GB2079753A - Conversion of acid anhydrides to alkylidene diesters - Google Patents
Conversion of acid anhydrides to alkylidene diesters Download PDFInfo
- Publication number
- GB2079753A GB2079753A GB8122415A GB8122415A GB2079753A GB 2079753 A GB2079753 A GB 2079753A GB 8122415 A GB8122415 A GB 8122415A GB 8122415 A GB8122415 A GB 8122415A GB 2079753 A GB2079753 A GB 2079753A
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- GB
- United Kingdom
- Prior art keywords
- parts
- ethylidene diacetate
- hydrogen
- reaction
- acid
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- -1 alkylidene diesters Chemical class 0.000 title claims abstract description 19
- 150000008065 acid anhydrides Chemical class 0.000 title claims description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 84
- 238000000034 method Methods 0.000 claims description 30
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- YMFAWOSEDSLYSZ-UHFFFAOYSA-N carbon monoxide;cobalt Chemical group [Co].[Co].[Co].[Co].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] YMFAWOSEDSLYSZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 90
- GOKCJCODOLGYQD-UHFFFAOYSA-N 4,6-dichloro-2-imidazol-1-ylpyrimidine Chemical compound ClC1=CC(Cl)=NC(N2C=NC=C2)=N1 GOKCJCODOLGYQD-UHFFFAOYSA-N 0.000 description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 26
- 239000006227 byproduct Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 150000004678 hydrides Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000008422 chlorobenzenes Chemical class 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IXWIAFSBWGYQOE-UHFFFAOYSA-M aluminum;magnesium;oxygen(2-);silicon(4+);hydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] IXWIAFSBWGYQOE-UHFFFAOYSA-M 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RAFYDKXYXRZODZ-UHFFFAOYSA-N octanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)CCCCCCC RAFYDKXYXRZODZ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical class [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/16—Acetic acid esters of dihydroxylic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Carboxylic acid anhydrides are reacted with hydrogen to produce alkylidene diesters with high yield and with ratios of alkylidene diesters and coproduct carboxylic acid near the theoretical by carrying out the reaction in the presence of a cobalt carbonyl.
Description
SPECIFICATION
Process for conversion of acid anhydrides
This invention relates to the preparation of alkylidene diesters and more particularly relates to the preparation of ethylidene diacetate by the action of hydrogen on acetic anhydride.
Ethylidene diacetate is a chemical intermediate of prime commercial interest in view of its ready convertibility to a number of different tonnage chemicals of commerce. By one known conversion technique, ethylidene diacetate is readily transformed to vinyl acetate plus acetic acid; see Kirk-Othmer "Encyclopedia of Chemical Technology", (2nd ed.), vol. 21, page 321, Interscience, New York (1970). By another well-known conversion process, ethylidene diacetate can be transformed into acetic an hydride plus acetaldehyde; see Kirk-Othmer "Encyclopedia of Chemical Technology" (2nd ed.),vol. 8, pages 410-413, Inter-science, New York (1965). Reference is also made to U.S. Patent No.2,425,389 as indicative of the flexibility of ethylidene diacetate as a chemical intermediate.
Various processes have been proposed for the preparation of ethylidene diacetate. One such process involves the reaction of acetaldehyde and acetic an hydride, the ethylidene diacetate being produced as an intermediate in the preparation of vinyl acetate, a process which has been employed to a limited extent on a commercial scale; see "Hydrocarbon Process" 44(11), 287 (1965). British Patent 1,538,782 discloses another technique for producing ethylidene diacetate which employs the carbonylation of methyl acetate or dimethyl ether in the presence of hydrogen. Fenton U.S. Patent 3,579,566 treats organic acid anhydrides such as acetic anhydride with hydrogen in the presence of a catalyst comprising a complex of a Group VIII noble metal with a biphyllic ligand from the group consisting of trihydrocarbyl phosphines, arsines and stibines.The Fenton examples show the preparation of ethylidene diacetate from acetic an hydride by this technique.
The Fenton examples, however, show that the quantity of ethylidene diacetate which is produced is relatively small in relation to the theoretical quantity producible from the acetic anhydride employed. While
Fenton illustrates his generic process in terms of the following "shorthand" equation:
the complete equation is as follows:
In the foregoing equation, when R is -CH3 the treatment of acetic anhydride with hydrogen is illustrated. In other words, in such a reaction, one molecule of acetic acid is formed for each molecule of ethylidene diacetate produced. Competing reactions tend to form other products such as acetaldehyde and ethyl acetate to the detriment of the yield of ethylidene diacetate.
Belgian Patent 879,178 converts carboxylic acid anhydrides to 1,1 -diesters with hydrogen in the presence of certain supported metals, including metals of Group VIII of the Periodic Table, and in the presence of a strong protonic acid such as hydrochloric and hydrofluoric acids. The examples show substantial carboxylic acid formation.
It is accordingly an object of this invention to provide an improved process for the preparation of alkyldene diesters, e.g., ethylidene diacetate, from carboxylic acid anhydrides, e.g., acetic an hydride, wherein increased proportions of alkylidene diesters in relation to carboxylic acid can be realized and the formation of other by-products can be minimized, i.e., the ratio of alkylidene diester, e.g., ethylidene diacetate to carboxylic acid, e.g., acetic acid, and the yields of the diester product, are high.
It is a further object of the invention to provide an improved process for the production of alkylidene diesters from carboxylic acid anhydrides which does not require the use of Group VIII noble metals.
In accordance with the invention, these and other objects are realized by the reaction of a carboxylic acid anhydride, e.g., acetic anhydride, with hydrogen in the presence of a cobalt carbonyl. It has been surprisingly discovered that a cobalt carbonyl very effectively catalyzes the reaction and does not require the presence of a promoter or ligand as in the case of the process disclosed by Fenton, in addition to not requiring the presence of a Group VIII noble metal. It also does not require the presence of an acid of any kind. Although the presence of an acid may promote the formation of by-products and complicate product separation, an acid can be tolerated, if desired, but the absence of an acid such as used in Belgian patent 879,178, is preferred.
Thus, in accordance with the invention, hydrogen is reacted with an acid anhydride in the presence of a cobalt carbonyl such as dicobalt octacarbonyl [Co(CO)4k or tetracobalt dodecacarbonyl [Co(CO)3j4, although any other cobalt carbonyl can also be used. Thus, ethylidene diacetate can be effectively prepared in a representative case by subjecting acetic anhydride to reaction with hydrogen in the presence of dicobalt octacarbonyl. In all cases, the reaction is carried out under anhydrous conditions.
In carrying out the process of the invention, a wide range of temperatures, e.g., 100 to 250"C. are suitable, but temperatures of 50 to 150"C. are preferably employed and the more preferred temperatures generally lie in the range of 700 to 120 . Temperatures lower than those mentioned can be used but they tend to lead to reduced reaction rates, and higher temperatures may also be employed but there is no particular advantage in their use. Preferably the reaction is carried out at a substantially constant temperature.
The time of reaction is also not a parameter of the process and depends largely upon the temperature employed, but typical reaction or residence times, by way of example, will generally fall in the range of 0.1 to 6 hours. The reaction is preferably carried out under super-atmospheric pressures but excessively high pressures, which require special high-pressure equipment, are not necessary. In general, the reaction is effectively carried out by employing a hydrogen partial pressure which is preferably 50 to 2,000 p.s.i., and most preferably 300 to 1,000 p.s.i., although hydrogen partial pressures of 1 to 10,000 p.s.i. can also be employed. In the usual case, pressures below about 2,000 psi are generally used. By maintaining the partial pressure of hydrogen at the values specified, adequate amounts of th is reactant are always present.The total pressure is preferably that required to maintain the liquid phase and, in this case, the reaction can be advantageously carried out in an autoclave or similar apparatus.
At the end of the desired residence time, the reaction mixture is separated into its several constituents, as by distillation. Preferably, the reaction product is introduced into a distillation zone, which may be a fractional distillation column, or a series of columns, effective to separate the unreacted acetic anhydride, acetic acid, and other by-products, from the product ethylidene diacetate. The cobalt carbonyl is recycled.
The hydrogen is preferably employed in substantially pure form, as available commercially, but inert diluents such as carbon monoxide, carbon dioxide, nitrogen, methane, and noble gases can be present if desired. The presence of inert diluents does not affect the reaction but their presence makes it necessary to increase the total pressure in order to maintain the desired hydrogen partial pressure. The hydrogen, like other reactants should, however, be essentially dry, i.e., the hydrogen and the other reactants should be reasonably free from water. The presence of minor amounts of water such as may be found in the commercial forms of the reactants is, however, entirely acceptable.
As previously mentioned, the presence of gaseous diluents such as carbon monoxide increases the overall pressure required to provide the desired hydrogen partial pressure but the presence of carbon monoxide can be effective to maintain the catalyst for prolonged periods of time. Cobalt carbonyl has a tendency to decompose in response to elevation of temperature but it has been found that such decomposition is minimized and even completely suppressed when the temperature is maintained below 100 C. under the pressure conditions specified above. The presence of carbon monoxide provides further insurance against catalyst decomposition.
The amountofcobaltcarbonyl is in no way critical and is not a parameter of the process of the invention and can vary over a wide range. As is well known to persons skilled in the art, the amount of catalyst used is that which will provided the desired suitable and reasonable reaction rate since reaction is influenced by the amount of catalyst. However, essentially any amount of catalyst will facilitate the reaction. Typically, however, the cobalt catalyst is employed in the amount of 1 mol per 1 to 100,000 mols of carboxylic acid anhydride, preferably 1 mol per 10 to 10,000 mols of carboxylic acid anhydride and most preferably 1 mol per 50 to 5,000 mols of carboxylic acid anhydride.
The anhydrides which can be used in carrying out the process of the invention are anhydrides of carboxylic acids having upto 10 carbon atoms, preferably lower alkanoic acids having up to 6carbon atoms.
These anhydrides can be represented by the formula:
0 0
R-C-O-C-R wherein R is a hydrocarbyl radical which can be an alkyl group or a monocyclic aryl group. Representative anhydrides include acetic an hydride, propionic an hydride, valeric anhydride, caprylic anhydride, benzoic anhydride, and the like. Acetic an hydride is preferred.
The process of this invention can be carried out in the presence of a solvent or diluent, if desired.
Ordinarily, a solvent is not required. The solvent or diluent can be any organic solvent which is inert in the environment of the process, such as hydrocarbons, e.g., octane, benzene, toluene, xylene and tetralin, or halogenated hydrocarbons such as the chlorobenzenes, e.g., trichlorobenzene, or carboxylic acids, e.g., those containing up to 16 carbon atoms such as acetic acid, or esters such as methyl acetate and cellosolve acetate, and the like. Preferred solvents are halogenated hydrocarbons, chlorobenzenes and high boiling esters. Mixtures of solvents can also be used, such as mixtures of the solvents named above. In general, chlorobenzenes have been found to be the most suitable for use when a solvent is employed in the process.
A solvent or diluent is suitably selected which has a boiling point sufficiently different from the other components in the reaction mixture that it can be readily separated by distillation, as will be readily apparent to persons skilled in the art.
It will be apparent that the above-described reaction lends itself readily to continuous operation in which the reactants and catalyst are continuously supplied to the appropriate reaction zone and the reaction mixture continuously distilled to separate the volatile organic constituents and to provide a net product consisting essentially of alkylidene diester, with the other organic components being recycled and, in the case of liquid-phase reaction, a residual catalyst-containing fraction also be recycled.
It will be apparent that the catalytic reaction involved in the process of the invention can be carried out in the vapor phase, if desired, by appropriate control of the total pressure in relation to the temperature so that the reactants are in vapor form when in contact with the catalyst. In the case of vapor-phase operation, and in the case of liquid-phase operation, if desired, the catalyst components may be supported, i.e., they may be dispersed on a carrier of conventional type such as alumina, silica, silicon carbide, zirconia, carbon, bauxite, attapulgus clay, solid organic polymers, e.g., polyvinyl pyridine and polystyrene, and the like.The catalyst components can be applied to the carriers in conventional manner, e.g., by impregnation of the carrier with a solution of the catalyst, or the catalytst mixture, followed by drying. Catalyst component concentrations upon the carrier may vary widely, e.g., 0.01 weight percent to 10 weight percent, or higher. The supported catalyst is in the active form if it has a hydride or carbonyl substituent on the supported cobalt. Typical operating conditions for vapor-phase operation are a temperature of 50 to 300"C., preferably 70" to 250"C.
and most preferably 1000 to 200"C., a pressure of 1 to 5,000 p.s.i.a., preferably 50 to 1,500 p.s.i.a. and most preferably 150 to 500 p.s.i.a., with space velocities of 50 to 10,000 hr.-7, preferably 200 to 6,000 hr.-' and most preferably 500 to 4,000 hr.-l (STP).
The following examples will serve to provide a fuller understanding of the invention, but it is to be understood that they are given for illustrative purposes only, and are not to be construed as limitative of the invention. In the examples, all parts are by weight and percentages are on a molar basis, unless otherwise indicated.
Example 1
In this example, a magnetically-stirred Hastelloy (Registered Trade Mark) Parr bomb with a glass liner is employed as the reaction vessel. The bomb is charged with 2 parts of dicobalt octacarbonyl as catalyst, then with 40 parts of acetic anhydride, is swept out with argon and pressured to 700 p.s.i.g. with hydrogen. The bomb is then placed in an oil bath at room temperature and brought up to 100"C. in about 15 minutes. The pressure is maintained at 1,450 p.s.i.g. by recharging H2 when needed. The reaction is then carried out at this constant temperature for 3 hours, whereupon the bomb is cooled to approximately room temperature, vented and opened.G.C. (gas chromatography) analysis ofthe reaction mixture shows itto contain 13 parts of ethylidene diacetate and 12.1 parts acetic anhydride along with 7.4 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylidene diacetate is 65% and the ratio of ethylidene diacetate to acetic acid is 72% of theoretical.
Example 2
A Parr bomb as described in Example 1 is charged with 2 parts of dicobalt octacarbonyl as catalyst, then with 40 parts of acetic an hydride, is swept out with argon and pressurized to 400 psig with hydrogen. The bomb is then placed in an oil bath at room temperature and brought up to 100 C. in about 15 minutes. The pressure is maintained at 1,200 p.s.i.g. by recharging H2 when needed. The reaction is then carried out at this constant temperature for 3 hours, whereupon the bomb is cooled to approximately room temperature, vented and cooled. Gas chromatography analysis of the reaction mixture shows it to contain 10.3 parts of ethylidene diacetate and 22.7 parts acetic anhydride along with 5.9 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylidene diacetate is 84% and the ratio of ethylidene diacetate to acetic acid is 72% of theoretical.
Example 3
A reaction vessel as described in Example 1 is charged with 1 part of tetra cobalt dodecacarbonyl as catalyst, then with 20 parts of acetic anhydride, is swept out with argon and pressured to 150 p.s.i.g. with CO and then to 1,000 p.s.i.g. with hydrogen. The bomb is then placed in an oil bath at room temperature and grought up to 100"C. in about 15 minutes. The pressure is maintained at 1,000 p.s.i.g. with hydrogen. The reaction is then carried out at this constant temperature for 3 hours, whereupon the bomb is cooled to approximately room temperature, vented and opened. Gas chromatography analysis of the reaction mixture shows itto contain 8.2 parts of ethylidene diacetate and 7.4 parts acetic anhydride along with 3.6 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde byproducts.The yield of ethylidene diacetate is 91% and the ratio of ethylidene diacetate to acetic acid is 93.3% of theoretical.
Example 4
In this Example and in the following examples, a stirred autoclave is used as the reaction vessel. The autoclave is charged with 4.1 parts of dicobalt octacarbonyl as catalyst and 400.4 parts acetic anhydride and pressured with 350 p.s.i.g. carbon monoxide and 1,150 p.s.i.g. hydrogen. The vessel is then heated up to 90"C. in about 15 minutes. During the heating period, there is absorption of gas and the pressure falls in spite of the increased temperature. The pressure is returned to 1,500 p.s.i.g. with hydrogen and this pressure and temperature are maintained for 6 hours. G.C. analysis of the reaction mixture shows it to contain 178.6 parts of ethylidene diacetate and 134.9 parts acetic anhydride along with 84.4 parts of acetic acid, 4 parts acetaldehyde and trace levels of ethyl acetate by-product.The yield of ethylidene diacetate is 94, and the ratio of ethylidene diacetate to acetic acid is 86.6% of theoretical. The ratio of ethylidene diacetate plus acetaldehyde to acetic acid is 93% of theoretical.
Example 5
The reaction vessel is charged with 2.1 parts of dicobalt octacarbonyl, 5 parts p-toluene sulfonic acid and 400 parts acetic anhydride and pressured with 500 p.s.i.g. carbon monoxide and 1,150 p.s.i.g. hydrogen. The vessel is then heated up to 100 C. in about 15 minutes. The pressure is returned to 1,500 p.s.i.g. with hydrogen and this pressure and temperture are maintained for 4 hours. Gas chromatography analysis of the reaction mixture shows it to contain 83 parts of ethylidene diacetate and 282 parts acetic anhydride along with 36 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylene diacetate is 98% and the ratio of ethylidene diacetate to acetic acid is 95% of theoretical.
Example 6
The autoclave is charged with 2 parts of dicobalt octacarbonyl as catalyst and 400 parts acetic anhydride and pressured to 200 p.s.i.g. carbon monoxide and 1,300 p.s.i.g. hydrogen. The vessel is then heated up to 90"C. in about 20 minutes. The pressure is returned to 1,500 p.s.i.g. with hydrogen and is this pressure and temperature are maintained for 6 hours. Gas chromatography analysis of the reaction mixture shows it to contain 103.6 parts of ethylidene diacetate and 253 parts acetic anhydride along with 44.3 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylidene diacetate is 98.5 and the ratio of ethylidene diacetateto acetic acid is 96.1% of theoretical.
Example 7
Into the reaction vessel are charged 4 parts of dicobalt octacarbonyl as catalyst and 400 parts acetic anhydride and the vessel is pressured with 130 p.s.i.g. carbon monoxide and 870 p.s.i.g. hydrogen. The vessel is then heated up to 90"C. in about 15 minutes. The pressure is returned to 1,000 p.s.i.g. with hydrogen and this pressure and temperature are maintained for 1 hour. Gas chromatography analysis of the reaction mixture shows it to contain 74 parts of ethylidene diacetate and 296.6 parts acetic anhydride along with 30 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylidene diacetate is 100% and the ratio of ethylidene diacetate to acetic acid is 100% of theoretical.
Example 8
Into the autoclave are charged 4.0 parts of dicobalt octacarbonyl as catalyst and 400 parts acetic anhydride and the vessel is pressured with 750 p.s.i.g. carbon monoxide and 750 p.s.i.g. hydrogen. The vessel is then heated up to 90"C. in about 15 minutes. The pressure is returned to 1,500 p.s.i.g. with hydrogen and this pressure and temperature are maintained for 7 hours. Gas chromatography analysis of the reaction mixture shows itto contain 141.8 parts of ethylidene diacetate and 205.2 parts acetic anhydride along with 58.5 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde by-products. The yield of ethylidene diacetate is 100% and the ratio of ethylidene diacetate to acetic acid is 99.6% of theoretical.
Example 9
The stirred pressure vessel is charged with 4.0 parts of dicobalt octacarbonyl as catalyst and 400 parts acetic anhydride and pressured with 350 p.s.i.g. carbon monoxide and 1,150 p.s.i.g. with hydrogen. The vessel is then heated up to 100"C. in about 15 minutes. The pressure is returned to 1,500 p.s.i.g. with hydrogen and this pressure and temperature are maintained for 2 hours. Gas chromatography analysis of the reaction mixture shows it to contain 97.6 parts of ethylidene diacetate and 263.3 parts acetic anhydride along with 40.1 parts of acetic acid and trace levels of ethyl acetate and acetaldehyde byproducts. The yield of ethylidene diacetate is 99.8% and the ratio of ethylidene diacetate to acetate acid is 100% of theoretical.
Example 10
The stirred pressure vessel is charged with 20 parts of dicobalt octacarbonyl as catalyst and 400 parts acetic an hydride and pressured with 400 p.s.i. carbon monoxide. The vessel is then heated up to 100 C. in about 15 minutes. The pressure is increased to 1,200 p.s.i.g. with hydrogen and this pressure and
temperature are maintained for 7 hours. Gas chromatography analysis of the reaction mixture shows it to
contain 197 parts of ethylidene diacetate and 22.4 parts acetic anhydride along with 119.8 parts of acetic acid
and 17.1 parts acetaldehyde and trace levels on ethyl acetate by-product. The yield of ethylidene diacetate is
73% and the ratio of ethylidene diacetate to acetic acid is 68% of theoretical. The ratio of ethylidene diacetate
and acetaldehyde to acetic acid is 87% of theoretical.
Example ii The reaction vessel is charged with 20 parts of dicobalt octacarbonyl as catalyst, 12 parts acetic acid and
388 parts acetic anhydride and pressured with 200 p.s.i. carbon and 700 p.s.i. hydrogen. The vessel is then
heated up to 100"C. in about 30 minutes. The pressure is increased to 1,000 p.s.i.g. with hydrogen and this
pressure and temperature are maintained for 2 hours. Gas chromatography analysis of the reaction mixture shows it to contain 153.5 parts of ethylidene diacetate and 198.9 parts acetic anhydride along with 88.3 parts
of acetic acid, 2.4 parts acetaldehyde and trace levels on ethyl acetate by-product. The yield of ethylidene
diacetate is 95.7% and the ratio of ethylidene diacetate to acetic acid is 83% of theoretical.The ratio of
ethylidene diacetate plus acetaldehyde to acetic acid is 87% of theoretical.
Example 12
A reaction vessel as described in Example 1, is charged with 1 part of tetra cobalt dodecarbonyl as catalyst,
then with 20 parts of propionic anhydride and the reaction is carried out as described in Example 3,
producing results comparable to those obtained in Example 3, except that propionic acid and the
corresponding alkylidene diester are produced.
Example 13
Example 12 is repeated but there are employed 20 parts ofvaleric anhydride, and similar results are
obtained, except that valeric acid and the corresponding alkylidene diester are produced.
Example 14
Example 12 is again repeated but the propionic anhydride is replaced by 20 parts benzoic anhydride.
Again, results comparable to those obtained in Example 3 are realized, except that benzoic acid and the
corresponding alkylidene diester are produced.
Claims (8)
1. A process for the conversion of an acid anhydride to an alkylidene diester of the acid, the process
comprising reacting said acid anhydride with hydrogen in the presence of a cobalt carbonyl.
2. A process as defined in Claim 1, wherein the cobalt carbonyl is dicobalt octacarbonyl.
3. A process as defined in Claim 1, wherein the cobalt carbonyl is tetracobalt dodecacarbonyl.
4. A process as defined in any one of Claims 1 to 3, wherein the reaction is carried out in the presence of
carbon monoxide.
5. A process as defined in any one of Claims 1 to 4, wherein the acid anhydride is acetic anhydride.
6. A process as claimed in Claim 1 substantially as hereinbefore described with particular reference to
the Examples.
7. A process as claimed in Claim 1, substantially as illustrated in any one of the Examples.
8. An alkylidene diester of a carboxylic acid, when prepared by the process claimed in any one of the
preceding claims.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US17106480A | 1980-07-22 | 1980-07-22 |
Publications (2)
Publication Number | Publication Date |
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GB2079753A true GB2079753A (en) | 1982-01-27 |
GB2079753B GB2079753B (en) | 1984-09-05 |
Family
ID=22622359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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GB8122415A Expired GB2079753B (en) | 1980-07-22 | 1981-07-21 | Conversion of acid anhydrides to alkylidene diesters |
Country Status (13)
Country | Link |
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JP (1) | JPS5753433A (en) |
KR (1) | KR840001306B1 (en) |
AR (1) | AR226116A1 (en) |
BE (1) | BE889678A (en) |
BR (1) | BR8104727A (en) |
CA (1) | CA1165774A (en) |
DE (1) | DE3129013C2 (en) |
FR (1) | FR2495140A1 (en) |
GB (1) | GB2079753B (en) |
IT (1) | IT1142588B (en) |
NL (1) | NL8103339A (en) |
NO (1) | NO154549C (en) |
SE (1) | SE449861B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3407092A1 (en) * | 1984-02-28 | 1985-08-29 | Hoechst Ag | Process for the preparation of ethylidene diacetate and/or ethyl acetate |
JPS63101348A (en) * | 1986-10-20 | 1988-05-06 | Idemitsu Kosan Co Ltd | Production of 1,1-diester |
-
1981
- 1981-07-10 CA CA000381565A patent/CA1165774A/en not_active Expired
- 1981-07-14 NL NL8103339A patent/NL8103339A/en not_active Application Discontinuation
- 1981-07-16 AR AR286118A patent/AR226116A1/en active
- 1981-07-17 IT IT48919/81A patent/IT1142588B/en active
- 1981-07-20 BE BE0/205444A patent/BE889678A/en not_active IP Right Cessation
- 1981-07-21 NO NO812501A patent/NO154549C/en unknown
- 1981-07-21 FR FR8114158A patent/FR2495140A1/en active Granted
- 1981-07-21 GB GB8122415A patent/GB2079753B/en not_active Expired
- 1981-07-22 SE SE8104479A patent/SE449861B/en not_active IP Right Cessation
- 1981-07-22 KR KR1019810002661A patent/KR840001306B1/en active
- 1981-07-22 JP JP56115002A patent/JPS5753433A/en active Pending
- 1981-07-22 DE DE3129013A patent/DE3129013C2/en not_active Expired
- 1981-07-22 BR BR8104727A patent/BR8104727A/en unknown
Also Published As
Publication number | Publication date |
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BE889678A (en) | 1982-01-20 |
NO812501L (en) | 1982-01-25 |
KR830006161A (en) | 1983-09-17 |
DE3129013A1 (en) | 1982-03-11 |
BR8104727A (en) | 1982-04-13 |
JPS5753433A (en) | 1982-03-30 |
IT1142588B (en) | 1986-10-08 |
GB2079753B (en) | 1984-09-05 |
KR840001306B1 (en) | 1984-09-11 |
NO154549C (en) | 1986-10-15 |
CA1165774A (en) | 1984-04-17 |
SE8104479L (en) | 1982-01-23 |
IT8148919A0 (en) | 1981-07-17 |
DE3129013C2 (en) | 1984-05-10 |
SE449861B (en) | 1987-05-25 |
AR226116A1 (en) | 1982-05-31 |
FR2495140A1 (en) | 1982-06-04 |
NL8103339A (en) | 1982-02-16 |
FR2495140B1 (en) | 1984-04-27 |
NO154549B (en) | 1986-07-07 |
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