PROCESS FOR PRODUCING ETHYLIDENE DIACETATE AND/OR ACETALDEHYDE

Abstract: A process for producing ethylidene diacetate and/or acetaldehyde which comprises causing hydrocarbonylation reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst consist­ ing essentially of (i) as a main component palladium sup­ ported on a porous inorganic material and (ii) as a secondary component at least one halide selected from the group con­ sisting of iodides, bromides and mixtures thereof under sub­ stantially anhydrous condition is disclosed.

Description: PROCESS FOR PRODUCING ETHYLIDENE DIACETATE AND/OR ACETALDEHYDE This invention relates to a process for producing ethylidene diacetate and/or acetaldehyde which comprises causing hydrocarbonylation reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst comprising as a main component palladium supported on a porous inorganic material and as a secondary component at least one halide selected from the group consisting of iodide, bromide and mixtures thereof under substantially anhydrous conditions. In the prior art, ethylidene diacetate was synthesized from acetylene and acetic acid or by reacting acetaldehyde with acetic anhydride. Recently, a process for producing ethylidene diacetate by reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst was proposed (refer to Japanese Patent Publication (laid open) No. 115409/1976). In the process disclosed in this Patent Publication, noble metals belonging to Group VIII of the Periodic Table and halides were essential components of the catalyst for hydrocarbonylation reaction. There is the passage "co-catalysts can be used together with the noble metal catalyst in order to enhance the reactivity" in the Patent Publication. In Working Examples 1 - 29 of the Patent Publication, rhodium salt or complex, or palladium salt or complex was used as the main catalyst. Besides, in Working Examples 5 and 8, little ethylidene diacetate is formed in the absence of an organic nitrogen group compound or an inorganic metal compound. In other words, the invention of Patent Publication No. 115409/1976 relates to a process for synthesizing ethylidene diacetate from methyl acetate or dimethyl ether, carbon monoxide and hydrogen in the presence of a catalyst consisting of (i) a metal compound, which is soluble in the reaction mixture, selected from the group consisting of rhodium salt or complex and palladium salt or complex and (ii) a halide and (iii) a co-catalyst composed of an organic nitrogen group compound or an inorganic metal compound. In the process as disclosed in the patent publication a liquidphase homogeneous reaction is effected by using rhodium salt or complex, or palladium salt or complex. When a noble metal, such as rhodium and palladium is used as a catalyst, expensive rhodium and palladium must be recovered from the homogeneous reaction mixture after completing the reaction. However, in general, such recovery needs complicated steps and loss of the noble metal can not be avoided in the recovering step. This loss is described in Hydrocarbon Processing 54 June 83 (1975), Patent Publication (laid open) No. 90204/1978 and JAPAN CHEMICAL INDUSTRY ASSOCIATION MONTHLY, 14th March 1973. As a result, the resulting product becomes costly. In order to simplify the separation of a product from a reaction mixture and recovery of a catalyst employed and in order to make easy circulation of a reaction solution in a continuous reaction a heterogeneous catalyst is effective, so development of such catalyst is very important. (Refer to CHEMTECH 560, 1973 by Charles U. Pihman, Jr. and George O. Evans) Referring Z.M. Michalska and D.E. Webster: "Supported Homogeneous Catalyst" CHEMTECH, 117 (1975), Patent Publication (laid open) No. 115409/1976 suggests disclose an organic polymer metal complex containing a main chain composed of polystyrene-divinylbenzene as a heterogeneous catalyst. Many solid catalysts containing polymer-metal complex, namely ion-exchange resin as a main component, are used on a laboratory scale. However, the catalysts must be used at a temperature less than 100 C. (Organo Inc catalog and Mitsubishi Chemical Industries Inc Catalog) At a temperature more than 1000C, physical durability and chemical stability of the catalyst are poor, and reaction rate and selectivity in case of using such heterogeneous catalyst are inferior to those in case of using a homogeneous catalyst; metal in the catalyst is released from the catalyst and is dissolved in the liquid phase; and the catalyst tends to be deactivated. As explained above the known heterogeneous prior catalyst have fatal shortcomings. So, it is difficult to use such catalysts on an industrial scale. The present inventors carried out research to find a process for synthesizing ethylidene diacetate using a heterogeneous catalyst. As a result, we found that palladium supported on a porous inorganic material is effective for synthesis of ethylidene diacetate. An object of this invention is to provide a process for synthesis of ethylidene diacetate and/or acetaldehyde in which recovery of the catalyst employed is easy. This invention relates to a process for producing ethylidene diacetate and/or acetaldehyde which comprises reacting methyl acetate or dimethyl ether, carbon monoxide and hydrogen in the presence of a catalyst consisting essentially of (i) as a main component palladium supported on a porous inorganic material and (ii) as a secondary component at least one halide selected from the group consisting of iodides, bromides and mixtures thereof under substantially anhydrous conditions. Though expensive rhodium (belonging to Group VIII of the Periodic Table) supported on a porous inorganic materials have effective catalytic activity, rhodium supported on the material tends to be released from the material and be dissolved in the liquid phase. Though ruthenium is cheaper than rhodium, ruthenium supported on a porous inorganic materials are poor catalytic activity. Similarly, platinum supported on a porous inorganic materials are poor in catalytic reactivity. Refer to Control tests 1 and 2 as explained below. On the other hand, we found that palladium supported on a porous inorganic materials are effective for such synthesis of ethylidene diacetate and/or acetaldehyde, because they have excellent catalytic activity and little palladium is released from the material. As shown in the foregoing Examples, more than 90.0%, in general more than 99.0% of the palladium remains intact on the porous inorganic material per hour; and more than 99.9% of the palladium remains intact on the porous inorganic material under preferable conditions per hour. A catalyst consisting of metallic palladium, a halide and a promoter did not have catalytic activity. (refer to control test 1). In other words, a catalyst comprising palladium supported on a porous inorganic material and a bromide or an iodide not only has high catalytic activity, but also prevents the palladium from dissolving in the reaction solution. It could not be anticipated from the prior art that a palladium supported on a porous inorganic material has the above mentioned advantages. This is proved by comparing reaction speed, yield and resistance to palladium dissolving into reaction system of this invention with those of the prior art systems disclosed in [K.M. Webber and B.C. Cates, J. Mol. Catal. 3(1977/78)1-9]. The mechanism of the hydrocarbonylation reaction of methyl acetate or dimethyl ether is not perfectly clear. However, it is believed that the reaction by which ethylidene diacetate is synthesized can be expressed in the following equations: (1) When methyl acetate is used as a raw material 2CH3COOH3+2CO+H2 EMI4.1 CH3CH (OCOCH3) 2+CH3COOH (2) When dimethyl ether is used as a raw material 2CH3OCH3 +4CO+H2 EMI4.2 CH3CH(OCOCH3)2+CH3COOH The main component employed in the practice of this invention may be prepared by supporting palladium on a prous inorganic material by coprecipitation, impregnation, blending, adsorption, ion exchange and the like. One of the processes for supporting palladium on a porous inorganic material is as follows: A porous inorganic material is impregnated with a solution of palladium metal or a palladium compound and other components, followed by reducing the palladium compound in the material to palladium metal with a reducing agent, such as formalin, hydrogen, sodium formate, carbon monoxide, sodium borohydride, lithium aluminum hydride, or hydrazine and then drying the resulting palladium supported on the material. Of course, the palladium supported on the material may be prepared by other methods. The palladium to be supported on a porous material can be used in any form of zero valence state and higher valence state. Palladium metal or palladium compounds include for example metallic palladium, PdO, Pd(OH)2, Pd(NO3)21 Pd (NO2)2, PdSO41 4)2' ( (PO4) 2' (NH4) x4, (NH4)2PdX4, Na2PdX4, K2PdX4, Li2PdX4, PdX2, Pd(OAc)2, Pd(AcAc)2, and PdX2(PhCN)2 wherein X is C1, Br or I, Ph is phenyl group, OAc is acetoxy group and AcAc is acetylacetonate group. The porous inorganic materials employed for supporting palladium are the ones having particle size of 400 mesh to 1 inch so that palladium supported on a porous inorganic materials may be used in a fluidized bed reactor or fixed bed reactor. The pore volume of the material in proportion to weight of 3 the material may be in the range of 0.03 to 2.5 cm preferably 0.05 to 1.5 cm /g. Surface area of the material in proportion to weight of the material may be in the range of 0.1 to 1500 m2/g, preferably 1 to 1500 m2/g. Average semi-diameter of the pore in the material may be in the range of 0.1 to 20000 , preferably 1 to 2000 A and most preferably 5 to 1500 . The ratio of palladium to a porous inorganic material is not critical and any amount of palladium can be supported on a porous inorganic material. In general, the proportion by weight of palladium to be supported on a porous inorganic material may be in the range of 0.0001 to 50%, preferably 0.001 to 40%, more preferably 0.01 to 30% and most preferably 0.05 to 20%. Examples of the porous inorganic material include carbon, activated carbon, graphite, bone black, alumina, silica, silica alumina, barium sulfate, natural or synthetic zeolite, spinel, magnesia adhered alumina, thoria, titanium oxide, zirconium oxide, thorium oxide, lÅanthanum oxide, cerium oxide, zinc oxide, tantalum, clay, diatomaceous earth, Celite (trade name of product being commercially available from Johns-Manville Co.), asbestos, pumice stone, bauxite, terra abla, natual and treated terra abla, such as Super-Filtrol, silicon c-z"bidli , zeolite molecular sieves, ceramic honeycomb, boria, cements, alundum, corundum, brick, talk, gypsum and the like. Carbon, graphite, bqne black, alumina, silica, silica alumina, barium sulfate, zeolite spinel and magnesia adhered alumina are preferable. Activated carbon, graphite, bone black, alumina, silica, silica alumina and barium sulfate are more preferable. Activated carbon is most preferable. The carriers may be in the form of particles having uniform or non-uniform size. The carriers may be in the form of molded articles, extruded articles, ceramic bars, balls, fragments, tiles and the like. The palladium supported on a porous inorganic materials can easily be prepared from commercially available compounds. Special conditions are not required for the preparation of the palladium supported on a porous inorganic materials. The palladium can be released from the material to regenerate the main component. An iodide, a bromide and mixture thereof may be used as a secondary component. An iodide is preferred. Examples of the halides include methyl halides, acetyl halides, hydrogen halides and mixtures thereof. Methyl iodide, acetyl iodide hydrogen iodide or mixture thereof can be used as a halide. An iodide and/or a bromide may be added to the reaction system as it is. Materials which can convert to methyl halides, such as methyl iodide; acetyl halide, such as acetyl iodide or hydrogen halides, such as hydrogen iodide by reacting with components in the reaction system can also be used as a secondary component. Examples of the materials include inorganic halides, such as alkali metal halides, such as lithium halides, sodium halides, or potassium halides; alkaline earth metal hlaides, such calcium halides or magnesium halides; metal halides, such as aluminum halides, zinc halides, copper halides, lanthalum halides, or cerium halides; and halogens, such as bromine or iodine. The hydrocarbonylation reaction of methyl acetate or dimethyl ether of this invention sufficiently proceeds in the presence of the catalyst containing the above mentioned main component and the above mentioned secondary component. Promoters composed of compounds of nitrogen family elements may be used with the catalyst in order to increase the reaction rate. -Preferable compounds of nitrogen family elements include organic compounds containing nitrogen, phosphorus, antimony or arsenic, ammonia or ammonium salts. Examples of the compounds are shown in the following. However, compounds which are not listed in the following may be used as a promoter. (1) trivalent compounds of nitrogen family elements (A) Compounds represented by the formula EMI7.1 wherein M is N, P, Sb or As. (a) compounds wherein RÚ, Rê and R may be the same or different, and are independently hydrogen, saturated alkyl having 1 - 10 carbon atoms, saturated cycloalkyl having 3 - 10 carbon atoms, or aryl M is N The compounds include, for example, ammonia, and amines, such as monomethyl amine, dimethyl amine, trimethyl amine, monoethylamine, diethyl amine, triethyl amine, dimethyl ethyl amine, tri-n-propyl amine, tri-isopropyl amine, tri-n-butyl amine, tri-tert.-butyl amine, aniline, dimethyl aniline, diethyl aniline, dimethylbenzyl amine, toluidine, triphenyl amine, cyclohexyl amine and the like. M is P The compounds include, for example, phosphines, such as tri-n-propyl phosphine, tri-iso-propyl phosphine, tri-n-butyl phosphine, tri-tert.-butyl phosphine, tricyclohexyl phosphine, ethylene bis(diphenyl phosphine), triphenyl phosphine and the like M is Sb The compounds. include, for example, stibines, such as tri-iso-propyl stibine, ethyl-di-iso-propyl stibine, triphenyl stibine, tri(o-tolyl)stibine, phenyl diamyl stibine, tris(diethyl aminomethyl)stibine, bis(diethylstibino)pentane and the like. M is As The compounds include, for example, arsines, such as trimethyl arsine, triethyl arsine, tri-iso-propyl arsine, tripropyl arsine, tricyclohexyl arsine, phenyl di-iso-propyl arsine, diphenyl arsine, bis(diphenyl arsino)ethane, bis(di-iso-propyl arsino)hexane, and the like (b) wherein RÚ is hydrogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms, or aryl and R2 and R3 are taken together and represents methylene or polymethylene having 2 - 5 carbon atoms; the compounds include, for example, pyrrolidine, N-methyl pyrrolidine or piperidine or N-phenyl piperidine: R1 wherein RÚ and R2 (c) wherein R1 and Rê may be the same or different and independently represent hydrogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms, or aryl and R3 is aliphatic saturated acyl, or R1 is hydrogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms or aryl, and R2 and R3 are taken together and represent lactam ring; the compounds include, for example carboxylamides such as acetamide, N ,N-dimethylacetamide, acetoanilide, N-methyl-Nphenylacetamide, and lactam, such as N-methylpyrrolidinone: (d) wherein at least one of RÚ, Rê and R is carboxymethyl and the remainder is hydrogen, alkyl having 1 - 10 carbon atms, cycloalkyl having 3 - 10 carbon atoms or aryl; the compounds include, for example carboxylic acid derivatives, such as N,N-dimethyl glycine, N,N-diethyl glycine, imino diacetic acid, N-methyl iminodiacetic acid, or nitrilotriacetic acid: (B) Organic compounds represented by the formula N--C-R wherein R represents an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 - 10 carbon atoms or aryl; the compounds include for example nitriles, such as acetonitrile, propionitrile, or benzonitrile. (C) Organic nitrogen group compounds represented by the formula EMI9.1 (a) wherein R4 , R5 , R6 and R7 may be the same or different and independently hydrogen, alkyl having 1 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms, or aryl and R8 is methylene group or polymethylene group having 2 - 10 carbon atoms, phenylene, or carbonyl group M1 and N2 are N, P, Sb or As The compounds include, for example, ethylene bis(diphenylphosphine), phenylene bis(dimethylphosphine), bis (diphenylarsine)ethane, bis(di-iso-propylarsino)hexane, bis (diethylstibino)pentane, N,N,N' ,N'-tetramethyl- ethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetra-n-propylethylenediamine, N,N,N' ,N'- tetramethylmethylenediamine, N,N,N' ,N' -tetramethyl urea, N-methyl-2-pyrrodinone and triethylenediamine, (b) R4 and R6 may be the same or different and independently represent hydrogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms or aryl and R5 and R7 are taken together and represent methylene or polymethylene having 2 - 5 carbon atoms and R8 is methylene or polymethylene having 2 - 5 carbon atoms; the compounds include, for example, heterocyclic compounds, such as piperazine, N-methyl-piperazine, N-ethyl-piperazine, or 2-methyl-N,N' -dimethylpiperazine. (c) other compounds include, for example, tris(diethyl aminomethyl) stibine, 2,5-dicarboxy-piperazine, cyclohexane-1,2-diamine-N,N,N',N'-tetraacetic acid or salts thereof, tetramethylester, ethylenediaminetetraacetic acid, or its salt or tetramethyl ester thereof, l,4-azabicyclo[2,2,2]octane, methyl substituted, 1,4-diazabicyclo[2,2,2]octane, adiponitrile or N-methyl-morpholine. (II) H & ero cyclic compounds include, for example, pyridines, such as pyridine; a-picoline, B-picoline, y-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 4-propylpyridine, 4-butylpyridine, 4-isobutylpyridine, 4-tert.-butylpyridine, 2,6-lutidine, 2,4-lutidine, 2,5lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 2-methyl-4-ethylpyridine, 2-methyl-5-ethylpyridine, 3-methyl4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,4-diethylpyridine, 3,5-diethylpyridine, 2-methyl-5-butylpyridine, 4-pentylpyridine, 4- (5-nonyl) -pyridine, 2,6-dipropylpyridine, 2-methyl-3-ethyl6-propylpyridine, 2,6-diethylpyridine, 2,6-dipropylpyridine, 2,6-dibutylpyridine, 2,6-di-tert.-butylpyridine, functional group-containing pyridines, such as 2-cyanopyridine, 3cyanopyridine, 4-cyanopyridine, 2,6-dicyanopyridine, 3,5dicyanopyridine, 2-cyano-6-methylpyridine, 3-cyano-5-methylpyridine, picolinic amide, nicotinic amide, isonicotinic amide, picolinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dinicotinic acid, cinchomethorinic acid, 5-butylpicolinic acid, alkyl ester of nicotinic acid, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5diaminopyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4-(5-nonyl) pyridine, 2-amino-4,6-dimethylpyridine, 2,6-diamino-4methylpyridine, 2,2' -dipyridylamine, 4-dimethylaminopyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6dihydroxypyridine, 3-hydroxy-6-me,thylpyridine, 2-chloropyridine, 2,6-dichloropyridine, 4-chloropyridine, 2-amino5-chloropyridine, 2-amino-3,5-dichloropyridine, 2,6-dimethyl3,5-dichloropyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4-methylpyridine, 2-amino-3,5-dichloro4,6-dimethylpyridine, 4-amino-3,5-dichloropyridine, pyridine N-oxide, 8-picoline-N-oxide, a-picoline-N-oxide, y-picoline N-oxide, 2,6-lutidine-N-oxide, 3,5-lutidine-N-oxide, 4 phenylpropylpyridine-N-oxide, 1,3-di-(4-pyridyl)-propane-di N-oxide, 4-(5-nonyl)-pyridine-N-oxide, 2-chloropyridine-Noxide, 4-cyanopyridine-N-oxide, 2-pyridine-methanol, 3pyridinemethanol, 4-pyridinemethanol, 2,6-pyridinemethanol, 2-pyridineethanol, 4-pyridineethanol, 3-picolylamine, 4picolylamine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridines, 4-piperidinoethylpyridine, 4-(4-pipecolinoethyl)pyridine, and 4-morpholinoethylpyridine, pyridines containing heterocyclic or homocyclic group, such as 2-phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4phenylpropylpyridine, 4,4' -dipyridyl, 4,4'-dimethyl-2,2'dipyridyl, 1,3-di-(4-pyridyl)propane, 1,2-di-(4-pyridyl)-ethane, 1,2-di-(4-pyridyl-ethylene, 1,2,3-tri-(4-pyridyl)propane, 2,4,6-tri-(4-pyridyl)-S-triazine, 2,4-di-(4-pyridyl)-6-methyl S-triazine, and 2,5-di-(4-pyridyl)-S-tetrazine, alkenylpyridine or polymer pyridine, such as 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, 2-vinyl-5-ethylpyridine, 4-butenyl pyridine, 4-vinylpyridine homopolymer, 2-vinylpyridine homopolymer, 2-vinylpyridine-acrylonitrile copolymer, 4-vinylpyridine-acrylonitrile copolymer, 4-vinylpyridine-styrene copolymer, 4-vinylpyridine-divinylbenzene copolymer, 2vinylpyridine-divinylbenzene copolymer, and 4-vinylpyridine homopolymer-N-oxide; pyrroles; pyrrolines; pyrinidines; pyrazines; pyrazoles; pyrazolines; pyridazines; imidazoles; 1, 10-phenanthrolines, such as 4-chloro-l , 10-phenanthroline, and 5- (thiabentyl) -1, 10-phenanthroline; quinolines, such as 2-(dimethylamino)-6-methoxyquinoline, 8-hydroxyquinoline and 2-carboxyquinoline. (III) Pentavalent nitrogen group compounds The compounds include, for example ammonium acetate, ammonium propionate, and triphenylphosphineiminiumchloride. Of these nitrogen group compounds, ammonia, ammonium salts and organic compounds containing nitrogen atom or phosphrous atom are preferable; organic compounds containing trivalent phosphorus atom or trivalent nitrogen atom are more preferable; and phosphine compounds containing trivalent phosphorus atom and hetercyclic compounds containing trivalent nitrogen atom, such as pyridines are most preferable. These promoters may be supported on a porous inorganic material with a palladium metal. Alternatively, promoters may be used without being supported on a porous inorganic material. It is preferred that promoter be supported on a porus inorganic material with a palladium metal. The amount of the main component employed depends on type of reaction, that is, whether it is in a fixed bed or a fluidized bed. In general, the amount of the main component employed may be in the range of from 1 x 10 4 to 25 wt%, preferably in the the range of from 1 x 10 J to 20 wt% more preferably from 2.5 x 10 3 to 15 wt% and most preferably from 5 x 10 3 to 10 wt% on the basis of weight of a reaction solution in terms of metal. The amount of halides employed as a secondary component employed may be in the range of from 1 x 10 6 to 15 mol, preferably 1 x 10 5 to 5 mol, most preferably 1 x 10 4 - 3 mol per 1 liter of a reaction solution in terms of halogen atom. Amount of ammonia or other promoter compound employed may be in the range of from 10-6 to 10 mol, preferably 10 to 5 mol and more preferably 10 3 to 2.5 mol per 1 liter of a reaction solution. In practicing this invention, the reaction temperature is not critical. In general, the reaction temperature may be in the range of 20 - 5000C, preferably 80 - 3500C, more preferably 100 - 2500C. The reaction pressure is kept high enough to keep the raw material(s), the solvent and the product in a liquid phase and to maintain appropriate partial pressures of hydrogen and carbon monoxide. The partial pressure each of hydrogen and carbon monoxide may be in the range of 0.5 - 700 atm., preferably 1 - 600 atm., and more preferably 3 - 500 atm. However, partial pressures of hydrogen and carbon monoxide may be in the range of 0.05 - 1000 atm. Dimethyl ether and methyl acetate which are used as raw materials in this invention may b prepared by known methods. For example, dimethyl ether may be produced by dehydrationdimerization reaction of methanol. The methyl acetate may be produced by esterification of methanol and acetic acid. In this reaction acetic acid may be produced by reacting methanol with carbon monoxide (refer to Patent Publication (laid open) Nos. 59211/1979, 63002/1979 and 66614/1979). Acetic acid which is formed as a by-product in synthesis of vinyl acetate from ethylide diacetate may be used for synthesis of methyl acetate. Synthesis of vinyl acetate from ethylidene diacetate is disclosed USP No. 2,425,389; Kogho Kogaku Zasshi 74(9)1825(1971) and Hydrocarbon Process 44(11)287(1965). Methyl acetate may also be produced by reacting methanol with synthesis gas. [Patent Publication for opposition No. 2525/1973, Patent Publication (laid open) Nos. 136110/1977 and 136111/1977]. Vinyl acetate is converted to polyvinyl acetate. Methyl acetate formed as a by-product when the polyvinyl acetate is converted to polyvinyl alcohol may be used as a raw material. Methanol, dimethyl ether, acetic acid, acetaldehyde, dimethyl acetal and iodides, such as methyl iodide be incorporated in the methyl acetate employed as a raw material of this invention as long as an overall balance is obtained. Preparation of methyl acetate from acetic acid formed as a by-product in synthesis of vinyl acetate from ethylidene diacetate is preferable in an overall process for producing vinyl acetate from methanol and synthesis gas. Stoichimetric amounts of the raw materal gas depend on which one of methyl acetate, dimethyl ether and mixture thereof is used. Therefore, stoichimetric amounts of carbon monoxide and hydrogen may vary from molar ratio of CO to H2 of 2:1 to molar ratio of CO to H2 of 4:1. It is not necessarily critical to use CO and H2 in stoichimetric amounts. In general, the molar ratio of CO to H2 may be in the range of from 1:100 to 100:1, preferably 1:50 to 50:1 and more preferably 1:10 to 10:1. However, it is preferable that carbon monoxide and hydrogen be used in an approximately stoichimetric amount. So, preferably, the ratio of carbon monoxide to hydrogen may be in the range of 0.5:1 to 5:1. In the practice of this invention, carbon monoxide and hydrogen may be introduced into the reaction system as separate streams. Synthesis gas comprising carbon monoxide and hydrogen may be introduced into the reaction system. The raw material gas composed of carbon monoxide and hydrogen does not need to be highly pure and may contain carbon dioxide, methane, nitrogen, and rare gases. Extremely low concentration of either of carbon monoxide or hydrogen in the mixed gas is not desirable, because the reaction pressure must rise when using such gas. In the present process, methyl acetate or dimethyl ether as a raw material and ethylidene diacetate or acetaldehyde as a product serve as a solvent for reaction, so another solvent is not necessary. An organic solvent and a diluent compatible with the raw materials and the product under the reaction conditions may be used. Examples of the organic solvent include organic acids, such as acetic acid, acetic anhydride, propionic acid, butyric acid, octanoic acid, phthalic acid, benzoic acid; esters of organic acids, such as methyl acetate, ethyl acetate, ethylene glycol diacetate, propylene glycol diacetate, dimethyl adipate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, phenyl acetate, and tolyl acetate; hydrocarbons, such as dodecane, hexadecane, benzene, naphthalene, and biphenyl; esters of inorganic acids, such as triphenyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, silicates such as tetramethyl ortho-silicate, and tetrabutyl silicate; aromatic ethers, such as diphenyl ethers; ketnones, such as acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone. The use of acetic acid or acetic anhydride as a solvent is preferred in the present invention. The product, ethylidene diacetate and/or acetaldehyde produced according to this invention is likely to decompose in the presence of water. After the raw material and the solvent have been dried to a substantially anhydrous state, they should be introduced into the reaction system. The reaction sytem should be kept in a substantially anhydrous state. By substantially anhydrous conditions is meant that the water content of the reaction system is less than 10 mol % on the basis of total mol of the liquid components present in the system. In general, a water content of less than 5 mol % is preferable, and a water content of less than 3 mol % gives best results. When the materials contain a large amount of water, they should be dried before introducing them into the reaction system. Though commercially available synthesis gas and methyl acetate or dimethyl ether contain water, in general, the water content of these materials is within the above limits. So, commercially available synthesis gas and methyl acetate or dimethyl ether can be used as they are as raw materials of this invention. The present process may be carried out by batch, semicontinuous or continuous methods. The reaction may be effected in either of a fixed bed or a fluidized bed. In continuous process, the raw materials and the catalyst are continuously introduced into the reaction zone for the hydrocarbonylation reaction is effected; and the reaction mixture is continuously removed from the zone. The ethylidene diacetate and/or acetaldehyde is separated from the reaction mixture, for example, distillation. In another embodiment, the reaction mixture containing ethylidene diacetate and/or acetaldehyde removed from the reaction zone is introduced into another reaction zone as it is, or alternatively after part of the components other than ethylidene diacetate and/or acetaldehyde have been separated from the reaction mixture, the resulting reaction mixture may then be introduced into another reaction zone. In the reaction zone, ethylidene diacetate may be converted to acetic acid and vinyl acetate. Methyl acetate and acetic acid may be recovered from the resulting reaction mixture by distillation to leave vinyl acetate as a product. Esterification of the recovered acetic acid and methanol may be effected to form methyl acetate. The methyl acetate thus formed and unreacted methyl acetate may be introduced into the hydrocarbonylation reaction zone. As explained above, ethylidene diacetate and/or acetaldehyde is produced by using a novel solid catalyst according to the present invention. So, this invention is significant from an industrial point of view. According to the present invention, ethylidene diacetate alone, acetaldehyde alone and mixture of ethylidene diacetate and acetaldehyde can be obtained through the hydrocarbonylation reaction. The mixture can be separated to each compound by known methods. The mixture can be used for other purpose without separation to each compound. It is preferable to obtain ethylidene diacetate as a main product through the hydrocarbonylation reaction. The following examples are given as illustrative embodiments of the invention and should not be construed as limiting its scope. All parts and percents are by weight, unless otherwise specified. Example 1 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g), 2,6lutidine (0.367 g) and palladium (5 %) supported on activated carbon (1.44 g) being commercially available from Nippon Engelhard. Air in the autoclave was purged with nitrogen. The nitrogen gas was purged with mixed gas of carbon monoxide and hydrogen (ratio by volume of CO:H2 of 2:1). The temperature in the autoclave was raised to 1750C. The above mixture of CO and H2 under pressure was charged into the autoclave, until the pressure in the autoclave reached to 100 Kg/cmê Gauge. The reaction was continued for 4 hours at 1750C with stirring while maintaining the pressure in the autoclave at 100 Kg/cmê Gauge by continuously introducing the mixed gas into the autoclave. Then, the reaction mixture was cooled, and removed from the autoclave. Analysis showed that it contained 4.12 g of ethylidene diacetate, 0.0967 g of acetic anhydride and 0.88 g of acetaldehyde, and that the remaining components were mainly methyl acetate, acetic anhydride and methyl iodide. The palladium supported on activated carbon was separated from the reaction mixture. Atomic-absorption spectoscopy showed that in comparison with palladium supported on the activated carbon before using, 99.98 % of the palladium remained intact on the activated carbon. Example 2 Alumina-magnesia (alumina:magnesia = 9:1), 100 - 200 mesh, commercially available from Mizusawa Chemical KK, was washed with an NaOH solution and water. A palladium chloride solution in hydrochloric acid was added to the aluminamagnesia so treated. The mixture was stirred at 800C for a given time. The pH of the solution was adjusted to 9 - 10 by adding water and an NaOH solution thereto, and the palladium compound supported on alumina-magnesia was reduced with formalin. The pH of the solution was then adjusted to 7 by adding hydrochloric acid thereto, after which the palladium supported on alumina-magnesia was removed from the solution, and dried to obtain palladium supported alumina-magnesia. The amount of palladium held was 1 %. Into 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g), 2,6-lutidine (0.363 g) and alumina-magnesia (7.2 g) as prepared above. The reaction was effected in the same way as in Example 1. Analysis showed 0.330 g of ethylidene diacetate, 0.116 g of acetic anhydride and 0.465' g of acetaldehyde. Atomic-absorption spectroscopy showed that, in comparison with palladium supported on the activated carbon before using, 99.97 % of the palladium remained intact on the activated carbon. Example 3 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g) and palladium (10 t) supported on activated carbon (0.50 g) all being commercially available from Nippon Engelhard. Air was purged with nitrogen. Hydrogen under pressure was charged into the autoclave to 60 Kg/cmê Gauge and then carbon monoxide under pressure was charged into the autoclave to 180 Kg/cmê Gauge. The temperature in the autoclave was raised to 1750C. The reaction was continued for 4 hours with stirring at that temperature. After cooling the reaction mixture. Analysis showed that ethylidene diacetate and acetic anhydride were present therein. Example 4 Into a 100 ml autoclave were charged acetic acid (20.0 g), methyl iodide (13.0 g), 2,6-lutidine (0.368 g) and palladium (5 %) supported on activated carbon (1.43 g) as in Example 1. Air was purged with nitrogen. Dimethyl ether (20.0 g) was charged into the autoclave. After the temperature in the autoclave reached 1750C, mixed gas of CO and H2 (ratio by volume of CO:H2 of 4:1) was introduced into the autoclave until the pressure in the autoclave reached 200 Kg/cmê Gauge. The reaction was continued for 8 hours at 1750C with stirring. Analysis showed that the reaction mixture contained 0.73 g of ethylidene diacetate. Control test 1 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (8.0 g), 2,6lutidine (0.325 g) and palladium.black (0.0647 g) all being commercially available from Nippon Engelhard. Thereafter, the procedure of Example 1 was repeated. Analysis showed that no ethylidene diacetate was formed. Control test 2 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g), 2,6-lutidine (0.363 g) and rhodium (5 t) supported on activated carbon in the form of powder (1.44 g) all being commercially available from Nippon Engelhard. The reaction was continued at 1750C for 1.5 hours in the same way as in Example 1. Analysis showed that the reaction mixture contained 8.77 g of ethylidene diacetate, 3.93 g of acetic anhydride and 0.165 g of ethyl acetate. Rhodium supported on activated carbon was removed from the reaction mixture. Atomic-absorption spectroscopy showed that, in comparison with palladium supported on the activated carbon before using, 37.4 % of the palladium remained intact on the activated carbon. Control test 3 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g) and ruthenium (5 %) supported on activated carbon in the form of powder (1.44 g) all being commercially available from Nippon Engelhard. Thereafter, the procedure of Example 1 was repeated. Analysis showed that the reaction mixture contained ethylidene diacetate with acetic anhydride (0.0193 g), acetaldehyde (0.006 g) and ethyl acetate (0.131 g). Examples 5 - 17 The procedures were repeated in accordance with Example 1. The raw materials employed, the reaction conditions and the results are shown in Table. Table EMI20.1 <tb> <SEP> methyl <SEP> reaction <SEP> conditions <tb> Methyl <SEP> solvent <SEP> main <SEP> iodide <tb> No. <SEP> (s) <SEP> Y <SEP> (g) <SEP> component <SEP> (secondary <SEP> promoter <SEP> sure <SEP> (KUgr/2aa2) <SEP> (Hr) <tb> <SEP> (g) <SEP> (g) <SEP> ocpcnent) <SEP> (Kg/an2) <SEP> <tb> <SEP> (g) <SEP> <tb> <SEP> tripheny <SEP> 1 <SEP> <tb> <SEP> 5 <SEP> acetic <SEP> acid <SEP> 10% <SEP> Pd/c <SEP> 13 <SEP> phosphine <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 5 <SEP> 20 <SEP> 15 <SEP> 0.720 <SEP> 13 <SEP> 175 <SEP> 0.887 <SEP> <tb> <SEP> 0,887 <tb> <SEP> ditto <SEP> ditto <SEP> 10% <SEP> 720 <SEP> 13 <SEP> ami e <SEP> 175 <SEP> 100 <SEP> 4 <SEP> Pc/C <SEP> 13 <SEP> tri-n-butyl <tb> <SEP> 6 <SEP> 20 <SEP> 3 <SEP> amine <SEP> 175 <SEP> 100 <SEP> 4 <SEP> <tb> <SEP> 15 <SEP> 0.720 <SEP> 0.627 <tb> <SEP> ditto <SEP> 5% <SEP> Pd/C <SEP> 4-vinyl- <SEP> <tb> <SEP> 7 <SEP> 20 <SEP> 1.44 <SEP> 51,P4d4/C <SEP> 13 <SEP> pyridine <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 0.356 <SEP> <tb> <SEP> ammonium <SEP> <tb> <SEP> 8 <SEP> 20 <SEP> ditto <SEP> 5% <SEP> Pd/C <SEP> 8 <SEP> acetate <SEP> 175 <SEP> 100 <SEP> 8 <tb> <SEP> 15 <SEP> 1.44 <SEP> 0.522 <SEP> <tb> <SEP> 9 <SEP> 20 <SEP> ditto <SEP> 5% <SEP> Pd/C <SEP> 8 <SEP> 0.240 <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 1. <SEP> 29 <tb> 11 <SEP> 20 <SEP> ditto <SEP> 5% <SEP> pd/c <SEP> 8 <SEP> 0.650 <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 1.29 <tb> 12 <SEP> 20 <SEP> ditto <SEP> 5% <SEP> Pd/C <SEP> 4 <SEP> ditto <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 1.17 <tb> 13 <SEP> 20 <SEP> ditto <SEP> 5% <SEP> Pd/C <SEP> 8 <SEP> ditto <SEP> 190 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 1.29 <SEP> 0.324 <tb> 14 <SEP> 20 <SEP> ditto <SEP> 51.P2d9/C <SEP> 8 <SEP> ditto <SEP> 160 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 1.29 <SEP> 0.324 <SEP> <tb> 15 <SEP> 35 <SEP> none <SEP> 10% <SEP> Pd/C <SEP> 13 <SEP> ditto <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 0.72 <SEP> 0.363 <tb> <SEP> acetic <SEP> acid <tb> <SEP> 8.3 <SEP> + <SEP> acetic <SEP> 5 <SEP> Pd/C <SEP> 8 <SEP> ditto <SEP> <tb> 16 <SEP> 20 <SEP> anhydride <SEP> 1.29 <SEP> <SEP> 8 <SEP> 0.324 <SEP> 175 <SEP> 100 <SEP> 4 <SEP> <tb> <SEP> 6.7 <tb> 17 <SEP> 20 <SEP> acetic <SEP> acid <SEP> 15 <SEP> Pd/C <SEP> 8 <SEP> ditto <SEP> 175 <SEP> 100 <SEP> 4 <tb> <SEP> 15 <SEP> 5.16 <SEP> 1.30 <tb> Table (continued) EMI21.1 <tb> <SEP> I <SEP> product <SEP> <tb> Ex. <SEP> CO:H2 <SEP> ethylidene <SEP> acetic <SEP> acet- <SEP> ethyl <SEP> proportion <SEP> of <SEP> Pd <tb> No. <SEP> by-volume <SEP> diacetate <SEP> <SEP> anhydride <SEP> dehyde <SEP> acetate <SEP> remained <SEP> intact <tb> <SEP> by-volrrme <SEP> (g) <SEP> on <SEP> carbon <SEP> * <SEP> <tb> <SEP> (%) <SEP> <tb> <SEP> 5 <SEP> 2:1 <SEP> 2.39 <SEP> 1.65 <SEP> 0.285 <SEP> 0.054 <SEP> 99.15 <tb> <SEP> 6 <SEP> 2:1 <SEP> 0.547 <SEP> 1.02 <SEP> 0.140 <SEP> 0.023 <SEP> 97.30 <tb> <SEP> 7 <SEP> 2:1 <SEP> 2.39 <SEP> 0.068 <SEP> 1.77 <SEP> 0.059 <SEP> 99.01 <tb> <SEP> 8 <SEP> 2:1 <SEP> 0.0584 <SEP> 0.063 <SEP> 0.015 <SEP> 0.034 <SEP> 97.90 <tb> <SEP> 9 <SEP> 2:1 <SEP> 1.68 <SEP> 0.076 <SEP> 1.37 <SEP> 0.051 <SEP> 99.98 <tb> 10 <SEP> 3.8:1 <SEP> 2.41 <SEP> 0.515 <SEP> 0.732 <SEP> 0.083 <SEP> 99.98 <tb> 11 <SEP> 2:1 <SEP> 3.24 <SEP> 0.413 <SEP> 0.590 <SEP> 0.055 <SEP> 99.98 <tb> 12 <SEP> 2: :1 <SEP> 1.14 <SEP> 1.03 <SEP> 0.469 <SEP> 0.044 <SEP> 99.97 <tb> 13 <SEP> 2:1 <SEP> 2.42 <SEP> 1.44 <SEP> 0.468 <SEP> 0.071 <SEP> 99.99 <tb> 14 <SEP> 2:1 <SEP> 0.788 <SEP> 0.238 <SEP> 0.477 <SEP> 0.029 <SEP> 99.98 <tb> 15 <SEP> 2:1 <SEP> 0.553 <SEP> 5.20 <SEP> 0.198 <SEP> 0.183 <SEP> 99.99 <tb> 16 <SEP> 2:1 <SEP> 4.26 <SEP> 2.65 <SEP> 0.305 <SEP> 0.136 <SEP> 99.99 <tb> 17 <SEP> 2:1 <SEP> 4.72 <SEP> 0.226 <SEP> 3.38 <SEP> 0.146 <SEP> 99.91 <tb> * The proportion of Pd was based on Pd supported on activated carbon. Example 18 Activated carbon (9.3 g) commercially available from Takeda Chemical Industries Inc. as Shirasagi for Brewage was heated to 800C with 120 ml of water. Thereafter, palladium chloride (0.82 g) dissolved in concentrated hydrochloric acid (2 ml) and water (5 ml) was added to the suspension. A 37 % formalin solution (1 ml) was added to the suspension. A 30 % sodium hydroxide solution was added to the suspension until litmus paper showed the suspension to be weakly alkaline. The suspension was heated for 5 minutes with stirring. Palladium-supported on carbon was filtered and washed with water. Poly-4-vinylpyridine (molecular weight 97000) (2.47 g) was dissolved in methanol (50 ml). Water was added to the mixture until the total amount came to 100 ml. The palladium supported on activated carbon powder as prepared above was added to the mixture. Water and methanol were distilled under reduced pressure in a rotary evaporator. The resulting powder was vacuum dried. Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g) and palladium and poly-4-vinylpyridine supported activated carbon powder (1.61 g). The procedure of Example 1 was repeated. Analysis showed that the reaction mixture contained ethyldene diacetate (0.588 g), acetic anhydride (0.100 g) and acetaldehyde (0.809 g). Analysis showed that, in comparison with palladium supported on the activated carbon before using, 99.93 % of the palladium remained intact on the activated carbon. Example 19 Into a 100 ml autoclave were charged methyl acetate (20.0 g), acetic acid (15.0 g), methyl iodide (13.0 g), 2,6-lutidine (0.367 g) and palladium (5 %) supported activated carbon powder (1.44 g) all being commercially available from Nippon Engelhard. Thereafter, the procedure of Example 1 was repeated. Then the palladium-carbon was filtered. Analysis showed that the reaction mixture contained 4.12 g of ethylidene diacetate. Using the palladium-carbon so filtered, the above procedure was repeated. As a result 4.22 g of ethylidene diacetate was obtained. Example 20 Into an autoclave equipped with blade for agitation and filter were charged 2.88 g of palladium (5 %) supported on activated carbon powder as in Example 1, 20.0 g of methyl acetate, 13.0 g of methyl iodide, 15.0 g of acetic acid and 0.734 of 2,6-lutidine. Air in the autoclave was purged with nitrogen. The nitrogen gas was purged with mixed gas of carbon monoxide and hydrogen (ratio by volume of CO:H2 of 2:1). The temperature in the autoclave was raised to 1750C. The above mixture of CO and H2 under pressure was charged into the autoclave, until the pressure in the autoclave reached 100 kg/cmê Gauge. The reaction was continued for 3 hours at 1750C with stirring while maintaining the pressure in the autoclave at 100 kg/cm2 Gauge by continuously introducing the mixed gas into the autoclave. A solution consisting of 41.0 % of methyl acetate, 30.8 % of acetic acid, 26.7 % of methyl iodide and 1.5 % of 2,6-lutidine was purged into the autoclaved continuously at a rate of 12.2 g/hour, and at the same time the resulting reaction mixture was continuously removed through a filter from the autoclave at 13.1 g/hour. During the reaction, the mixed gas was continuously introduced into the autoclave so as to maintain the pressure in the 2 autoclave at 100 Kg/cm , and the temperature in the autoclave was maintained at 1750C. After 3 hours from starting of the reaction, the reaction mixture from'the autoclave contained 11.0 % of ethylidene diacetate. After 10 hours, the reaction mixture contained 10.7 % of ethylidene diacetate. After 10 hours, the reaction was discontinued. The palladium supported on activated carbon was removed from the autoclave. Atomicabsorption spectroscopy showed that in comparison with palladium supported on the activated carbon before using, 99.93 % of the palladium remained intact on the activated carbon.

Claims: We claim: 1. A process for producing ethylidene diacetate and/or acetaldehyde which comprises causing hydrocarbonylation reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst consisting essentially of (i) as a main component palladium supported on a porous inorganic material and (ii) as a secondary component at least one halide selected from the group consisting of iodides, bromides and mixtures thereof under substantially anhydrous conditions. 2. The process as defined in Claim 1 wherein the porous inorganic material for supporting palladium is selected from the group consisting of carbon, activated carbon, graphite, bone black, alumina, silica, silica alumina, barium sulfate, natural or synthetic zeolite, spinel, magnesia adhered alumina, thoria, titanium oxide, zirconium oxide, thorium oxide, lanthanum oxide, cerium oxide, zinc oxide, tantalum, clay, diatomaceous earth, asbestos, pumice stone, bauxite, terra abla, natural and treated terra abla, silicon carbide, zeolite molecular sieves, ceramic honeycomb, boria, cements, alundum, corundum, brick, talk, and gypsum. 3. The process as defined in Claim 2 wherein the porous inorganic material for supporting palladium is selected from the group consisting of activated carbon, carbon, graphite, bone black, alumina silica, silica alumina and barium sulfate. 4. The process as defined in Claim 1 wherein the secondary component is at least one iodide. 5. The process as defined in Claim 1 wherein the amount of the main component employed is in the range of 1 x 10 4 to 25 percent by weight on the basis of weight of a reaction solution in terms of metal. 6. The process as defined in Claim 1 wherein the amount of the secondary component employed is in the range of 1 x 10 6 to 15 mol per 1 liter of a reaction solution in terms of halogen atom. 7. The process as defined in Claim 1 wherein the reaction is effected in the presence of a promoter and the catalyst. 8. The process as defined in Claim 7 wherein the promoter is selected from the group consisting of ammonia, ammonium salts and organic compounds containing nitrogen atom or phosphorus atom. 9. The process as defined in Claim 8 wherein the promoter is selected from the group consisting of organic compounds containing trivalent phosphorus atom or trivalent nitrogen atom. 10. A process for producing ethylidene diacetate which comprises causing hydrocarbonylation reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst consisting essentially of (i) as a main component palladium supported on a porous inorganic material and (ii) as a secondary component at least one halide selected from the group consisting of iodides, bromides and mixtures thereof under substantially anhydrous conditions.

Inventors: ISSHIKI, TOMIYA, ITO, AKIRA, KIJIMA, YASUHIKO, WATANABE, TAKAYUKI
Applicants: MITSUBISHI GAS CHEMICAL COMPANY, INC.
Application year: 1981
Main classification: C07C69
IPC codes: C07C27, C07C45