U.S. patent application number 11/261720 was filed with the patent office on 2007-05-03 for polycyclic dihydroxy compounds and methods for preparation.
This patent application is currently assigned to General Electric Company. Invention is credited to Jan Henk Kamps, Jan-Pleun Lens, A.S. Radhakrishna, T. Tilak Raj, Ravindra Vikram Singh.
Application Number | 20070100156 11/261720 |
Document ID | / |
Family ID | 37950773 |
Filed Date | 2007-05-03 |
United States Patent
Application |
20070100156 |
Kind Code |
A1 |
Kamps; Jan Henk ; et
al. |
May 3, 2007 |
POLYCYCLIC DIHYDROXY COMPOUNDS AND METHODS FOR PREPARATION
Abstract
A dihydroxy aromatic compound having a Formula (I) wherein
R.sup.1 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic functionality
having 1 to 10 carbons, an aliphatic ester functionality having 2
to 10 carbons, a cycloaliphatic ester functionality having 4 to 10
carbons and an aromatic ester functionality having 4 to 10 carbons;
R.sup.2 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic ester
functionality having 2 to 10 carbons, a cycloaliphatic ester
functionality having 4 to 10 carbons and an aromatic ester
functionality having 4 to 10 carbons; and each R.sup.3 and R.sup.4,
at each occurrence, can be the same or different and are
independently at each occurrence an aliphatic functionality having
1 to 10 carbons or a cycloaliphatic functionality having 3 to 10
carbons, "n" is an integer having a value 0 to 4 and "m" is an
integer having a value 0 to 4.
Inventors: |
Kamps; Jan Henk; (Bergen op
Zoom, NL) ; Lens; Jan-Pleun; (Breda, NL) ;
Radhakrishna; A.S.; (Bangalore, IN) ; Raj; T.
Tilak; (Bangalore, IN) ; Singh; Ravindra Vikram;
(Basti, IN) |
Correspondence
Address: |
CANTOR COLBURN LLP - GE PLASTICS - SMITH
55 GRIFFIN RD SOUTH
BLOOMFIELD
CT
06002
US
|
Assignee: |
General Electric Company
Schenectady
NY
|
Family ID: |
37950773 |
Appl. No.: |
11/261720 |
Filed: |
October 28, 2005 |
Current U.S.
Class: |
560/59 ;
560/20 |
Current CPC
Class: |
C07C 69/757 20130101;
C07C 45/69 20130101; C07C 2601/14 20170501; C07C 45/74 20130101;
C07C 67/347 20130101; C07C 67/343 20130101; C07C 45/74 20130101;
C07C 49/223 20130101; C07C 67/343 20130101; C07C 69/757 20130101;
C07C 67/347 20130101; C07C 69/757 20130101 |
Class at
Publication: |
560/059 ;
560/020 |
International
Class: |
C07C 69/76 20060101
C07C069/76 |
Claims
1. A dihydroxy aromatic compound having a Formula (I), ##STR14##
wherein R.sup.1 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic functionality
having 1 to 10 carbons, an aliphatic ester functionality having 2
to 10 carbons, a cycloaliphatic ester functionality having 4 to 10
carbons and an aromatic ester functionality having 4 to 10 carbons;
R.sup.2 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic ester
functionality having 2 to 10 carbons, a cycloaliphatic ester
functionality having 4 to 10 carbons and an aromatic ester
functionality having 4 to 10 carbons; and each R.sup.3 and R.sup.4,
at each occurrence, can be the same or different and are
independently at each occurrence an aliphatic functionality having
1 to 10 carbons or a cycloaliphatic functionality having 3 to 10
carbons; "n" is an integer having a value 0 to 4 and "m" is an
integer having a value 0 to 4.
2. The dihydroxy aromatic compound of claim 1 having a Formula (II)
##STR15##
3. A process comprising; reacting acetone with a compound of
Formula (III) in the presence of a first catalyst to produce
dibenzalacetone of Formula (IV) ##STR16## reacting the
dibenzalacetone of Formula (IV) in the presence of a second
catalyst with a compound of Formula (V) to produce a compound of
Formula (VI) ##STR17## reacting the compound of Formula (VI) with a
compound of Formula (VII) in the presence of an acid catalyst and a
promoter to produce a compound of Formula (I), ##STR18## wherein
R.sup.1 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic functionality
having 1 to 10 carbons, an aliphatic ester functionality having 2
to 10 carbons, a cycloaliphatic ester functionality having 4 to 10
carbons and an aromatic ester functionality having 4 to 10 carbons;
R.sup.2 is selected from the group consisting of a cyano
functionality, a nitro functionality, an aliphatic ester
functionality having 2 to 10 carbons, a cycloaliphatic ester
functionality having 4 to 10 carbons and an aromatic ester
functionality having 4 to 10 carbons; and each R.sup.3 and R.sup.4,
at each occurrence, can be the same or different and are
independently at each occurrence an aliphatic functionality having
1 to 10 carbons or a cycloaliphatic functionality having 3 to 10
carbons; "n" is an integer having a value 0 to 4 and "m" is an
integer having a value 0 to 4.
4. The process of claim 3 wherein the compound of Formula (III)
comprises benzaldehyde.
5. The process of claim 3 wherein the compound of Formula (V)
comprises dimethyl malonate.
6. The process of claim 3 wherein the compound of Formula (VII)
comprises phenol.
7. The process of claim 3 wherein the promoter comprises resorcinol
or 3-mercaptopropionic acid.
8. The process of claim 3 wherein the acid catalyst comprises
hydrogen chloride gas.
9. The process of claim 3 wherein the first catalyst comprises
alkali metal hydroxide, dry hydrogen chloride or glacial acetic
acid with sulfuric acid.
10. The process of claim 9 wherein the first catalyst comprises
sodium hydroxide.
11. The process of claim 3 wherein the second catalyst comprises
alkoxide, ammonium ylides, 1,4-diazabicyclo[2.2.2] octane, rhodium
acetate, sodium carbonate or benzyltriethylammonium hydroxide.
12. The process of claim 3, wherein the reaction of acetone with a
compound of Formula (III) occurs at a temperature of about
20.degree. C. to about 40.degree. C.
13. The process of claim 3, wherein the reaction of the
dibenzalacetone of Formula (IV) with the compound of Formula (V)
occurs at a temperature of about 40.degree. C. to about 80.degree.
C.
14. The process of claim 3, wherein the reaction of the compound of
Formula (VI) with the compound of Formula (VII) occurs at a
temperature of about 40.degree. C. to about 80.degree. C.
15. A process comprising; reacting acetone with benzaldehyde having
Formula (VIII) in presence of sodium hydroxide to produce
dibenzalacetone having Formula (IX) ##STR19## reacting the
dibenzalacetone having Formula (IX) in presence of sodium methoxide
with dimethyl malonate having Formula (X) to produce
methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate having
Formula (XI) ##STR20## reacting
methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate with phenol
having Formula (XII) in presence of an acid catalyst and a promoter
to produce
methyl-4,4'-bis(4-hydroxy-phenyl)-2,6-diphenyl-cyclohexane-1,1-di-
carboxylate having Formula (II), ##STR21##
Description
BACKGROUND
[0001] This disclosure generally relates to polycyclic dihydroxy
compounds. More particularly the disclosure relates to polycyclic
dihydroxy aromatic compounds and methods for preparing the
compounds.
[0002] Polycyclic dihydroxy compounds are generally known to be
useful in the preparation of polycarbonates that exhibit
exceptional properties like high glass transition temperature (Tg),
high refractive index (RI), chemical resistance, and barrier
properties. Materials having higher Tg and higher RI properties are
in great demand for use in various applications like automotives
and optical media.
[0003] Accordingly, there is a continuing need for new compounds
that will provide polymers with better visual properties on account
of high RI and at the same time retaining high Tg values, to enable
their use at high temperatures to form a gamut of articles.
BRIEF SUMMARY
[0004] Disclosed herein are polycyclic dihydroxy compounds having
Formula (I), ##STR1## wherein R.sup.1 is selected from the group
consisting of a cyano functionality, a nitro functionality, an
aliphatic functionality having 1 to 10 carbons, an aliphatic ester
functionality having 2 to 10 carbons, a cycloaliphatic ester
functionality having 4 to 10 carbons and an aromatic ester
functionality having 4 to 10 carbons; R.sup.2 is selected from the
group consisting of a cyano functionality, a nitro functionality,
an aliphatic ester functionality having 2 to 10 carbons, a
cycloaliphatic ester functionality having 4 to 10 carbons and an
aromatic ester functionality having 4 to 10 carbons; and each
R.sup.3 and R.sup.4, at each occurrence, can be the same or
different and are independently at each occurrence an aliphatic
functionality having 1 to 10 carbons or a cycloaliphatic
functionality having 3 to 10 carbons, "n" is an integer having a
value 0 to 4 and "m" is an integer having a value 0 to 4.
[0005] In another embodiment a process for producing the polycyclic
dihydroxy compounds of Formula (I) comprises reacting acetone with
a compound of Formula (III) in the presence of a first catalyst to
produce dibenzalacetone of Formula (IV) ##STR2##
[0006] reacting the dibenzalacetone of Formula (IV) in the presence
of a second catalyst with a compound of Formula (V) to produce a
compound of Formula (VI) ##STR3##
[0007] reacting the compound of Formula (VI) with a compound of
Formula (VII) in the presence of an acid catalyst and a promoter to
produce a compound of Formula (I),
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, "n" and "m" are defined
as above.
[0008] In one embodiment a composition comprises a polycyclic
dihydroxy compound having a Formula (I), ##STR4## wherein R.sup.1,
R.sup.2, R.sup.3, R.sup.4, "n" and "m" are defined as above.
[0009] In one embodiment a process for producing the polycyclic
dihydroxy compounds of Formula (II) comprises
[0010] reacting acetone with benzaldehyde having Formula (VIII) in
presence of sodium hydroxide to produce dibenzalacetone having
Formula (IX) ##STR5##
[0011] reacting the dibenzalacetone having Formula (IX) in presence
of sodium methoxide with dimethyl malonate having Formula (X) to
produce methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate
having Formula (XI) ##STR6##
[0012] reacting
methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate with phenol
having Formula (XII) in presence of an acid catalyst and a promoter
to produce
methyl-4,4'-bis(4-hydroxy-phenyl)-2,6-diphenyl-cyclohexane-1,1-dicarboxyl-
ate having Formula (II), ##STR7##
[0013] The disclosure may be understood more readily by reference
to the following detailed description of the various features of
the disclosure and the examples included therein.
DETAILED DESCRIPTION
[0014] Disclosed herein are polycyclic dihydroxy compounds and
methods for preparing these compounds. These compounds may find
applications as monomers in the preparation of polymers, especially
in the preparation of polymers having high Tg and high RI.
[0015] The singular forms "a", "an" and "the" include plural
referents unless the context clearly dictates otherwise. All ranges
disclosed herein are inclusive and combinable (for example ranges
of "up to 25 wt %, with 5 wt % to 20 wt % desired," is inclusive of
the endpoints and all intermediate values of the ranges of "5 wt %
to 25 wt %").
[0016] The modifier "about" used in connection with a quantity is
inclusive of the stated value and has the meaning dictated by the
context (for example, includes the degree of error associated with
measurement of the particular quantity).
[0017] Cycloaliphatic ester functionality, as used herein,
designates a cycloaliphatic functionality attached to a ester
functionality, for example, cycloaliphatic-OC(O)--. Unless
otherwise specified, the term "cycloaliphatic functionality"
designates cyclic aliphatic functionalities having a valence of at
least one, and comprising an array of atoms which is cyclic but
which is not aromatic. A "cycloaliphatic functionality" may
comprise one or more noncyclic components. For example, a
cyclohexylmethyl group (C.sub.6H.sub.11CH.sub.2--) is a
cycloaliphatic functionality which comprises a cyclohexyl ring (the
array of atoms which is cyclic but which is not aromatic) and a
methylene group (the noncyclic component). The cycloaliphatic
functionality may include heteroatoms such as nitrogen, sulfur,
selenium, silicon and oxygen, or may be composed exclusively of
carbon and hydrogen. For convenience, the term "cycloaliphatic
functionality" is defined herein to encompass a wide range of
functional groups such as alkyl groups, alkenyl groups, alkynyl
groups, haloalkyl groups, conjugated dienyl groups, alcohol groups,
ether groups, carboxylic acid groups, acyl groups (for example
carboxylic acid derivatives such as esters and amides), amine
groups and nitro groups. For example, the 4-methylcyclopent-1-yl
group is a C.sub.6 cycloaliphatic functionality comprising a methyl
group, wherein the methyl group is a functional group which is an
alkyl group. Similarly, the 2-nitrocyclobut-1-yl group is a C.sub.4
cycloaliphatic functionality comprising a nitro group, wherein the
nitro group is a functional group. A cycloaliphatic functionality
may comprise one or more halogen atoms which may be the same or
different. Halogen atoms include, for example, fluorine, chlorine,
bromine, and iodine. Exemplary cycloaliphatic functionalities
comprise cyclopropyl, cyclobutyl, 1,1,4,4-tetramethylcyclobutyl,
piperidinyl, 2,2,6,6-tetramethylpiperydinyl and cyclohexyl,
cyclopentyl.
[0018] As used herein, the term "aromatic ester functionality"
refers to an array of atoms having a valence of at least one
comprising at least one aromatic group attached to a ester
functionality, for example, aromatic group-OC(O)--. The array of
atoms having a valence of at least one comprising at least one
aromatic group may include heteroatoms such as nitrogen, sulfur,
selenium, silicon and oxygen, or may be composed exclusively of
carbon and hydrogen. As used herein, the term "aromatic
functionality" includes but is not limited to phenyl, pyridyl,
furanyl, thienyl, naphthyl, phenylene, and biphenyl
functionalities. The aromatic functionality may also include
nonaromatic components. For example, a benzyl group is an aromatic
functionality that comprises a phenyl ring (the aromatic group) and
a methylene group (the nonaromatic component). Similarly a
tetrahydronaphthyl functionality is an aromatic functionality
comprising an aromatic group (C.sub.6H.sub.3) fused to a
nonaromatic component --(CH.sub.2).sub.4--. For convenience, the
term "aromatic functionality" is defined herein to encompass a wide
range of functional groups such as alkyl groups, haloalkyl groups,
haloaromatic groups, alcohol groups, ether groups, carboxylic acid
groups, acyl groups (for example carboxylic acid derivatives such
as esters and amides), amine groups and nitro groups. For example,
the 4-methylphenyl functionality is a C.sub.7 aromatic
functionality comprising a methyl group, wherein the methyl group
is a functional group which is an alkyl group. Similarly, the
2-nitrophenyl group is a C.sub.6 aromatic functionality comprising
a nitro group, wherein the nitro group is a functional group.
Aromatic functionalities include halogenated aromatic
functionalities. Exemplary aromatic functionalities include, but
are not limited to phenyl, 4-trifluoromethylphenyl,
4-chloromethylphen-1-yl, 3-trichloromethylphen-1-yl
(3-CCl.sub.3Ph-), 4-(3-bromoprop-1-yl)phen-1-yl
(4-BrCH.sub.2CH.sub.2CH.sub.2Ph-),4-aminophen-1-yl (4-H.sub.2NPh-),
4-hydroxymethylphen-1-yl (4-HOCH.sub.2Ph-), 4-methylthiophen-1-yl
(4-CH.sub.3SPh-), 3-methoxyphen-1-yl and 2-nitromethylphen-1-yl
(2-NO.sub.2CH.sub.2Ph), naphthyl.
[0019] As used herein the term "aliphatic functionality" refers to
an organic functionality having a valence of at least one
consisting of a linear or branched array of atoms that is not
cyclic. As used herein, the term "aliphatic ester functionality"
refers to an array of atoms having a valence of at least one
comprising at least one aliphatic functionality group attached to a
ester functionality, i.e., aliphatic group-OC(O)--. Aliphatic
functionalities are defined to comprise at least one carbon atom.
The array of atoms comprising the aliphatic functionality may
include heteroatoms such as nitrogen, sulfur, silicon, selenium and
oxygen or may be composed exclusively of carbon and hydrogen. For
convenience, the term "aliphatic functionality" is defined herein
to encompass, as part of the "linear or branched array of atoms
which is not cyclic" a wide range of functional groups such as
alkyl groups, haloalkyl groups, alcohol groups, ether groups,
carboxylic acid groups, acyl groups (for example carboxylic acid
derivatives such as esters and amides), amine groups and nitro
groups. For example, the 4-methylpent-1-yl is a C.sub.6 aliphatic
functionality comprising a methyl group, wherein the methyl group
is a functional group which is an alkyl group. Similarly, the
4-nitrobut-1-yl group is a C.sub.4 aliphatic functionality
comprising a nitro group, wherein the nitro group is a functional
group. An aliphatic functionality may be a haloalkyl group which
comprises one or more halogen atoms which may be the same or
different. Halogen atoms include, for example; fluorine, chlorine,
bromine, and iodine. Exemplary aliphatic functionalities include,
but are not limited to methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, pentyl, isopentyl, trifluoromethyl, bromodifluoromethyl,
chlorodifluoromethyl, chloromethyl, trichloromethyl, bromoethyl,
2-hexyl, hexamethylene, hydroxymethyl (i.e., --CH.sub.2OH),
mercaptomethyl (--CH.sub.2SH), methylthio (--SCH.sub.3),
methylthiomethyl (--CH.sub.2SCH.sub.3), methoxy, methoxycarbonyl
(CH.sub.3OCO--) , nitromethyl (--CH.sub.2NO.sub.2) and
thiocarbonyl.
[0020] Disclosed herein are polycyclic dihydroxy compounds having a
Formula (I), ##STR8## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4,
"n" and "m" are defined as above.
[0021] In one embodiment the polycyclic dihydroxy compound
comprises a compound of Formula (II) ##STR9## The compound of
Formula (II) may hereinafter also be referred to as
methyl-4,4-bis(4-hydroxyphenyl)-2,6-diphenyl
cyclohexane-1,1-dicarboxylate.
[0022] The process for making the dihydroxy compound of Formula (I)
comprises the following steps. The first step comprises reacting
acetone with a compound of Formula (III) in the presence of a first
catalyst to produce dibenzalacetone of Formula (IV) ##STR10##
wherein R.sup.3 and "n" have the same meaning as defined above.
[0023] Exemplary compounds of Formula (III) include, but are not
limited to benzaldehyde, 4-methyl benzaldehyde, 2-methyl
benzaldehyde, 3-methyl benzaldehyde, 4-ethyl benzaldehyde, 2-ethyl
benzaldehyde, 3-isopropyl-6-methyl benzaldehyde,
4-(N,N-dipropylamino)benzaldehyde, 4-ethoxybenzaldehyde,
4-butylbenzaldehyde, 4-tertbutyl benzaldehyde, and
4-isopropylbenzaldehyde. In one embodiment the compound of Formula
(III) comprises benzaldehyde.
[0024] The amount of the compound of Formula (III) employed in the
reaction can be about 2 to about 10 moles per mole of acetone
employed. Within this range the amount may be greater than or equal
to about 3 moles, or, more specifically, greater than or equal to
about 6 moles. Also within this range the amount may be less than
or equal to about 9 moles, or, more specifically less than or equal
to about 7 moles.
[0025] Suitable first catalysts include but are not limited to
alkali metal hydroxide and dry hydrogen chloride.
[0026] Specific examples of suitable alkali metal hydroxides that
may be employed as the first catalyst in the reaction of acetone
with the compound of Formula (III) include, but are not limited to
sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium
hydroxide cesium hydroxide or a combination of two or more of the
foregoing alkali metal hydroxides. In one embodiment the alkali
metal hydroxide comprises sodium hydroxide. The alkali metal
hydroxides can be added as an aqueous solution or as solids. The
amount of alkali metal hydroxide employed in the reaction can be
about 6 moles to about 15 moles per mole of acetone employed.
Within this range the amount may be greater than or equal to about
7 moles, or, more specifically greater than or equal to about 9
moles. Also within this range the amount may be less than or equal
to about 13 moles, or, more specifically less than or equal to
about 12 moles.
[0027] Specific examples of suitable solvents that can be employed
in the reaction of acetone with a compound of Formula (III) in the
presence of an alkali earth metal hydroxide to produce the
dibenzalacetone of Formula (IV) include, but are not limited know
ethanol, methanol, isopropanol, n-propanol, n-butanol, isobutanol
or mixtures of two or more of the foregoing solvents. In one
embodiment the solvent employed comprises ethanol, methanol, or a
combination of ethanol and methanol. The amount of solvent employed
in the reaction of acetone with a compound of Formula (III) in the
presence of an alkali earth metal hydroxide to produce the
dibenzalacetone of Formula (IV) can be about 2 liters to about 10
liters per mole of acetone. Within this range the amount may be
greater than or equal to about 3 liters, or, more specifically,
greater than or equal to about 5 liters. Also within this range the
amount may be less than or equal to about 9 liters, or, more
specifically less than or equal to about 7 liters.
[0028] The temperature at which the reaction of acetone with the
compound of Formula (III) occurs to produce the dibenzalacetone of
Formula (IV) is about 20.degree. C. to about 40.degree. C. Within
this range the temperature may be greater than or equal to about
22.degree. C., or, more specifically, greater than or equal to
about 25.degree. C. Also within this range the temperature may be
less than or equal to about 35.degree. C., or, more specifically,
less than or equal to about 30.degree. C. The time taken for the
reaction of acetone with the compound of Formula (III) to produce
the dibenzalacetone of Formula (IV) can be about 15 minutes to
about 4 hours. Within this range the time may be greater than or
equal to about 1 hour, or, more specifically, greater than or equal
to about 1.5 hours. Also within this range the time may be less
than or equal to about 3 hours, or, more specifically, less than or
equal to about 2 hours.
[0029] The second step comprises reacting the dibenzalacetone of
Formula (IV) in the presence of a second catalyst with a compound
of Formula (V) to produce a compound of Formula (VI) ##STR11##
wherein R.sup.1, R.sup.2, R.sup.3, and "n" have the same meaning as
defined above.
[0030] Suitable compounds having Formula (V) include, but are not
limited to dimethyl malonate, diethyl malonate, diisopropyl
malonate, ethyl cyanoacetate and methyl cyanoacetate. In one
embodiment the compound of Formula (V) may comprise dimethyl
malonate or ethyl cyanoacetate.
[0031] The amount of the compound of Formula (V) employed in the
reaction can be about 1 mole to about 6 moles per mole of
dibenzalacetone compound having Formula (IV). Within this range the
amount may be greater than or equal to about 2 moles, or, more
specifically, greater than or equal to about 2.5 moles. Also within
this range the amount may be less than or equal to about 5.5 moles,
or, more specifically, less than or equal to about 5 moles.
[0032] Suitable second catalysts include, but are not limited to an
alkoxide, glacial acetic acid with sulfuric acid, ammonium ylides,
1,4-diazabicyclo[2.2.2] octane, rhodium acetate, sodium carbonate
or benzyltriethylammonium hydroxide (hereinafter also mentioned as
Triton.RTM. B).
[0033] Specific examples of alkoxides that may be employed as
second catalysts in the reaction of compound having Formula (IV)
with the compound of Formula (V) include, but are not limited to
aluminum isopropoxide, aluminum phenoxide, aluminum tributoxide,
lithium 2-ethylhexodide, lithium ethoxide, lithium isopropoxide,
lithium methoxide, magnesium ethoxide, magnesium methoxide,
potassium ethoxide, potassium isobutoxide, potassium methoxide,
potassium tert-butoxide, sodium benzyloxide, sodium ethoxide,
sodium phenoxide, sodium tert-butoxide, sodium tert-pentoxide,
sodium methanethiolate, or mixtures of two or more of the
foregoing. In one embodiment the alkoxide employed is sodium
methoxide.
[0034] Specific examples of suitable solvents that may be employed
in the reaction of compound having Formula (IV) in the presence of
alkoxide, with the compound of Formula (V) include, but are not
limited to ethanol, methanol, isopropanol, n-propanol, n-butanol,
isobutanol or mixtures of two or more of the foregoing. In one
embodiment the solvent employed comprises ethanol, methanol, or a
combination of methanol and ethanol. The amount of solvent employed
in the reaction of compound having Formula (IV) in the presence of
alkoxide with the compound of Formula (V) comprises about 1 liter
to about 10 liters per mole of dibenzalacetone compound having
Formula (IV). Within this range the amount may be greater than or
equal to about 2 liters, or, more specifically, greater than or
equal to about 3 liters. Also within this range the amount may be
less than or equal to about 6 liters, or, more specifically, less
than or equal to about 5 liters.
[0035] The temperature of the reaction of compound having Formula
(IV) in the presence of alkoxide, with the compound of Formula (V)
can be about 50.degree. C. to about 80.degree. C. Within this range
the temperature may be greater than or equal to about 55.degree.
C., or, more specifically, greater than or equal to about
60.degree. C. Also within this range the temperature may be less
than or equal to about 75.degree. C., or, more specifically, less
than or equal to about 70.degree. C. The time for the reaction of
compound having Formula (IV) in the presence of alkoxide, with the
compound of Formula (V) can be about 3 hours to about 24 hours.
Within this range the time may be greater than or equal to about 4,
or, more specifically, greater than or equal to about 6. Also
within this range the time may be less than or equal to about 16
hours, or, more specifically, less than or equal to about 12
hours.
[0036] The amount of alkoxide employed in the reaction can be about
0.01 to about 0.6 mole per mole of dibenzalacetone compound of
Formula (IV). Within this range the amount may be greater than or
equal to about 0.02 moles, or, more specifically, greater than or
equal to about 0.08 moles. Also within this range the amount may be
less than or equal to about 0.5 moles, or, more specifically, less
than or equal to about 0.4 moles.
[0037] The third step comprises reacting the compound of Formula
(VI) with a compound of Formula (VII) in the presence of an acid
catalyst and a promoter to produce the compound of Formula (I),
##STR12## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, "n" and "m"
have the same meaning as defined above.
[0038] Specific examples of suitable compounds of Formula (VII)
include, but are not limited to phenol, 2,6-dimethylphenol,
2,3,6-trimethylphenol, 2,6-di-tert-butylphenol, 2-tert-butylphenol,
meta-cresol, ortho-cresol, ortho-phenylphenol, ortho-chlorophenol,
ortho-benzylphenol, ortho-vinylphenol, and mixtures of two or more
of the foregoing. In one embodiment, the compound of Formula (VII)
comprises phenol, m-cresol, o-cresol, or a mixture of two or more
of the foregoing. In another embodiment the compound of Formula
(VII) is phenol.
[0039] The amount of the compound of Formula (VII) employed in the
reaction can be about 5 moles to about 20 moles per mole of
compound of Formula (VI). Within this range the amount may be
greater than or equal to about 6 moles, or, more specifically,
greater than or equal to about 8 moles. Also within this range the
amount may be less than or equal to about 15 moles, or, more
specifically, less than or equal to about 10 moles.
[0040] Suitable acid catalysts that may be employed in the reaction
of the compound having Formula (VI) with the compound of Formula
(VII) include, but are not limited to mineral acids, cation
exchange resins and solid acid catalysts. Non-limiting examples of
mineral acids include hydrogen chloride liquid, hydrogen chloride
gas, sulfuric acid and nitric acid. As used herein the term "cation
exchange resin" refers to an ion exchange resin in the hydrogen
form, wherein the hydrogen ions are bound to the active sites which
can be removed either by dissociation in solution or by replacement
with other positive ions. The active sites of the resin have
different attractive strengths for different ions, and this
selective attraction serves as a means for ion exchange.
Non-limiting examples of suitable cation exchange resins include
the series of sulfonated divinylbenzene-crosslinked styrene
copolymers, such as for example, copolymers crosslinked with about
1 to about 20 weight percent of divinylbenzene relative to the
overall weight of the acidic ion exchange resin. More specifically,
suitable catalysts include cation exchange resins crosslinked with
greater than or equal to about 8 weight percent of divinylbenzene
relative to the overall weight of the acidic ion exchange resin
catalyst, such as for example, Amberlyst 15.RTM. commercially
available from Aldrich Chemical Company, Bayer K2431.RTM.
commercially available from Bayer Company and T-66.RTM.
commercially available from Thermax, Ltd.
[0041] In one embodiment the amount of acid catalyst employed in
the reaction can be about 0.5 weight percent to about 10 weight
percent of an overall weight of the reaction mixture. Within this
range the amount may be greater than or equal to about 1 weight
percent, or, more specifically, greater than or equal to about 3
weight percent. Also within this range the amount may be less than
or equal to about 8 weight percent, or, more specifically, less
than or equal to about 5 weight percent. As used herein, the term
"reaction mixture" refers to a mixture comprising the compounds of
Formula (VI) and Formula (VII). As used herein, the term "overall
weight of the reaction mixture" refers to the weight of a reaction
mixture comprising the compounds of Formula (VI) and Formula
(VII).
[0042] Suitable examples of promoters include, but are not limited
to 3-mercaptopropionic acid (hereinafter called 3-MPA), a
substituted or an unsubstituted benzyl mercaptan,
3-mercapto-1-propanol, ethyl 3-mercaptopropionate,
1,4-bis(mercaptomethyl)benzene, 2-mercaptoethane-sulfonic acid,
3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid,
4-mercaptopentane-sulfonic acid,
3-mercapto-2,2-dimethylpropanesulfonic acid,
2,3-dimercaptopropanesulfonic acid, mercaptopropane-2,3-disulfonic
acid, 2-benzyl-4-mercaptobutanesulfonic acid,
5-mercaptopentane-sulfonic acid, methanethiol, ethanethiol,
isopropanethiol, butanethiol, resorcinol, catechol, hytdroquionone,
or the mono- and di-methyl or mono- and di-ethyl ethers thereof,
para-ethylphenol, ortho-cresol, para-cresol, phloroglucinol,
alpha-naphthol, 5-methyl-alpha-naphthol, 6-isobutyl-alpha-naphthol,
1,4-dihydroxynaphthalene, 6-hexyl-1,4-dihydroxy naphthalene and
6-methyl-4-methoxy-alpha-naphthalene. In one embodiment resorcinol
or 3-mercaptopropionic acid is employed as the promoter.
[0043] In one embodiment the amount of promoter employed in the
reaction is about 0.2 moles to about 0.5 moles based on the moles
of the compound of Formula (VI) employed. Within this range the
amount may be greater than or equal to about 0.25 moles, or, more
specifically greater than or equal to about 0.3 moles. Also within
this range the amount may be less than or equal to about 0.45
moles, or, more specifically, less than or equal to about 0.4
moles.
[0044] Specific examples of suitable solvents that may be employed
in the reaction of compound having in the reaction of the compound
having Formula (VI) with the compound of Formula (VII) include, but
are not limited to toluene, petroleum ether, xylene, benzene
hexane, heptane, octane, decane or a mixture of two or more of the
foregoing solvents. In one embodiment the solvent employed
comprises toluene or petroleum ether. In another embodiment the
solvent employed comprises toluene. The amount of solvent employed
in the reaction of the compound having Formula (VI) with the
compound of Formula (VII) can be about 1 liter to about 10 liters
per mole of Formula (VI) employed. Within this range the amount may
be greater than or equal to about 2 liters, or, more specifically,
greater than or equal to about 3 liters. Also within this range the
amount may be less than or equal to about 6 liters, or, more
specifically, less than or equal to about 5 liters. In one
embodiment an excess of the compound of Formula (VII) may be
employed as the solvent in the reaction.
[0045] The temperature at which the reaction of the compound having
Formula (VI) with the compound of Formula (VII) can be about
40.degree. C. to about 120.degree. C. Within this range the
temperature may be greater than or equal to about 45.degree. C.,
or, more specifically, greater than or equal to about 60.degree. C.
Also within this range the temperature may be less than or equal to
about 100.degree. C., or, more specifically, less than or equal to
about 80.degree. C. The time taken for the reaction of the compound
having Formula (VI) with the compound of Formula (VII) can be about
10 hours to about 16 hours. Within this range the time may be
greater than or equal to about 12 hours, or, more specifically,
greater than or equal to about 13 hours. Also within this range the
time may be less than or equal to about 15 hours, or, more
specifically, less than or equal to about 14 hours.
[0046] The product compound having Formula (I) may be isolated by
using appropriate methods. For example when isolating compounds
having Formula (I) the reaction mixture may be initially mixed with
an organic solvent or a mixture of organic solvents such as toluene
and petroleum ether and filtered. The resultant filter cake may be
suspended in hot water and filtered again. In some cases the
resulting solids may further be crystallized from a solvent such as
isopropanol.
[0047] In one embodiment a composition comprises a compound of
Formula (I) ##STR13## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4,
"n" and "m" have the same meaning as defined above.
[0048] As previously discussed, one of the end uses of the
compounds of Formula (I) is use in the preparation of polymers for
example, polycarbonates, polyesters, polyurethanes, and epoxides.
Suitable methods for preparation of polycarbonates include, but are
not limited to interfacial polymerization where compounds of
Formula (I) react with phosgene, and melt-transesterification
reactions of the compound of Formula (I) and possibly other
bisphenols with e.g. diphenylcarbonate in the presence of
quaternary phosphonium salts, tetraalkylammonium salts, and/or
sodium hydroxide as catalyst systems.
[0049] A further understanding of the techniques described above
can be obtained by reference to certain specific examples that are
provided herein for purposes of illustration only, and are not
intended to be limiting.
EXAMPLES
[0050] Proton NMR spectra for all the starting materials and
products described herein were measured using a 300 megahertz
Bruker NMR spectrometer using deuterated chloroform or
Cd.sub.6-dimethylsulfoxide as a solvent. Compounds were further
characterized by a liquid chromatograph-mass spectrometer (LC-MS)
system, comprising a liquid chromatograph and a Quattro Ultima Pt
mass spectrometer.
[0051] Liquid Chromatographic (LC) method was used to identity the
conversion of product compound. A Xterra C18 column, length 50
meters, inner diameter 4.6 millimeters and thickness 5 micrometers
was used for the analysis. The column temperature was maintained at
30.degree. C. The column was eluted with a ratio of water to
acetonitrile of 80:20. The flow rate of sample in the column was
maintained at 1.00 milliliter per minute (ml/min) and the amount of
sample injected was 5 micro liter. The total run time was 23
min.
Example 1
[0052] This example provides a method for the preparation of
methyl-4,4'-bis(4-hydroxy-phenyl)-2,6-diphenyl-cyclohexane-1,1-dicarboxyl-
ate (Formula (I)). The method includes 3 steps as described
below.
[0053] STEP A: Preparation of Dibenzalacetone (Formula (IV))
[0054] To an aqueous solution of sodium hydroxide(200 grams (g) in
one liter of water) was added ethanol (1.6 liters; purity greater
than 95%) and the resultant mixture was stirred well. Another
mixture having acetone (29 g) and benzaldehyde (106 g) was added to
this solution under stirring. A yellow colored precipitate was
observed. The stirring was continued for about 15 minutes (min).
Subsequently additional acetone (29 g) and benzaldehyde (106 g)
were added and the mixture was stirred for another 45 min. The
yellow colored precipitate was separated by filtration, washed with
water (2 liters), and dried at room temperature to get 223 g of
crude dibenzalacetone. Melting point of the compound was obtained
as 104-106.degree. C. This product was used in the next step
without further purification.
[0055] STEP B: Preparation of
methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate (Formula
(VI)). Dimethyl malonate (58 g) was added to a clear solution of
dibenzalacetone (93.6 g, as prepared in STEP A) in absolute
methanol (1.2 liters) and the resultant reaction mixture was
stirred well. To this reaction mixture was added 5% sodium
methoxide solution (20 ml) under stirring. The color of the
reaction mixture is observed to change from yellow to orange color
almost immediately. The stirring was then continued for another 4-6
hours at 60.degree. C. The reaction mixture was then allowed to
cool to room temperature, and left overnight. The colorless white
precipitate was separated by filtration and washed with chilled
methanol to get about 111 g of product. The filtrate was
concentrated to 30% of its volume to recover the second crop of 12
g. Melting point of the combined product (first crop+second crop)
was observed as 135.degree. C. This material was used in the next
step without purification.
[0056] STEP C: Preparation of
methyl-4,4'-bis(4-hydroxy-phenyl)2,6-diphenyl-cyclohexane-1,1-dicarboxyla-
te (Formula (I)).
[0057] A mixture of
methyl-2,6-diphenyl-cyclohexane-4-one-1,1-dicarboxylate(109.8 g;
prepared in STEP B), phenol (141 g) and resorcinol (6.27 g), was
heated to 60.degree. C. in a three necked reaction flask to obtain
a homogenous solution. Dry hydrogen chloride gas was purged into
the reaction mixture for 12 hours and the temperature was
maintained at 60.degree. C. After 12 hours, the reaction mixture
was allowed to attain room temperature over a period of 2 to 3
hours. At the end of this time, white precipitate was observed in
the reaction flask. Toluene (200 ml) was added to the reaction
mixture and stirred for about 30 minutes and the resultant mixture
was filtered. The filter cake obtained was triturated with 1.5
liters of 1:1 mixture of toluene and petroleum ether and stirred
for about 15 minutes. The solid was filtered and dried to get a
yellow cake which was further suspended in hot water (500 ml),
stirred for about 5 minutes and filtered again. The obtained solid
was crystallized with isopropanol to get a crystalline white
methyl-4,4'-bis(4-hydroxy-phenyl)-2,6-diphenyl-cyclohexane-1,1-dicarboxyl-
ate with a yield of about 101 g and having a melting point greater
than 270.degree. C. The solid was dissolved in deuterated
chloroform and analyzed using NMR. The corresponding peaks obtained
were at .delta. 2.35-2.73 (4H, m, CH.sub.2), 3.0-3.2(6H, s,
OCH.sub.3), 3.25-3.75(2H, br-s, OH), 4.26-4.52(2H, m, CH),
6.68-6.81(4H, dd, Ar-H), 6.97-7.07(4H, dd, Ar-H), 7.16-7.4(10H, m,
Ar-H).
Example 2
[0058] Preparation of methyl-1-cyano-4,4'-bis(4-hydroxy-phenyl)
2,6-diphenyl-cyclohexane-1-carboxylate (Formula (I)).
[0059] STEP I: Cyanoethyl acetate (13.3 g) and Triton.RTM.-B
(Benzyltriethylammonium hydroxide); 20-22 drops) were added to a
suspension of dibenzalacetone (25.0 g; as prepared in step A of
example I above) in absolute ethanol (200 cc) and the resultant
mixture was stirred well. A clear solution was obtained which
immediately changed to a thick white precipitate. Ethanol (150 cc)
was added to the reaction mass and stirred well for about 1-2 hours
at 0.degree. C. The colorless precipitate obtained was separated by
filtration, washed with chilled ethanol to obtain 22.3 g of
methyl-1-cyano-2,6-diphenyl-cyclohexane-4-one-1,1-carboxylate
having a melting point of about 133-138.degree. C. This material
was used in step II without purification. The solid was analyzed
using NMR (Acetone-D.sub.6). The corresponding peaks were at
.delta. 0.70-0.78 (3H, t), 2.65-3.05(4H, m), 3.45-4.17(4H, m),
7.32-7.45(10H, br-s).
[0060] Step II: A mixture of
methyl-1-cyano-2,6-diphenyl-cyclohexane-4-one-1,1-carboxylate (34.8
g; as prepared in step I), phenol (47 g) and resorcinol (2.05 g),
was heated to 60.degree. C. in a three necked reaction flask until
a homogenous solution was obtained. Dry hydrogen chloride gas was
passed into the reaction mixture for 12 hours maintaining the
temperature at 60.degree. C. After 12 hours, the reaction mixture
was allowed to attain room temperature and during this period
formation of white precipitate was observed. Toluene (100 ml) was
added to the reaction mixture and the reaction mixture stirred for
30 minutes. The resultant solid was filtered. The solid cake was
triturated with 500 ml of 1:1 mixture of toluene and petroleum
ether and the resultant mixture stirred for about 15 minutes. The
mixture was filtered. The filter cake on drying provided a yellow
cake which was further suspended in hot water (500 ml, temperature
70.degree. C.), stirred for about 15 minutes and filtered again.
The resultant solid was crystallized with isopropanol to get a
crystalline white solid weighing 36.3 g, having a melting point
greater than 250.degree. C. The solid was dissolved in deuterated
acetone and analyzed using NMR. The corresponding peaks were at
.delta. 0.70-0.78 (3H, t), 2.65-3.05(4H, m), 3.45-4.17(4H, m),
6.74-6.85(4H, dd),7.05-7.15(4H,dd), 7.32-7.45(10H, br-s), 8.23
(2H.br-s).
[0061] As can be seen from the foregoing examples a compound having
Formula (I) can be readily prepared as shown in Examples 1 and
2.
[0062] While the invention has been described with reference to an
exemplary embodiment, it will be understood by those skilled in the
art that various changes may be made and equivalents may be
substituted for elements thereof without departing from the scope
of the invention. In addition, many modifications may be made to
adapt a situation or material to the teachings of the invention
without departing from the essential scope thereof. Therefore, it
is intended that the invention not be limited to the embodiment
disclosed as the best mode contemplated for carrying out this
invention, but that the invention will include all embodiments
falling within the scope of the appended claims.
* * * * *