each R.sup..cndot. is unsubstituted or where
preceded by "halo" is substituted only with one or more halogens,
and is independently C.sub.1-4 aliphatic, --CH.sub.2Ph,
--O(CH.sub.2).sub.0-1Ph, or a 5-6-membered saturated, partially
unsaturated, or aryl ring having 0-4 heteroatoms independently
selected from nitrogen, oxygen, and sulfur.
[0058] As used herein, the term "catalyst" refers to a substance
the presence of which increases the rate of a chemical reaction,
while not being consumed or undergoing a permanent chemical change
itself.
[0059] As used herein, the term "about" preceding one or more
numerical values means the numerical value .+-.5%. It should be
understood that reference to "about" a value or parameter herein
includes (and describes) embodiments that are directed to that
value or parameter per se. For example, description referring to
"about x" includes description of "x" per se.
DETAILED DESCRIPTION
Compositions of Matter
[0060] In some aspects, provided are compositions comprising
compounds of Formula I:
##STR00006##
wherein R.sup.Y is hydrogen, or an optionally substituted moiety
selected the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; an oxygen protecting group; and a
nitrogen protecting group.
[0061] In certain embodiments, provided are substantially pure
compounds of Formula I. In certain embodiments, provided are
reaction mixtures or process streams comprising compounds of
Formula I.
[0062] In certain embodiments, provided are compositions comprising
the compound of Formula I, wherein R.sup.Y is --H. In certain
embodiments, provided are compositions comprising a compound of
Formula I, wherein R.sup.Y is C.sub.1-20 aliphatic, or where
R.sup.Y is C.sub.1-12 aliphatic, or where R.sup.Y is C.sub.1-8
aliphatic, or where R.sup.Y is C.sub.1-6 aliphatic, or where
R.sup.Y is C.sub.1-4 aliphatic. In certain embodiments, provided
are compositions comprising the compound of Formula I, wherein
R.sup.Y is selected from the group consisting of methyl, ethyl,
propyl, n-butyl, and 2-ethylhexyl.
[0063] In certain embodiments, provided is a compound selected from
the group consisting of:
##STR00007##
[0064] In certain aspects, provided are compositions comprising
compounds of Formula I':
##STR00008##
wherein Z is selected from the group consisting of --OR.sup.Y,
--Cl, --Br, --NR.sup.y.sub.2, and --SR.sup.y, wherein each R.sup.y
is independently hydrogen, or an optionally substituted group
selected the group consisting of: acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to I 0-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; an oxygen
protecting group; and a nitrogen protecting group; or wherein two
R.sup.y on a nitrogen atom may be taken with the nitrogen atom to
form an optionally substituted 4- to 7-membered heterocyclic ring
having 0-2 additional heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur.
[0065] In certain embodiments, provided are substantially pure
compounds of Formula I'. In certain embodiments, provided are
reaction mixtures or process streams comprising compounds of
Formula I'.
[0066] In some variations, Z is --OR.sup.y. In one variation,
R.sup.y is --H, and Z is --OH. Thus, in certain embodiments,
provided are compositions comprising the compound of Formula I',
wherein Z is --OH. In certain embodiments, provided are
compositions comprising a compound of Formula I', wherein Z is
--OR.sup.y and R.sup.y is C.sub.1-20 aliphatic, or where R.sup.y is
C.sub.1-12 aliphatic, or where R.sup.y is C.sub.1-8 aliphatic, or
where R.sup.y is C.sub.1-6 aliphatic, or where R.sup.y is C.sub.1-4
aliphatic. In certain embodiments, provided are compositions
comprising the compound of Formula I', wherein Z is --OR.sup.y and
R.sup.y is selected from the group consisting of methyl, ethyl,
propyl, n-butyl, and 2-ethylhexyl.
[0067] In certain embodiments, provided is a compound selected from
the group consisting of:
##STR00009##
[0068] In some variations, Z is --NR.sup.y2. In one variation, the
two R.sup.y may be taken with the nitrogen atom to which they are
attached to form an optionally substituted 4- to 7-membered
heterocyclic ring having 0-2 additional heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and
sulfur.
[0069] In other variations, Z is --SR.sup.y.
[0070] In certain embodiments, provided are compositions comprising
compounds of Formula II:
##STR00010##
wherein R.sup.Y is as defined above and in the classes and
subclasses herein, and R.sup.k is, independently at each
occurrence, selected from the group consisting of acyl; arylalkyl;
6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; where
two R.sup.k may be taken with intervening atoms to form an
optionally substituted 4- to 7-membered heterocyclic ring having
0-2 additional heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur.
[0071] In certain embodiments, provided are substantially pure
compounds of Formula II. In certain embodiments, provided are
reaction mixtures or process streams comprising compounds of
Formula H.
[0072] In certain embodiments, provided is a composition comprising
compounds of Formula II, wherein R.sup.y is --H. In certain
embodiments, provided are compositions comprising a compound of
Formula II, wherein R.sup.y is C.sub.1-20 aliphatic, or where
R.sup.y is C.sub.1-12 aliphatic, or where R.sup.y is C.sub.1-8
aliphatic, or where R.sup.y is C.sub.1-6 aliphatic, or where
R.sup.y is C.sub.1-4 aliphatic. In certain embodiments, provided
are compositions comprising the compound of Formula II, wherein
R.sup.Y is selected from the group consisting of methyl, ethyl,
propyl, n-butyl, and 2-ethylhexyl.
[0073] In certain embodiments, provided are compositions comprising
one or more compounds selected from the group consisting of:
##STR00011##
where R.sup.y is as defined above and in the classes and subclasses
herein.
[0074] In certain embodiments, for compounds of Formula II, each
R.sup.k is the same as R.sup.y. In certain embodiments, provided is
a compound selected from the group consisting of:
##STR00012##
[0075] In some variations, provided are compositions comprising
compounds of Formula II':
##STR00013##
wherein each of R.sup.k and Z is as defined above and in the
classes and subclasses herein.
[0076] In certain embodiments, provided are substantially pure
compounds of Formula II'. In certain embodiments, provided are
reaction mixtures or process streams comprising compounds of
Formula II'.
[0077] In certain embodiments, the invention encompasses a compound
selected from the group consisting of:
##STR00014##
wherein Z is as defined above and in the classes and subclasses
herein.
[0078] In certain embodiments, provided is a composition comprising
compounds of Formula II', wherein Z is --OR.sup.y. In certain
embodiments, provided is a composition comprising compounds of
Formula II', wherein Z is --OH. In certain embodiments, provided
compositions comprising a compound of Formula II', wherein Z is
--OR.sup.y and R.sup.y is C.sub.1-20 aliphatic, or where R.sup.y is
C.sub.1-12 aliphatic, or where R.sup.y is C.sub.1-5 aliphatic, or
where R.sup.y is C.sub.1-6 aliphatic, or where R.sup.y is C.sub.1-4
aliphatic. In certain embodiments, provided are compositions
comprising the compound of Formula II', wherein Z is --OR.sup.y and
R.sup.y is selected from the group consisting of methyl, ethyl,
propyl, n-butyl, and 2-ethylhexyl.
[0079] In certain embodiments, for compounds of Formula II', Z is
--OR.sup.y and each of R.sup.k is the same as R.sup.y. In certain
embodiments, the invention encompasses a compound selected from a
group consisting of:
##STR00015##
[0080] In certain embodiments, provided are mixtures comprising
compounds of Formula II and compounds of Formula IIb:
##STR00016##
wherein each of R.sup.y and R.sup.k is as defined above and in the
classes and subclasses herein
[0081] In certain embodiments, provided are compositions comprising
a mixture of compounds having the formula:
##STR00017## ##STR00018##
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0082] In certain embodiments, for the mixtures of compounds of
Formulae II and IIb, each R.sup.k and R.sup.y is the same. In
certain embodiments, provided are compositions containing mixtures
of compounds having the formulae:
##STR00019##
[0083] In certain embodiments, provided are compositions comprising
compounds of Formula III:
##STR00020##
wherein Q is a solid support.
[0084] In certain embodiments, Q comprises an inorganic support. In
certain embodiments, Q comprises an organic resin. In certain
embodiments, the linkage to the solid support Q comprises an ester
bond. In certain embodiments, the linkage to the solid support
comprises an amide bond.
[0085] In certain embodiments, provided are compositions comprising
compounds of Formula IIIa:
##STR00021##
wherein each of Q and R.sup.k is as defined above and in the
classes and subclasses herein.
[0086] In certain embodiments, provided are compositions comprising
compounds of formula:
##STR00022##
wherein Q is as defined above and in the classes and subclasses
herein.
[0087] In certain embodiments, provided are compositions comprising
compounds of formula:
##STR00023##
wherein each of Q and R.sup.k is as defined above and in the
classes and subclasses herein.
Methods and Making
[0088] In some aspects, provided herein are various methods to
produce phthalic acid, isophthalic acid, and terephthalic acid, and
esters and derivatives thereof In some embodiments, provided are
methods to produce isophthalic acid and terephthalic acid, and
esters and derivatives thereof, from (i) furfural and (ii) beta
propiolactone or an alpha beta unsaturated acid (or an ester, amide
or thioester of such an unsaturated acid).
[0089] For example, with reference to FIG. 1, an exemplary pathway
is depicted to produce compounds of Formula IV, which may include
isophthalic acid, and compounds of Formula V, which may include
terephthalic acid, from furfural and beta propiolactone. In some
variations, as depicted in FIG. 3A, furfural and beta propiolactone
may combined to produce acetal compounds. In certain variations,
such acetal compounds may be hydrolyzed and oxidized to produce
compounds of Formula IV, which may include isophthalic acid. The
compounds of Formula IV may be isolated. In other variations, the
compounds of Formula IV may rearrange under suitable conditions to
produce compounds of Formula V, which may include terephthalic
acid.
[0090] With reference to FIG. 2A, an exemplary pathway is depicted
to produce compounds of Formula IV, which may include isophthalic
acid, and compounds of Formula V, which may include terephthalic
acid, from furfural and an alpha beta unsaturated acid or an ester
thereof. In some variations, as depicted in FIG. 3B, acetal
compounds may be produced from furfural and the alpha beta
unsaturated acid or ester thereof in certain variations, such
acetal compounds may be oxidized to produce compounds of Formula
IV, which may include isophthalic acid. The compounds of Formula IV
may be isolated. In other variations, the compounds of Formula IV
may rearrange under suitable conditions to produce compounds of
Formula V, which may include terephthalic acid.
[0091] With reference to FIG. 2B, an exemplary pathway is depicted
to produce phthalic acid or esters thereof, and compounds of
Formula V, which may include terephthalic acid, from furfural and
an alpha beta unsaturated acid or an ester thereof. In some
variations, as depicted in FIG. 3B, acetal compounds may be
produced from furfural and the alpha beta unsaturated acid or ester
thereof. In certain variations, such acetal compounds may be
oxidized to produce phthalic acid or esters thereof. The phthalic
acid or esters may be isolated. In other variations, the phthalic
acid or esters may rearrange under suitable conditions to produce
compounds of Formula V, which may include terephthalic acid.
[0092] In other aspects, provided herein are methods to produce
acetal compounds. Such acetal compounds may, in certain variations,
be used to produce phthalic acid, isophthalic acid, and
terephthalic acid, and esters and derivatives thereof.
[0093] For example, with reference to FIGS. 3A-3C, exemplary
pathways are depicted to produce various acetal compounds from
furfural and an alcohol of formula R.sup.kOH or OH--R.sup.k--OH.
With reference to FIGS. 3B and 3C, the acetal compounds may undergo
hydrolysis to produce compounds that may be further oxidized to
produce compounds of Formula IV, which may include isophthalic
acid, and compounds of Formula V, which may include terephthalic
acid (as depicted in FIGS. 1 and 2).
[0094] With reference again to FIGS. 3A-3C, the acetal compounds
from furfural and an alcohol of formula R.sup.k--OH of
OH--R.sup.k--OH may be used in other reactions to produce compounds
of Formulae IV and V. For example, in one variation, with reference
to FIG. 4A, the acetal compound may be combined with beta
propiolactone, and the product may undergo dehydration and
oxidation to produce compounds of Formula IV. In another variation,
with reference to FIG. 4B, the acetal compound may be combined with
an alpha beta unsaturated acid or ester, and the product may
undergo dehydration and oxidation to produce compounds of Formula
IV. In other variations, the compounds of Formula IV may rearrange
under suitable conditions to produce compounds of Formula V.
[0095] The various methods to make compounds of Formula IV and V,
along with various acetal compounds, are described in further
detail below.
[0096] The reaction of furfural (or acetals thereof) with BPL,
alpha beta unsaturated acids or alpha beta unsaturated acid
derivatives (such as esters, amides and thioesters) can, in
principal produce two regioisomeric products wherein either: the
aldehyde (or acetal) carbon atom of furfural and the carboxylic
carbon atom from the BPL or alpha beta unsaturated acid (or
derivative thereof) are situated on adjacent carbon atoms of the
cyclohexene ring of the product, or wherein the carboxylic carbon
atom from the BPL or alpha beta unsaturated acid (or derivative
thereof) are situated with unsubstituted ring carbon separating
them (as shown in FIG. 3A). Such isomers may be shown separately in
the methods described below, but it is to be understood that
mixtures of the two regioisomers may also be formed and that such
isomeric mixtures may be separated to isolate a desired isomer.
Such regioisomeric mixtures may also be carried on as a mixture to
one or more subsequent steps. All such variations are contemplated
herein though all variations may not be explicitly shown in the
schemes and descriptions that follow.
Methods Based on Addition of BPL to Furfural
##STR00024##
[0098] In certain aspects provided are methods that utilize BPL and
furfural as starting materials.
[0099] In certain aspects, provided are methods of making compounds
including adducts of BPL and furfural, as well as aromatized and
oxidized products of such adducts including aromatic dicarboxylic
acids.
[0100] In some embodiments, provided are methods of making a
compound of Formula I:
##STR00025##
the method comprising reacting furfural with beta propiolactone,
and optionally an alcohol of formula HOR.sup.y wherein R.sup.y is
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 14
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0101] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of Formula I.
[0102] In certain embodiments, provided are methods of making a
compound of Formula I:
##STR00026##
the method comprising reacting furfural with beta propiolactone,
where R.sup.y is as defined above and in the classes and subclasses
herein.
[0103] In certain embodiments, the methods include reacting
furfural with beta propiolactone in the presence of an alcohol. In
certain embodiments where the reaction is conducted in the presence
of an alcohol, the resulting product is an ester of that alcohol
(e.g., the alcohol is the form HO--R.sup.y where R.sup.y is other
than --H).
[0104] In certain embodiments, where the method comprises reacting
furfural and beta propiolactone in the presence of an alcohol of
formula HOR.sup.y, R.sup.y is C.sub.1-20 aliphatic, or C.sub.1-12
aliphatic, or C.sub.1-5 aliphatic, or C.sub.1-6 aliphatic, or
C.sub.1-4 aliphatic. In certain embodiments, R.sup.y is selected
from the group consisting of methyl, ethyl, n-butyl, and
2-ethylhexyl.
[0105] In certain embodiments, the reacting of furfural with the
beta propiolactone comprises heating a mixture of the furfural and
the beta propiolactone. In certain embodiments, the mixture is
heated to a temperature between 50.degree. C. and 300.degree. C. In
certain embodiments, the mixture is heated to a temperature between
50.degree. C. and 150.degree. C., between 100.degree. C. and
200.degree. C., between 120.degree. C. and 180.degree. C. or
between 150.degree. C. and 220.degree. C. In certain embodiments,
heating of the mixture of the furfural and the beta propiolactone
comprises flowing the mixture through a heated plug flow
reactor.
[0106] In certain embodiments, the reacting of furfural with the
beta propiolactone comprises contacting a mixture of the two
substances with a catalyst. In certain embodiments, the catalyst is
a Diels Alder catalyst. In certain embodiments, the catalyst is a
Lewis acidic catalyst.
[0107] In some embodiments, provided are methods of making a
compound of Formula:
##STR00027##
the method comprising reacting furfural with beta propiolactone,
and optionally an alcohol of formula HOR.sup.y, wherein R.sup.y is
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0108] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of Formula:
##STR00028##
[0109] In certain embodiments, the methods include reacting
furfural with beta propiolactone in the presence of an alcohol. In
certain embodiments where the reaction is conducted in the presence
of an alcohol, the resulting product is an ester of that alcohol
(e.g. the alcohol is the form HO--R.sup.y where R.sup.y is other
than --H.)
[0110] In certain embodiments, where the method comprises reacting
furfural and beta propiolactone in the presence of an alcohol of
formula HOR.sup.y is C.sub.1-20 aliphatic, or C.sub.1-12 aliphatic,
or C.sub.1-8 aliphatic, or C.sub.1-6 aliphatic, or C.sub.1-4
aliphatic. In certain embodiments, R.sup.y is selected from the
group consisting of methyl, ethyl, n-butyl, and 2-ethylhexyl.
[0111] In certain embodiments, the reacting of furfural with the
beta propiolactone comprises heating a mixture of the furfural and
the beta propiolactone. In certain embodiments, the mixture is
heated to a temperature between 50.degree. C. and 300.degree. C. In
certain embodiments, the mixture is heated to a temperature between
50.degree. C. and 150.degree. C., between 100.degree. C. and
200.degree. C., between 120.degree. C. and 180.degree. C. or
between 150.degree. C. and 220.degree. C. In certain embodiments,
heating of the mixture of the furfural and the beta propiolactone
comprises flowing the mixture through a heated plug flow
reactor.
[0112] In certain embodiments, the reacting of furfural with the
beta propiolactone comprises contacting a mixture of the two
substances with a catalyst. In certain embodiments, the catalyst is
a Diels Alder catalyst. In certain embodiments, the catalyst is a
Lewis acidic catalyst.
Methods Based on Adducts of BPL with Acetals of Furfural
##STR00029##
[0114] In certain aspects provided are methods that utilize BPL and
acetals of furfural as starting materials. In certain aspects,
provided are methods of making compounds including adducts of BPL
and furfural acetals, as well as aromatized and oxidized products
of such adducts including aromatic dicarboxylic acids. In some
embodiments, provided are methods of making compounds of Formula
IIb:
##STR00030##
the method comprising: [0115] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00031##
[0115] and [0116] b) contacting the acetal with beta propiolactone,
and optionally an alcohol of formula HOR.sup.Y, to produce the
compounds of Formula Bb, [0117] wherein: [0118] R.sup.k is,
independently at each occurrence, selected from the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; an oxygen protecting group; and a
nitrogen protecting group; where two R.sup.k may be taken with
intervening atoms to form an optionally substituted 4- to
7-membered heterocyclic ring having 0-2 additional heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur, and [0119] R.sup.y is hydrogen, or an
optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group.
[0120] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of Formula IIIb.
[0121] In certain embodiments, where the method comprises reacting
the acetal and beta propiolactone in the presence of an alcohol of
formula HOR.sup.y R.sup.Y is C.sub.1-20 aliphatic, or C.sub.1-12
aliphatic, or C.sub.1-8 aliphatic, or C.sub.1-6 aliphatic, or
C.sub.1-4 aliphatic. In certain embodiments, R.sup.y is selected
from the group consisting of methyl, ethyl, n-butyl, and
2-ethylhexyl.
[0122] In certain embodiments provided are methods of making
compounds of Formula IIb:
##STR00032##
the method comprising: [0123] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00033##
[0123] and [0124] b) contacting the acetal with beta propiolactone,
wherein each of R.sup.k and R.sup.y are as defined above and in the
classes and subclasses herein.
[0125] In some embodiments, provided are methods of making
compounds of Formula II:
##STR00034##
the method comprising: [0126] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00035##
[0126] and [0127] b) contacting the acetal with beta propiolactone,
and optionally an alcohol of formula HOR.sup.y, to produce the
compounds of Formula II, wherein: [0128] R.sup.k is, independently
at each occurrence, selected from the group consisting of acyl;
arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; where
two R.sup.k may be taken with intervening atoms to form an
optionally substituted 4- to 7-membered heterocyclic ring having
0-2 additional heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur, and [0129] R.sup.Y is
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0130] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of Formula H.
[0131] In certain embodiments, where the method comprises reacting
the acetal and beta propiolactone in the presence of an alcohol of
formula HOR.sup.y R.sup.y is C.sub.1-20 aliphatic, or C.sub.1-12
aliphatic, or C.sub.1-8 aliphatic, or C.sub.1-6 aliphatic, or
C.sub.1-4 aliphatic. In certain embodiments, R.sup.y is selected
from the group consisting of methyl, ethyl, n-butyl, and
2-ethylhexyl.
[0132] In certain embodiments provided are methods of making
compounds of Formula II:
##STR00036##
the method comprising: [0133] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00037##
[0133] and [0134] b) contacting the acetal with beta propiolactone,
wherein each of R.sup.k and R.sup.y are as defined above and in the
classes and subclasses herein.
[0135] In certain embodiments, the forming of the acetal and the
contacting with beta propiolactone are performed concomitantly. In
certain embodiments, the method comprises treating furfural and
beta propiolactone under dehydrating conditions in the presence of
an alcohol of formula R.sup.k--OH (or HO--R.sup.k--OH).
[0136] In certain embodiments, provided are methods for making
compounds of Formulae II and/or IIb, wherein each R.sup.k is the
same as R.sup.y. In certain embodiments, such methods comprise the
step of contacting beta propiolactone and furfural under
dehydrating conditions in the presence of an alcohol of formula
HOR.sup.k:
##STR00038##
[0137] In certain embodiments the method comprises reacting the
furfural and beta propiolactone in the presence of an alcohol of
formula HOR.sup.y, wherein R.sup.y is C.sub.1-20 aliphatic, or
C.sub.1-12 aliphatic, or C.sub.1-8 aliphatic, or C.sub.1-6
aliphatic, or C.sub.1-4 aliphatic. In certain embodiments, the
method comprises reacting the furfural and beta propiolactone in
the presence of an alcohol of formula HOR.sup.y, wherein R.sup.y is
selected from the group consisting of methyl, ethyl, n-butyl, and
2-ethylhexyl.
[0138] In some variations, provided are methods of making compounds
of Formula II:
##STR00039##
the method comprising: [0139] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00040##
[0139] and [0140] b) contacting the acetal with beta propiolactone,
and optionally an alcohol of formula HOR.sup.y, to produce the
compounds of Formula II, wherein: [0141] R.sup.k is, independently
at each occurrence, selected from the group consisting of acyl;
arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; where
two R.sup.k may be taken with intervening atoms to form an
optionally substituted 4- to 7-membered heterocyclic ring having
0-2 additional heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur, and [0142] R.sup.y is
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0143] In one variation of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.Y is H with respect to the
compound of Formula II.
##STR00041##
[0144] In some embodiments, provided are methods of making a
compound of Formula IV:
##STR00042##
the method comprising contacting furfural with BPL, and oxidizing
the resulting product, wherein R.sup.z is independently --H,
R.sup.y, optionally substituted C.sub.1-20 aliphatic, or optionally
substituted aryl.
[0145] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00043##
the method comprising contacting furfural with BPL and oxidizing
and dehydrating the resulting product, where R.sup.z is as defined
above and in the classes and subclasses herein.
[0146] In certain embodiments of the provided methods of making
compounds of Formula IV, R.sup.z is --H (e.g. compound of Formula
IV is isophthalic acid). Where R.sup.z is --H, the hydrogen atom
may derive from any proton source present during the dehydration or
oxidation processes. Such proton sources may include, for example,
water, alcohols, organic acids, or mineral acids.
[0147] In certain embodiments of the provided methods of making
compounds of Formula IV, R.sup.z is optionally substituted
C.sub.1-20 aliphatic or optionally substituted aryl. Where R.sup.z
is alkyl or aryl it may derive from an aliphatic or aromatic
alcohol present in the dehydration or oxidation steps.
##STR00044##
[0148] In some embodiments, provided are methods of making a
compound of Formula IV:
##STR00045##
wherein R.sup.z is, independently at each occurrence, --H, R.sup.Y,
optionally substituted C.sub.1-20 aliphatic, or optionally
substituted aryl, the method comprising contacting a compound of
formula:
##STR00046## [0149] wherein R.sup.k is, independently at each
occurrence, selected from the group consisting of acyl; arylalkyl;
6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; where
two R.sup.k may be taken with intervening atoms to form an
optionally substituted 4- to 7-membered heterocyclic ring having
0-2 additional heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur, with BPL, and
dehydrating and oxidizing the resulting product to produce the
compound of Formula IV.
[0150] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00047##
the method comprising contacting a compound of formula:
##STR00048##
with BPL and hydrolyzing, dehydrating and oxidizing the resulting
product, wherein each of R.sup.k and R.sup.z is as defined above
and in the classes and subclasses herein.
[0151] In certain embodiments of the above methods of making
compounds of Formula IV, R.sup.z is --H (e.g. compound IV is
isophthalic acid). Where R.sup.z is --H, the hydrogen atom may
derive from any proton source present during the dehydration or
oxidation processes. Such proton sources may include for example,
water, alcohols, organic acids, or mineral acids.
[0152] In certain embodiments of methods of making compounds of
Formula IV, R.sup.z is optionally substituted C.sub.1-20 aliphatic
or optionally substituted aryl. Where R is alkyl or aryl it may
derive from an aliphatic or aromatic alcohol present in the
dehydration or oxidation steps.
Methods Based on Diels Alder Adducts of Furfural and Furfural
Acetals
[0153] In another aspect, provided are methods of making compounds
including Diels Alder adducts, aromatized analogs thereof, and
aromatic dicarboxylic acids.
[0154] In certain aspects the provided methods utilize alpha beta
unsaturated acids (or their esters, amides or thioesters) and
furfural as starting materials to make aromatic diacids (or
intermediates suitable for making such diacids). In certain
aspects, provided are methods of making compounds including adducts
of acrylic acid or its esters and furfural, as well as aromatized
and oxidized products of such adducts including aromatic
dicarboxylic acids.
[0155] In certain embodiments, provided methods conform to the
following scheme:
##STR00049##
wherein Z is selected from the group consisting of --OR.sup.Y,
--Cl, --Br, --NR.sup.y.sub.2, and --SR.sup.y, wherein each R.sup.y
is independently hydrogen, or an optionally substituted group
selected the group consisting of: acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; an oxygen
protecting group; and a nitrogen protecting group; or wherein two
R.sup.y on a nitrogen atom may be taken with the nitrogen atom to
form an optionally substituted 4- to 7-membered heterocyclic ring
having 0-2 additional heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur.
[0156] In certain embodiments, Z is OR.sup.y and provided are
methods depicted in the following scheme:
##STR00050##
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0157] In certain embodiments, provided are methods of making a
compound of formula:
##STR00051##
the method comprising reacting furfural with an alpha beta
unsaturated acid or ester, wherein R.sup.y is as defined above and
in the classes and subclasses herein.
[0158] In certain variations, provided are methods of making a
compound of formula:
##STR00052##
the method comprising reacting furfural with an alpha beta
unsaturated acid, wherein R.sup.y is as defined above and in the
classes and subclasses herein.
[0159] In certain embodiments, the methods include reacting
furfural with an alpha beta unsaturated acid or ester having the
formula:
##STR00053##
where R.sup.y is as defined above and in the classes and subclasses
herein.
[0160] In certain variations, the methods include reacting furfural
with an alpha beta unsaturated acid having the formula:
##STR00054##
where R.sup.y is as defined above and in the classes an su classes
herein.
[0161] In certain embodiments, R.sup.y is --H. In certain
embodiments, R.sup.y is C.sub.1-20 aliphatic, or C.sub.1-12
aliphatic, or C.sub.1-8 aliphatic, or C.sub.1-6 aliphatic, or
C.sub.1-4 aliphatic. In certain embodiments R.sup.y is selected
from the group consisting of: methyl, ethyl, n-butyl, and
2ethylhexyl.
##STR00055##
[0162] In certain embodiments, provided methods utilize a
solid-supported alpha beta unsaturated acid. In certain
embodiments, provided are methods of making a compound of Formula
III:
##STR00056##
the method comprising reacting furfural with an alpha beta
unsaturated acid having the formula:
##STR00057##
wherein Q is a solid support.
[0163] In certain embodiments, Q comprises an inorganic support. In
certain embodiments, Q comprises an organic resin. In certain
embodiments, the linkage to the solid support Q comprises an ester
bond. In certain embodiments, the linkage to the solid support
comprises an amide bond.
[0164] In certain embodiments, provided methods comprise
hydrolyzing products of Formula III to release them from the solid
support. In certain embodiments provided methods include contacting
the compound of Formula III with an alcohol of formula
ROR.sup.y:
##STR00058##
wherein each of Q and R.sup.y is as defined above and in the
classes and subclasses herein.
[0165] In certain embodiments, provided are methods of making a
compound of formula:
##STR00059##
the method comprising treating a compound of formula
##STR00060##
with a compound of formula H--OR.sup.y, where each of Q and R.sup.y
is as defined above and in the classes and subclasses herein. In
certain embodiments, the reacting of furfural with the alpha beta
unsaturated acid comprises heating a mixture of the furfural and
the alpha beta unsaturated acid. In certain embodiments, the
mixture is heated to a temperature between 50.degree. C. and
300.degree. C. In certain embodiments, the mixture is heated to a
temperature between 50.degree. C. and 150.degree. C., between
100.degree. C. and 200.degree. C., between 120.degree. C. and
180.degree. C. or between 150.degree. C. and 220 OC. In certain
embodiments, the heating of the mixture of the furfural and the
alpha beta unsaturated acid comprises flowing the mixture through a
heated plug flow reactor.
[0166] In certain embodiments, the reacting of furfural with the
alpha beta unsaturated acid comprises contacting a mixture of the
two substances with a catalyst. In certain embodiments, the
catalyst is a Diels Alder catalyst. In certain embodiments, the
catalyst is a Lewis acidic catalyst.
[0167] In certain aspects the provided methods utilize alpha beta
unsaturated acids (or their esters, amides or thioesters) and
acetals of furfural as starting materials to make aromatic diacids
(or intermediates suitable for making such diacids). In certain
aspects, provided are methods of making compounds including adducts
of acrylic acid or its esters and furfural acetals, as well as
aromatized and oxidized products of such adducts including aromatic
dicarboxylic acids.
[0168] In certain embodiments, provided methods conform to the
following scheme:
##STR00061##
wherein each of R.sup.k and Z is as defined above and in the
classes and subclasses herein.
[0169] In certain embodiments, Z is OR.sup.y and provided methods
conform to the scheme:
##STR00062##
wherein each of R.sup.k and R.sup.y is as defined above and in the
classes and subclasses herein.
[0170] In certain embodiments, provided are methods of making a
compound of formula:
##STR00063##
the method comprising [0171] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00064##
[0171] and [0172] b) contacting the acetal with an alpha beta
unsaturated acid or ester having formula:
##STR00065##
[0173] wherein: [0174] R.sup.k is, independently at each
occurrence, selected from the group consisting of acyl; arylalkyl;
6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and a nitrogen protecting group; where
two R.sup.k may be taken with intervening atoms to form an
optionally substituted 4- to 7-membered heterocyclic ring having
0-2 additional heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur, and [0175] R.sup.y is
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0176] In certain embodiments, R.sup.y is --H. In certain
embodiments, R.sup.y is C.sub.1-20 aliphatic, or C.sub.1-12
aliphatic, or C.sub.1-8 aliphatic, or C.sub.1-6 aliphatic, or
C.sub.1-4 aliphatic. In certain embodiments R.sup.y is selected
from the group consisting of: methyl, ethyl, n-butyl, and
2ethylhexyl.
##STR00066##
[0177] In certain embodiments, provided methods utilize a
solid-supported alpha beta unsaturated acid to react with a
furfural acetal.
[0178] In certain embodiments, provided are methods of making a
compound of Formula IIIa:
##STR00067##
the method comprising: [0179] a) reacting furfural with an alcohol
of formula R.sup.k--OH (or HO--R.sup.k--OH) under dehydrating
conditions to provide an acetal compound of formula:
##STR00068##
[0179] and [0180] b) contacting the acetal with an alpha beta
unsaturated acid having the formula:
##STR00069##
[0181] where Q is as defined above and in the classes and
subclasses herein.
[0182] In certain embodiments, provided methods comprise
hydrolyzing products of Formula IIIa to release them from the solid
support. In certain embodiments provided methods include contacting
the compound of Formula IIIa with an alcohol of formula
HO--R.sup.y:
##STR00070##
wherein each of Q, R.sup.k and R.sup.Y is as defined above and in
the classes and subclasses herein.
[0183] In certain embodiments, provided are methods of making a
compound of formula:
##STR00071##
the method comprising treating a compound of Formula IIIa
##STR00072##
with a compound of formula H-QR.sup.y, wherein each of Q, R.sup.k
and R.sup.y is as defined above and in the classes and subclasses
herein.
[0184] In certain embodiments, the reacting of the acetal with the
alpha beta unsaturated acid or ester comprises heating a mixture of
the acetal and the alpha beta unsaturated acid or ester. In certain
embodiments, the mixture is heated to a temperature between
50.degree. C. and 300.degree. C. In certain embodiments, the
mixture is heated to a temperature between 50.degree. C. and
150.degree. C., between 100.degree. C. and 200.degree. C., between
120.degree. C. and 180.degree. C. or between 150.degree. C. and
220.degree. C. In certain embodiments, the heating of the mixture
of the acetal and the alpha beta unsaturated acid or ester
comprises flowing the mixture through a heated plug flow
reactor.
[0185] In certain embodiments, the reacting of acetal with the
alpha beta unsaturated acid or ester comprises contacting a mixture
of the two substances with a catalyst. In certain embodiments, the
catalyst is a Diels Alder catalyst. In certain embodiments, the
catalyst is a Lewis acidic catalyst.
##STR00073##
[0186] In some variations, provided are methods of making compounds
of Formula II':
##STR00074##
the method comprising: [0187] a) reacting furfural with an alcohol
of formula R.sup.k--OH under dehydrating conditions to provide an
acetal compound of formula:
##STR00075##
[0187] and [0188] b) contacting the acetal with an alpha beta
unsaturated acid, where Z and R.sup.k are as defined above and in
the classes and subclasses herein.
[0189] In certain embodiments, provided are methods of making
compounds of Formula II':
##STR00076##
[0190] the method comprising: [0191] a) reacting furfural with an
alcohol of formula R.sup.k--OH under dehydrating conditions to
provide an acetal compound of formula:
##STR00077##
[0191] and [0192] b) contacting the acetal with a compound of
formula
##STR00078##
[0193] wherein Z and R.sup.k are as defined above and in the
classes and subclasses herein.
##STR00079##
[0194] In certain embodiments, provided are methods of making a
compound of formula:
##STR00080##
the method comprising treating a compound of formula
##STR00081##
with a compound of formula H-QR.sup.y, where each of Q and R.sup.y
is as defined above and in the classes and subclasses herein.
##STR00082##
[0195] In certain embodiments, provided are methods of making a
compound of Formula I':
##STR00083##
the method comprising hydrolyzing a compound of Formula II'
##STR00084##
wherein each of Z and R.sup.k are as defined above and in the
classes and subclasses herein.
##STR00085##
[0196] In certain embodiments, provided are methods of making a
compound of formula:
##STR00086##
[0197] the method comprising hydrolyzing a compound of formula
##STR00087##
where each of Q and R.sup.k are as defined above and in the classes
and subclasses herein.
[0198] The hydrolysis may be performed under any suitable
conditions. For example, in some variations, the hydrolysis
comprises heating the acetal in the presence of water. In certain
embodiments, the hydrolysis comprises contacting the acetal with
water in the presence of an acid. In certain embodiments, the
hydrolysis comprises contacting the acetal with water in the
presence of a base.
##STR00088##
[0199] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00089##
wherein each R.sup.z is independently selected from the group
consisting of: --H, IV', optionally substituted C.sub.1-20
aliphatic, and optionally substituted aryl, the method comprising
oxidizing a compound of formula:
##STR00090## [0200] wherein R.sup.y is hydrogen, or an optionally
substituted moiety selected the group consisting of acyl;
arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group.
[0201] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00091##
the method comprising dehydrating and oxidizing a compound of
formula:
##STR00092##
wherein: [0202] R.sup.y is as defined above and in the classes and
subclasses herein; and each R.sup.z is independently selected from
the group consisting of: --H, R.sup.y, optionally substituted
C.sub.1-20 aliphatic, and optionally substituted aryl.
[0203] In certain embodiments, the oxidizing of the compound of
formula:
##STR00093##
comprises heating the compound in the presence of air. In certain
embodiments, the oxidizing step comprises heating the compound in
the presence of air and a solid catalyst. In certain embodiments,
the oxidizing step comprises heating the compound in the presence
of air and an acidic compound. In certain embodiments, the
oxidizing step is performed under conditions wherein water is
continuously removed from the reaction mixture.
[0204] In certain embodiments, for the compound of formula:
##STR00094##
in the methods above, each R.sup.z is --H.
[0205] In certain embodiments, for the compound of formula:
##STR00095##
in the methods above, each R.sup.z is --CH.sub.3.
[0206] In certain embodiments of the above methods of making
compounds of Formula IV, each R.sup.z is --H (e.g. compound of
Formula IV is isophthalic acid). Where R.sup.z is --H, the hydrogen
atom may derive from any proton source present during the
dehydration or oxidation processes. Such proton sources may include
for example, water, alcohols, organic acids, or mineral acids.
[0207] In certain embodiments of methods of making compounds of
Formula IV, R.sup.z is optionally substituted C.sub.1-20 aliphatic
or optionally substituted aryl. Where R.sup.z is alkyl or aryl it
may derive from an aliphatic or aromatic alcohol present in the
dehydration or oxidation steps.
##STR00096##
[0208] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00097##
wherein each R.sup.z is independently selected from the group
consisting of: --H, R.sup.y, optionally substituted C.sub.1-20
aliphatic, and optionally substituted aryl, the method comprising
contacting furfural with an alpha beta unsaturated carboxylic acid,
(or an ester, amide or thioester thereof) and dehydrating and
oxidizing the resulting product to produce the compound of Formula
IV.
[0209] In certain variations, provided are methods of making a
compound of Formula IV:
##STR00098##
the method comprising contacting furfural with an alpha beta
unsaturated carboxylic acid (or a derivative thereof) and oxidizing
the resulting product, where R.sup.z is as defined above and in the
classes and subclasses herein.
[0210] In some variations, the alpha beta unsaturated carboxylic
acid or derivative thereof is a compound of formula
##STR00099##
wherein R.sup.y is as defined above and in the classes and
subclasses herein
[0211] In some variations, the alpha beta unsaturated carboxylic
acid is acrylic acid.
##STR00100##
[0212] In certain embodiments, provided are methods of making a
compound of Formula IV:
##STR00101##
wherein each R.sup.z is, independently at each occurrence, selected
from the group consisting of: --H, R.sup.y, optionally substituted
C.sub.1-20 aliphatic, and optionally substituted aryl, the method
comprising contacting a compound of formula:
##STR00102##
wherein each R.sup.k is, independently at each occurrence, selected
from the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; an oxygen protecting group; and a
nitrogen protecting group; where two R.sup.k may be taken with
intervening atoms to form an optionally substituted 4- to
7-membered heterocyclic ring having 0-2 additional heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur, with an alpha beta unsaturated acid (or an
ester, amide, or thioester thereof) and oxidizing the resulting
product to produce the compound of Formula IV.
[0213] In certain variations, provided are methods of making a
compound of Formula IV:
##STR00103##
the method comprising contacting a compound of formula:
##STR00104##
with an alpha beta unsaturated acid (or a derivative thereof) and
oxidizing the resulting product, where each of R.sup.k and R.sup.z
is as defined above and in the classes and subclasses herein.
[0214] In some variations, the alpha beta unsaturated carboxylic
acid is a compound of formula
##STR00105##
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0215] In some variations, the alpha beta unsaturated carboxylic
acid is acrylic acid.
[0216] In certain embodiments of the above methods of making
compounds of Formula IV, R.sup.z is --H (e.g. compound of Formula
IV is isophthalic acid). Where R.sup.z is --H, the hydrogen atom
may derive from any proton source present during the dehydration or
oxidation processes. Such proton sources may include for example,
water, alcohols, organic acids, or mineral acids.
[0217] In certain embodiments of methods of making compounds of
Formula IV, R.sup.z is optionally substituted C.sub.1-20 aliphatic
or optionally substituted aryl. Where R.sup.z is alkyl or aryl it
may derive from an aliphatic or aromatic alcohol present in the
dehydration or oxidation steps.
Continuous Processes
[0218] In another aspect, provided are continuous processes for
producing aromatic dicarboxylic acids and precursors thereof.
##STR00106##
[0219] In some embodiments, provided is a continuous process for
the production of compounds of formula:
##STR00107##
the continuous process comprising continuously feeding a reaction
zone with furfural and BPL, and optionally an alcohol of formula
HOR.sup.y, wherein R.sup.y is hydrogen, or an optionally
substituted moiety selected the group consisting of acyl;
arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20
heteroaliphatic having 1-4 heteroatoms independently selected from
the group consisting of nitrogen, oxygen, and sulfur; 5- to
10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group.
[0220] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound produced.
[0221] In certain embodiments, provided is a continuous process for
the production of compounds of formula:
##STR00108##
the continuous process comprising continuously feeding a reaction
zone with furfural and BPL, where R.sup.y is as defined above and
in the classes and subclasses herein.
[0222] In certain embodiments, the reaction zone fed with furfural
and the BPL is heated. In certain embodiments, the reaction zone is
heated to a temperature between 50.degree. C. and 300.degree. C. In
certain embodiments, the reaction zone is heated to a temperature
between 50.degree. C. and 150.degree. C., between 100.degree. C.
and 200.degree. C., between 120.degree. C. and 180.degree. C., or
between 150.degree. C. and 220.degree. C.
[0223] In certain embodiments, the reaction zone fed with furfural
and the BPL contains a catalyst. In certain embodiments, the
reaction zone contains a Lewis acidic catalyst. In certain
embodiments, the reaction zone contains a heterogeneous Lewis
acidic catalyst.
[0224] In certain embodiments, the process further includes
withdrawing a product stream containing a compound of formula
##STR00109##
from the reaction zone.
##STR00110##
[0225] In certain embodiments, provided is a continuous process for
the production of compounds of formula:
##STR00111##
the continuous process comprising continuously feeding a reaction
zone with furfural and an alpha beta unsaturated acid or ester,
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0226] In some variations, the alpha beta unsaturated acid or ester
is a compound of formula
##STR00112##
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0227] In certain embodiments, the reaction zone fed with furfural
and the alpha beta unsaturated acid or ester is heated. In certain
embodiments, the reaction zone is heated to a temperature between
50.degree. C. and 300.degree. C. In certain embodiments, the
reaction zone is heated to a temperature between 50.degree. C. and
150.degree. C., between 100.degree. C. and 200.degree. C., between
120.degree. C. and 180.degree. C., or between 150.degree. C. and
220.degree. C.
[0228] In certain embodiments, the reaction zone fed with furfural
and the alpha beta unsaturated acid or ester contains a catalyst.
In certain embodiments, the reaction zone contains a Lewis acidic
catalyst. In certain embodiments, the reaction zone contains a
heterogeneous Lewis acidic catalyst.
[0229] In certain embodiments, the process further includes
withdrawing a product stream containing a Diels Alder adduct of the
furfural and an alpha beta unsaturated acid or ester from the
reaction zone.
##STR00113##
[0230] In some embodiments, provided is a continuous process for
making a compound of Formula IV:
##STR00114##
wherein each R.sup.z is independently selected from the group
consisting of: --H, R.sup.y, optionally substituted C.sub.1-20
aliphatic, and optionally substituted aryl, the process comprising
continuously feeding to a reaction zone a compound of formula:
##STR00115##
wherein R.sup.y is hydrogen, or an optionally substituted moiety
selected the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5 to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4 to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group, where
it is contacted with air, optionally in the presence of a catalyst
to produce the compound of Formula IV.
[0231] In certain embodiments, the process includes providing a
proton source in the reaction zone. In such embodiments, R.sup.z in
compounds of Formula IV is --H (e.g. compound of Formula IV is
isophthalic acid). Suitable proton sources include water, alcohols,
organic acids, and mineral acids.
[0232] In certain embodiments, the process includes providing an
alcohol ROH in the reaction zone. Suitable alcohols include
aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the reaction zone, R.sup.z
in the product may be --H, or R.sup.z may be a group corresponding
to R in the provided alcohol or the product may comprise a mixture
where R.sup.z groups are a mixture of --H and --R.
[0233] In certain embodiments, R.sup.z in compounds of Formula IV
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present in the reaction
zone).
[0234] In certain embodiments, provided is a continuous process for
making a compound of Formula IV:
##STR00116##
the process comprising continuously feeding to a reaction zone a
compound of formula:
##STR00117##
where it is contacted with air, optionally in the presence of a
catalyst.
[0235] In certain embodiments, the reaction zone is heated. In
certain embodiments, the reaction zone is heated to a temperature
between 100.degree. C. and 500.degree. C. In certain embodiments,
the reaction zone is heated to a temperature between 100.degree. C.
and 200.degree. C., between 120.degree. C. and 180.degree. C.,
between 150.degree. C. and 220.degree. C., between 200.degree. C.
and 300.degree. C., or between 300.degree. C. and 450.degree.
C.
[0236] In certain embodiments, the reaction zone comprises an acid
catalyst. In certain embodiments, the reaction zone contains
sulfuric acid. In certain embodiments, the reaction zone comprises
a heterogeneous catalyst. In certain embodiments, the reaction zone
comprises a solid acid catalyst.
[0237] In certain embodiments, the process further includes
continuously withdrawing a product stream containing isophthalic
acid or an ester thereof from the reaction zone. In certain
embodiments, the process further includes a step of purifying the
isophthalic acid (or esters thereof) withdrawn from the reaction
zone. In certain embodiments, the purification includes
distillation, crystallization, or a combination of both of
these.
##STR00118##
[0238] In some embodiments, provided is a continuous process for
making a compound of Formula IV:
##STR00119##
wherein R.sup.z is independently selected from the group consisting
of: --H, R.sup.y, optionally substituted C.sub.1-20 aliphatic, and
optionally substituted aryl, the process comprising continuously
feeding a first reaction zone with furfural and BPL, and optionally
an alcohol of formula HOR.sup.y, wherein R.sup.y is hydrogen, or an
optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group, to produce a compound of
formula:
##STR00120##
which is fed to a second reaction zone where it is contacted with
air, optionally in the presence of a catalyst to produce the
compound of Formula IV.
[0239] In certain embodiments, the process includes providing a
proton source in the second reaction zone. In such embodiments,
R.sup.z in compounds of Formula IV is --H (e.g. compound of Formula
IV is isophthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0240] In certain embodiments, the process includes providing an
alcohol ROH in the second reaction zone. Suitable alcohols include
aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0241] In certain embodiments, R.sup.z in compounds of Formula IV
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present in the second
reaction zone).
[0242] In some variations of the foregoing, when the alcohol of
formula HOR.sup.Y is absent, then R.sup.y is H with respect to the
compound of formula
##STR00121##
[0243] In certain embodiments, provided is a continuous process for
making a compound of Formula:
##STR00122##
the process comprising continuously feeding a first reaction zone
with furfural and BPL, to produce a compound of formula:
##STR00123##
which is fed to a second reaction zone where it is contacted with
air, optionally in the presence of a catalyst.
[0244] In certain embodiments, the first reaction zone is heated.
In certain embodiments, the first reaction zone is heated to a
temperature between 50.degree. C. and 300.degree. C. In certain
embodiments, the reaction zone is heated to a temperature between
50.degree. C. and 150.degree. C., between 100.degree. C. and
200.degree. C., between 120.degree. C. and 180.degree. C., or
between 150.degree. C. and 220.degree. C.
[0245] In certain embodiments, the first reaction zone contains a
catalyst. In certain embodiments, the first reaction zone contains
a Lewis acidic catalyst. In certain embodiments, the first reaction
zone contains a heterogeneous Lewis acidic catalyst.
[0246] In certain embodiments, the second reaction zone is heated.
In certain embodiments, the second reaction zone is heated to a
temperature between 100.degree. C. and 500.degree. C. In certain
embodiments, the reaction zone is heated to a temperature between
100.degree. C. and 200.degree. C., between 120.degree. C. and
180.degree. C., between 150.degree. C. and 220.degree. C., between
200.degree. C. and 300.degree. C., or between 300.degree. C. and
450.degree. C.
[0247] In certain embodiments, the second reaction zone comprises
an acid catalyst. In certain embodiments, the second reaction zone
contains sulfuric acid. In certain embodiments, the second reaction
zone comprises a heterogeneous catalyst. In certain embodiments,
the second reaction zone comprises a solid acid catalyst.
[0248] In certain embodiments, the process further includes
continuously withdrawing a product stream containing isophthalic
acid or an ester thereof from the second reaction zone. In certain
embodiments, the process further includes purifying the isophthalic
acid (or esters thereof) withdrawn from the second reaction zone.
In certain embodiments, the purification includes distillation,
crystallization, or a combination of both of these.
##STR00124##
certain embodiments, provided is a continuous process for making a
compound of Formula V:
##STR00125##
wherein R.sup.z is independently selected from the group consisting
of: --H, R.sup.y, optionally substituted C.sub.1-20 aliphatic, and
optionally substituted aryl, the process comprising continuously
feeding to an oxidizing reaction zone a compound of formula:
##STR00126##
wherein it is contacted with air, optionally in the presence of a
catalyst to form a compound of Formula IV:
##STR00127##
and then, either within the same reaction zone or in a subsequent
rearrangement reaction zone, converted to a compound of Formula
(V).
[0249] In certain embodiments, the process includes providing a
proton source in the oxidizing reaction zone. In such embodiments,
R.sup.z in compounds of Formula V is --H (e.g. compound of Formula
V is terephthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0250] In certain embodiments, the process includes providing an
alcohol ROH in the oxidizing reaction zone. Suitable alcohols
include aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0251] In certain embodiments, R.sup.z in compounds of V may
represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present in the oxidizing
reaction zone).
[0252] In certain embodiments, provided is a continuous process for
making a compound of Formula V:
##STR00128##
the process comprising continuously feeding a first reaction zone
with furfural or a derivative thereof and BPL to provide a product
of formula:
##STR00129##
which is fed to a second reaction zone where it is contacted with
air, optionally in the presence of a catalyst to form a compound of
formula;
##STR00130##
and then, either within the same reaction zone or in a subsequent
rearrangement reaction zone, converted to a compound of Formula V,
wherein each of R.sup.z, and R.sup.y are as defined above and in
the classes and subclasses herein.
[0253] In certain embodiments of this process, the oxidation
reaction zone and the rearrangement reaction zone are contiguous
and the process stream flows from a reactor inlet through an
oxidation zone and into a rearrangement zone. In certain
embodiments, there is a temperature gradient whereby the
rearrangement reaction zone is maintained at a higher temperature
than the oxidation reaction zone.
[0254] In certain embodiments, the oxidation reaction zone is
heated. In certain embodiments, the oxidation reaction zone is
heated to a temperature between 100.degree. C. and 300.degree. C.
In certain embodiments, the reaction zone is heated to a
temperature between 100.degree. C. and 200.degree. C., between
120.degree. C. and 180.degree. C., between 150.degree. C. and
220.degree. C., or between 200.degree. C. and 250.degree. C.
[0255] In certain embodiments, the rearrangement reaction zone is
heated. In certain embodiments, the reaction zone is heated to a
temperature between 300.degree. C. and 500.degree. C. In certain
embodiments, the reaction zone is heated to a temperature between
300.degree. C. and 400.degree. C., between 350.degree. C. and
450.degree. C., between 400.degree. C. and 500.degree. C., between
400.degree. C. and 450.degree. C., or between 450.degree. C. and
500.degree. C.
[0256] In certain embodiments, the oxidation reaction zone
comprises a catalyst. In certain embodiments, the oxidation
reaction zone comprises an acid catalyst. In certain embodiments,
the oxidation reaction zone contains sulfuric acid. In certain
embodiments, the oxidation reaction zone comprises a heterogeneous
catalyst. In certain embodiments, the oxidation reaction zone
comprises a solid acid catalyst.
[0257] In certain embodiments, the rearrangement reaction zone
comprises a catalyst. In certain embodiments, the rearrangement
reaction zone comprises a transition metal catalyst. In certain
embodiments, the rearrangement reaction zone contains a
cadmium-based catalyst. In certain embodiments, the rearrangement
reaction zone comprises a heterogeneous catalyst. In certain
embodiments, the rearrangement reaction zone comprises a
heterogeneous transition metal catalyst. In certain embodiments,
the rearrangement reaction zone comprises a solid
cadmium-containing catalyst.
[0258] In certain embodiments, the process includes providing a
proton source in the one or more of the oxidation reaction zone and
the rearrangement reaction zone. In such embodiments, R.sup.z in
compounds of Formula V is --H (e.g. compound of Formula V is
terephthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0259] In certain embodiments, the process includes providing an
alcohol ROH in the one or more of the oxidation reaction zone and
the rearrangement reaction zone. Suitable alcohols include
aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0260] In certain embodiments, R.sup.z in compounds of Formula V
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present one or more reaction
zones).
[0261] In certain embodiments, the process further includes
continuously withdrawing a product stream containing terephthalic
acid or an ester thereof from the rearrangement reaction zone. In
certain embodiments, the process includes withdrawing a product
stream containing terephthalic acid or an ester thereof which also
contains one or more coproducts selected from benzene, benzoic acid
(or esters thereof), phthalic acid (or esters thereof), and
isophthalic acid (or esters thereof). In certain embodiments the
process further includes a step of separating terephthalic acid (or
esters thereof) from one or more of these co-products. In certain
embodiments the separating process includes one or more of
distillation, and crystallization.
##STR00131##
[0262] In certain embodiments, provided is a continuous process for
the production of compounds of Formula IV:
##STR00132## [0263] the continuous process comprising continuously
feeding a Diels Alder reaction zone with furfural and an alpha beta
unsaturated acid or ester, to provide a compound of formula:
##STR00133##
[0263] and further comprising feeding this compound to an oxidation
reaction zone, where it is oxidized to a compound of Formula IV,
wherein each of R.sup.z and R.sup.y are as defined above and in the
classes and subclasses herein.
[0264] In some variations, the alpha beta unsaturated acid or ester
is
##STR00134##
wherein R.sup.y is as defined above and in the classes and
subclasses herein.
[0265] In certain embodiments, the Diels Alder reaction zone is
heated. In certain embodiments, the Diels Alder reaction zone is
heated to a temperature between 50.degree. C. and 300.degree. C. In
certain embodiments, the Diels Alder reaction zone is heated to a
temperature between 50.degree. C. and 150.degree. C., between
100.degree. C. and 200.degree. C., between 120.degree. C. and
180.degree. C., or between 150.degree. C. and 220.degree. C.
[0266] In certain embodiments, the Diels Alder reaction zone
contains a catalyst. In certain embodiments, the Diels Alder
reaction zone contains a Lewis acidic catalyst. In certain
embodiments, the reaction zone contains a heterogeneous Lewis
acidic catalyst.
[0267] In certain embodiments, the process further includes
purifying a product stream obtained from the Diels Alder reaction
zone prior to inputting it to the oxidation reaction zone. In
certain embodiments, the purifying step comprises distilling away
unreacted furfural or alpha beta unsaturated acids or esters. In
certain embodiments, these materials are returned to the inlet of
the Diels Alder reaction zone for further conversion. In certain
embodiments, the purifying comprises crystallizing Diels Alder
adducts from the product stream and separating the crystalline
material from dissolved materials. In certain embodiments, the
dissolved fraction is returned to the inlet of the Diels Alder
reaction zone.
##STR00135##
[0268] In some embodiments, provided is a continuous process for
the production of compounds of Formula IV:
##STR00136##
the continuous process comprising continuously feeding a first
reaction zone with furfural and BPL, and optionally an alcohol of
formula HOR.sup.y, to provide a compound of formula:
##STR00137##
and wherein R.sup.y is hydrogen, or an optionally substituted
moiety selected the group consisting of acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group; and feeding this compound to an oxidation
reaction zone, where it is oxidized to a compound of Formula
IV.
[0269] In certain embodiments, the process includes providing a
proton source in the oxidizing reaction zone. In such embodiments,
R.sup.z in compounds of Formula IV is --H (e.g. compound of Formula
IV is isophthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0270] In certain embodiments, the process includes providing an
alcohol ROH in the oxidizing reaction zone. Suitable alcohols
include aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0271] In certain embodiments, R.sup.z in compounds of Formula IV
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present in the oxidizing
reaction zone).
[0272] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of formula
##STR00138##
[0273] In certain embodiments, provided is a continuous process for
the production of compounds of formula:
##STR00139##
the continuous process comprising continuously feeding a first
reaction zone with furfural and BPL, to provide a compound of
formula:
##STR00140##
and further comprising feeding this compound to an oxidation
reaction zone, where it is oxidized to a compound of formula
##STR00141##
[0274] In certain embodiments, the first reaction zone is heated.
In certain embodiments, the first reaction zone is heated to a
temperature between 50.degree. C. and 300.degree. C. In certain
embodiments, the first reaction zone is heated to a temperature
between 50.degree. C. and 150.degree. C., between 100.degree. C.
and 200.degree. C., between 120.degree. C. and 180.degree. C., or
between 150.degree. C. and 220.degree. C.
[0275] In certain embodiments, the first reaction zone contains a
catalyst. In certain embodiments, the first reaction zone contains
a Lewis acidic catalyst. In certain embodiments, the first reaction
zone contains a heterogeneous Lewis acidic catalyst.
[0276] In certain embodiments, the process further includes
purifying a product stream obtained from the first zone prior to
inputting it to the oxidation reaction zone. In certain embodiments
the purifying step comprises distilling away unreacted furfural or
alpha beta unsaturated acids or esters. In certain embodiments,
these materials are returned to the inlet of the first reaction
zone for further conversion. In certain embodiments, the step of
purifying comprises crystallizing product from the product stream
and separating the crystalline material from dissolved materials.
In certain embodiments, the dissolved fraction is returned to the
inlet of the first reaction zone.
[0277] In certain embodiments, the oxidation reaction zone is
heated. In certain embodiments, the oxidation reaction zone is
heated to a temperature between 100.degree. C. and 500.degree. C.
In certain embodiments, the oxidation reaction zone is heated to a
temperature between 100.degree. C. and 200.degree. C., between
120.degree. C. and 180.degree. C., between 150.degree. C. and
220.degree. C., between 200.degree. C. and 300.degree. C., or
between 300.degree. C. and 450.degree. C.
[0278] In certain embodiments, the oxidation reaction zone
comprises an acid catalyst. In certain embodiments, the oxidation
reaction zone contains sulfuric acid. In certain embodiments, the
oxidation reaction zone comprises a heterogeneous catalyst. In
certain embodiments, the oxidation reaction zone comprises a solid
acid catalyst.
[0279] In certain embodiments, the process further includes
continuously withdrawing a product stream containing isophthalic
acid or an ester thereof from the oxidation reaction zone. In
certain embodiments, the process further includes a step of
purifying the isophthalic acid (or esters thereof) withdrawn from
the oxidation reaction zone. In certain embodiments, the
purification includes distillation, crystallization, or a
combination of both of these.
##STR00142##
[0280] In some embodiments, provided is a continuous process for
making a compound of Formula V:
##STR00143##
wherein R.sup.z is independently selected from the group consisting
of: --H, R.sup.y, optionally substituted C.sub.1-20 aliphatic, and
optionally substituted aryl, the continuous process comprising
continuously feeding a Diels Alder reaction zone with furfural and
an alpha beta unsaturated acid or ester, to provide a compound of
formula:
##STR00144##
wherein R.sup.y is hydrogen, or an optionally substituted moiety
selected the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group;
feeding the compound to an oxidation reaction zone where it is
contacted with air, optionally in the presence of a catalyst, to
form a compound of Formula IV:
##STR00145##
and feeding the compound of Formula IV to a rearrangement reaction
zone, where it is converted to a compound of Formula V.
[0281] In certain embodiments, the process includes providing a
proton source in the oxidizing reaction zone. In such embodiments,
R.sup.z in compounds of Formula V is --H (e.g. compound of Formula
V is terephthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0282] In certain embodiments, the process includes providing an
alcohol ROH in the oxidizing reaction zone. Suitable alcohols
include aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0283] In certain embodiments, R.sup.z in compounds of Formula V
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present in the oxidizing
reaction zone).
[0284] In certain embodiments, provided is a continuous process for
making a compound of formula:
##STR00146##
the continuous process comprising continuously feeding a Diels
Alder reaction zone with furfural and an alpha beta unsaturated
acid or ester, to provide a compound of formula:
##STR00147##
which is then fed to an oxidation reaction zone where it is
contacted with air, optionally in the presence of a catalyst, to
form a compound of formula:
##STR00148##
which is then fed to a rearrangement reaction zone, where it is
converted to a compound of formula:
##STR00149##
wherein each of R.sup.z, and R.sup.y are as defined above and in
the classes and subclasses herein.
[0285] In certain embodiments of the processes described herein,
the Die Is Alder reaction zone is heated. In certain embodiments,
the Diels Alder reaction zone is heated to a temperature between
50.degree. C. and 300.degree. C. In certain embodiments, the Diels
Alder reaction zone is heated to a temperature between 50.degree.
C. and 150.degree. C., between 100.degree. C. and 200.degree. C.,
between 120.degree. C. and 180.degree. C., or between 150.degree.
C. and 220.degree. C.
[0286] In certain embodiments, the Diels Alder reaction zone
contains a catalyst. In certain embodiments, the Diels Alder
reaction zone contains a Lewis acidic catalyst. In certain
embodiments, the reaction zone contains a heterogeneous Lewis
acidic catalyst.
[0287] In certain embodiments, the processes described herein
further include purifying a product stream obtained from the Diels
Alder reaction zone prior to inputting it to the oxidation reaction
zone. In certain embodiments the purifying step comprises
distilling away unreacted furfural or alpha beta unsaturated acids
or esters. In certain embodiments, these materials are returned to
the inlet of the Diels Alder reaction zone for further conversion.
In certain embodiments, the step of purifying comprises
crystallizing Diels Alder adducts from the product stream and
separating the crystalline material from dissolved materials. In
certain embodiments, the dissolved fraction is returned to the
inlet of the Diels Alder reaction zone.
##STR00150##
[0288] In some embodiments, provided is a continuous process for
making a compound of Formula V:
##STR00151##
wherein R.sup.z is independently selected from the group consisting
of: --H, R.sup.y, optionally substituted C.sub.1-20 aliphatic, and
optionally substituted aryl, the continuous process comprising
continuously feeding a first reaction zone with furfural and BPL,
and optionally an alcohol of formula HOR.sup.y, to provide a
compound of formula:
##STR00152##
and wherein R.sup.y is hydrogen, or an optionally substituted
moiety selected the group consisting of acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group, to provide a compound of formula:
##STR00153##
feeding the compound to an oxidizing reaction zone where it is
contacted with air, optionally in the presence of a catalyst, to
form a compound of Formula IV:
##STR00154##
which is then fed to a rearrangement reaction zone, where it is
converted to a compound of Formula V.
[0289] In certain embodiments, the process includes providing a
proton source in the one or more of the oxidation reaction zone and
the rearrangement reaction zone. In such embodiments, R.sup.z in
compounds of Formula V is --H (e.g. compound of Formula V is
terephthalic acid). Suitable proton sources include water,
alcohols, organic acids, and mineral acids.
[0290] In certain embodiments, the process includes providing an
alcohol ROH in the one or more of the oxidation reaction zone and
the rearrangement reaction zone. Suitable alcohols include
aliphatic alcohols (e.g. C.sub.1-20 alcohols) and aromatic
alcohols. When an alcohol is present in the second reaction zone,
R.sup.z in the product may be --H, or R.sup.z may be a group
corresponding to R in the provided alcohol or the product may
comprise a mixture where R.sup.z groups are a mixture of --H and
--R.
[0291] In certain embodiments, R.sup.z in compounds of Formula V
may represent a mixture including groups corresponding to any
combination of R.sup.y (e.g., from the starting material), --H, and
R (e.g., from the alcohol ROH if it is present one or more reaction
zones).
[0292] In some variations of the foregoing, when the alcohol of
formula HOR.sup.y is absent, then R.sup.y is H with respect to the
compound of formula
##STR00155##
[0293] In certain embodiments, provided is a continuous process for
making a compound of formula:
##STR00156##
the continuous process comprising continuously feeding a first
reaction zone with furfural and BPL, to provide a compound of
formula:
##STR00157##
which is then fed to an oxidizing reaction zone where it is
contacted with air, optionally in the presence of a catalyst, to
form a compound of formula:
##STR00158##
which is then fed to a rearrangement reaction zone, where it is
converted to a compound of formula:
##STR00159##
where each of R.sup.z and R.sup.y are independently as defined
above and in the classes and subclasses herein.
[0294] In certain embodiments of the processes described herein,
the first reaction zone is heated. In certain embodiments, the
first reaction zone is heated to a temperature between 50.degree.
C. and 300.degree. C. In certain embodiments, the first reaction
zone is heated to a temperature between 50.degree. C. and
150.degree. C., between 100.degree. C. and 200.degree. C., between
120.degree. C. and 180.degree. C., or between 150.degree. C. and
220.degree. C.
[0295] In certain embodiments of the processes described herein,
the first reaction zone contains a catalyst. In certain
embodiments, the first reaction zone contains a Lewis acidic
catalyst. In certain embodiments, the first reaction zone contains
a heterogeneous Lewis acidic catalyst.
[0296] In certain embodiments, the processes described herein
further include purifying a product stream obtained from the first
reaction zone prior to inputting it to the oxidation reaction zone.
In certain embodiments the purifying step comprises distilling away
unreacted furfural, BPL, or alpha beta unsaturated acids or esters.
In certain embodiments, these materials are returned to the inlet
of the first reaction zone for further conversion. In certain
embodiments, the step of purifying comprises crystallizing products
from the product stream and separating the crystalline material
from dissolved materials. In certain embodiments, the material from
the dissolved fraction is returned to the inlet of the first
reaction zone.
[0297] In certain embodiments of the processes described herein,
the oxidation reaction zone is heated. In certain embodiments, the
oxidation reaction zone is heated to a temperature between
100.degree. C. and 300.degree. C. In certain embodiments, the
reaction zone is heated to a temperature between 100.degree. C. and
200.degree. C., between 120.degree. C. and 180.degree. C., between
150.degree. C. and 220.degree. C., or between 200.degree. C. and
250.degree. C.
[0298] In certain embodiments of the processes described herein,
the oxidation reaction zone comprises a catalyst. In certain
embodiments, the oxidation reaction zone comprises an acid
catalyst. In certain embodiments, the oxidation reaction zone
contains sulfuric acid. In certain embodiments, the oxidation
reaction zone comprises a heterogeneous catalyst. In certain
embodiments, the oxidation reaction zone comprises a solid acid
catalyst.
[0299] In certain embodiments of the processes described herein,
the rearrangement reaction zone is heated. In certain embodiments,
the reaction zone is heated to a temperature between 300.degree. C.
and 500.degree. C. In certain embodiments, the reaction zone is
heated to a temperature between 300.degree. C. and 400.degree. C.,
between 350.degree. C. and 450.degree. C., between 400.degree. C.
and 500.degree. C., between 400.degree. C. and 450.degree. C., or
between 450.degree. C. and 500.degree. C.
[0300] In certain embodiments, the rearrangement reaction zone
comprises a catalyst. In certain embodiments, the rearrangement
reaction zone comprises a transition metal catalyst. In certain
embodiments, the rearrangement reaction zone contains a
cadmium-based catalyst. In certain embodiments, the rearrangement
reaction zone comprises a heterogeneous catalyst. In certain
embodiments, the rearrangement reaction zone comprises a
heterogeneous transition metal catalyst. In certain embodiments,
the rearrangement reaction zone comprises a solid
cadmium-containing catalyst.
[0301] In certain embodiments of the processes described herein,
the oxidation reaction zone and the rearrangement reaction zone are
contiguous and the process stream flows from a reactor inlet
through an oxidation zone and into a rearrangement zone. In certain
embodiments, there is a temperature gradient whereby the
rearrangement reaction zone is maintained at a higher temperature
than the oxidation reaction zone.
[0302] In certain embodiments of the processes described herein,
the product of the oxidation reaction zone is converted to a salt
prior to being fed to the rearrangement reaction zone. In certain
embodiments of this process, the product of the oxidation reaction
zone is converted to its alkali metal salt prior to being fed to
the rearrangement reaction zone. In certain embodiments of this
process, the product of the oxidation reaction zone is converted to
its potassium salt prior to being fed to the rearrangement reaction
zone. In some variations of this process, the product of the
oxidation reaction zone is converted to its alkali metal salt prior
to being fed to the rearrangement reaction zone. In other
variations of this process, the stream withdrawn from the
rearrangement reaction zone is subsequently treated with an acid to
convert the alkali metal salt of the terephthalic acid back to its
acid form, or optionally with inclusion of an appropriate alcohol
or similar reagent to a terephthalate ester. In certain embodiments
of this process, the stream withdrawn from the rearrangement
reaction zone is subsequently treated with an acid to convert the
alkali metal salt of the terephthalic acid back to its acid form,
or optionally with inclusion of an appropriate alcohol or similar
reagent to form a terephthalate ester.
[0303] In certain embodiments, the processes described herein
further include continuously withdrawing a product stream
containing terephthalic acid or an ester thereof from the
rearrangement reaction zone. In certain embodiments, the process
includes withdrawing a product stream containing terephthalic acid
(or an ester or salt thereof) which also contains one or more
co-products selected from benzene, benzoic acid (or esters or salts
thereof), phthalic acid (or esters thereof), and isophthalic acid
(or esters thereof). In certain embodiments, the process further
includes a step of separating terephthalic acid (or esters thereof)
from one or more of these co-products. In certain embodiments, the
separating process includes one or more of distillation, and
crystallization.
Polymer Compositions
[0304] In another aspect, provided are biobased monomers and
polymer compositions derived therefrom.
[0305] In certain embodiments, provided are polymer compositions
comprising isophthalic acid and esters thereof, characterized by
their biobased carbon content. In certain embodiments, such
compositions comprise compounds having a formula:
##STR00160##
and characterized in that carbon atoms I through 5 are derived from
biobased furfural. In certain embodiments of such compositions,
R.sup.z is --H. In certain embodiments of such compositions,
R.sup.z is C.sub.1-20 aliphatic. In certain embodiments of such
compositions R.sup.z is selected from the group consisting of:
methyl, ethyl, n-butyl, and 2-ethylhexyl.
[0306] In certain embodiments, provided is biobased terephthalic
acid compositions derived by rearrangement of such isophthalic acid
compositions (or esters thereof).
[0307] In certain embodiments, such compositions comprise compounds
having a formula:
##STR00161##
and characterized in that carbon atoms 6 through 8 are derived from
a biobased alpha beta unsaturated acid. In certain embodiments of
such compositions, R.sup.z is --H. In certain embodiments of such
compositions, R.sup.z is C.sub.1-20 aliphatic. In certain
embodiments of such compositions, R.sup.z is selected from the
group consisting of: methyl, ethyl, n-butyl, and 2ethylhexyl.
[0308] In certain embodiments, provided are biobased terephthalic
acid compositions derived by rearrangement of such isophthalic acid
compositions (or esters thereof).
[0309] In certain embodiments, provided are isophthalic acid
compositions characterized in that five carbon atoms are derived
from biobased furfural and the remaining three carbon atoms are
derived from biobased acrylic acid. In certain embodiments,
provided are biobased isophthalate esters derived from such
isophthalic acid compositions. In certain embodiments, provided are
biobased terephthalic acid compositions derived by rearrangement of
such isophthalic acid compositions (or esters thereof).
[0310] In certain embodiments, provided are biobased polymers
derived from the biobased isophthalic acid and terephthalic acid
compositions described above. In certain embodiments, such polymers
comprise polyesters. In certain embodiments, such polymers comprise
polyamides.
[0311] In certain embodiments, provided are biobased polyester
compositions comprising the biobased isophthalic acid and/or
terephthalic acid compositions described above. In certain
embodiments, such polyesters are the result of condensation of the
acids (or esters thereof) with diols. In certain embodiments, the
diol is a C.sub.2-20 aliphatic diol. In certain embodiments, the
diol is selected from the group consisting of: ethylene glycol,
propylene glycol, 1,3-propanediol, 1,4 butanediol, and isosorbide.
In certain embodiments, the diol is an aromatic diol. In certain
embodiments, the diol is selected from the group consisting of:
benzene dimethanol and bisphenol-A.
[0312] In certain embodiments, provided are biobased polyethylene
terephthalate (PET) derived from the biobased terephthalic acid
compositions described above. In certain embodiments, provided is
biobased polytrimethylene terephthalate (PTT) derived from the
biobased terephthalic acid compositions described above. In certain
embodiments, provided is biobased polybutylene terephthalate (PBT)
derived from the biobased terephthalic acid compositions described
above.
[0313] In certain embodiments, provided is biobased polyethylene
isophthalate (PEI) derived from the biobased isophthalic acid
compositions described above. In certain embodiments, provided is
biobased polytrimethylene isophthalate (PTI) derived from the
biobased isophthalic acid compositions described above. In certain
embodiments, provided is biobased polybutylene isophthalate (PBI)
derived from the biobased isophthalic acid compositions described
above.
[0314] In certain embodiments, provided is biobased polyethylene
isophthalate derived from the biobased isophthalic acid
compositions described above.
Enumerated Embodiments
[0315] The following enumerated embodiments/claims are
representative of some aspects of the invention. [0316] 1. A
compound having the formula:
[0316] ##STR00162## [0317] wherein Z is selected from the group
consisting of --OR.sup.y, --Cl, --Br, --NR.sup.y.sub.2, and
--SR.sup.y, [0318] where, where each R.sup.y is independently
hydrogen, an optionally substituted group selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; an oxygen protecting group; and a
nitrogen protecting group; where two R.sup.y on a nitrogen atom may
be taken with the nitrogen atom to form an optionally substituted
4- to 7-membered heterocyclic ring having 0-2 additional
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur. [0319] 2. The compound of embodiment
1, wherein Z is --OR.sup.y. [0320] 3. The compound of embodiment 2,
wherein Z is --OH. [0321] 4. The compound of embodiment 3, wherein
R.sup.Y is C.sub.1-20 aliphatic, or where R.sup.y is C.sub.1-12
aliphatic, or where R.sup.y is C.sub.1-8 aliphatic, or where
R.sup.y is C.sub.1-6 aliphatic, or where R.sup.y is C.sub.1-4
aliphatic. [0322] 5. A method of making a compound of formula:
[0322] ##STR00163## [0323] the method comprising the step of
reacting furfural with an alpha beta unsaturated acid, [0324] where
R.sup.y is independently hydrogen, or an optionally substituted
moiety selected the group consisting of acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group. [0325] 5b. The method of embodiment 5, wherein
the alpha beta unsaturated acid has the formula:
[0325] ##STR00164## [0326] 6. The method of embodiment 5, wherein
R.sup.y is --H. [0327] 7. The method of embodiment 5, wherein
R.sup.y is C.sub.1-20 aliphatic, or where R.sup.y is C.sub.1-12
aliphatic, or where R.sup.y is C.sub.1-8 aliphatic, or where
R.sup.y is C.sub.1-6 aliphatic, or where R.sup.y is C.sub.1-4
aliphatic. [0328] 8. A method for the production of a compound of
formula:
##STR00165##
[0328] the method comprising the step of oxidizing a compound of
formula:
##STR00166## [0329] where each R.sup.z is independently selected
from the group consisting of: --H, R.sup.y, optionally substituted
C.sub.1-20 aliphatic, and optionally substituted aryl; and [0330]
R.sup.y is independently hydrogen, or an optionally substituted
moiety selected the group consisting of acyl; arylalkyl; 6- to
10-membered aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic
having 1-4 heteroatoms independently selected from the group
consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered
heteroaryl having 1-4 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered
heterocyclic having 1-2 heteroatoms independently selected from the
group consisting of nitrogen, oxygen, and sulfur; and an oxygen
protecting group. [0331] 9. The method of embodiment 8, wherein
R.sup.z is --H. [0332] 10. The method of embodiment 8, wherein
R.sup.z is --CH.sub.3. [0333] 11. The method of embodiment 8,
wherein the compound of formula:
[0333] ##STR00167## [0334] is produced by reaction of furfural with
a compound having a formula:
[0334] ##STR00168## [0335] 12. A isophthalic acid composition
produced via cycloaddition reaction of furfural with an alpha beta
unsaturated carboxylic acid. [0336] 13. The isophthalic acid
composition of embodiment 12, characterized in that the isophthalic
acid is at least partially derived from a biobased feedstock.
[0337] 14. The isophthalic acid composition of embodiment 13,
wherein carbon atoms one through five as shown in the formula:
[0337] ##STR00169## [0338] are derived from biobased furfural.
[0339] 15. The isophthalic acid composition of embodiment 13,
wherein carbon atoms six through eight as shown in the formula:
[0339] ##STR00170## [0340] are derived from a biobased alpha beta
unsaturated acid. [0341] 16. A biobased polymer composition derived
from an isophthalic acid composition of any of embodiments 12
through 15. [0342] 17. The biobased polymer composition of
embodiment 16, wherein the polymer comprises polyethylene
isophthalate (PIT). [0343] 18. The biobased polymer composition of
embodiment 17, wherein the polyethylene isophthalate further
comprises biobased ethylene glycol. [0344] 19. A process for the
production of biobased terephthalic acid or derivatives thereof,
the method comprising the steps of: [0345] a) reacting ethylene
oxide with carbon monoxide in one or more steps to provide a
product selected from acrylic acid and acrylate ester; [0346] b)
reacting the product of step (a) with furfural to provide a Diels
Alder adduct; [0347] c) oxidizing the Diels Alder adduct of step
(b) to provide product selected from isophthalic acid and
isophthalate ester. [0348] d) treating the product of step (c) to
convert the isophthalic acid to terephthalic acid. [0349] 20. The
process of embodiment 2, wherein one or more steps are performed in
a continuous process. [0350] 21. The process of embodiment 2,
characterized in that at least one of the ethylene oxide, the
carbon monoxide or the furfural is biobased. [0351] 22. A method of
making a compound of formula:
[0351] ##STR00171## [0352] the method comprising the step of
reacting furfural with beta propiolactone, [0353] where R.sup.y is
independently hydrogen, or an optionally substituted moiety
selected the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0354] 23. The method of embodiment 22, wherein Ry is --H. [0355]
24. The method of embodiment 22, wherein Ry is C1-20 aliphatic, or
where Ry is C1-12 aliphatic, or where Ry is C1-8 aliphatic, or
where Ry is C1-6 aliphatic, or where Ry is C1-4 aliphatic. [0356]
25. The method of embodiment 24, wherein the step of reacting is
performed in the presence of a compound of formula R.sup.y OH.
[0357] 26. A method for the production of a compound of
formula:
[0357] ##STR00172## [0358] the method comprising the steps of
reacting furfural with beta propiolactone and oxidizing the
resulting adduct, [0359] where each R.sup.z is independently
selected from the group consisting of: [0360] hydrogen, or an
optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group. [0361] 27. The method of embodiment
26, wherein R.sup.z is --H. [0362] 28. The method of embodiment 26,
wherein R.sup.z is --CH.sub.3. [0363] 29. A method of making a
compound of formula:
[0363] ##STR00173## [0364] the method comprising the step of
reacting furfural with beta propiolactone, [0365] where R.sup.y is
independently hydrogen, or an optionally substituted moiety
selected the group consisting of acyl; arylalkyl; 6- to 10-membered
aryl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having
1-4 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group.
[0366] 30. The method of embodiment 29, wherein Ry is --H. [0367]
31. The method of embodiment 29, wherein Ry is C1-20 aliphatic, or
where Ry is C1-12 aliphatic, or where Ry is C.sub.1-8 aliphatic, or
where R.sup.y is C.sub.1-6 aliphatic, or where R.sup.y is C.sub.1-4
aliphatic. [0368] 32. A method for the production of a compound of
formula:
[0368] ##STR00174## [0369] the method comprising the steps of
reacting furfural with beta propiolactone and oxidizing the
resulting adduct, [0370] where each R.sup.z is independently
selected from the group consisting of: [0371] hydrogen, or an
optionally substituted moiety selected the group consisting of
acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group. [0372] 33. The method of embodiment
32, wherein Rz is --H. [0373] 34. The method of embodiment 32,
wherein Rz is --CH3. [0374] 35. A process for the production of
biobased terephthalic acid or derivatives thereof, the method
comprising the steps of: [0375] a) reacting ethylene oxide with
carbon monoxide in one or more steps to provide beta propiolactone;
[0376] b) reacting the product of step (a) with furfural to provide
an adduct selected from the group consisting of:
##STR00175##
[0376] and mixtures of both of these; [0377] c) oxidizing the
adduct of step (b) to provide product selected from phthalic acid,
phthalic acid ester, isophthalic acid and isophthalate ester.
[0378] d) treating the product of step (c) to convert the phthalic
of isophthalic acid to terephthalic acid. [0379] 36. The process of
embodiment 35, wherein one or more steps are performed in a
continuous process. [0380] 37. The process of embodiment 35,
characterized in that at least one of the ethylene oxide, the
carbon monoxide or the furfural is biobased. [0381] 38. A method,
comprising: [0382] continuously feeding a first reaction zone with
furfural and a compound of formula:
[0382] ##STR00176## [0383] wherein R.sup.y is independently
hydrogen, or an optionally substituted moiety selected the group
consisting of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20
aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms
independently selected from the group consisting of nitrogen,
oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4
heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having
1-2 heteroatoms independently selected from the group consisting of
nitrogen, oxygen, and sulfur; and an oxygen protecting group, to
provide a first product stream comprising a first product of
formula:
[0383] ##STR00177## [0384] continuously feeding the first product
stream to an oxidizing reaction zone where the first product is
contacted with air to form a second product stream comprising a
second product having formula:
[0384] ##STR00178## [0385] wherein each R.sup.z is independently
selected from the group consisting of --H, R.sup.y, optionally
substituted C.sub.1-20 aliphatic, and optionally substituted aryl;
and [0386] continuously feeding the second product stream to a
rearrangement reaction zone where the second product is converted
to the compound of formula:
[0386] ##STR00179## [0387] 39. A method, comprising: [0388]
continuously feeding a first reaction zone with furfural and beta
propiolactone, and optionally an alcohol of formula HOR.sup.y, to
provide a first product stream comprising a first product having
formula:
[0388] ##STR00180## [0389] where R.sup.y is independently hydrogen,
or an optionally substituted moiety selected the group consisting
of acyl; arylalkyl; 6- to 10-membered aryl; C.sub.1-20 aliphatic;
C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10 membered heteroaryl having 1-4 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently
selected from the group consisting of nitrogen, oxygen, and sulfur;
and an oxygen protecting group; and; [0390] continuously feeding
the first product stream to an oxidizing reaction zone where the
first product is contacted with air to form a second product stream
comprising a second product having formula:
[0390] ##STR00181## [0391] wherein each R.sup.z is independently
selected from the group consisting of --H, R.sup.y, optionally
substituted C.sub.1-20 aliphatic, and optionally substituted aryl;
and [0392] continuously feeding the second product stream to a
rearrangement reaction zone where the second product is converted
to the compound of formula:
[0392] ##STR00182## [0393] 40. The method of embodiment 38 or 39,
wherein R.sup.y is --H. [0394] 41. The method of embodiment 38 or
39, wherein Ry is C1-20 aliphatic. [0395] 42. The method of any one
of embodiments 38 to 41, wherein Rz is --H. [0396] 43. The method
of any one of embodiments 38 to 41, wherein Rz is --CH3. [0397] 44.
An isophthalic acid composition produced via cycloaddition reaction
of furfural with an alpha beta unsaturated carboxylic acid, wherein
the isophthalic acid is at least partially derived from a biobased
feedstock. [0398] 45. An isophthalic acid composition produced via
reaction of furfural with beta propiolactone, wherein the
isophthalic acid is at least partially derived from a biobased
feedstock. [0399] 46. The isophthalic acid composition of
embodiment 44 or 45, wherein carbon atoms one through five as shown
in the formula:
##STR00183##
[0399] are derived from biobased furfural. [0400] 47. The
isophthalic acid composition of embodiment 44, wherein carbon atoms
six through eight as shown in the formula:
##STR00184##
[0400] are derived from a biobased alpha beta unsaturated acid.
[0401] 48. The isophthalic acid composition of embodiment 45,
wherein carbon atoms six through eight as shown in the formula:
##STR00185##
[0401] are derived from a biobased beta propiolactone. [0402] 49. A
biobased polymer composition derived from an isophthalic acid
composition of any one of embodiments 44 to 48. [0403] 50. The
biobased polymer composition of embodiment 49, wherein the polymer
comprises polyethylene isophthalate (PIT). [0404] 51. The biobased
polymer composition of embodiment 50, wherein the polyethylene
isophthalate further comprises biobased ethylene glycol. [0405] 52.
A method for the production of biobased terephthalic acid,
comprising: [0406] a) reacting ethylene oxide with carbon monoxide
to provide a product selected from beta propiolactone, acrylic acid
and acrylate ester; [0407] b) reacting the product of step (a) with
furfural to provide a Diels Alder adduct; [0408] c) oxidizing the
Diels Alder adduct of step (b) to provide product selected from
isophthalic acid and isophthalate ester; and [0409] d) treating the
product of (c) to convert the isophthalic acid to terephthalic
acid. [0410] 53. The method of embodiment 52, wherein one or more
steps are performed in a continuous process. [0411] 54. The method
of embodiment 52 or 53, wherein at least one of the ethylene oxide,
the carbon monoxide or the furfural is biobased.
* * * * *