U.S. patent application number 14/090762 was filed with the patent office on 2014-06-19 for methods of making functionalized internal olefins and uses thereof.
This patent application is currently assigned to Elevance Renewable Sciences, Inc.. The applicant listed for this patent is Elevance Renewable Sciences, Inc.. Invention is credited to Paul A. Bertin, Jordan R. Quinn.
Application Number | 20140171677 14/090762 |
Document ID | / |
Family ID | 49780365 |
Filed Date | 2014-06-19 |
United States Patent
Application |
20140171677 |
Kind Code |
A1 |
Bertin; Paul A. ; et
al. |
June 19, 2014 |
Methods of Making Functionalized Internal Olefins and Uses
Thereof
Abstract
A method of isomerizing a substance includes combining a
substance including a terminal alkenyl group and a substance
including a fluorosulfonic acid group in a reaction mixture, and
forming a substance including a 2-alkenyl group from the substance
including a terminal alkenyl group in the reaction mixture. The
method may be used to functionalize a substance, as the substance
including a 2-alkenyl group can be reacted with a functionalizing
agent to form a substance including a first functional group. The
methods may be used to form a dicarboxylic acid, such as suberic
acid, from a renewable feedstock.
Inventors: |
Bertin; Paul A.; (Chicago,
IL) ; Quinn; Jordan R.; (Mundelein, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Elevance Renewable Sciences, Inc. |
Woodridge |
IL |
US |
|
|
Assignee: |
Elevance Renewable Sciences,
Inc.
Woodridge
IL
|
Family ID: |
49780365 |
Appl. No.: |
14/090762 |
Filed: |
November 26, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61731567 |
Nov 30, 2012 |
|
|
|
Current U.S.
Class: |
560/205 ;
562/524; 562/592; 585/664 |
Current CPC
Class: |
C07C 51/09 20130101;
C07C 67/475 20130101; C07C 51/34 20130101; C07C 1/26 20130101; C07C
67/333 20130101; C07C 51/09 20130101; C07C 5/25 20130101; C07C
5/2562 20130101; C07C 5/2562 20130101; C07C 69/44 20130101; C07C
11/02 20130101; C07C 67/00 20130101; C07C 67/333 20130101; C07C
2531/24 20130101; C07B 35/08 20130101; C07C 55/02 20130101; C07C
11/08 20130101; C07C 69/533 20130101; C07C 69/593 20130101; C07C
67/303 20130101; C07C 51/295 20130101; C07C 67/303 20130101; C07C
1/26 20130101; C07C 67/475 20130101; C07C 67/347 20130101 |
Class at
Publication: |
560/205 ;
585/664; 562/524; 562/592 |
International
Class: |
C07C 67/347 20060101
C07C067/347; C07C 51/34 20060101 C07C051/34; C07C 51/09 20060101
C07C051/09; C07C 5/25 20060101 C07C005/25; C07C 51/295 20060101
C07C051/295 |
Claims
1. A method of isomerizing a substance, comprising: combining a
substance comprising a terminal alkenyl group and a substance
comprising a fluorosulfonic acid group in a reaction mixture; and
forming a substance comprising a 2-alkenyl group from the substance
comprising the terminal alkenyl group in the reaction mixture.
2. The method of claim 1, where the substance comprising the
terminal alkenyl group further comprises a substituent selected
from the group consisting of a halide group, a heteroalkyl group,
an aryl group, a heteroaryl group, a nitrile group, an amide group,
an imide group, a nitro group, a ketone group, an ether group, a
sulfide group, a sulfoxide group, a sulfone group, and combinations
thereof.
3. The method of claim 2, where the substance comprising the
terminal alkenyl group is an .alpha.-ester-alk-.omega.-ene
molecule.
4. The method of claim 3, where the substance comprising the
terminal alkenyl group is 9-decenoic acid methyl ester.
5. The method of claim 1, where the substance comprising the
fluorosulfonic acid group is trifluoromethanesulfonic acid.
6-8. (canceled)
9. The method of claim 1, where the substance comprising the
terminal alkenyl group is 9-decenoic acid methyl ester; the
substance comprising the fluorosulfonic acid group is
trifluoromethanesulfonic acid or comprises a copolymer comprising
perfluorosulfonic acid monomeric units and monomer units derived
from tetrafluoroethylene; and the substance comprising the
2-alkenyl group is 8-decenoic acid methyl ester.
10-11. (canceled)
12. A method of functionalizing a substance, comprising: combining
a substance comprising a terminal alkenyl group and a substance
comprising a fluorosulfonic acid group in a first reaction mixture;
forming a substance comprising a 2-alkenyl group from the substance
comprising the terminal alkenyl group in the first reaction
mixture; combining the substance comprising the 2-alkenyl group and
a functionalizing agent in a second reaction mixture; and forming a
substance comprising a first functional group from the substance
comprising the 2-alkenyl group in the second reaction mixture.
13-14. (canceled)
15. The method of claim 12, where the functionalizing agent
comprises an oxidizing agent selected from the group consisting of
KMnO.sub.4, ozone, periodic acid, lead tetraacetate, and
combinations thereof; and the first functional group is a
carboxylic acid group.
16. The method of claim 15, where the substance comprising the
terminal alkenyl group is an .alpha.-ester-alk-.omega.-ene
molecule; and the substance comprising the first functional group
is a dicarboxylic acid molecule.
17-18. (canceled)
19. The method of claim 12, where the substance comprising the
terminal alkenyl group is 9-decenoic acid methyl ester; the
substance comprising the 2-alkenyl group is 8-decenoic acid methyl
ester; and the substance comprising the first functional group
comprises a 7-heptanoic acid group or a salt thereof, or a methyl
7-heptanoate group.
20-25. (canceled)
26. A method of making a dicarboxylic acid, comprising: forming a
first reaction mixture from ingredients comprising a first olefin
ester, a second olefin ester, and a metathesis catalyst; forming an
unsaturated dicarboxylic ester from the first reaction mixture;
forming a second reaction mixture from ingredients comprising the
unsaturated dicarboxylic ester and a hydrogenating agent; forming a
second dicarboxylic ester; forming a third reaction mixture from
ingredients comprising the second dicarboxylic ester and a
hydrolyzing agent; and hydrolyzing the second dicarboxylic ester,
to form a dicarboxylic acid.
27-31. (canceled)
32. The method of claim 26, where the first olefin ester is a
terminal olefin ester and the second olefin ester is an internal
olefin ester.
33. The method of claim 32, where the terminal olefin ester is a
compound of formula (V): ##STR00008## where: X.sup.1 is C.sub.3-18
alkylene, C.sub.3-18 alkenylene, C.sub.2-18 heteroalkylene, or
C.sub.2-18 heteroalkenylene, each of which is optionally
substituted one or more times by substituents selected
independently from R.sup.12; V is C.sub.1-12 alkyl, C.sub.1-12
heteroalkyl, C.sub.2-12 alkenyl, or C.sub.2-12 heteroalkenyl, each
of which is optionally substituted one or more times by
substituents selected independently from R.sup.12; and R.sup.12 is
a halogen atom, --OH, --NH.sub.2, C.sub.1-6 alkyl, C.sub.1-6
heteroalkyl, C.sub.2-6 alkenyl, C.sub.2-6 heteroalkenyl, C.sub.3-10
cyclokalkyl, or C.sub.2-10 heterocycloalkyl.
34-40. (canceled)
41. The method of claim 32, where the terminal olefin ester is
9-decenoic acid alkyl ester.
42. (canceled)
43. The method of claim 26, where the first olefin ester is an
internal olefin ester, and the second olefin ester is an internal
olefin ester.
44. The method of claim 43, where the first olefin ester and the
second olefin ester are independently compounds of Formula (VI):
##STR00009## where: X.sup.2 is C.sub.3-18 alkylene, C.sub.3-18
alkenylene, C.sub.2-18 heteroalkylene, or C.sub.2-18
heteroalkenylene, each of which is optionally substituted one or
more times by substituents selected independently from R.sup.15;
R.sup.13 is C.sub.1-12 alkyl, C.sub.1-12 heteroalkyl, C.sub.2-12
alkenyl, or C.sub.2-12 heteroalkenyl, each of which is optionally
substituted one or more times by substituents selected
independently from R.sup.15; R.sup.14 is a halogen atom, --OH,
--NH.sub.2, C.sub.1-6 alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6
alkenyl, C.sub.2-6 heteroalkenyl, C.sub.3-10 cyclokalkyl, or
C.sub.2-10 heterocycloalkyl; R.sup.15 is a halogen atom, --OH,
--NH.sub.2, C.sub.1-6 alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6
alkenyl, C.sub.2-6 heteroalkenyl, C.sub.3-10 cyclokalkyl, or
C.sub.2-10 heterocycloalkyl.
45-55. (canceled)
56. The method of claim 43, where the first olefin ester is an
9-decenoic acid alkyl ester, and the second olefin ester is an
8-decenoic acid alkyl ester.
57. The method of claim 56, where the 8-decenoic acid alkyl ester
is formed by isomerizing an ester of 9-decenoic acid.
58. The method of claim 26, where the hydrogenating agent comprises
hydrogen gas and a hydrogenation catalyst.
59-60. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of priority to
U.S. Provisional Patent Application No. 61/731,567, entitled
"Methods of Isomerizing a Substance, Methods of Functionalizing a
Substance, and Methods Of Making Suberic Acid" filed Nov. 30, 2012,
which is hereby incorporated by reference as though fully set forth
herein.
TECHNICAL FIELD
[0002] This disclosure relates generally methods of making
functionalized internal olefins and the use of such compounds to
make useful organic compounds. In some embodiments, the
functionalized internal olefins are formed by isomerizing a
functionalized terminal olefin to a functionalized internal olefin.
In some embodiments, the functionalized internal olefins are
derived from a renewable source, such as a natural oil or
derivative thereof. In some such embodiments, the functionalized
internal olefin is derived from the metathesis of a natural oil or
a derivative thereof.
BACKGROUND
[0003] Renewable feedstocks, such as fatty acids or fatty esters
derived from natural oils, have opened new possibilities for the
development of industrially useful organic compounds. For example,
renewable feedstocks can be used to prepare compounds that are not
readily obtainable from conventional petroleum feedstocks. In
another example, renewable feedstocks can be used to prepare known
compounds more efficiently, without requiring undesirable reagents
or solvents, and/or with decreased amounts of waste or side
products.
[0004] Metathesis reactions can be used to convert natural oils and
their fatty acid or fatty ester derivatives into useful renewable
feedstocks. When compounds containing a carbon-carbon double bond
undergo metathesis reactions in the presence of a metathesis
catalyst, some or all of the original carbon-carbon double bonds
are broken, and new carbon-carbon double bonds are formed. The
products of such metathesis reactions include carbon-carbon double
bonds in different locations, which can provide unsaturated organic
compounds having useful chemical structures. Examples of useful
unsaturated organic compounds that can be produced by metathesis
reactions with natural oils or their derivatives include olefin
ester compounds, e.g., terminal olefin esters such as
".alpha.-ester-alk-.omega.-ene molecules", for instance 9-decenoic
acid methyl ester (9-DAME) and internal olefin esters, such as
".alpha.-ester-alk-.psi.-ene molecules", for instance 9-dodecenoic
acid methyl ester (9-DDAME).
[0005] Dibasic acids, such as dicarboxylic acids or their esters,
are used to make a variety of different materials, including, but
not limited to, polyamides, polyesters, and polyanhydrides. While
some dicarboxylic acids can be readily synthesized from
conventional petroleum-based feedstocks, others cannot. Suberic
acid is one non-limiting example of an industrially useful organic
compound that is difficult to prepare from conventional petroleum
feedstocks. Suberic acid is one of a class of aliphatic, linear
dicarboxylic acids having the chemical formula
HOOC--(CH.sub.2).sub.n--COOH, which are useful organic compounds
having a variety of commercial applications. Some members of this
class of dicarboxylic acids, such as adipic acid (n=4), azelaic
acid (n=7), sebacic acid (n=8), and dodecanedioic acid (n=10), are
produced commercially on relatively large scales. These
dicarboxylic acids may be described as C.sub.6, C.sub.9, C.sub.10
and C.sub.12 dicarboxylic acids, respectively, where the subscript
refers to the number of carbon atoms in the linear aliphatic chain,
including the carbon atoms of the carboxylic acid groups. Suberic
acid (n=6; C.sub.8 dicarboxylic acid), however, is not readily
produced on a large scale.
[0006] The lack of commercially available suberic acid can
represent a gap in the toolbox of synthetic chemistry. The values
of properties such as melting point, refractive index, and
decarboxylation temperature alternate as the number of carbon atoms
in the aliphatic, linear dicarboxylic acids changes between even
numbers and odd numbers in the series of C.sub.2 to C.sub.12. For
example, in species below C.sub.12 the odd numbered dicarboxylic
acids have lower melting points and higher solubilities in water
than do the even numbered dicarboxylic acids before and after them
in the series. These differences in properties of the dicarboxylic
acids can result in macroscopic differences in the properties of
polymers formed from monomers that include the acids. While adipic
(C.sub.6) and sebacic (C.sub.10) acids are commonly used as
monomers for polyamides, polyesters and polyurethanes, suberic acid
(C.sub.8) is not commonly used due to its relative lack of
availability. Thus, polymers formed using suberic acid, which would
have properties between those of polymers formed using adipic acid
or sebacic acid, are not readily available.
[0007] It would be desirable to provide methods of making useful
organic compounds, such as suberic acid, from renewable feedstocks.
In one example, it would be desirable to provide methods of making
other useful organic compounds from 9-decenoic acid methyl ester.
In another example, it would be desirable to provide methods of
making useful organic compounds such as suberic acid from renewable
feedstocks, such as 9-decenoic acid methyl ester. Preferably the
methods of making useful organic compounds from renewable
feedstocks can be performed using smaller amounts of solvents
and/or reagents relative to conventional processes, and/or can
produce smaller amounts of undesirable side products.
SUMMARY
[0008] The scope of the present invention is defined solely by the
appended claims, and is not affected to any degree by the
statements within this summary.
[0009] In one aspect, a method of isomerizing a substance is
provided that includes combining a substance including a terminal
alkenyl group and a substance including a fluorosulfonic acid group
in a reaction mixture, and forming a substance including a
2-alkenyl group from the substance including a terminal alkenyl
group in the reaction mixture.
[0010] In another aspect, a method of functionalizing a substance
is provided that includes combining a substance including a
terminal alkenyl group and a substance including a fluorosulfonic
acid group in a first reaction mixture, forming a substance
including a 2-alkenyl group from the substance including a terminal
alkenyl group in the first reaction mixture, combining the
substance including the 2-alkenyl group and a functionalizing agent
in a second reaction mixture, and forming a substance including a
first functional group from the substance including the 2-alkenyl
group in the second reaction mixture.
[0011] In another aspect, a method of making suberic acid is
provided that includes combining 9-decenoic acid methyl ester and
an acid in a first reaction mixture, forming 8-decenoic acid methyl
ester from the 9-decenoic acid methyl ester in the first reaction
mixture, combining the 8-decenoic acid methyl ester and an
oxidizing agent in a second reaction mixture, and forming suberic
acid from the 8-decenoic acid methyl ester in the second reaction
mixture.
[0012] In a further aspect, a method of making a dicarboxylic acid
is provided that includes forming a first reaction mixture from
ingredients comprising a first olefin ester, a second olefin ester,
and a metathesis catalyst; forming an unsaturated dicarboxylic
ester from the first reaction mixture; forming a second reaction
mixture from ingredients comprising the unsaturated dicarboxylic
ester and a hydrogenating agent; forming a second dicarboxylic
ester; forming a third reaction mixture from ingredients comprising
the second dicarboxylic ester and a hydrolyzing agent; and
hydrolyzing the second dicarboxylic ester, to form a dicarboxylic
acid.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The invention can be better understood with reference to the
following drawings and description. The components in the figures
are not necessarily to scale and are not intended to accurately
represent molecules or their interactions, emphasis instead being
placed upon illustrating the principles of the invention. Moreover,
in the figures, like referenced numerals designate corresponding
parts throughout the different views.
[0014] FIG. 1 represents a method of isomerizing a substance.
[0015] FIG. 2 represents a method of functionalizing a
substance.
[0016] FIG. 3 represents a method of making suberic acid.
[0017] FIG. 4 depicts a representative reaction scheme for a
transformation of 9-decenoic acid methyl ester (9-DAME) to suberic
acid.
[0018] FIG. 5 represents a method of forming a dicarboxylic
acid.
[0019] FIG. 6 represents a method of forming a dicarboxylic
acid.
[0020] FIG. 7 represents a method of forming a dicarboxylic
acid.
[0021] FIG. 8 represents a method of forming a dicarboxylic
acid.
[0022] FIG. 9 represents a method of forming a dicarboxylic
acid.
DETAILED DESCRIPTION
[0023] To provide a clear and more consistent understanding of the
specification and claims of this application, the following
definitions are provided.
[0024] The terms "reaction" and "chemical reaction" refer to the
conversion of a substance into a product, irrespective of reagents
or mechanisms involved.
[0025] The term "reaction product" refers to a substance produced
from a chemical reaction of one or more reactant substances.
[0026] The term "yield" refers to the amount of reaction product
formed in a reaction. When expressed with units of percent (%), the
term yield refers to the amount of reaction product actually
formed, as a percentage of the amount of reaction product that
would be formed if all of the reactant were converted into the
product.
[0027] The terms "isomerizing" and "isomerization" refer to a
chemical reaction in which the atoms within a substance are
retained, but are rearranged to have a different configuration.
[0028] The term "alkyl group" refers to a group formed by removing
a hydrogen from a carbon of an alkane, where an alkane is an
acyclic or cyclic compound consisting entirely of hydrogen atoms
and saturated carbon atoms.
[0029] The term "alkenyl group" refers to a group formed by
removing a hydrogen from a carbon of an alkene, where an alkene is
an acyclic or cyclic compound consisting entirely of hydrogen atoms
and carbon atoms, and including at least one carbon-carbon double
bond.
[0030] The term "terminal alkenyl group" refers to an alkenyl group
that is positioned at the end of a chain of at least 4 carbon
atoms.
[0031] The term "allyl alkenyl group" refers to an alkenyl group
that is positioned at the penultimate position of a chain of at
least 4 carbon atoms.
[0032] The term "unsaturated group" refers to a group that includes
a carbon-carbon double bond or a carbon-carbon triple bond.
[0033] The term "fluorosulfonic acid group" refers to a group
having the formula R--CF.sub.xH.sub.2-xSO.sub.3H, where R is a
fluorine atom or an organic group. If R is a fluorine atom, then x
is 0, 1 or 2. If R is an organic group, then x is 1 or 2.
[0034] The term "functional group" refers to a group that includes
one or a plurality of atoms other than hydrogen and sp.sup.3 carbon
atoms. Examples of functional groups include but are not limited to
hydroxyl (--OH), protected hydroxyl, ether (--C--O--C--), ketone
(--C(.dbd.O)--), ester (--C(.dbd.O)O--C--), carboxylic acid
(--C(.dbd.O)OH), cyano (--C.ident.N), amido (--C(.dbd.O)NH--C--),
isocyanate (--N.dbd.C.dbd.O), urethane (--O--C(.dbd.O)--NH--), urea
(--NH--C(.dbd.O)--NH--), protected amino, thiol (--SH), sulfone,
sulfoxide, phosphine, phosphite, phosphate, halide (--X), and the
like.
[0035] The term "functionalizing agent" refers to a reactant that
is combined with a substance to convert the substance into a
product having at least one new functional group not present in the
substance.
[0036] The term "oxidizing agent" refers to a functionalizing agent
that is combined with a substance to convert at least one group in
the substance into a new functional group having a higher oxidation
state.
[0037] The term "hydrogenating agent" refers to an agent that is
combined with a substance to hydrogenate at least one unsaturated
group in the substance.
[0038] The term "hydrolyzing agent" refers to a functionalizing
agent that is combined with a substance to convert at least one
ester group in the substance to a carboxylic acid group or one of
its salts.
[0039] The term "substituent" refers to a group that replaces one
or more hydrogen atoms in a molecular entity. Examples of
substituents include but are not limited to halide groups, alkyl
groups, heteroalkyl groups, aryl groups, and heteroaryl groups. A
heteroalkyl or heteroaryl substituent may be bonded to the
remainder of the molecular entity through a carbon or through a
heteroatom.
[0040] The term "metathesis catalyst" refers to any catalyst or
catalyst system configured to catalyze a metathesis reaction.
[0041] The terms "metathesize" and "metathesizing" refer to a
chemical reaction involving a single type of olefin or a plurality
of different types of olefin, which is conducted in the presence of
a metathesis catalyst, and which results in the formation of at
least one new olefin product. The phrase "metathesis reaction"
encompasses cross-metathesis (a.k.a. co-metathesis),
self-metathesis, ring-opening metathesis (ROM), ring-opening
metathesis polymerizations (ROMP), ring-closing metathesis (RCM),
and acyclic diene metathesis (ADMET), and the like, and
combinations thereof.
[0042] The terms "natural oils", "natural feedstocks", or "natural
oil feedstocks" mean oils derived from plants or animal sources.
Examples of natural oils include but are not limited to vegetable
oils, algal oils, animal fats, tall oils, derivatives of these
oils, combinations of any of these oils, and the like. Examples of
vegetable oils include but are not limited to canola oil, rapeseed
oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil,
peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil,
linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil,
camelina oil, pennycress oil, castor oil, and the like, and
combinations thereof. Examples of animal fats include but are not
limited to lard, tallow, poultry fat, yellow grease, fish oil, and
the like, and combinations thereof. Tall oils are by-products of
wood pulp manufacture. A natural oil may be refined, bleached,
and/or deodorized.
[0043] The term "natural oil derivatives" refers to compounds or
mixtures of compounds derived from one or more natural oils using
any one or combination of methods known in the art. Such methods
include but are not limited to saponification, transesterification,
esterification, hydrogenation (partial or full), isomerization,
oxidation, reduction, and the like, and combinations thereof.
Examples of natural oil derivatives include but are not limited to
gums, phospholipids, soapstock, acidulated soapstock, distillate or
distillate sludge, fatty acids and fatty acid alkyl ester such as
2-ethylhexyl ester, hydroxy-substituted variations thereof of the
natural oil, and the like, and combinations thereof. For example,
the natural oil derivative may be a fatty acid methyl ester (FAME)
derived from the glyceride of the natural oil.
[0044] The term "metathesized natural oil" refers to the metathesis
reaction product of a natural oil in the presence of a metathesis
catalyst, where the metathesis product includes a new olefinic
compound. A metathesized natural oil may include a reaction product
of two triglycerides in a natural feedstock (self-metathesis) in
the presence of a metathesis catalyst, where each triglyceride has
an unsaturated carbon-carbon double bond, and where the reaction
product includes a "natural oil oligomer" having a new mixture of
olefins and esters that may include one or more of metathesis
monomers, metathesis dimers, metathesis trimers, metathesis
tetramers, metathesis pentamers, and higher order metathesis
oligomers (e.g., metathesis hexamers). A metathesized natural oil
may include a reaction product of a natural oil that includes more
than one source of natural oil (e.g., a mixture of soybean oil and
palm oil). A metathesized natural oil may include a reaction
product of a natural oil that includes a mixture of natural oils
and natural oil derivatives.
[0045] The term "dicarboxylic acid" refers to a compound featuring
at least two carboxylic acid functional groups, or their salts.
Non-limiting examples of dicarboxylic acids include aliphatic,
linear dicarboxylic acids having the chemical formula
HOOC--(CH.sub.2).sub.n--COOH, where n is a positive integer number.
Other representative examples of dicarboxylic acids feature other
types of carbon chains, e.g. linear olefinic, branched aliphatic,
and branched olefinic. In additional representative examples, the
carboxylic acid functional groups may be appended to cycloalkyl,
cycloalkenyl, or aromatic moieties.
[0046] The term "catalyst poison" includes any chemical species or
impurity in a reaction mixture that reduces or is capable of
reducing the functionality (e.g., efficiency, conversion, turnover
number) of a metathesis catalyst. The term "turnover number" or
"catalyst turnover" generally refers to the number of moles of
feedstock that a mole of catalyst can convert before becoming
deactivated.
[0047] The terms "hydrogenation" and "hydrogenating", refer to
processes where one or more unsaturated groups in a molecule are
hydrogenated. For example, a carbon-carbon double bond may be
hydrogenated to a single bond between two sp.sup.3 carbon atoms,
while a carbon-carbon triple bond may be hydrogenated to a
carbon-carbon double bond or to a single bond between two sp.sup.3
carbon atoms.
[0048] The terms "selective hydrogenation", or "partial
hydrogenation" refers to a hydrogenation process which converts an
unsaturated molecule such as an alkyne or a diolefin to a less
unsaturated molecule, such as a mono-olefin, without hydrogenating
the less unsaturated molecule to a saturated or a more saturated
hydrocarbon, such as an alkane.
[0049] A method of isomerizing a substance includes combining a
substance including a terminal alkenyl group and a substance
including a fluorosulfonic acid group in a reaction mixture, and
forming a substance including a 2-alkenyl group from the substance
including a terminal alkenyl group in the reaction mixture. The
substance including a 2-alkenyl group may be functionalized, such
as by reacting the 2-alkenyl group with a functionalizing agent, to
form a substance including a first functional group. In one
example, the isomerization and subsequent functionalization may be
used to form suberic acid from 9-decenoic acid methyl ester
(9-DAME).
[0050] Isomerizing a substance containing a terminal alkenyl group
can facilitate the production of useful organic compounds from
renewable feedstocks. As renewable feedstocks may include
substances having terminal alkenyl groups, selective isomerization
of these substances can provide substances having a 2-alkenyl group
instead of a terminal alkenyl group. Substances that differ only in
the position of an alkenyl group may have distinct chemical and/or
physical properties. In one example, the product of a reaction
between a functionalizing agent and a substance having a 2-alkenyl
group may have different chemical and/or physical properties from
the product of a reaction between the functionalizing agent and the
original substance having the terminal alkenyl group.
[0051] Producing organic compounds from renewable feedstocks may
provide new compounds that have not been produced previously.
Producing organic compounds from renewable feedstocks also may
provide certain advantages over existing production methods,
including but not limited to simpler and/or more cost-effective
production, reduced variability, improved sourcing, and increased
biorenewability.
[0052] FIG. 1 represents a method 100 of isomerizing a substance.
The method 100 includes combining 101 a substance including a
terminal alkenyl group 110 and a substance including a
fluorosulfonic acid group 112 in a reaction mixture 114; and
forming 102 a substance including a 2-alkenyl group 120 from the
substance including a terminal alkenyl group 110 in the reaction
mixture.
[0053] The substance including a terminal alkenyl group 110 may
include any organic molecule that includes a chain of at least 4
carbon atoms and an alkenyl group positioned at the end of the
chain. Examples of substances including a terminal alkenyl group
include but are not limited to unsaturated hydrocarbons, such as
1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and
1-decene. Examples of substances including a terminal alkenyl group
include but are not limited to substituted unsaturated hydrocarbons
that include a substituent in place of a hydrogen atom. Examples of
substituents include but are not limited to halide groups,
heteroalkyl groups, aryl groups, heteroaryl groups, nitrile groups,
amide groups, imide groups, nitro groups, ketone groups, ether
groups, sulfide groups, sulfoxide groups and sulfone groups.
[0054] The substance including a terminal alkenyl group 110 may
include an .alpha.-ester-alk-.omega.-ene molecule. An
.alpha.-ester-alk-.omega.-ene molecule has the chemical formula
R--O--C(.dbd.O)--(R.sup.1)--CH.dbd.CH.sub.2, where R is a alkyl
group having from 1 to 5 carbon atoms, and R.sup.1 is an alkyl
group having from 2 to 20 carbon atoms. Examples of
.alpha.-ester-alk-.omega.-ene molecules include but are not limited
to 9-decenoic acid methyl ester, 9-decenoic acid ethyl ester,
9-decenoic acid propyl ester, 10-undecenoic acid methyl ester,
10-undecenoic acid ethyl ester, 10-decenoic acid propyl ester,
11-dodecenoic acid methyl ester, 11-dodecenoic acid ethyl ester,
and 11-dodecenoic acid propyl ester.
[0055] The substance including a terminal alkenyl group 110 may
include a terminal alkenyl group 110 that is the product of a
metathesis reaction of a natural oil in the presence of a
metathesis catalyst. The metathesis catalyst in this reaction may
include any catalyst or catalyst system that catalyzes a metathesis
reaction. Any known metathesis catalyst may be used, alone or in
combination with one or more additional catalysts. Examples of
metathesis catalysts and process conditions are described in
paragraphs [0069]-[0155] of US 2011/0160472, incorporated by
reference herein in its entirety, except that in the event of any
inconsistent disclosure or definition from the present
specification, the disclosure or definition herein shall be deemed
to prevail. A number of the metathesis catalysts described in US
2011/0160472 are presently available from Materia, Inc. (Pasadena,
Calif.).
[0056] In some embodiments, the metathesis catalyst comprises a
transition metal. In some embodiments, the metathesis catalyst
comprises ruthenium. In some embodiments, the metathesis catalyst
comprises rhenium. In some embodiments, the metathesis catalyst
comprises tantalum. In some embodiments, the metathesis catalyst
comprises nickel. In some embodiments, the metathesis catalyst
comprises tungsten. In some embodiments, the metathesis catalyst
comprises molybdenum.
[0057] In some embodiments, the metathesis catalyst comprises a
ruthenium carbene complex and/or an entity derived from such a
complex. In some embodiments, the metathesis catalyst comprises a
material selected from the group consisting of a ruthenium
vinylidene complex, a ruthenium alkylidene complex, a ruthenium
methylidene complex, a ruthenium benzylidene complex, and
combinations thereof, and/or an entity derived from any such
complex or combination of such complexes. In some embodiments, the
metathesis catalyst comprises a ruthenium carbene complex
comprising at least one phosphine ligand and/or an entity derived
from such a complex. In some embodiments, the metathesis catalyst
comprises a ruthenium carbene complex comprising at least one
tricyclohexylphosphine ligand and/or an entity derived from such a
complex. In some embodiments, the metathesis catalyst comprises a
ruthenium carbene complex comprising at least two
tricyclohexylphosphine ligands [e.g.,
(PCy.sub.3).sub.2Cl.sub.2Ru.dbd.CH--CH.dbd.C(CH.sub.3).sub.2, etc.]
and/or an entity derived from such a complex. In some embodiments,
the metathesis catalyst comprises a ruthenium carbene complex
comprising at least one imidazolidine ligand and/or an entity
derived from such a complex. In some embodiments, the metathesis
catalyst comprises a ruthenium carbene complex comprising an
isopropyloxy group attached to a benzene ring and/or an entity
derived from such a complex.
[0058] In some embodiments, the metathesis catalyst comprises a
Grubbs-type olefin metathesis catalyst and/or an entity derived
therefrom. In some embodiments, the metathesis catalyst comprises a
first-generation Grubbs-type olefin metathesis catalyst and/or an
entity derived therefrom. In some embodiments, the metathesis
catalyst comprises a second-generation Grubbs-type olefin
metathesis catalyst and/or an entity derived therefrom. In some
embodiments, the metathesis catalyst comprises a first-generation
Hoveyda-Grubbs-type olefin metathesis catalyst and/or an entity
derived therefrom. In some embodiments, the metathesis catalyst
comprises a second-generation Hoveyda-Grubbs-type olefin metathesis
catalyst and/or an entity derived therefrom. In some embodiments,
the metathesis catalyst comprises one or a plurality of the
ruthenium carbene metathesis catalysts sold by Materia, Inc. of
Pasadena, Calif. and/or one or more entities derived from such
catalysts. Representative metathesis catalysts from Materia, Inc.
for use in accordance with the present teachings include but are
not limited to those sold under the following product numbers as
well as combinations thereof: product no. C823 (CAS no.
172222-30-9), product no. C848 (CAS no. 246047-72-3), product no.
C601 (CAS no. 203714-71-0), product no. C627 (CAS no. 301224-40-8),
product no. C571 (CAS no. 927429-61-6), product no. C598 (CAS no.
802912-44-3), product no. C793 (CAS no. 927429-60-5), product no.
C801 (CAS no. 194659-03-9), product no. C827 (CAS no. 253688-91-4),
product no. C884 (CAS no. 900169-53-1), product no. C833 (CAS no.
1020085-61-3), product no. C859 (CAS no. 832146-68-6), product no.
C711 (CAS no. 635679-24-2), product no. C933 (CAS no.
373640-75-6).
[0059] In some embodiments, the metathesis catalyst comprises a
molybdenum and/or tungsten carbene complex and/or an entity derived
from such a complex. In some embodiments, the metathesis catalyst
comprises a Schrock-type olefin metathesis catalyst and/or an
entity derived therefrom. In some embodiments, the metathesis
catalyst comprises a high-oxidation-state alkylidene complex of
molybdenum and/or an entity derived therefrom. In some embodiments,
the metathesis catalyst comprises a high-oxidation-state alkylidene
complex of tungsten and/or an entity derived therefrom. In some
embodiments, the metathesis catalyst comprises molybdenum (VI). In
some embodiments, the metathesis catalyst comprises tungsten (VI).
In some embodiments, the metathesis catalyst comprises a
molybdenum- and/or a tungsten-containing alkylidene complex of a
type described in one or more of (a) Angew. Chem. Int. Ed. Engl.,
2003, 42, 4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c)
Chem. Rev., 2009, 109, 3211-3226, each of which is incorporated by
reference herein in its entirety, except that in the event of any
inconsistent disclosure or definition from the present
specification, the disclosure or definition herein shall be deemed
to prevail.
[0060] Metathesis is a catalytic reaction that involves the
interchange of alkylidene units among compounds containing one or
more double bonds (i.e., olefinic compounds) via the formation and
cleavage of the carbon-carbon double bonds. The substance including
a terminal alkenyl group 110 may be formed by a metathesis reaction
of a natural oil containing unsaturated polyol esters, including a
cross-metathesis reaction of a natural oil with an alpha-olefin or
with ethylene. The substance including a terminal alkenyl group 110
may be formed by a metathesis reaction of a metathesized natural
oil containing unsaturated polyol esters, including a
cross-metathesis reaction of a metathesized natural oil with an
alpha-olefin or with ethylene. Examples of cross-metathesis
reactions of natural oils and/or of metathesized natural oils that
can produce substances including terminal alkenyl groups are
described in US 2010/0145086 and in US 2012/0071676, which are
incorporated by reference herein in their entirety, except that in
the event of any inconsistent disclosure or definition from the
present specification, the disclosure or definition herein shall be
deemed to prevail.
[0061] Examples of natural oils include but are not limited to
vegetable oil, algal oil, animal fat, tall oil, derivatives of
these oils, or mixtures thereof. Examples of vegetable oils include
but are not limited to canola oil, rapeseed oil, coconut oil, corn
oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower
oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm
kernel oil, tung oil, jatropha oil, mustard oil, camelina oil,
pennycress oil, castor oil, and the like, and combinations thereof.
Examples of animal fats include but are not limited to lard,
tallow, poultry fat, yellow grease, fish oil, and the like, and
combinations thereof. Examples of natural oil derivatives include
but are not limited to metathesis oligomers, gums, phospholipids,
soapstock, acidulated soapstock, distillate or distillate sludge,
fatty acids and fatty acid alkyl ester such as 2-ethylhexyl ester,
hydroxyl-substituted variations of the natural oil, and the like,
and combinations thereof. For example, the natural oil derivative
may be a fatty acid methyl ester (FAME) derived from the glyceride
of the natural oil.
[0062] The natural oil may include canola or soybean oil, such as
refined, bleached and deodorized soybean oil (i.e., RBD soybean
oil). Soybean oil typically includes 95 percent by weight (wt %) or
greater (e.g., 99 wt % or greater) triglycerides of fatty acids.
Major fatty acids in the polyol esters of soybean oil include but
are not limited to saturated fatty acids such as palmitic acid
(hexadecanoic acid) and stearic acid (octadecanoic acid), and
unsaturated fatty acids such as oleic acid (9-octadecenoic acid),
linoleic acid (9,12-octadecadienoic acid), and linolenic acid
(9,12,15-octadecatrienoic acid).
[0063] Examples of metathesized natural oils include but are not
limited to a metathesized vegetable oil, a metathesized algal oil,
a metathesized animal fat, a metathesized tall oil, a metathesized
derivatives of these oils, or mixtures thereof. For example, a
metathesized vegetable oil may include metathesized canola oil,
metathesized rapeseed oil, metathesized coconut oil, metathesized
corn oil, metathesized cottonseed oil, metathesized olive oil,
metathesized palm oil, metathesized peanut oil, metathesized
safflower oil, metathesized sesame oil, metathesized soybean oil,
metathesized sunflower oil, metathesized linseed oil, metathesized
palm kernel oil, metathesized tung oil, metathesized jatropha oil,
metathesized mustard oil, metathesized camelina oil, metathesized
pennycress oil, metathesized castor oil, metathesized derivatives
of these oils, or mixtures thereof. In another example, the
metathesized natural oil may include a metathesized animal fat,
such as metathesized lard, metathesized tallow, metathesized
poultry fat, metathesized fish oil, metathesized derivatives of
these oils, or mixtures thereof.
[0064] The substance including a terminal alkenyl group 110 may be
formed by a cross-metathesis reaction of a natural oil and/or a
metathesized natural oil containing unsaturated polyol esters with
an alpha-olefin or with ethylene. An alpha-olefin is a hydrocarbon
having an alkene group, where a first carbon of the alkene group is
unsubstituted and a second carbon of the alkene group is
substituted with one or two non-hydrogen substituents. The
alpha-olefin may include from 3 to 20 carbon atoms, 10 carbon
atoms, 6 carbon atoms, or 3 carbon atoms. A cross-metathesis
reaction may involve a single species of alpha-olefin, or it may
involve a mixture of alpha-olefin species.
[0065] As an example, an alpha-olefin for use in cross-metathesis
may have the structure H.sub.2C.dbd.C(R.sup.2)(R.sup.3), where
R.sup.2 and R.sup.3 are independently hydrogen, a hydrocarbyl
group, or a heteroalkyl group, provided that at least one of
R.sup.2 and R.sup.3 is not hydrogen. The heteroatoms of a
heteroalkyl group may be present as part of a functional group
substituent. R.sup.2 and R.sup.3 may be linked to form a cyclic
structure. In a preferred embodiment, R.sup.2 and R.sup.3 are
independently selected from C.sub.1-C.sub.20 alkyl,
C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl,
C.sub.1-C.sub.20 heteroalkyl, C.sub.2-C.sub.20 heteroalkenyl,
C.sub.2-C.sub.20 heteroalkynyl, C.sub.5-C.sub.24 aryl,
C.sub.6-C.sub.24 alkylaryl, C.sub.6-C.sub.24 arylalkyl,
C.sub.5-C.sub.24 heteroaryl, and C.sub.6-C.sub.24
heteroarylalkyl.
[0066] Examples of monosubstituted alpha-olefins that may be used
in cross-metathesis include 1-propene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene
and larger alpha olefins, 2-propenol, 3-butenol, 4-pentenol,
5-hexenol, 6-heptenol, 7-octenol, 8-nonenol, 9-decenol,
10-undecenol, 11-dodecenol, 12-tridecenol, 13-tetradecenol,
14-pentadecenol, 15-hexadecenol, 16-heptadecenol, 17-octadecenol,
18-nonadecenol, 19-eicosenol and larger alpha alkenols, 2-propenyl
acetate, 3-butenyl acetate, 4-pentenyl acetate, 5-hexenyl acetate,
6-heptenyl acetate, 7-octenyl acetate, 8-nonenyl acetate, 9-decenyl
acetate, 10-undecenyl acetate, 11-dodecenyl acetate, 12-tridecenyl
acetate 13-tetradecenyl acetate, 14-pentadecenyl acetate,
15-hexadecenyl acetate, 16-heptadecenyl acetate, 17-octadecenyl
acetate, 18-nonadecenyl acetate, 19-eicosenyl acetate and larger
alpha-alkenyl acetates, 2-propenyl chloride, 3-butenyl chloride,
4-pentenyl chloride, 5-hexenyl chloride, 6-heptenyl chloride,
7-octenyl chloride, 8-nonenyl chloride, 9-decenyl chloride,
10-undecenyl chloride, 11-dodecenyl chloride, 12-tridecenyl
chloride, 13-tetradecenyl chloride, 14-pentadecenyl chloride,
15-hexadecenyl chloride, 16-heptadecenyl chloride, 17-octadecenyl
chloride, 18-nonadecenyl chloride, 19-eicosenyl chloride and larger
alpha-alkenyl chlorides, bromides, and iodides, allyl cyclohexane,
allyl cyclopentane, and the like. Examples of disubstituted
alpha-olefins that may be used in cross-metathesis include
isobutylene, 2-methylbut-1-ene, 2-methylpent-1-ene,
2-methylhex-1-ene, 2-methylhept-1-ene, 2-methyloct-1-ene, and the
like.
[0067] Any combination of any of these alpha-olefins may be used in
a cross-metathesis reaction with a natural oil and/or a
metathesized natural oil containing unsaturated polyol esters, to
provide the substance including a terminal alkenyl group 110. In an
exemplary embodiment, a composition including 9-DAME, which
includes a terminal alkenyl group, can be prepared by the
cross-metathesis of 1-propene with a natural oil and/or a
metathesized natural oil containing unsaturated polyol esters. For
example, oleic acid and/or methyl oleate may undergo
cross-metathesis with 1-propene to provide a composition including
9-DAME. Due to the stoichiometry of the cross-metathesis reaction,
the product composition typically comprises 50 mole percent (mol %)
9-DAME and 50 mol % 9-undecenoic acid methyl ester.
[0068] Ethylene also may be used in a cross-metathesis reaction
with a natural oil and/or a metathesized natural oil containing
unsaturated polyol esters, to provide the substance including a
terminal alkenyl group 110. In an exemplary embodiment, a
composition including 9-DAME, which includes a terminal alkenyl
group, can be prepared by the cross-metathesis of ethylene with a
natural oil and/or a metathesized natural oil containing
unsaturated polyol esters. For example, methyl oleate may undergo
cross-metathesis with ethylene to provide a composition including
9-DAME. Due to the stoichiometry of the cross-metathesis reaction,
the product composition typically comprises 50 mol % 9-DAME and 50
mol % 1-decene.
[0069] The substance including a fluorosulfonic acid group 112
includes a group having the formula
R.sup.4--CF.sub.xH.sub.2-xSO.sub.3H, where R is a fluorine atom or
an organic group. In one example R.sup.4 is a fluorine atom, and x
is 0, 1 or 2. In this example, the substance including the
fluorosulfonic acid group is fluoromethanesulfonic acid,
difluoromethanesulfonic acid, or trifluoromethanesulfonic acid. In
another example R.sup.4 is an organic group, and x is 1 or 2. In
this example, the substance including the fluorosulfonic acid group
may be a partially fluorinated alkyl sulfonic acid such as
tetrafluoroethanesulfonic acid, or a perfluorinated alkyl sulfonic
acid such as pentafluoroethanesulfonic acid.
[0070] In another example, the substance including a fluorosulfonic
acid group may be a material having a surface that includes
fluorosulfonic acid groups attached to the surface. Examples of
materials having a surface that includes fluorosulfonic acid groups
attached to the surface include copolymers having perfluorosulfonic
acid monomeric units and monomer units derived from
tetrafluoroethylene, such as a NAFION copolymer (DuPont,
Wilmington, Del.). In one example, a NAFION copolymer may be in the
form of a dispersion of copolymer particles in a liquid, or in the
form of a dispersion of particles having a coating of copolymer on
the particles.
[0071] The reaction mixture 114 includes the substance including a
terminal alkenyl group 110 and the substance including a
fluorosulfonic acid group 112. The reaction mixture may include
only these two substances, or it may include one or more other
substances, such as a solvent, a buffer or a salt. Examples of
solvents include but are not limited to protic solvents such as
water, methanol, ethanol, isopropyl alcohol (IPA) and butanol, and
include aprotic solvents such as tetrahydrofuran (THF), dioxane,
dimethyl formamide (DMF), toluene and xylene.
[0072] The forming 102 of a substance including a 2-alkenyl group
120 from the substance including a terminal alkenyl group 110 in
the reaction mixture may include heating the reaction mixture. The
reaction mixture may be heated to a temperature of at least
30.degree. C., including but not limited to a temperature from
30.degree. C. to 200.degree. C., from 40.degree. C. to 175.degree.
C., from 50.degree. C. to 150.degree. C., or from 60.degree. C. to
120.degree. C. The reaction mixture may be heated for at least 1
hour, including but not limited to from 1 hour to 100 hours, from 5
hours to 50 hours, from 10 hours to 30 hours, or from 15 hours to
25 hours.
[0073] The substance including a 2-alkenyl group 120 may include
any organic molecule that includes a chain of at least 4 carbon
atoms and an alkenyl group positioned at the penultimate position
of the chain. Examples of substances including a 2-alkenyl group
include but are not limited to unsaturated hydrocarbons, such as
2-butene, 2-pentene, 2-hexene, 2-heptene, 2-octene, 2-nonene, and
2-decene. Examples of substances including a 2-alkenyl group
include but are not limited to substituted unsaturated hydrocarbons
that include a substituent in place of a hydrogen atom. Examples of
substituents include but are not limited to halide groups, alkyl
groups, heteroalkyl groups, aryl groups, heteroaryl groups, nitrile
groups, amide groups, imide groups, nitro groups, ketone groups,
ether groups, sulfide groups, sulfoxide groups and sulfone
groups.
[0074] The substance including a 2-alkenyl group 120 may include an
.alpha.-ester-alk-.psi.-ene molecule. An
.alpha.-ester-alk-.psi.-ene molecule has the chemical formula
R.sup.5--O--C(.dbd.O)--(R.sup.6)--CH.dbd.CH--CH.sub.3, where
R.sup.5 is a alkyl group having from 1 to 5 carbon atoms, and
R.sup.6 is an alkyl group having from 1 to 19 carbon atoms.
Examples of .alpha.-ester-alk-.psi.-ene molecules include
8-decenoic acid methyl ester, 8-decenoic acid ethyl ester,
8-decenoic acid propyl ester, 9-undecenoic acid methyl ester,
9-undecenoic acid ethyl ester, 9-decenoic acid propyl ester,
10-dodecenoic acid methyl ester, 10-dodecenoic acid ethyl ester,
and 10-dodecenoic acid propyl ester.
[0075] The yield of the substance comprising a 2-alkenyl group 120
may be at least 50%. Preferably the yield of the substance
comprising a 2-alkenyl group 120 is at least 60%, at least 70%, at
least 80%, at least 90%, or at least 95%.
[0076] Method 100 may produce a substance containing a 2-alkenyl
group 120 from renewable feedstocks, and may advantageously provide
simpler and/or more cost-effective production, reduced variability,
improved sourcing, and increased biorenewability than conventional
methods for producing substances containing a 2-alkenyl group from
petrochemical feedstocks. In addition, method 100 may have less
environmental impact than conventional isomerization methods, which
typically utilize organic solvents and transition metal catalysts
such as iron, nickel or palladium complexes.
[0077] FIG. 2 represents a method 200 of functionalizing a
substance. The method 200 includes combining 201 a substance
including a terminal alkenyl group 210 and a substance including a
fluorosulfonic acid group 212 in a first reaction mixture 214,
forming 202 a substance including a 2-alkenyl group 220 from the
substance including a terminal alkenyl group 210 in the first
reaction mixture, combining 203 the substance including a 2-alkenyl
group 220 and a functionalizing agent 230 in a second reaction
mixture 232, and forming 204 a substance including a first
functional group 240 from the substance including a 2-alkenyl group
220 in the second reaction mixture.
[0078] The substance including a terminal alkenyl group 210, the
substance including a fluorosulfonic acid group 212, and the
substance including a 2-alkenyl group 220 may be as described above
for the substances including a terminal alkenyl group 110, a
fluorosulfonic acid group 112 or a 2-alkenyl group 120,
respectively. The first reaction mixture 214 and the forming 202 of
a substance including a 2-alkenyl group 220 from the substance
including a terminal alkenyl group 210 in the first reaction
mixture may be as described above for the reaction mixture 114 and
the forming 102, respectively.
[0079] The functionalizing agent 230 may include any reagent known
to convert a carbon-carbon double bond into another functional
group. The functionalizing agent 230 may include a halogen, such as
Cl.sub.2 or Br.sub.2, which can react with the substance including
a 2-alkenyl group 220 to form a 1,2-dihalide functional group or a
1,2-halohydrin functional group. The functionalizing agent 230 may
include hydrobromic acid (HBr), which can react with the substance
including a 2-alkenyl group 220 to form a halide functional group.
The functionalizing agent 230 may include an aqueous acid, such as
sulfuric acid, which can react with the substance including a
2-alkenyl group 220 to form an alcohol functional group. The
functionalizing agent 230 may include oxymercuration reagents, such
as water, mercuric acetate (Hg(OAc).sub.2) and sodium borohydride
(NaBH.sub.4), which can react with the substance including a
2-alkenyl group 220 to form an alcohol functional group. The
functionalizing agent 230 may include hydroxylation reagents, such
as potassium permanganate (KMnO.sub.4) or osmium tetraoxide
(OsO.sub.4), which can react with the substance including a
2-alkenyl group 220 to form a 1,2-diol functional group.
[0080] The functionalizing agent 230 may include epoxidation
reagents, such as peracetic acid, which can react with the
substance including a 2-alkenyl group 220 to form an epoxide
functional group. The functionalizing agent 230 may include
alkoxymercuration reagents, such as an alcohol, mercuric acetate or
mercuric trifluoroacetate (Hg(OOCCF.sub.3).sub.2) and sodium
borohydride (NaBH.sub.4), which can react with the substance
including a 2-alkenyl group 220 to form an ether functional group.
The functionalizing agent 230 may include maleination reagents,
such as maleic anhydride, which can react with the substance
including a 2-alkenyl group 220 to form an maleinate functional
group. The functionalizing agent 230 may include hydroamination
reagents, such as a primary or secondary amine and a rhodium
catalyst, which can react with the substance including a 2-alkenyl
group 220 to form an amine functional group. The functionalizing
agent 230 may include borane (BH.sub.3), which can react with the
substance including a 2-alkenyl group 220 to form an alkyl borane
functional group. The functionalizing agent 230 may include
dimethyl disulfide and iodine (I.sub.2), which can react with the
substance including a 2-alkenyl group 220 to form a
.alpha.,.beta.-bis-methylthioether functional group. The
functionalizing agent 230 may include a metathesis catalyst and
another alkene that includes a functional group, which can react
with the substance including a 2-alkenyl group 220 to form a
metathesized product that includes the functional group originally
present in the alkene.
[0081] In one example, the functionalizing agent 230 includes an
oxidizing agent. Examples of oxidizing agents include KMnO.sub.4,
ozone, periodic acid, and lead tetraacetate. An oxidizing agent can
react with the substance including a 2-alkenyl group 220 to form a
carboxylic acid group. A carboxylic acid group may be formed by a
single reaction, such as the oxidation of the alkenyl group by
ozone or KMnO.sub.4. A carboxylic acid group may be formed by two
or more reactions, such as the formation of a 1,2-diol functional
group, followed by oxidative cleavage of the 1,2-diol group with
periodic acid or lead tetraacetate.
[0082] The second reaction mixture 232 includes the substance
including a 2-alkenyl group 220 and the functionalizing agent 230.
The second reaction mixture may be limited to include essentially
these two substances, or it may include one or more other
substances, such as a solvent, a buffer or a salt. Examples of
solvents include but are not limited to protic solvents such as
water, methanol, ethanol, isopropyl alcohol (IPA) and butanol, and
include aprotic solvents such as tetrahydrofuran (THF), dioxane,
dimethyl formamide (DMF), toluene and xylene.
[0083] The forming 204 of a substance including a first functional
group 240 from the substance including a 2-alkenyl group 220 in the
second reaction mixture may include heating the reaction mixture.
The reaction mixture may be heated to a temperature of at least
30.degree. C., including but not limited to a temperature from
30.degree. C. to 200.degree. C., from 40.degree. C. to 175.degree.
C., from 50.degree. C. to 150.degree. C., or from 60.degree. C. to
120.degree. C. The reaction mixture may be heated for at least 1
hour, including but not limited to from 1 hour to 100 hours, from 5
hours to 50 hours, from 10 hours to 30 hours, or from 15 hours to
25 hours.
[0084] The substance including a first functional group 240 may
include an alkyl ester or alkyl carboxylic acid group, as a second
functional group, in addition to the first functional group.
Examples of alkyl ester groups include but are not limited to a
methylheptanoate group, an ethylheptanoate group, a
propylheptanoate group, a methyloctanoate group, an ethyloctanoate
group, a propyloctanoate group, a methylnonanoate group, an
ethylnonanoate group, and a propylnonanoate group. Examples of
alkyl carboxylic acid groups include but are not limited to a
heptanoic acid group, an octanoic acid group, a nonanoic acid
group, and salts thereof.
[0085] The substance including a first functional group 240 may
include two carboxylic acid groups. In one example, the substance
including a 2-alkenyl group 220 includes an
.alpha.-ester-alk-.psi.-ene molecule, such as a molecule as
described above for the substance including a 2-alkenyl group 120.
Oxidation of the alkenyl group and in situ ester hydrolysis can
provide a dicarboxylic acid molecule. Examples of dicarboxylic acid
molecules that can be formed in this manner include but are not
limited to suberic acid, azelaic acid, and sebacic acid.
[0086] FIG. 3 represents a method 300 of making suberic acid. The
method 300 includes combining 301 9-decenoic acid methyl ester 310
and an acid 312 in a first reaction mixture 314, forming 302
8-decenoic acid methyl ester 320 from the 9-decenoic acid methyl
ester 310 in the first reaction mixture, combining 303 the
8-decenoic acid methyl ester 320 and an oxidizing agent 330 in a
second reaction mixture 332, and forming 304 suberic acid 340 from
the 8-decenoic acid methyl ester 320 in the second reaction
mixture.
[0087] The 9-decenoic acid methyl ester 310 may be formed by
metathesis, as described above for the substance including a
terminal alkenyl group 110. Specifically, the 9-decenoic acid
methyl ester 310 may be formed by a cross-metathesis reaction of a
natural oil and/or a metathesized natural oil containing
unsaturated polyol esters with an alpha-olefin or with ethylene. In
an exemplary embodiment, a composition including 9-DAME 310 can be
prepared by the cross-metathesis of 1-propene with a natural oil
and/or a metathesized natural oil containing unsaturated polyol
esters, such as oleic acid or methyl oleate. In another exemplary
embodiment, a composition including 9-DAME 310 can be prepared by
the cross-metathesis of ethylene with a natural oil and/or a
metathesized natural oil such as methyl oleate.
[0088] The acid 312 may include a substance including a
fluorosulfonic acid group, as described above for the substance
including a fluorosulfonic acid group 112. For example, the acid
312 may include fluoromethanesulfonic acid, difluoromethanesulfonic
acid, trifluoromethanesulfonic acid, a partially fluorinated alkyl
sulfonic acid such as tetrafluoroethanesulfonic acid, and/or a
perfluorinated alkyl sulfonic acid such as
pentafluoroethanesulfonic acid. In another example, the acid 312
may be a material having a surface that includes fluorosulfonic
acid groups attached to the surface, such as copolymers having
perfluorosulfonic acid monomeric units and monomer units derived
from tetrafluoroethylene, such as a NAFION copolymer (DuPont,
Wilmington, Del.).
[0089] The first reaction mixture 314 includes the 9-decenoic acid
methyl ester 310 and the acid 312. The first reaction mixture may
include only these two substances, or it may include one or more
other substances, such as a solvent, a buffer or a salt. Examples
of solvents include but are not limited to protic solvents such as
water, methanol, ethanol, isopropyl alcohol (IPA) and butanol, and
include aprotic solvents such as tetrahydrofuran (THF), dioxane,
dimethyl formamide (DMF), toluene and xylene.
[0090] The forming 302 of 8-decenoic acid methyl ester 320 may
include heating the reaction mixture. The reaction mixture may be
heated to a temperature of at least 30.degree. C., including but
not limited to a temperature from 30.degree. C. to 200.degree. C.,
from 40.degree. C. to 175.degree. C., from 50.degree. C. to
150.degree. C., or from 60.degree. C. to 120.degree. C. The
reaction mixture may be heated for at least 1 hour, including but
not limited to from 1 hour to 100 hours, from 5 hours to 50 hours,
from 10 hours to 30 hours, or from 15 hours to 25 hours.
[0091] The oxidizing agent 330 may be as described above for the
functionalizing agent 230, when the functionalizing agent includes
an oxidizing agent. Examples of oxidizing agents include
KMnO.sub.4, ozone, hydrogen peroxide, peroxy acids, periodic acid,
and lead tetraacetate. An oxidizing agent can react with 8-decenoic
acid methyl ester 320 to form a carboxylic acid group. A carboxylic
acid group may be formed by a single reaction, such as the
oxidation of the alkenyl group by ozone or KMnO.sub.4. A carboxylic
acid group may be formed by two or more reactions, such as the
formation of a 1,2-diol functional group, followed by oxidative
cleavage of the 1,2-diol group with periodic acid or lead
tetraacetate.
[0092] The second reaction mixture 332 includes the 8-decenoic acid
methyl ester 320 and the oxidizing agent 330. The second reaction
mixture may include only these two substances, or it may include
one or more other substances, such as a solvent, a buffer or a
salt. Examples of solvents include but are not limited to protic
solvents such as water, methanol, ethanol, isopropyl alcohol (IPA)
and butanol, and include aprotic solvents such as tetrahydrofuran
(THF), dioxane, dimethyl formamide (DMF), toluene and xylene.
[0093] The forming 304 of suberic acid 340 from the 8-decenoic acid
methyl ester 320 may include heating the second reaction mixture.
The second reaction mixture may be heated to a temperature of at
least 30.degree. C., including but not limited to a temperature
from 30.degree. C. to 200.degree. C., from 40.degree. C. to
175.degree. C., from 50.degree. C. to 150.degree. C., or from
60.degree. C. to 120.degree. C. The second reaction mixture may be
heated for at least 1 hour, including but not limited to from 1
hour to 100 hours, from 5 hours to 50 hours, from 10 hours to 30
hours, or from 15 hours to 25 hours.
[0094] FIG. 4 depicts chemical structures and reaction schemes for
an example of a method 400 of transforming 9-decenoic acid methyl
ester (9-DAME) to suberic acid. Method 400 includes combining
9-decenoic acid methyl ester 410 and a fluorosulfonic acid 412 in a
first reaction mixture 414, forming 8-decenoic acid methyl ester
420 from the 9-decenoic acid methyl ester 410, combining the
8-decenoic acid methyl ester 420 and an oxidizing agent 430 in a
second reaction mixture 432, and forming suberic acid 440 from the
8-decenoic acid methyl ester 420. The fluorosulfonic acid 420 may
be, for example trifluoromethane sulfonic acid, NAFION, or the
like. The oxidizing agent 430 may be, for example, potassium
permanganate, ozone, or the like.
[0095] Forming suberic acid using the above methods (i.e. as
product 240, 340, or 440), may provide advantages over conventional
methods of forming suberic acid. Conventional methods typically
convert petrochemical reactants such as cyclooctene or cyclooctane
into suberic acid through one or two oxidation steps. In contrast,
the above methods can convert 9-DAME, which can be produced from
renewable feedstocks, into suberic acid. The use of renewable
feedstocks may advantageously provide simpler and/or more
cost-effective production, reduced variability, improved sourcing,
and increased biorenewability than the conventional methods.
[0096] Suberic acid formed from the above methods (i.e. as product
240, 340, or 440), may be used as a reactant to form a variety of
products, including but not limited to lubricants, greases and
polymers. One advantage of using suberic acid formed by the above
methods is that molecules or materials may be formed from the
suberic acid more economically and in larger quantities than was
previously possible. Another advantage of using suberic acid formed
by the above methods is that the resulting molecules or materials
can have a higher percentage of their content from renewable
sources.
[0097] In one example, suberic acid can be used to form a
polyester. Polyesters formed from suberic acid and having molecular
weights from 250 to 10,000 daltons may be used as lubricants.
Polyesters formed from suberic acid and having higher molecular
weights and/or including branching or crosslinking may be used as
plastic materials. A polyester may be formed by polymerizing
suberic acid and a monomer having two or more hydroxyl functional
groups. Examples of di-hydroxyl functional monomers include but are
not limited to ethylene glycol, diethylene glycol, triethylene
glycol, tetraethylene glycol, propylene glycol, dipropylene glycol,
tripropylene glycol, neopentyl glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol, 1,4-di(2-hydroxy-ethyoxy)benzene,
and the like, and combinations thereof.
[0098] A polyester may be formed by polymerizing suberic acid and a
polyol having two or more hydroxyl functional groups. Examples of
such polyols include but are not limited to poly(alkylene ether)
polyols, polyester polyols, polycarbonate polyols having molecular
weights from 250 to 10,000 daltons, and the like, and combinations
thereof. Poly(alkylene ether) polyols may be formed, for example,
by polymerizing cyclic ethers, glycols and dihydroxyethers.
Examples of poly(alkylene ether) polyols include but are not
limited to poly(propylene glycol) and polytetramethylene ether
glycols (PTMEG). Polyester polyols may be formed, for example, by
polymerizing caprolactone or by reacting dicarboxylic acids such as
adipic, glutaric, sebacic and/or phthalic acid with diols such as
ethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol,
diethylene glycol and/or 1,6-hexanediol, and/or with substances
having three or more hydroxyl functional groups such as glycerol,
trimethylolpropane, pentaerythritol and/or saccharides such as
sorbitol. Examples of polyols include but are not limited to
poly(diethylene glycol adipate).
[0099] In another example, suberic acid can be used to form a
polyamide. A polyamide may be formed by polymerizing suberic acid
and a monomer having two or more amine functional groups. Examples
of amine functional monomers include but are not limited to alkyl
and/or aromatic diamines, triamines, and tetramines. Specific
examples of amine functional monomers include but are not limited
to ethanediamine, triethylenetriamine, diethylenetriamine (DETA),
hexamethylenetetramine, tetraethylenepentamine (TEPA), urea, and
melamine. A polyamide may be formed by polymerizing suberic acid
and a polyamine having two or more amine functional groups.
Examples of such polyamines include but are not limited to
amine-terminated polymers or prepolymers such as
.alpha.-aminomethylethyl-.omega.-aminomethyl-ethoxy-poly[oxy(methyl-1,2-e-
thanediyl)].
[0100] FIG. 5 represents a method 500 of forming a dicarboxylic
acid. The method 500 includes providing 502 a first reaction
mixture 504 including a first olefin ester 512, a second olefin
ester 514, and a metathesis catalyst 516; forming 510 an
unsaturated dicarboxylic ester 522 and an alkene byproduct from the
first reaction mixture 504; forming 520 a second reaction mixture
524 including unsaturated dicarboxylic ester 522 and a
hydrogenating agent 526; hydrogenating 530 at least one unsaturated
group of the unsaturated dicarboxylic ester 522 in the second
reaction mixture 524, to form a second dicarboxylic ester 532;
forming 540 a third reaction mixture 531 including second
dicarboxylic ester 532 and a hydrolyzing agent 534, and hydrolyzing
550 second carboxylic ester 532 in the third reaction mixture 531
to dicarboxylic acid 552. Alternatively, unsaturated dicarboxylic
ester 522 may be hydrolyzed to produce an unsaturated dicarboxylic
acid 554 which may be hydrogenated to produce dicarboxylic acid
552.
[0101] Metathesis catalyst 516 may be any suitable metathesis
catalyst or metathesis catalyst system, such as those described
above in in conjunction with the production of terminal alkenyl
group 110. In some instances, first olefin ester 512 and second
olefin ester 514 are the same, which can be referred to as a
"self-metathesis" reaction. In other instances, however, 512 and
514 are different, thereby giving rise to a cross-metathesis
reaction. Other types of metathesis reactions are also known.
[0102] Example reactions of olefinic esters to make unsaturated
dicarboxylic esters are described in PCT Publication WO
2008/140468, and United States Patent Application Publication Nos.
2009/0264672 and 2013/0085288, all three of which are hereby
incorporated by reference as though fully set forth herein in their
entireties, except that in the event of any inconsistent disclosure
or definition from the present specification, the disclosure or
definition herein shall be deemed to prevail.
[0103] In some embodiments, one or more of the reactants for the
reaction(s) of 510 can be generated from a renewable source, e.g.,
by refining a natural oil or a derivative thereof. In some
embodiments, the refining process includes cross-metathesizing the
natural oil or a derivative thereof with an alkene. In such
instances, the reactants may not be entirely pure, as certain other
alkene and ester byproducts of the natural oil refining may be
present in the input stream. Therefore, in some embodiments, the
reactants can be subjected to a pre-treatment, such as a thermal
pre-treatment, to remove certain impurities, including, but not
limited to, water, volatile organics (esters and alkenes), and
certain aldehydes.
[0104] Metathesis reactions can be carried out under any conditions
adequate to produce the desired metathesis products. For example,
stoichiometry, atmosphere, solvent, temperature, and pressure can
be selected by one skilled in the art to produce a desired product
and to minimize undesirable byproducts. In some embodiments, the
metathesis process may be conducted under an inert atmosphere.
Similarly, in embodiments where a reagent is supplied as a gas, an
inert gaseous diluent can be used in the gas stream. In such
embodiments, the inert atmosphere or inert gaseous diluent
typically is an inert gas, meaning that the gas does not interact
with the metathesis catalyst 516 to impede catalysis to a
substantial degree. For example, non-limiting examples of inert
gases or non-reactive gases include helium, neon, argon, nitrogen,
methane (flared), and carbon dioxide, used individually or in with
each other and other inert gases or non-reacting gases.
[0105] Metathesis reactions, including those disclosed herein, can
be carried out in any suitable reactor, depending on a variety of
factors. Relevant factors include, but are not limited to, the
scale of the reaction, the selection of conditions (e.g.,
temperature, pressure, etc.) the identity of the reacting species,
the identity of the resulting products and the desired product(s),
and the identity of the metathesis catalyst 516. Suitable reactors
can be designed by those of skill in the art, depending on the
relevant factors, and incorporated into a reaction process such,
such as those disclosed herein.
[0106] In certain embodiments, the metathesis catalyst 516 is
dissolved in a solvent prior to conducting the metathesis reaction.
In certain such embodiments, the solvent chosen may be selected to
be substantially inert with respect to the metathesis catalyst. For
example, substantially inert solvents include, without limitation:
aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.;
halogenated aromatic hydrocarbons, such as chlorobenzene and
dichlorobenzene; aliphatic solvents, including pentane, hexane,
heptane, cyclohexane, etc.; and chlorinated alkanes, such as
dichloromethane, chloroform, dichloroethane, etc. In some
embodiments, the solvent comprises toluene.
[0107] In other embodiments, the metathesis catalyst 516 is not
dissolved in a solvent prior to conducting the metathesis reaction.
The catalyst, instead, for example, can be slurried with the
natural oil or unsaturated ester, where the natural oil or
unsaturated ester is in a liquid state. Under these conditions, it
is possible to eliminate the solvent (e.g., toluene) from the
process and eliminate downstream olefin losses when separating the
solvent. In other embodiments, the metathesis catalyst 516 may be
added in solid state form (and not slurried) to the natural oil or
unsaturated ester (e.g., as an auger feed).
[0108] The metathesis reaction temperature may, in some instances,
be a rate-controlling variable where the temperature of the first
reaction mixture is brought to a metathesis reaction temperature
that is selected to provide a desired product at an acceptable
rate. In certain embodiments, the metathesis reaction temperature
is greater than -40.degree. C., or greater than -20.degree. C., or
greater than 0.degree. C., or greater than 10.degree. C. In certain
embodiments, the metathesis reaction temperature is less than
200.degree. C., or less than 150.degree. C., or less than
120.degree. C. In some embodiments, the metathesis reaction
temperature is between 0.degree. C. and 150.degree. C., or is
between 10.degree. C. and 120.degree. C.
[0109] The metathesis reaction can be run under any desired
pressure. In some instances, it may be desirable to maintain the
first reaction mixture a total pressure that is high enough to keep
the cross-metathesis reagent in solution. Therefore, as the
molecular weight of the cross-metathesis reagent increases, the
lower pressure range typically decreases since the boiling point of
the cross-metathesis reagent increases. The total pressure may be
selected to be greater than 0.1 atm (10 kPa), or greater than 0.3
atm (30 kPa), or greater than 1 atm (100 kPa). In some embodiments,
the reaction pressure is no more than 70 atm (7000 kPa), or no more
than 30 atm (3000 kPa). In some embodiments, the pressure for the
metathesis reaction ranges from 1 atm (100 kPa) to 30 atm (3000
kPa).
[0110] A noted above, two or more olefin esters can be used to make
a dibasic ester. In some embodiments, the first olefin ester 512 is
a terminal olefin ester and the second olefin ester 514 is an
internal olefin ester. In some such embodiments, the internal
olefin ester 514 is formed by isomerizing a terminal olefin ester
according to any of the embodiments disclosed above. For example,
9-decenoic acid esters produced from renewable feedstocks in a
typical bio-refinery stream may be isomerized to 8-decenoic acid
esters. In some alternative embodiments, the first olefin ester 512
and the second olefin ester 514 are both internal olefin esters.
For example, when the internal olefin esters are both 8-decenoic
acid esters, the resulting dibasic esters will be
C.sub.16-diesters. In some such embodiments, one or both of these
internal olefin esters are formed by isomerizing a terminal olefin
ester according to any of the embodiments disclosed above.
[0111] In some embodiments, the terminal olefin ester is a compound
of formula (V):
##STR00001##
wherein:
[0112] X.sup.1 is C.sub.3-18 alkylene, C.sub.3-18 alkenylene,
C.sub.2-18 heteroalkylene, or C.sub.2-18 heteroalkenylene, each of
which is optionally substituted one or more times by substituents
selected independently from R.sup.12;
[0113] R.sup.11 is C.sub.1-12 alkyl, C.sub.1-12 heteroalkyl,
C.sub.2-12 alkenyl, or C.sub.2-12 heteroalkenyl, each of which is
optionally substituted one or more times by substituents selected
independently from R.sup.12; and
[0114] R.sup.12 is a halogen atom, --OH, --NH.sub.2, C.sub.1-6
alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6 alkenyl, C.sub.2-6
heteroalkenyl, C.sub.3-10 cyclokalkyl, or C.sub.2-10
heterocycloalkyl.
[0115] In some such embodiments, X.sup.1 is C.sub.3-18 alkylene,
C.sub.3-18 alkenylene, or C.sub.2-18 oxyalkylene, each of which is
optionally substituted one or more times by substituents selected
from the group consisting of a halogen atom, --OH,
--O(C.sub.1-6alkyl), --NH.sub.2, --NH(C.sub.1-6 alkyl), and
N(C.sub.1-6alkyl).sub.2. In some further embodiments, X.sup.1 is
C.sub.3-18 alkylene, C.sub.3-18 alkenylene, or C.sub.2-18
oxyalkylene, each of which is optionally substituted one or more
times by --OH. In some even further embodiments, X.sup.1 is
--(CH.sub.2).sub.2--CH.dbd., --(CH.sub.2).sub.3--CH.dbd.,
--(CH.sub.2).sub.4--CH.dbd., --(CH.sub.2).sub.5--CH.dbd.,
--(CH.sub.2).sub.6--CH.dbd., --(CH.sub.2).sub.7--CH.dbd.,
--(CH.sub.2).sub.8--CH.dbd., --(CH.sub.2).sub.9--CH.dbd.,
--(CH.sub.2).sub.10--CH.dbd., --(CH.sub.2).sub.11--CH.dbd.,
--(CH.sub.2).sub.12--CH.dbd., --(CH.sub.2).sub.13--CH.dbd.,
--(CH.sub.2).sub.14--CH.dbd., or --(CH.sub.2).sub.15--CH.dbd.. In
some even further embodiments, X.sup.1 is
--(CH.sub.2).sub.7--CH.dbd..
[0116] In some such embodiments, R.sup.11 is C.sub.1-8 alkyl,
C.sub.2-8 alkenyl, or C.sub.1-8 oxyalkyl, each of which is
optionally substituted one or more times by --OH. In some further
embodiments, R.sup.11 is methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, neopentyl,
hexyl, or 2-ethylhexyl. In some even further embodiments, R.sup.11
is methyl.
[0117] In some embodiments, the terminal olefin ester is 9-deneoic
acid alkyl ester, such as 9-decenoic acid methyl ester.
[0118] In some other embodiments, the first olefin ester 512 and
the second olefin ester 514 are both internal olefin esters. In
some such embodiments, the first olefin ester 512 and the second
olefin ester 514 are independently compounds of formula (VI):
##STR00002##
where:
[0119] X.sup.2 is C.sub.3-18 alkylene, C.sub.3-18 alkenylene,
C.sub.2-18 heteroalkylene, or C.sub.2-18 heteroalkenylene, each of
which is optionally substituted one or more times by substituents
selected independently from R.sup.15;
[0120] R.sup.13 is C.sub.1-12 alkyl, C.sub.1-12 heteroalkyl,
C.sub.2-12 alkenyl, or C.sub.2-12 heteroalkenyl, each of which is
optionally substituted one or more times by substituents selected
independently from R.sup.15;
[0121] R.sup.14 is a halogen atom, --OH, --NH.sub.2, C.sub.1-6
alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6 alkenyl, C.sub.2-6
heteroalkenyl, C.sub.3-10 cyclokalkyl, or C.sub.2-10
heterocycloalkyl; and
[0122] R.sup.15 is a halogen atom, --OH, --NH.sub.2, C.sub.1-6
alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6 alkenyl, C.sub.2-6
heteroalkenyl, C.sub.3-10 cyclokalkyl, or C.sub.2-10
heterocycloalkyl.
[0123] In some such embodiments, X.sup.2 is C.sub.3-18 alkylene,
C.sub.3-18 alkenylene, or C.sub.218 oxyalkylene, each of which is
optionally substituted one or more times by substituents selected
from the group consisting of a halogen atom, --OH,
--O(C.sub.1-6alkyl), --NH.sub.2, --NH(C.sub.1-6 alkyl), and
N(C.sub.1-6alkyl).sub.2. In some further such embodiments, X.sup.2
is C.sub.3-18 alkylene, C.sub.3-18 alkenylene, or C.sub.2-18
oxyalkylene, each of which is optionally substituted one or more
times by --OH. In some even further such embodiments, X.sup.2 is
--(CH.sub.2).sub.2--CH.dbd., --(CH.sub.2).sub.3CH.dbd.,
--(CH.sub.2).sub.4--CH.dbd., --(CH.sub.2).sub.5--CH.dbd.,
--(CH.sub.2).sub.6--CH.dbd., --(CH.sub.2).sub.2--CH.dbd.,
--(CH.sub.2).sub.8--CH.dbd., --(CH.sub.2).sub.9--CH.dbd.,
--(CH.sub.2).sub.10--CH.dbd., --(CH.sub.2).sub.11--CH.dbd.,
--(CH.sub.2).sub.12--CH.dbd., --(CH.sub.2).sub.13--CH--,
--(CH.sub.2).sub.14--CH.dbd., or --(CH.sub.2).sub.15--CH.dbd.. In
some such embodiments, X.sup.2 is --(CH.sub.2).sub.6--CH.dbd..
[0124] In some such embodiments, R.sup.13 is C.sub.1-8 alkyl,
C.sub.2-8 alkenyl, or C.sub.1-8 oxyalkyl, each of which is
optionally substituted one or more times by --OH. In some further
such embodiments, R.sup.13 is methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, sec-butyl, tert-butyl, pentyl, tert-pentyl,
neopentyl, hexyl, or 2-ethylhexyl. In some even further such
embodiments, R.sup.13 is methyl.
[0125] In some such embodiments, R.sup.14 is C.sub.1-8 alkyl,
C.sub.2-8 alkenyl, or C.sub.1-8 oxyalkyl, each of which is
optionally substituted one or more times by --OH. In some further
such embodiments, R.sup.14 is methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, or nonyl. In some even further such
embodiments, R.sup.14 is methyl or ethyl. In some embodiments,
R.sup.14 is methyl.
[0126] In some embodiments, the internal olefin ester is an
8-decenoic acid alkyl ester, such as 8-decenoic acid methyl ester.
In some such embodiments, the ester of 8-decenoic acid is formed by
isomerizing an ester of 9-decenoic acid.
[0127] The hydrogenating 530 of at least one unsaturated group in
the unsaturated dicarboxylic ester 522 may be carried with any
suitable hydrogenating agent 526. In certain embodiments, hydrogen
gas is reacted with the unsaturated dicarboxylic ester 522 in the
presence of a hydrogenation catalyst to form a saturated
dicarboxylic acid, for example, in a hydrogenation reactor. Any
suitable hydrogenation catalyst can be used. In some embodiments,
the hydrogenation catalyst comprises nickel, copper, palladium,
platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium,
individually or in any combinations thereof. Such catalysts may be
heterogeneous or homogeneous. In some embodiments, the catalysts
are supported nickel or sponge nickel type catalysts. In some
embodiments, the hydrogenation catalyst comprises nickel that has
been chemically reduced with hydrogen to an active state (i.e.,
reduced nickel) provided on a support. The support may comprise
porous silica (e.g., kieselguhr, infusorial, diatomaceous, or
siliceous earth) or alumina. The catalysts are characterized by a
high nickel surface area per gram of nickel. Commercial examples of
supported nickel hydrogenation catalysts include those available
under the trade designations NYSOFACT, NYSOSEL, and NI 5248 D (from
BASF Catalysts LLC, Iselin, N.J.). Additional supported nickel
hydrogenation catalysts include those commercially available under
the trade designations PRICAT Ni 62/15 P, PRICAT Ni 55/5, PRICAT
9910, PRICAT 9920, PRICAT 9908, PRICAT 9936 (from Johnson Matthey
Catalysts, Ward Hill, Mass.).
[0128] The supported nickel catalysts may be of the type described
in U.S. Pat. No. 3,351,566, U.S. Pat. No. 6,846,772, European
Patent Publication No. 0168091, and European Patent Publication No.
0167201, each of which are incorporated by reference herein in
their entireties, except that in the event of any inconsistent
disclosure or definition from the present specification, the
disclosure or definition herein shall be deemed to prevail.
Hydrogenation may be carried out in a batch or in a continuous
process and may be partial hydrogenation or complete hydrogenation.
In certain embodiments, the temperature ranges from 50.degree. C.
to 350.degree. C., 100.degree. C. to 300.degree. C., 150.degree. C.
to 250.degree. C., or 100.degree. C. to 150.degree. C. The desired
temperature may vary, for example, with hydrogen gas pressure.
Typically, a higher gas pressure will require a lower temperature.
Hydrogen gas is pumped into the reaction vessel to achieve a
desired pressure of H.sub.2 gas. In certain embodiments, the
H.sub.2 gas pressure ranges from 15 psig (1 barg) to 3000 psig
(204.1 barg), 15 psig (1 barg) to 90 psig (6.1 barg), or 100 psig
(6.8 barg) to 500 psig (34 barg). As the gas pressure increases,
more specialized high-pressure processing equipment may be
required. In certain embodiments, the reaction conditions are
"mild", wherein the temperature is between 50.degree. C. and
100.degree. C. and the H.sub.2 gas pressure is less than 100 psig.
In other embodiments, the temperature is between 100.degree. C. and
150.degree. C., and the pressure is between 100 psig (6.8 barg) and
500 psig (34 barg). When the desired degree of hydrogenation is
reached, the reaction mass is cooled to the desired filtration
temperature.
[0129] The amount of hydrogenation catalyst is typically selected
in view of a number of factors including, for example, the type of
hydrogenation catalyst used, the amount of hydrogenation catalyst
used, the degree of unsaturation in the material to be
hydrogenated, the desired rate of hydrogenation, the desired degree
of hydrogenation (e.g., as measure by iodine value (IV)), the
purity of the reagent, and the H.sub.2 gas pressure. In some
embodiments, the hydrogenation catalyst is used in an amount of 10
percent by weight or less, for example, 5 percent by weight or less
or 1 percent by weight or less.
[0130] The products of the forming 510 of unsaturated dicarboxylic
ester 522 can contain various impurities. These impurities can be
compounds that were made by various kinds of unproductive
metathesis. Or, in some instances, the impurities may result from
the presence of impurities in the starting compositions. In any
event, it can, in some embodiments, be desirable to strip out
and/or distill out 560 these impurities. In some such embodiments,
the stripping and/or distilling can occur after 510, but before the
hydrogenating 530. In some alternative embodiments, the stripping
and/or distilling can occur after both 510 and the hydrogenating
530. These impurities may contain more esters than hydrocarbons
(e.g., monobasic esters), as certain alkene impurities can be
vented out of the reactor during the metathesis reaction, e.g., due
to the lower relative boiling point of the alkene impurities. Of
course, in some instances, these alkene impurities may stay in the
reactor long enough to involve themselves in certain metathesis
reactions, thereby generating other impurities (e.g., an additional
alkene impurity and an additional ester impurity). Paraffin
impurities can also be present, which can be removed by the
stripping and/or distilling 560, for example, after
hydrogenation.
[0131] In some embodiments, the stripping and/or distilling 560 may
lead to the removal of certain amounts of the first olefin ester
512 and/or the second olefin ester 514. In some such embodiments,
these stripped out reactants can be collected and reused for
further metathesis reactions.
[0132] In some embodiments, it may be desirable to further purify
the second dicarboxylic ester 532 prior to the hydrolyzing 550. For
example, in some embodiments, the second dicarboxylic ester 532 can
be recrystallized. The recrystallization can be carried out by any
suitable technique. The second dicarboxylic ester 532 may be
dissolved in a solvent system, for example, with heating, followed
by cooling until solid crystals of the second dicarboxylic ester
532 appear. This can be a suitable means of removing impurities
that are more soluble in the solvent system than the second
dicarboxylic ester 532, e.g., shorter-chain monobasic and
dicarboxylic esters and/or acids.
[0133] The hydrolizyng 550 second dicarboxylic ester 532 to a
dicarboxylic acid 552 can be carried out by any suitable
hydrolyzing agents. In some embodiments, the second dicarboxylic
ester 532 is converted to dicarboxylic acid 552 by saponification,
followed by acidification. In some embodiments, the dicarboxylic
acid 552 is a compound having the formula: H--OOC--Y--COO--H,
wherein Y denotes any organic moiety (such as hydrocarbyl or silyl
groups), including those bearing heteroatom containing substituent
groups. In some such embodiments, Y is a divalent hydrocarbyl
group, which can be optionally substituted with
heteroatom-containing substituents, or whose carbon atoms can be
replaced by one or more heteroatoms. Such divalent hydrocarbyl
groups can include substituted and unsubstituted alkylene,
alkenylene, and oxyalkylene groups.
[0134] In some embodiments, the dicarboxylic acid 552 is a compound
of formula (II):
##STR00003##
wherein,
[0135] Y.sup.1 is C.sub.6-36 alkylene or C.sub.6-36 heteroalkylene,
each of which is optionally substituted one or more times by
substituents selected independently from R.sup.3; and
[0136] R.sup.3 is a halogen atom, --OH, --NH.sub.2, C.sub.1-6
alkyl, C.sub.1-6 heteroalkyl, C.sub.2-6 alkenyl, C.sub.2-6
heteroalkenyl, C.sub.3-10 cyclokalkyl, or C.sub.2-10
heterocycloalkyl.
[0137] In some embodiments, Y.sup.1 is C.sub.6-36 alkylene or
C.sub.4-36 oxyalkylene, each of which is optionally substituted one
or more times by substituents selected from the group consisting of
a halogen atom, --OH, --O(C.sub.1-6 alkyl), --NH.sub.2,
--NH(C.sub.1-6 alkyl), and N(C.sub.1-6alkyl).sub.2. In some further
such embodiments, Y.sup.1 is C.sub.6-36 alkylene, C.sub.6-36
alkenylene, or C.sub.4-36 oxyalkylene, each of which is optionally
substituted one or more times by --OH. In some further such
embodiments, Y.sup.1 is --(CH.sub.2).sub.8--, --(CH.sub.2).sub.9--,
--(CH.sub.2).sub.10--, --(CH.sub.2).sub.11--,
--(CH.sub.2).sub.12--, --(CH.sub.2).sub.13--,
--(CH.sub.2).sub.14--, --(CH.sub.2).sub.15--,
--(CH.sub.2).sub.16--, --(CH.sub.2).sub.17--,
--(CH.sub.2).sub.18--, --(CH.sub.2).sub.19--,
--(CH.sub.2).sub.20--, --(CH.sub.2).sub.21--, or
--(CH.sub.2).sub.22--.
[0138] In some embodiments, the dicarboxylic acid 552 can be
further purified. In some embodiments, the purification is carried
out using the recrystallization methods described above.
[0139] The reactions of method 500 may lead to the production of
colored impurities. As used herein, the term "colored impurities"
refers to compounds that absorb light having a wavelength of 440 nm
or 550 nm. Thus, these are compounds that absorb light in the
blue-violet or the green portions of the visible electromagnetic
spectrum. In some embodiments, the mole-to-mole ratio of formed
dicarboxylic acids to colored impurities is at least 250:1, or at
least 350:1, or at least 500:1, or at least 1000:1, or at least
2000:1. In some embodiments, a composition including dicarboxylic
acid 552 can be treated to lower even further the concentration of
colored impurities in the composition. For example, in some such
embodiments, the composition can be decolorized, for example, by
contacting the composition with a decolorizing agent. Suitable
decolorizing agents include, but are not limited to, activated
carbon, silica, silicates (e.g., magnesium silicates), clay,
diatomaceous earth, and alumina. In some embodiments, for example,
decolorizing agent is added to the composition, and the
decolorizing agent is subsequently filtered out. Or, in some
alternative embodiments, the composition can be passed through a
bed containing the decolorizing agent. Additional treatments can
also be carried out, either in addition to decolorization or
instead of decolorization. In some embodiments, the composition can
be treated with a bleaching agent (e.g., an oxidizing agent),
followed by an extraction to remove the bleaching agent from the
composition.
[0140] FIG. 6 shows an illustrative embodiment for forming a
dicarboxylic acid. The method 600 includes: providing 602 a first
reaction mixture 604 including a first olefin ester 606 and a
second olefin ester 608; optionally thermally pre-treating 610 the
first reaction mixture 604; reacting 620 the first olefin ester 606
with the second olefin ester 608 in the presence of a metathesis
catalyst 622 to form an unsaturated dicarboxylic ester 624; forming
a second reaction mixture 623 including the unsaturated
dicarboxylic ester 624 and a hydrogenating agent 626; hydrogenating
630 the unsaturated dicarboxylic ester 624 in the second reaction
mixture 623 to form a saturated dicarboxylic ester 632 (including
optional recovery of a hydrogenation catalyst, e.g., by
filtration); optionally stripping and/or distilling 634 the
saturated dicarboxylic ester 632 of at least one alkene or ester
impurity; hydrolyzing 640 the saturated dicarboxylic ester 632 to
form a saturated dicarboxylic acid 642; optionally decolorizing 650
colored impurities (including optional recovery of a decolorizing
agent); optionally purifying 660 the saturated dicarboxylic acid
642 (e.g., by recrystallization); optionally drying 670 the solid
saturated dicarboxylic acid 642; and optionally packaging 680 of
the saturated dicarboxylic acid 642. In some embodiments, the
saturated dicarboxylic acid 642 is hexadecanedioic acid. In some
such embodiments, the first olefin ester 606 and second olefin
ester 608 both are 9-decenoic acid methyl ester. In some other such
embodiments, the first olefin ester 606 and the second olefin ester
608 are both 9-dodecenoic acid methyl ester. In some even further
such embodiments, the first olefin ester 606 is 9-decenoic acid
methyl ester and the second olefin ester 608 is 9-dodecenoic acid
methyl ester. In additional embodiments, the first olefin ester 606
and the second olefin ester 608 are both 8-decenoic acid methyl
ester (8-DAME).
[0141] FIG. 7 shows an illustrative embodiment for forming a
dicarboxylic acid. The method 700 includes: providing 702 a first
reaction mixture 704 comprising a first olefin ester 706 and a
second olefin ester 708; optionally thermally pre-treating 710 the
first reaction mixture 704; reacting 720 the first olefin ester 706
with the second olefin ester 708 in the presence of a metathesis
catalyst 722 to form an unsaturated dicarboxylic ester 724; forming
a second reaction mixture including the unsaturated dicarboxylic
ester 724 and a hydrogenating agent 726; hydrogenating 730 the
unsaturated dicarboxylic ester 724 to form a saturated dicarboxylic
ester 732 (including optional recovery of a hydrogenation catalyst,
e.g., by filtration); optionally stripping and/or distilling 734
the saturated dicarboxylic ester 732 of at least one alkene or
ester impurity; hydrolyzing 740 the saturated dicarboxylic ester
732 to form a saturated dicarboxylic acid 742; optionally purifying
750 the saturated dicarboxylic acid 742 (e.g., by
recrystallization); optionally drying 760 the solid saturated
dicarboxylic acid 742; and optionally packaging 770 of the
saturated dicarboxylic acid 742. In some embodiments, the saturated
dicarboxylic acid 742 is hexadecanedioic acid. In some such
embodiments, the first olefin ester 706 and second olefin ester 708
both are 9-decenoic acid methyl ester. In some other such
embodiments, the first olefin ester 706 and the second olefin ester
708 both are 9-dodecenoic acid methyl ester. In some even further
such embodiments, the first olefin ester 706 is 9-decenoic acid
methyl ester and the second olefin ester 708 is 9-dodecenoic acid
methyl ester. In additional embodiments, the first olefin ester 706
and the second olefin ester 708 are both 8-DAME.
[0142] FIG. 8 shows an illustrative embodiment for forming a
dicarboxylic acid. The method 800 includes: providing 802 a first
reaction mixture 804 including a first olefin ester 806 and a
second olefin ester 808; optionally thermally pre-treating 810 the
first reaction mixture 804; reacting 820 the first olefin ester 806
with the second olefin ester 808 in the presence of a metathesis
catalyst 822 to form an unsaturated dicarboxylic ester 824;
hydrogenating 830 the unsaturated dicarboxylic ester 824 in the
presence of a hydrogenating agent 826 to form a saturated
dicarboxylic ester 832 (including optional recovery of a
hydrogenation catalyst, e.g., by filtration); optionally stripping
and/or distilling 840 the saturated dicarboxylic ester 832 of at
least one alkene or ester impurity; optionally purifying 850 the
saturated dicarboxylic ester 832, e.g., by recrystallization;
hydrolyzing 860 the saturated dicarboxylic ester 832 to form a
saturated dicarboxylic acid 862; optionally decolorizing 870
colored impurities (optionally including recovery of a decolorizing
agent); optionally drying 880 the saturated dicarboxylic acid 862;
and optionally packaging 890 of the saturated dicarboxylic acid
862. In some embodiments, the saturated dicarboxylic acid 862 is
hexadecanedioic acid. In some such embodiments, the first olefin
ester 806 and second olefin ester 808 both are 9-decenoic acid
methyl ester. In some other such embodiments, the first olefin
ester 806 and the second olefin ester 808 are both 9-dodecenoic
acid methyl ester. In some even further such embodiments, the first
olefin ester 806 is 9-decenoic acid methyl ester and the second
olefin ester 808 is 9-dodecenoic acid methyl ester. In additional
embodiments, the first olefin ester 806 and the second olefin ester
808 are both 8-DAME.
[0143] FIG. 9 shows an illustrative embodiment for forming a
dicarboxylic acid. The method 900 includes: providing 902 a first
reaction mixture 904 including a first olefin ester 906 and a
second olefin ester 908; optionally thermally pre-treating 910 the
first reaction mixture 904; reacting 920 the first olefin ester 906
with the second olefin ester 908 in the presence of a metathesis
catalyst 922 to form an unsaturated dicarboxylic ester 924;
hydrogenating 930 the unsaturated dicarboxylic ester 924 to form a
saturated dicarboxylic ester 932 (including optional recovery of a
hydrogenation catalyst, e.g., by filtration); optionally stripping
and/or distilling 940 the saturated dicarboxylic ester 932 of at
least two impurities, wherein the at least two stripped impurities
include an amount 942 of the first olefin ester 906 and an amount
944 second olefin ester 908, and optionally reacting 946 amounts
942 and 944 in the presence of metathesis catalyst 922; hydrolyzing
950 the saturated dicarboxylic ester 932 to form a saturated
dicarboxylic acid 952; optionally decolorizing 960 colored
impurities (including optional recovery of a decolorizing agent);
optionally purifying 970 the saturated dicarboxylic acid 952 (e.g.,
by recrystallization); optionally drying the saturated dicarboxylic
acid 952; and optionally packaging 980 of the saturated
dicarboxylic acid 952. In some embodiments, the saturated
dicarboxylic acid 952 is octadecanedioic acid. In some such
embodiments, the first olefin ester 906 and second olefin ester 908
both are 9-decenoic acid methyl ester. In some other such
embodiments, the first olefin ester 906 and the second olefin ester
908 are both 9-dodecenoic acid methyl ester. In some even further
such embodiments, the first olefin ester 906 is 9-decenoic acid
methyl ester and the second olefin ester 908 is 9-decenoic acid
methyl ester. In additional embodiments, the first olefin ester 906
and the second olefin ester 908 are both 8-DAME.
[0144] In some embodiments, an 8-decenoic acid alkyl ester
(8-DAAE), such as 8-DAME, is reacted with itself or another olefin
ester in a metathesis reaction to form an unsaturated dicarboxylic
ester that may be hydrogenated and hydrolyzed to produce a
dicarboxylic acid. In some such embodiments, the other olefin ester
is one of formula (V) or (VI), above. In order to obtain
dicarboxylic acids featuring relatively longer carbon chains, e.g.
chains having from 16 to 36 carbon atoms, the other olefin ester
preferably features at least 8 carbon atoms, e.g. an olefin ester
of formula (V), where X.sup.1 is C.sub.8-18 alkylene or C.sub.3-18
alkenylene, or an olefin ester of formula (VI), where X.sup.2 is
C.sub.8-18 alkylene or C.sub.3-18 alkenylene.
[0145] The olefin esters employed above can, in certain
embodiments, be derived from renewable sources, such as various
natural oils. Any suitable methods can be used to make these
compounds from such renewable sources. Suitable methods include,
but are not limited to, fermentation, conversion by bioorganisms,
and conversion by metathesis. In some embodiments, natural oils can
be subjected to various pre-treatment processes, which can
facilitate their utility for use in certain metathesis reactions.
Useful pre-treatment methods are described in United States Patent
Application Publication No. 2011/0113679 and U.S. Provisional
Patent Application Nos. 61/783,321 and 61/783,720, both filed Mar.
14, 2013, all three of which are incorporated by reference herein
in their entirety, except that in the event of any inconsistent
disclosure or definition from the present specification, the
disclosure or definition herein shall be deemed to prevail.
[0146] In some embodiments, after any optional pre-treatment of the
natural oil feedstock, the natural oil feedstock is reacted in the
presence of a metathesis catalyst in a metathesis reactor. In some
other embodiments, an olefin ester (e.g., an unsaturated glyceride,
such as an unsaturated triglyceride) is reacted in the presence of
a metathesis catalyst in a metathesis reactor. The olefin ester may
be a component of the natural oil feedstock, or may be derived from
other sources, e.g., from esters generated in earlier-performed
metathesis reactions. In certain embodiments, in the presence of a
metathesis catalyst, the natural oil or olefin ester can undergo a
self-metathesis reaction with itself. In other embodiments, the
natural oil or olefin ester undergoes a cross-metathesis reaction
with an olefin. The self-metathesis and/or cross-metathesis
reactions form a metathesized product wherein the metathesized
product comprises olefins and esters.
[0147] The following examples are provided to illustrate one or
more preferred embodiments of the invention. Numerous variations
can be made to the following examples that lie within the scope of
the invention.
EXAMPLES
Example 1
Isomerization of 9-decenoic acid methyl ester (9-DAME)
[0148] A reaction mixture was prepared by combining 100 g
9-decenoic acid methyl ester (9-DAME; Elevance Renewable Sciences,
Inc., Woodridge, Ill.) with 2.5 g of trifluoromethanesulfonic acid
(Aldrich; St. Louis, Mo.), providing an acid content of 2.5 wt %.
The reaction mixture was heated to 60.degree. C. and stirred for 17
hours, and then stirred as it cooled to room temperature. The
reaction mixture was washed with 50 mL of a saturated aqueous
solution of sodium bicarbonate. The organic phase from the washing
was dried with magnesium sulfate and filtered. The product was then
distilled at 3 Torr, with the major fraction (85 g) of a clear,
colorless liquid collected at a pot temperature of 103-120.degree.
C., and a head temperature of 95-100.degree. C.
[0149] The product was characterized by nuclear magnetic resonance
(NMR) using a Varian Inova 400 and CDCl.sub.3 solvent. .sup.1H NMR
(400 megahertz (MHz)) and .sup.13C NMR (100 MHz) spectra were
consistent with a product mixture containing mostly 8-decenoic acid
methyl ester (8-DAME), as well as small amounts of 7-decenoic acid
methyl ester (7-DAME) and 6-decenoic acid methyl ester (6-DAME)
byproducts, and of 9-DAME starting material.
[0150] The product was characterized by gas chromatography/mass
spectrometry. Prior to characterization, the product was combined
with dimethyl disulfide and iodine (I.sub.2) to convert the
carbon-carbon double bonds in the product into
.alpha.,.beta.-bis-methylthioether groups, following the method of
Shibahara, A. et al., J. Am. Oil Chem. Soc., 85, 93-94 (2008). This
conversion of the double bonds allowed for quantification of the
relative amounts of 8-DAME, 7-DAME, 6-DAME, and 9-DAME in the
product mixture.
[0151] Table 1 lists the substances identified in the product
mixture using NMR and GC/MS. The overall conversion of the 9-DAME
into an isomer was 95.6%
(95.6%=100%-(1.3%+3.8%+4.3%+17.7%+19.9%+48.6%)). The yield of
8-DAME, including both cis- and trans-isomers, was 68.5%
(68.5%=19.9%+48.6%). Of the isomers produced, 8-DAME constituted
72% of the isomerized product
(71.7%=100%.times.(19.9%+48.6%)/(1.3%+3.8%+4.3%+17.7%+19.9%+48.6%)).
TABLE-US-00001 TABLE 1 Substances in isomerization reaction product
mixture. Concentration in product mixture (%) cis- trans- 6-DAME
##STR00004## 1.3 3.8 7-DAME ##STR00005## 4.3 17.7 8-DAME
##STR00006## 19.9 48.6 9-DAME ##STR00007## 4.0
Example 2
Isomerization of 9-DAME Using Other Reaction Conditions
[0152] The effects of reaction temperature, reaction time, type of
acid, and amount of acid on the isomerization of 9-DAME were
investigated by performing the reaction under a variety of
different reaction conditions. Each reaction mixture was prepared
by combining 100 g 9-DAME with either trifluoromethanesulfonic acid
or a NAFION resin. The NAFION resin used was SAC-13 (Aldrich),
which is a fluorosulfonic acid polymer on amorphous silica at a
loading of 10-20%, having an average pore volume greater than 0.6
mL/g, an average pore diameter greater than 10 nm, a surface area
greater than 200 m.sup.2/g and a density of 2.1 g/m L at 25.degree.
C.
[0153] Table 2 lists the reactants present in the different
reaction mixtures, the reaction temperatures and times, and the
percent conversion of 9-DAME into an isomer product. The products
were isolated and characterized by NMR as described in Example
1.
TABLE-US-00002 TABLE 2 Reactants and reaction conditions for
isomerization reactions. Acid loading Temperature Time Conversion
of Acid used (%) (.degree. C.) (hours) 9-DAME (%) TfOH* 2.5 60 17
95 TfOH 2.5 20 72 <10 TfOH 1 60 18 50 TfOH 1 90 18 >90 NAFION
5 60 18 <10 NAFION 5 120 6 >98 *Trifluoromethanesulfonic
acid
Example 3
Isomerization of 1-decene
[0154] A reaction mixture was prepared by combining 100 g 1-decene
with 2.5 g of trifluoromethanesulfonic acid, providing an acid
content of 2.5 wt %. The reaction mixture was heated to 60.degree.
C. and stirred for 17 hours, and then stirred as it cooled to room
temperature. The products were isolated and characterized by NMR
and GC/MS as described in Example 1. The overall conversion of
1-decene into an isomer was 60%. Of the isomers produced, 2-decene
(both cis- and trans-isomers) constituted over 70% of the
isomerized product.
Example 4
Oxidation of 8-decenoic acid methyl ester (8-DAME)
[0155] A reaction mixture is prepared by combining 8-decenoic acid
methyl ester and water. The oxidizing agent KMnO.sub.4 is then
added, and the reaction mixture is heated and stirred. Suberic acid
is formed by oxidative cleavage of the carbon-carbon double bond,
and by hydrolysis of the methyl ester group.
[0156] Alternatively, a reaction mixture is prepared by combining
8-decenoic acid methyl ester and water, and then ozone (O.sub.3) is
bubbled through the reaction mixture as the reaction mixture is
heated and stirred. Suberic acid is formed by oxidative cleavage of
the carbon-carbon double bond, and by hydrolysis of the methyl
ester group.
Example 5
[0157] A reaction mixture is prepared by combining 8-decenoic acid
methyl ester, Hoveyda-Grubbs' catalyst, and dichloromethane. The
reaction mixture is then heated and stirred. Dimethyl
hexadec-8-enedioate and 2-butene are formed by metathesis of the
8-decenoic acid methyl ester; the hexadec-8-enedioate is then
converted to hexadecanedioic acid following hydrogenation of the
carbon-carbon double bond and hydrolysis of the methyl ester
groups.
[0158] Another reaction mixture is prepared by combining 8-decenoic
acid methyl ester, 9-undecanoic methyl ester, Hoveyda-Grubbs'
catalyst, and dichloromethane. The reaction mixture is then heated
and stirred. Dimethyl heptadec-8-enedioate and 2-butene are formed
by metathesis of the 8-decenoic acid methyl ester and the
9-undecanoic methyl ester; the dimethyl heptadec-8-enedioate is
then converted to heptadecanedioic acid following hydrogenation of
the carbon-carbon double bond and hydrolysis of the methyl ester
groups. While various embodiments of the invention have been
described, it will be apparent to those of ordinary skill in the
art that other embodiments and implementations are possible within
the scope of the invention. Accordingly, the invention is not to be
restricted except in light of the attached claims and their
equivalents.
* * * * *