JPH1053563A - Production of diarylcarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a diarylcarbonate useful as a material for carbonate production by a decarbonylation of diaryloxalate in the presence of a solid catalyst in which a phosphonium salt, and the like are carried a carrier under heating condition. SOLUTION: This production of a diarylcarbonate comprises heating a diaryloxalate in the presence of a catalyst in which tetraarylphosphonium halide, tetraarylphosphium hydrodiene dihalide or triarylphosphine is carried by a carrier, preferably further in the coexistence of an organic halogen compound having a structure in which a halogen atom is combined with a saturated carbon (C-Hal), or a halogen atom is combined with a carbonyl carbon (-CO-Hal), to carry out a decarbonyl reaction, thus obtaining diarylcarbonate at a high selection rate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a diaryl carbonate useful as a raw material for producing a polycarbonate.

[0002]

2. Description of the Related Art As a method for producing a diaryl carbonate, a method of reacting phosgene with an aromatic hydroxy compound in the presence of an alkali (Japanese Patent Laid-Open No. 62-190146).
And a method of subjecting a dialkyl carbonate and an aromatic hydroxy compound to a transesterification reaction in the presence of a catalyst (JP-B-56-42577, JP-B-1-558).
No. 8 is well known. However, the former method using phosgene is not necessarily industrially excellent because phosgene itself is a highly toxic compound and a large amount of alkali is used. In addition, the latter transesterification method, as described in many patents relating to this method, does not have a sufficient reaction rate despite the use of a highly active catalyst. There is a problem that a device is required.

As another method, a method of producing a diaryl carbonate by decarbonylating a diaryl oxalate is known, but this method has a low selectivity and a yield of the diaryl carbonate and a high reaction temperature. Therefore, there is a problem that it is very disadvantageous industrially. That is, a method of producing diphenyl carbonate (diphenyl carbonate) by boiling diphenyl oxalate (diphenyl oxalate) in a distillation flask without a catalyst (Journal of the Society of Organic Synthesis, 5, 47 (1948), 7).
In the case of 0), since the reaction temperature is high, phenol and carbon dioxide are by-produced, and the selectivity and yield of diphenyl carbonate are significantly reduced. Conversely, if the reaction temperature is low, diphenyl carbonate is hardly obtained. (See Comparative Examples 1 and 2).

Further, a method for producing a dialkyl carbonate by heating a dialkyl oxalate or the like in the liquid phase at 50 to 150 ° C. in the presence of an alcoholate catalyst (US Pat.
According to the examples described in this publication, even when diphenyl oxalate is heated in the presence of a potassium phenoxide catalyst, the main product obtained is diphenyl oxalate as a raw material. It is.

[0005]

An object of the present invention is to provide a method for easily obtaining a diaryl carbonate without using phosgene which is a highly toxic compound. That is, an object of the present invention is to provide a method for producing a diaryl carbonate from a diaryl oxalate, which method can produce a diaryl carbonate with high selectivity even at an industrially suitable low reaction temperature.

[0006]

An object of the present invention is to provide a diaryl carbonate characterized in that a diaryl oxalate is decarbonylated by heating in the presence of a solid catalyst in which a phosphonium salt or phosphine is supported on a carrier. Is achieved.

[0007]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a diaryl carbonate is produced by a decarbonylation reaction of a diaryl oxalate represented by the following formula.

[0008]

Embedded image (In the formula, Ar represents an aryl group.)

In the above decarbonylation reaction of diaryl oxalate, a solid catalyst in which a phosphonium salt or phosphine is supported on a carrier is used as a catalyst. Further, in this reaction, the reaction can be carried out in the presence of a halogen compound described later in addition to the solid catalyst. Hereinafter, the present invention will be described in detail.

As the diaryl oxalate used in the present invention, the aryl group includes (1) a phenyl group, (2) (a) an alkyl group having 1 to 12 carbon atoms such as a methyl group and an ethyl group, and (b) A alkoxy group having 1 to 12 carbon atoms such as a methoxy group and an ethoxy group, (c) a halogen atom such as a fluorine atom and a chlorine atom, or (d) a substituted phenyl group having a substituent such as a nitro group, or (3) naphthyl And the like.

The above substituted phenyl group includes various isomers. These isomers include (a) o- (or m-, p
-) A carbon number of 1 to o- (or m-, p-) such as methylphenyl group, o- (or m-, p-) ethylphenyl group;
An alkyl-substituted phenyl group having 12 alkyl groups,
(B) o- (or m-, p-) methoxyphenyl group, o
An alkoxy-substituted phenyl group having an alkoxy group having 1 to 12 carbon atoms at the o- (or m-, p-) position such as-(or m-, p-) ethoxyphenyl group, (c) o- (or m
-, P-) fluorophenyl group, o- (or m-, p
-) A halogen-substituted phenyl group having a halogen atom at the o- (or m-, p-) position such as a chlorophenyl group, (d)
o- (or m-, p-) nitrophenyl group and the like.

The phosphonium salt supported on the carrier is represented by the following general formula (I).

Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 16 carbon atoms, and 7 to 2 carbon atoms)
Represents an aralkyl group of 2, a heterocyclic group having 4 to 16 carbon atoms, or an aryloxy group having 6 to 14 carbon atoms, and X represents an atom or an atomic group capable of forming a counter ion of a phosphonium salt.
Further, these groups may be the same or different from each other, and may be cross-linked between the two groups to form a ring containing a phosphorus atom. )

The aryl, alkyl, aralkyl, heterocyclic, and aryloxy groups represented by R ¹ , R ² , R ³ , and R ⁴ include the following. That is, examples of the aryl group include an aryl group having 6 to 14 carbon atoms such as a phenyl group and a naphthyl group which may have a substituent, and the alkyl group may have a substituent. , A methyl group, an ethyl group, an n- (or i-) propyl group, an n- (or i-, sec-, tert-) butyl group and other alkyl groups having 1 to 16 carbon atoms. A benzyl group, a phenethyl group, a naphthylmethyl group or the like, which may have a substituent, having 7 to 2 carbon atoms.
2 aralkyl groups, and examples of the heterocyclic group include an optionally substituted heterocyclic group having 4 to 16 carbon atoms such as a thienyl group, a furyl group and a pyridyl group, and an aryloxy group Examples thereof include an aryloxy group having 6 to 14 carbon atoms such as a phenoxy group and a naphthoxy group which may have a substituent.

The above-mentioned aryl group, aralkyl group, heterocyclic group and aryloxy group each have an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, An amino group such as an alkoxycarbonyl group having 12 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an N, N-dialkyl-substituted amino group having 2 to 16 carbon atoms, a cyano group, a nitro group, and a halogen atom such as fluorine, chlorine and bromine. May have one or more substituents (including various isomers such as o, m, and p). The alkyl group is an alkoxy group having 1 to 15 carbon atoms, 2 carbon atoms.
At least one of various substituents such as an alkoxycarbonyl group having from 12 to 12, an amino group having 2 to 16 carbon atoms such as an N, N-dialkyl-substituted amino group, a cyano group, a nitro group, and a halogen atom such as fluorine, chlorine and bromine. You can have it.

The above phosphonium salts include, for example,
R ¹ , R ² , R ³ and R ⁴ in which all are aryl groups (tetraarylphosphonium salts), R ¹ , R ² and R 4
³ or R ⁴ is an aryl group and one is another group, or ^{two of} R ¹ , R ² , R ³ and R ⁴
One is an aryl group and two are different groups,
One of R ¹ , R ² , R ³ , and R ⁴ is an aryl group and three are other groups, and R ¹ , R ² , R ³ ,
R ⁴ is not an aryl group. Among these phosphonium salts, R ¹ , R ² , R ³ , R
All ⁴ are aryl groups, R ¹ , R ² ,
It is preferable that ^{three of} R ³ and R ⁴ are aryl groups and one of them is a heterocyclic group, and among them, R ¹ , R ² , R ³ and R
Those in which all ⁴ are aryl groups are preferred.

[0016] The pair of phosphonium salt ion X ^- as is,
Halogen ions (chlorine ions, bromine ions, iodine ions, etc.), hydrogen dihalide ions (hydrogen dichloride ion, hydrogen dibromide ion, hydrogen diiodide ion, hydrogen bromide chloride ion, etc.), and halogen acids Ion (chlorate ion, bromate ion, iodate ion, etc.), perhalate ion (perchlorate ion, perbromate ion, periodate ion, etc.), and aliphatic carboxylate ion (acetate ion, triacetate ion). Fluoroacetate ion, propionate ion, etc.), aromatic carboxylate ion (benzoate ion, α- (or β-) naphthalenecarboxylic acid ion, etc.), aromatic hydroxy ion (phenoxide ion, etc.), inorganic acid Ion (sulfate ion, hydrogen sulfate ion, phosphate ion , Hydrogen phosphate ion, borate ion,
Hydrogen borate ion, cyanate ion, thiocyanate ion, fluoroborate ion, etc.) and tetraalkyl borate ion (having an alkyl group having 1 to 10 carbon atoms such as tetramethyl borate ion, tetraethyl borate ion)
And tetraarylborate ions (having an aryl group having 6 to 14 carbon atoms such as tetraphenylborate ion and tetrakis-p-fluorophenylborate ion), and alkylsulfonic acid or alkylsulfinate ions (methyl group, ethyl group, an alkyl group having 1 to 16 carbon atoms such as an n- (or i-) propyl group, or an arylsulfonic acid or an arylsulfinate ion (phenyl group, p-
Having an aryl group such as a toluyl group and a p-nitrophenyl group).

Among these counter ions X ⁻ , halogen ions and hydrogen dihalide ions are preferred, and among them, chloride ion and hydrogen dichloride ion are particularly preferred, and chloride ion is most preferred.

Specific examples of the phosphonium salt include the following compounds. Examples of the phosphonium salt wherein all of R ¹ , R ² , R ³ and R ⁴ are aryl groups and X ⁻ is a halogen ion include tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, Tetrakis (p-chlorophenyl) phosphonium chloride, tetrakis (p-fluorophenyl) phosphonium chloride, tetrakis (p-tolyl) phosphonium chloride, p-chlorophenyltriphenylphosphonium chloride, p-chlorophenyltriphenylphosphonium bromide, p-chlorophenyltriphenyl Phosphonium iodide, p-tolyltriphenylphosphonium chloride, p-tolyltriphenylphosphonium bromide, p-tolyltriphenylphospho Honium iodide, m-trifluoromethylphenyltriphenylphosphonium chloride, p-biphenyltriphenylphosphonium chloride, m-methoxyphenyltriphenylphosphonium chloride, p-methoxyphenyltriphenylphosphonium chloride, p-
Ethoxyphenyltriphenylphosphonium chloride, p-ethoxyphenyltriphenylphosphonium bromide, p-ethoxyphenyltriphenylphosphonium iodide, p-dimethylaminophenyltriphenylphosphonium chloride, and p-ethoxycarbonylphenyltriphenylphosphonium chloride,
Examples thereof include m-cyanophenyltriphenylphosphonium chloride, 1-naphthyltriphenylphosphonium chloride, and 2-thiophenetriphenylphosphonium chloride. Among these phosphonium salts, tetraphenylphosphonium chloride is particularly preferred.

Examples of the phosphonium salt in which R ¹ , R ² , R ³ and R ⁴ are all aryl groups and X ⁻ is a hydrogendihalide ion include, for example, tetraphenylphosphonium hydrogendichloride, tetraphenylphosphonium Hydrogen dibromide, tetraphenyl phosphonium hydrogen diiodide, tetraphenyl phosphonium hydrogen bromide chloride are exemplified. Among these phosphonium salts, tetraphenylphosphonium hydrogen dichloride is particularly preferred.

Examples of the phosphonium salt in which ^{three of} R ¹ , R ² , R ³ and R ⁴ are an aryl group, one is an alkyl group and X ⁻ is a halogen ion include, for example, methyltriphenylphosphonium chloride , Methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, n
-Propyltriphenylphosphonium chloride, n-
Propyltriphenylphosphonium bromide, n-propyltriphenylphosphonium iodide, i-propyltriphenylphosphonium chloride, i-propyltriphenylphosphonium bromide, n-dodecyltriphenylphosphonium chloride, n-dodecyltriphenylphosphonium bromide, chloromethyltrioxide Phenylphosphonium chloride, methyl tris (m-
(Chlorophenyl) phosphonium chloride, methyltris (m-chlorophenyl) phosphonium bromide, ethyltris (m-chlorophenyl) phosphonium chloride, and ethyltris (m-chlorophenyl) phosphonium bromide.

Examples of the phosphonium salt in which ^{three of} R ¹ , R ² , R ³ and R ⁴ are an aryl group, one is an aralkyl group and X ⁻ is a halogen ion include, for example, benzyltriphenylphosphonium chloride , P-fluorobenzyltriphenylphosphonium chloride, p
-Fluorobenzyltriphenylphosphonium bromide, 2,4-dichlorobenzyltriphenylphosphonium chloride, 2,4-dichlorobenzyltriphenylphosphonium bromide, pn-butoxybenzyltriphenylphosphonium chloride, pn-butoxybenzyltriphenylphosphonium Bromide, 2-naphthylmethyltriphenylphosphonium chloride, 2
-Naphthylmethyltriphenylphosphonium bromide, 9-fluorenyltriphenylphosphonium chloride, 9-fluorenylphenyltriphenylphosphonium bromide and the like.

Examples of the phosphonium salt in which ^{three of} R ¹ , R ² , R ³ and R ⁴ are an aryl group, one is a heterocyclic group, and X ⁻ is a halogen ion include 2-thiophenetriene. Phenylphosphonium chloride.

Examples of the phosphonium salt in which ^{three of} R ¹ , R ² , R ³ and R ⁴ are an aryl group, one is an aryloxy group and X ⁻ is a halogen ion include:
Phenoxytriphenylphosphonium chloride is exemplified.

Examples of the phosphonium salt in which ^{two of} R ¹ , R ² , R ³ and R ⁴ are aryl groups, two are different groups, and the counter ion X ⁻ is a halogen ion include:
Examples include dimethyldiphenylphosphonium chloride, diethyldiphenylphosphonium chloride, dimethyldiphenylphosphonium bromide, and diethyldiphenylphosphonium bromide.

Examples of the phosphonium salt in which one of R ¹ , R ² , R ³ and R ⁴ is an aryl group, three are other groups and the counter ion X ⁻ is a halogen ion include:
Examples include diethylmethylphenylphosphonium chloride and diethylmethylphenylphosphonium bromide.

Examples of the phosphonium salt in which none of R ¹ , R ² , R ³ and R ⁴ is an aryl group and the counter ion X ⁻ is a halogen ion include tetra-n-butylphosphonium chloride and tetra-n- Butylphosphonium bromide.

The phosphine supported on the carrier is represented by the following general formula (II).

Embedded image (Wherein R ⁵ , R ⁶ and R ⁷ are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 16 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms) These groups may be the same or different from each other,
The two groups may be bridged to form a ring containing a phosphorus atom. The aryl group, alkyl group, aralkyl group and heterocyclic group represented by R ⁵ , R ⁶ and R ⁷ may have the same substituents as R ¹ , R ² , R ³ and R ^4. Good. )

As the phosphine, for example,
R ⁵ , R ⁶ , and R ⁷ in which all are aryl groups (triarylphosphine); and R ⁵ , R ⁶ , and R ⁷
One is an aryl group and one is another group,
One of R ⁵ , R ⁶ and R ⁷ is an aryl group;
Examples include those in which two are different groups, and those in which none of R ⁵ , R ⁶ , and R ⁷ is an aryl group. Among these phosphines, those in which all of R ⁵ , R ⁶ and R ⁷ are aryl groups are preferred.

Specific examples of phosphine include the following compounds. Examples of the compound in which all of R ⁵ , R ⁶ , and R ⁷ are aryl groups (triarylphosphine) include, for example, triphenylphosphine, tris (p-chlorophenyl) phosphine, tris (p-tolyl) phosphine, α-naphthyl ( Phenyl) -p-methoxyphenylphosphine. When two of R ⁵ , R ⁶ and R ⁷ are aryl groups and one is another group, for example, methyldiphenylphosphine and phenyl (p-methoxyphenyl) methylphosphine are exemplified. When one of R ⁵ , R ⁶ and R ⁷ is an aryl group and two are different groups, for example, dimethyl (phenyl) phosphine, ethyl (phenyl) n
-Propyl phosphine. R ⁵ , R ⁶ , R ⁷
Examples of the phosphine which is not an aryl group include benzyl (n-butyl) methylphosphine and tri-
tert-butylphosphine. Also,
Examples of those in which any one of R ⁵ , R ⁶ and R ⁷ is crosslinked include phenylbiphenylenephosphine.

Among the phosphonium salts and phosphines used in the present invention, tetraarylphosphonium halides and tetraarylphosphonium hydrogen dihalides are preferred, and tetraaryl phosphonium chloride and tetraaryl phosphonium hydrogen dichloride are particularly preferred.

As carriers on which phosphonium salts and phosphines are supported, organic carriers include ethylene, propylene, 1-butene, isobutene, cyclopentene, cyclohexene, allyl chloride, diallyl phthalate, allyl alcohol, vinyl chloride, vinyl acetate, styrene , Chlorostyrene, bromostyrene, α-methylstyrene, divinylbenzene, vinylnaphthalene, butadiene, isoprene, chloroprene, cyclopentadiene, acrylate, methacrylate, acrylonitrile, methacrylonitrile, vinylpyridine, vinylimidazole, vinylcarbazole, etc. Having a vinyl compound of the above as a monomer unit of the structure. Examples of the inorganic carrier include oxides such as silicon, aluminum, titanium, magnesium, phosphorus, and boron.

The method for supporting the phosphonium salt or phosphine on the carrier is not particularly limited as long as the phosphonium salt or phosphine can be supported so as not to elute in the reaction solution (for example, can be supported via a covalent bond). Absent. As a method of supporting phosphine on a carrier, an organic carrier is metallized by a known method, and this is then converted to P (Hal).
₃ to introduce a -P (Hal) ₂ group into the carrier, and then replace Hal with an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, or use an organic carrier having an aromatic ring as P (Hal). ₃ to react with -P (Hal)
After introducing _two groups, Hal is converted to an alkyl group, an aryl group,
Examples include a method of substituting with an aralkyl group or a heterocyclic group, and a method of bonding phosphine to an inorganic carrier via a crosslinking agent (however, Hal represents a halogen atom). Also, commercially available polymer-supported phosphines such as polymer-supported triphenylphosphine can be suitably used as the catalyst of the present invention.

As a method for supporting the phosphonium salt on the carrier, for example, a known method [Bull. Chem. So
c. Jpn. , 56, 2869 (1983); A
m. Chem. Soc. , 70, 737 (1948)].
Reacting a commercially available polymer-supported phosphine or a polymer-supported phosphine prepared as described above with an aryl halide, a halogenated heterocyclic compound, an alkyl halide or an aralkyl halide (iodo, bromo or chloro compound). Method. For example, a solid catalyst in which tetraphenylphosphonium chloride is supported on an organic carrier (polymer) is obtained by reacting a polymer-supported triphenylphosphine with a phenyl halide (iodo or bromo compound) in the absence or presence of a catalyst. It is prepared by a method of ion-exchanging tetraphenylphosphonium iodide or tetraphenylphosphonium bromide to tetraphenylphosphonium chloride.

In addition, when the carrier has a halophenyl group, a halomethylphenyl group or a halomethyl group, a method of reacting it with various phosphines in the absence or presence of a catalyst can be mentioned. If not, a method of introducing a halophenyl group, a halomethylphenyl group or a halomethyl group into the carrier by halogenation or halomethylation, and reacting it with various phosphines may be mentioned. When these groups cannot be directly introduced into a carrier (for example, with an inorganic carrier), these groups are introduced via a crosslinking agent.

The solid catalyst in which a phosphonium salt having a counter ion other than a halogen ion is supported on a carrier is the solid catalyst in which phosphonium chloride is supported on a carrier, which is obtained as described above, has a corresponding counter ion. It is prepared by reacting (ion exchange) with an alkali metal salt (sodium salt, potassium salt, etc.) or ammonium salt.

In the present invention, the decarbonylation reaction may be performed in the presence of a halogen compound. In particular, when a solid catalyst in which phosphine is supported on a carrier or a solid catalyst in which a phosphonium salt other than halide and hydrogendihalide is supported on a carrier is used, it is preferable to allow a halogen compound to coexist.

The halogen compounds used in the present invention include the following organic halogen compounds. Among these halogen compounds, a chlorine compound or a bromine compound is preferable, and a chlorine compound is particularly preferable.

As the organic halogen compound, for example, a structure in which a halogen atom is bonded to a saturated carbon (C-Ha)
l) or an organic halogen compound having a structure in which a halogen atom is bonded to a carbonyl carbon (-CO-Hal) is preferably used. Here, Hal represents a halogen atom such as a chlorine atom and a bromine atom. These structures, for example,
It is represented as general formulas (a) and (b).

[0039]

Embedded image (In the formula, Hal represents a halogen atom such as a chlorine atom or a bromine atom, and n represents an integer of 1 to 4.)

As such an organic halogen compound,
For example, the following compounds are specifically mentioned. Examples of the organic halogen compound having a structure in which a halogen atom is bonded to a saturated carbon as represented by the general formula (a) include chloroform, carbon tetrachloride, 1,2-dichloroethane, butyl chloride, dodecyl chloride and the like. Alkyl halides, aralkyl halides such as benzyl chloride, benzotrichloride, triphenylmethyl chloride, α-bromo-o-xylene, and halogen-substituted aliphatics such as β-chloropropionitrile and γ-chlorobutyronitrile Nitriles,
Halogen-substituted aliphatic carboxylic acids such as chloroacetic acid, bromoacetic acid and chloropropionic acid.

Examples of the organic halogen compound having a structure in which a halogen atom is bonded to a carbonyl carbon as represented by the general formula (b) include acetyl chloride, oxalyl chloride, propionyl chloride, stearoyl chloride, benzoyl chloride, Acid halides such as -naphthalenecarboxylic acid chloride, 2-thiophenecarboxylic acid chloride,
Examples include aryl halogenoglyoxylates such as phenyl chloroglyoxylate, and aryl halogenoformates such as phenyl chloroformate.

In the decarbonylation reaction of diaryl oxalate, the reactor is charged with diaryl oxalate and the above-mentioned solid catalyst and, if necessary, with the above-mentioned halogen compound, usually at 100 to 450 ° C., preferably 160 to 4 ° C.
50 ° C, more preferably 180 to 400 ° C, especially 18
By heating at 0 to 350 ° C., the reaction is performed in a batch or continuous liquid phase reaction. At this time, diaryl carbonate is generated from diaryl oxalate according to the above reaction formula, and carbon monoxide is generated. The reaction pressure is increased when the reaction temperature exceeds the boiling point of the diaryl oxalate, but is usually normal pressure or reduced pressure.

The above-mentioned solid catalyst is used in an amount of usually 0.001 to 50 mol%, preferably 0.01 to 20 mol%, based on phosphonium salt or phosphine, based on diaryl oxalate. The above solid catalysts may be used alone or in combination of two or more. The halogen compound is added to the reaction system such that the molar ratio (halogen compound / phosphonium salt or phosphine) to the phosphonium salt or phosphine is usually 0.01 to 300, preferably 0.1 to 100. The halogen compound may be used alone or in combination.

No solvent is required for the reaction, but diphenyl ether, sulfolane, N-methylpyrrolidone, dimethylimidazolidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H ) -Pyrimidinone and the like. The material of the reactor is not particularly limited, and for example, a reactor made of glass or stainless steel (SUS) can be used. After the reaction, the produced diaryl carbonate is separated and purified by distillation or the like.

[0045]

Next, the present invention will be described specifically with reference to examples and comparative examples. The conversion of diaryl oxalate (the ratio of consumed diaryl oxalate to the charged diaryl oxalate), the selectivity of the diaryl carbonate (the ratio of the generated diaryl carbonate to the consumed diaryl oxalate) and the yield (the charged diaryl oxalate) The ratio of the formed diaryl carbonate to oxalate) was determined on a molar basis (mol%).

Reference Example 1 [Synthesis of polymer-supported tetraphenylphosphonium chloride] Polymer-supported triphenylphosphine [Tri
phenylphosphine, polymer-s
upported (Polymer is polys
tilen cross-linked with
2% DVB, ３3 mmol P / g resin. 2.00 g and bromobenzene 1.06 g
Was placed in 3 ml of benzonitrile and anhydrous nickel bromide was added.
66 g was added and the mixture was refluxed under normal pressure for 15 hours. After the reaction, the polymer was collected by filtration and washed sequentially with methylene chloride (5 ml × 2 times), acetone (5 ml × 3 times), and water (5 ml × 2 times). The obtained polymer was packed in a column, and 36% by weight
After flowing 100 ml of hydrochloric acid through the column over 7 hours, the polymer was dried under reduced pressure (50 ° C., 100 ° C., 185 ° C. for 1 hour each) to obtain 2.25 g of polymer-supported tetraphenylphosphonium chloride. From the increase in weight, 37% of the triphenylphosphine was a phosphonium salt.

Example 1 A 50 ml glass flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 5.0 g of diphenyloxalate, and 0.093 g of the polymer-supported tetraphenylphosphonium chloride obtained in Reference Example as a catalyst was used. (0.5 mol% of tetraphenylphosphonium chloride with respect to diphenyl oxalate), and 10 μl of oxalyl chloride as a halide. The mixture was heated to 260 ° C., and carbon monoxide generated under normal pressure was removed from the system. While removing, decarbonylation reaction was performed at this temperature for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of diphenyl oxalate was 77.0%, and the selectivity of diphenyl carbonate was 98.0% (yield: 75.5%).

Example 2 In Example 1, the catalyst was changed to 0.0358 g of polymer-supported triphenylphosphine (0.5 mol% as triphenylphosphine based on diphenyloxalate), and the amount of oxalyl chloride added was changed to 15 μl. Others
The reaction and analysis were performed in the same manner as in Example 1. As a result, the conversion of diphenyl oxalate was 36.0%, and the selectivity for diphenyl carbonate was 94.0% (yield:
33.8%).

Comparative Example 1 In Example 1, 3.97 g of diphenyl oxalate was used.
And a decarbonylation reaction was carried out in the same manner as in Example 1 except that no catalyst was added. As a result, the conversion of diphenyl oxalate was 0%, and the production of diphenyl carbonate was not recognized (yield: 0%).

Comparative Example 2 A decarbonylation reaction was carried out in the same manner as in Example 1 except that 5.0 g of diphenyloxalate was used, the reaction temperature was changed to 330 ° C., and no catalyst was added. As a result, the conversion of diphenyl oxalate is 1
At 0.8%, the selectivity for diphenyl carbonate is 37.
It was 7% (yield: 4.1%).

Comparative Example 3 5.0 g of diphenyl oxalate and 5.0 g of tetrahydrofuran were placed in a 90 ml stainless steel closed reactor equipped with a thermometer and a stirrer, and 0.5 g of potassium phenolate was added as a catalyst. The temperature was raised to 100 ° C., and a decarbonylation reaction was performed at this temperature for 3 hours. As a result, the conversion of diphenyl oxalate was 0%, and the production of diphenyl carbonate was not recognized (yield: 0%).
Table 1 shows the results of Examples and Comparative Examples.

[0052]

[Table 1]

[0053]

According to the present invention, diaryl carbonate useful as a raw material for polycarbonate can be produced from diaryl oxalate with high selectivity. Also,
By using the excellent catalyst of the present invention, diaryl carbonate can be produced with high selectivity at a low reaction temperature that is industrially suitable, as compared with a known method of boiling a diaryl oxalate and performing a decarbonylation reaction, Separation of the catalyst and product after the reaction is also very easy. Furthermore, since phosgene, which is a highly toxic compound, is not used in the present invention, diaryl carbonate can be produced safely and easily. The present invention is the first method capable of industrially producing diaryl carbonate from diaryl oxalate, and is very useful.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshihiro Shimakawa 5 Ube Kogushi 1978 Kobe, Ube City, Yamaguchi Prefecture

Claims (5)

[Claims] 1. A process for producing a diaryl carbonate, comprising subjecting a diaryl oxalate to a decarbonylation reaction by heating in the presence of a solid catalyst in which a phosphonium salt or phosphine is supported on a carrier. 2. The method for producing a diaryl carbonate according to claim 1, wherein the solid catalyst is a solid catalyst in which a tetraarylphosphonium salt or a triarylphosphine is supported on a carrier. 3. The process for producing a diaryl carbonate according to claim 1, wherein the solid catalyst is a solid catalyst in which a tetraarylphosphonium halide or a tetraarylphosphonium hydrogendihalide is supported on a carrier. 4. An organic halogen compound having a structure in which a halogen atom is bonded to a saturated carbon (C-Hal) or a structure in which a halogen atom is bonded to a carbonyl carbon (-CO-Hal) is present in the presence of a compound. 2. The method for producing a diaryl carbonate according to claim 1, wherein the carbonyl reaction is carried out (Hal represents a halogen atom). 5. The method for producing a diaryl carbonate according to claim 4, wherein the halogen atom is a chlorine atom.