CA2094709A1 - Process for the preparation of phenyl carbonates - Google Patents
Process for the preparation of phenyl carbonatesInfo
- Publication number
- CA2094709A1 CA2094709A1 CA 2094709 CA2094709A CA2094709A1 CA 2094709 A1 CA2094709 A1 CA 2094709A1 CA 2094709 CA2094709 CA 2094709 CA 2094709 A CA2094709 A CA 2094709A CA 2094709 A1 CA2094709 A1 CA 2094709A1
- Authority
- CA
- Canada
- Prior art keywords
- phenyl
- acetic anhydride
- acetate
- carbonate
- methyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 title description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 45
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 15
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 15
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940049953 phenylacetate Drugs 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229960003424 phenylacetic acid Drugs 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000005402 stannate group Chemical group 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960003742 phenol Drugs 0.000 description 8
- -1 aromatic carbonates Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 101100109871 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) aro-8 gene Proteins 0.000 description 1
- 101100156763 Schizosaccharomyces pombe (strain 972 / ATCC 24843) wos2 gene Proteins 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for the preparation of an aromatic carbonate from a phenol, acetic anhydride, carbon monoxide and oxygen comprising the steps of A) reacting acetic anhydride with phenol to form phenyl acetate; B) reacting the phenyl acetate with dimethyl carbonate to produce a phenyl carbonate and methyl acetate; and C) reacting the methyl acetate with carbone monoxide to produce acetic anhydride for use in step A.
Description
W092/0955~ ~C'~ ~ 7 ~3 ~ PCT/US90/06860 PROCESS FOR THE PREPARATION
OF PHENYL CARBONATES
The present invention relates to a process for the preparation of phenyl carbonates. More particularly, the present invention allows for the preparation of phenyl carbonates utilizing as reactants a phenol; acetic anhydride; carbon monoxide; and oxygen.
In U.S. Patent 4,533,504 an integrated proce~s for the preparation of aromatic carbonates was di-~closed wherein the methyl acetate by-product formed in the tran~esterification of a phenyl ester with a dialkyl carbonate was recycled by heating the alkyl ester to form a ketene and subsequently such ketene was reconverted by reaction with a phenol to form additional quantities of the phenyl ester.
Preparation of a ketene intermediate has proven costly and inefficient due to the high temperatures involved. Recoveries on the order of only about 80 percent of theoretical or less are typical leading to the need to develop a more efficient means of generating phenyl carbonate precursors and disposing of alkyl ester by-products.
W092/095~ 2 Q 9 'i 7 ~ J PCT/US90/06860 According to the present invention, there is now provided a process for producing an aromatic carbonate comprising the steps of:
A. reacting acetic anhydride with a phenol to produce a phenyl acetate and acetic acid and ~eparating the phenyl acetate;
B. reacting dimethyl carbonate with at least a portion of the phenyl acetate from step A
to produce a phenyl carbonate and methyl acetate and separating the methyl acetate;
C. reacting the methyl acetate with carbon monoxide in the presence of a catalyst to prepare acetic anhydride; and D. employing the acetic anhydride as at least a portion of the acetic anhydrlde reactant of step A.
The reaction of phenols with acetic anhydride to form a phenyl acetate and acetic acid, step A of the present invention, is a well known acetylation reaction.
Suitable process conditions are disclo~ed, for example, in U.S. Patent 4,374,263. By the term "phenol" is included hydroxy benzene and C1_14 alkyl or halo substituted phenols, however, the preferred reactant is hydroxybenzene. In schematic form, the reaction of a phenol and acetic anhydride may be depicted by the following illustration.
`
wos2/osss; 2 ~ ~ 1 7 Q ~ PCT~USsO/06860 O O O
,. .. ..
ArOH + (CH3C)20 - > ArOCCH3 + HOCCH3 wherein Ar represents a C6_20 aryl group or alkyl or halo substituted aryl group, particularly phenyl.
The reaction is conducted at moderate temperatures from 25C to 180C, more preferably 75C to 150C. The products are easily separated by fractional distillation or other suitable technique. While 5 numerous catalysts are known for the esterification process, preferred catalysts are acids, especially heterogeneous macroporous ion exchange re~ins in the acid form.
The dimethyl carbonate reactant for step B may be prepared by the reaction between methanol, carbon monoxide and oxygen, according to any suitable procedure. Suitable are those processes disclosed in 25 V.S. Patents 3,846,468, 3,980,690, 4,452,690, 4,533,504, and 4,360,477. The reaction is generally expedited by the use of a catalyst, particularly a copper or cobalt complex and the use of elevated temperatures and pressures. Preferred catalysts are cuprous chloride 30 complexed with an organic base such as pyridine, dipyridyl, imidazole, alkyl or aryl phosphines, etc.
Preferred temperatures are from 20 to 75C, more preferably 25 to 50C. Preferred pressures of 2 and CO
are from atmospheric to 20 atmospheres pressure.
.
W092/09ss~ 2 Q ~ ~ 7 o 9 PCT/US90/06860 Reaction of dimethyl carbonate and a phenyl acetate to give the desired phenyl carbonate and by-product alkyl acetate is a known chemical tranqformation. This step of the proceqs may be illustrated schematically by the following diagram.
O O
ll ll 2 ArOCCH3 + (CH3)2C03 > ArOC02Ar + 2 CH30CCH3 wherein Ar is as previously defined.
The above reaction has been previously diqclosed, for example, in U.S. Patent 4,182, 726, and U.S. Patent 4,533,504. In a highly desirable embodiment of the preqent invention, this reaction is conducted in the presence of a catalyqt, particularly a Lewis acid, such as AlC13, or stannate or titanate catalysts.
Temperatures of the reaction are from 100C to 350C, preferably from 150C to 300C. Pressures are generally from atmospheric to 25 atmospheres, more preferably 5 to 25 10 atmospheres-The phenyl carbonate product is a highlydesired article of commerce for conversion into polycarbonate resins. Processes for such conversion are alqo well known having been disclosed in U.S. Patents 3,625,920, 3, 888, 826 and 4,330,664. Included in the synthesized product may be a mixture of both the mono-and ditransesterified products, that is both the 35 diphenyl carbonate and phenyl methyl carbonate products are formed.
. , ................................ ~ .
.
. ,~ ' . , W092/0955~ 2 Q ~ ~ 7 0 9 PCT/US90/0686~
The phenyl carbonate product and methyl acetate are readily separated by use of standard distillation techniques and the by-product, methyl acetate, is recycled by means of a reaction with carbon monoxide to produce acetic anhydride that is used in step A.
Suitable proces3es for such reaction between methyl acetate and carbon monoxide are known and previouQly disclosed in the art, for example, in U.S. Patents 4,374,070, 4,559,183, and 4,046,807 and in S. W.
Polichnowski, J. CHEM. ED., 63, 206 (1986). A preferred process utilizes a noble metal catalyst and temperatures from 50C to 250C, preferably 100C to 200C, and pressures from atmospheric to 500 atmospheres, preferably 10 to 250 atmospheres.
It may be readily observed that the present process scheme allows for the overall conversion of a phenol to the corresponding phenyl carbonate utilizing as reactants acetic anhydride, carbon monoxide and oxygen. The recycle of methyl acetate intermediate allows for great economy and simplicity in the resulting process compared to the generation of a ketene intermediate. The present process utilizes much lower reaction temperatures and results in greatly improved efficiency of operation. Moreover, intermediate by-product acetic acid may also be recycled if desired by reaction with additional methanol to form methyl acetate and then carbonylated as above explained to form acetic 3 anhydride. Alternatively, the acetic acid, which represents a significant increase in value over the starting material, methanol, may be sold.
OF PHENYL CARBONATES
The present invention relates to a process for the preparation of phenyl carbonates. More particularly, the present invention allows for the preparation of phenyl carbonates utilizing as reactants a phenol; acetic anhydride; carbon monoxide; and oxygen.
In U.S. Patent 4,533,504 an integrated proce~s for the preparation of aromatic carbonates was di-~closed wherein the methyl acetate by-product formed in the tran~esterification of a phenyl ester with a dialkyl carbonate was recycled by heating the alkyl ester to form a ketene and subsequently such ketene was reconverted by reaction with a phenol to form additional quantities of the phenyl ester.
Preparation of a ketene intermediate has proven costly and inefficient due to the high temperatures involved. Recoveries on the order of only about 80 percent of theoretical or less are typical leading to the need to develop a more efficient means of generating phenyl carbonate precursors and disposing of alkyl ester by-products.
W092/095~ 2 Q 9 'i 7 ~ J PCT/US90/06860 According to the present invention, there is now provided a process for producing an aromatic carbonate comprising the steps of:
A. reacting acetic anhydride with a phenol to produce a phenyl acetate and acetic acid and ~eparating the phenyl acetate;
B. reacting dimethyl carbonate with at least a portion of the phenyl acetate from step A
to produce a phenyl carbonate and methyl acetate and separating the methyl acetate;
C. reacting the methyl acetate with carbon monoxide in the presence of a catalyst to prepare acetic anhydride; and D. employing the acetic anhydride as at least a portion of the acetic anhydrlde reactant of step A.
The reaction of phenols with acetic anhydride to form a phenyl acetate and acetic acid, step A of the present invention, is a well known acetylation reaction.
Suitable process conditions are disclo~ed, for example, in U.S. Patent 4,374,263. By the term "phenol" is included hydroxy benzene and C1_14 alkyl or halo substituted phenols, however, the preferred reactant is hydroxybenzene. In schematic form, the reaction of a phenol and acetic anhydride may be depicted by the following illustration.
`
wos2/osss; 2 ~ ~ 1 7 Q ~ PCT~USsO/06860 O O O
,. .. ..
ArOH + (CH3C)20 - > ArOCCH3 + HOCCH3 wherein Ar represents a C6_20 aryl group or alkyl or halo substituted aryl group, particularly phenyl.
The reaction is conducted at moderate temperatures from 25C to 180C, more preferably 75C to 150C. The products are easily separated by fractional distillation or other suitable technique. While 5 numerous catalysts are known for the esterification process, preferred catalysts are acids, especially heterogeneous macroporous ion exchange re~ins in the acid form.
The dimethyl carbonate reactant for step B may be prepared by the reaction between methanol, carbon monoxide and oxygen, according to any suitable procedure. Suitable are those processes disclosed in 25 V.S. Patents 3,846,468, 3,980,690, 4,452,690, 4,533,504, and 4,360,477. The reaction is generally expedited by the use of a catalyst, particularly a copper or cobalt complex and the use of elevated temperatures and pressures. Preferred catalysts are cuprous chloride 30 complexed with an organic base such as pyridine, dipyridyl, imidazole, alkyl or aryl phosphines, etc.
Preferred temperatures are from 20 to 75C, more preferably 25 to 50C. Preferred pressures of 2 and CO
are from atmospheric to 20 atmospheres pressure.
.
W092/09ss~ 2 Q ~ ~ 7 o 9 PCT/US90/06860 Reaction of dimethyl carbonate and a phenyl acetate to give the desired phenyl carbonate and by-product alkyl acetate is a known chemical tranqformation. This step of the proceqs may be illustrated schematically by the following diagram.
O O
ll ll 2 ArOCCH3 + (CH3)2C03 > ArOC02Ar + 2 CH30CCH3 wherein Ar is as previously defined.
The above reaction has been previously diqclosed, for example, in U.S. Patent 4,182, 726, and U.S. Patent 4,533,504. In a highly desirable embodiment of the preqent invention, this reaction is conducted in the presence of a catalyqt, particularly a Lewis acid, such as AlC13, or stannate or titanate catalysts.
Temperatures of the reaction are from 100C to 350C, preferably from 150C to 300C. Pressures are generally from atmospheric to 25 atmospheres, more preferably 5 to 25 10 atmospheres-The phenyl carbonate product is a highlydesired article of commerce for conversion into polycarbonate resins. Processes for such conversion are alqo well known having been disclosed in U.S. Patents 3,625,920, 3, 888, 826 and 4,330,664. Included in the synthesized product may be a mixture of both the mono-and ditransesterified products, that is both the 35 diphenyl carbonate and phenyl methyl carbonate products are formed.
. , ................................ ~ .
.
. ,~ ' . , W092/0955~ 2 Q ~ ~ 7 0 9 PCT/US90/0686~
The phenyl carbonate product and methyl acetate are readily separated by use of standard distillation techniques and the by-product, methyl acetate, is recycled by means of a reaction with carbon monoxide to produce acetic anhydride that is used in step A.
Suitable proces3es for such reaction between methyl acetate and carbon monoxide are known and previouQly disclosed in the art, for example, in U.S. Patents 4,374,070, 4,559,183, and 4,046,807 and in S. W.
Polichnowski, J. CHEM. ED., 63, 206 (1986). A preferred process utilizes a noble metal catalyst and temperatures from 50C to 250C, preferably 100C to 200C, and pressures from atmospheric to 500 atmospheres, preferably 10 to 250 atmospheres.
It may be readily observed that the present process scheme allows for the overall conversion of a phenol to the corresponding phenyl carbonate utilizing as reactants acetic anhydride, carbon monoxide and oxygen. The recycle of methyl acetate intermediate allows for great economy and simplicity in the resulting process compared to the generation of a ketene intermediate. The present process utilizes much lower reaction temperatures and results in greatly improved efficiency of operation. Moreover, intermediate by-product acetic acid may also be recycled if desired by reaction with additional methanol to form methyl acetate and then carbonylated as above explained to form acetic 3 anhydride. Alternatively, the acetic acid, which represents a significant increase in value over the starting material, methanol, may be sold.
Claims (3)
1. A process for producing a phenyl carbonate comprising the steps of:
A. reacting acetic anhydride with a phenol to produce a phenyl acetate and acetic acid and separating the phenyl acetate;
B. reacting dimethyl carbonate with at least a portion of the phenyl acetate from step A
to produce a phenyl carbonate and methyl acetate and separating the methyl acetate;
C. reacting the methyl acetate with carbon monoxide in the presence of a catalyst to prepare acetic anhydride; and D. employing the acetic anhydride as a least a portion of the acetic anhydride reactant of step A.
A. reacting acetic anhydride with a phenol to produce a phenyl acetate and acetic acid and separating the phenyl acetate;
B. reacting dimethyl carbonate with at least a portion of the phenyl acetate from step A
to produce a phenyl carbonate and methyl acetate and separating the methyl acetate;
C. reacting the methyl acetate with carbon monoxide in the presence of a catalyst to prepare acetic anhydride; and D. employing the acetic anhydride as a least a portion of the acetic anhydride reactant of step A.
2. A process according to Claim 1 wherein the dimethyl carbonate and phenyl acetate are reacted in step B by contacting in the presence of a stannate or titanate catalyst.
3. A process according to claim 1, wherein the methyl acetate and carbon monoxide are reacted in step C
by contacting at a temperature of from 100°C to 200°C in the presence of a noble metal catalyst.
by contacting at a temperature of from 100°C to 200°C in the presence of a noble metal catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2094709 CA2094709A1 (en) | 1990-11-21 | 1990-11-21 | Process for the preparation of phenyl carbonates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2094709 CA2094709A1 (en) | 1990-11-21 | 1990-11-21 | Process for the preparation of phenyl carbonates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2094709A1 true CA2094709A1 (en) | 1992-05-22 |
Family
ID=4151515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2094709 Abandoned CA2094709A1 (en) | 1990-11-21 | 1990-11-21 | Process for the preparation of phenyl carbonates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2094709A1 (en) |
-
1990
- 1990-11-21 CA CA 2094709 patent/CA2094709A1/en not_active Abandoned
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| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |