JP2748242B2 - Production method of aromatic carbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an aromatic carbonate.
Regarding the production method, more specifically, aromatic hydroxylation
Reacting the compound with carbon monoxide and molecular oxygen
Accordingly, the present invention relates to a method for producing an aromatic carbonate. [0002] 2. Description of the Related Art Aromatic carbonates have conventionally been used in dechlorinated water.
Aromatic compounds and phosgene in the presence of
Or from the reaction with aryl chloroformate
ing. Aryl chloroformate is an aromatic hydroxy
Because it is manufactured from sil compounds and phosgene,
Also requires phosgene. However, Hoss
Gen is highly toxic and the equipment is highly corrosive
Of aromatic carbonate without phosgene
There is a need for a method, and several attempts have been made.
Is coming. As a preferred method among them, aromatic hydride
Roxyl compound is oxidized in the presence of carbon monoxide and an oxidizing agent.
A method for the selective carbonylation has been proposed. [0003] In Japanese Patent Publication No. 56-38143, a base is disclosed.
Phenols in the presence of carbon monoxide and palladium
It is proposed to react with
Is not a catalytic reaction, but a stoichiometric amount of palladium compound
is necessary. How to make palladium compound act catalytically
As the law, JP-B-56-38144 and JP-B
JP-A-56-38145 has been proposed. these
The method involves removing phenols in the presence of a palladium catalyst.
Aromatic by reacting with carbon oxide and oxygen
This is a method for producing carbonate, but palladium
In order to work as a medium, the zero valence reduced by the reaction
For conversion of palladium to divalent palladium
As a doxing agent, IIIA, IVA, V in the periodic table
Group A, VIA, IB, IIB, IVB and VII golds
It is essential to use compounds containing the genus
In addition to this, it is essential that a base coexist. Tokiko
In JP-A-56-38145, this catalytic reaction is improved.
As a method, desiccants such as molecular sieves
It has been proposed to add
It is messed up. In addition to these three publications,
A similar application from the same applicant (Japanese Patent Application Laid-Open No. 53-6784)
7, JP-A-54-135743, JP-A-5-135743
JP-A-4-135744, JP-A-55-102439
Gazette). [0004] [Problems to be solved by the invention]
In any of these methods, diisopropyl monoethyl
Luamine and 2,2,6,6, N-pentamethylpiperidi
It is necessary to use large amounts of expensive and complex bases such as
Manganese, copper, cobalt, and vanadium
Use of redox agents containing metal ions such as
The reaction system is very complicated and is a product
If it is difficult to separate and purify aromatic carbonate
In addition to separation and recovery of complex catalyst components
With great difficulty. [0005] [Means for Solving the Problems] The present inventors have proposed redo
Compounds containing metal ions that perform toxic
A simple catalyst system that does not use complex bases
Keen to develop a method to obtain succinate with high selectivity
As a result of research, the present invention has been completed. That is, the present invention provides: a) selected from palladium and palladium compounds
At least one, b) Alkali metal iodide, alkaline earth metal iodide
Selected from uranium and onium iodide compounds
An aromatic hydroxyl in the presence of at least one of the compounds
Reacting compounds with carbon monoxide and molecular oxygen
A method for producing an aromatic carbonate, characterized in that:
Things. As described above, a major feature of the present invention is that
At least one selected from the group consisting of indium and palladium compounds
And one kind, alkali metal iodide, alkaline earth metal
Selected from iodide and onium iodide compounds
Simple system in combination with at least one iodine compound
From aromatic hydroxyl compounds to aromatic carbonates
Is obtained with a high selectivity. These facts are now
It was a truly amazing thing that was never known until now
Could not be expected from the above series of prior art
That is. That is, in these prior arts,
Same as the present invention in using palladium as the main catalyst
Is the co-catalyst necessary for the catalytic progress of the reaction.
Contains ions of heavy metals such as copper, manganese, and cobalt.
It is essential to use a compound as a redox agent
You. In addition, bases are also essential and are found in the examples.
Typical catalyst systems are palladium bromide and bis (benzoyi
Oxime) manganese (II) and 2,2,6,6
A combination of N-pentamethylpiperidine
You. [0009] In such a system, the divalent paraziu
Is involved in the reaction and is reduced as the reaction progresses.
To zero-valent palladium, which is divalent manganese ion
Is reoxidized by palladium and returned to divalent palladium.
Sometimes divalent manganese ions are reduced to zero-valent man
It becomes cancer metal or monovalent manganese ion,
These low oxidation manganese are reoxidized by oxygen
To be manganese in a highly oxidized state with two or more valences.
The so-called Wacker reaction type catalytic cycle is
Aromatic carbonate which is a product is manufactured
Conceivable. Thus, in the prior art methods, the reaction system
In the heavy metal ions having a redox effect,
Palladium shown to be essential as reoxidant
I have. Examples of such heavy metals include III in the periodic table.
A, IVA, VA, VIA, IB, IIB, VB, VI
Compounds of metals of groups B, VIIB and VIIIB include
Specifically, copper, iron, manganese, cobalt,
Mercury, lead, cerium, uranium, bismuth, chromium, etc.
Are listed, among which copper, manganese,
Cobalt is only described in the examples. Also, in the prior art method, the
The presence of a large excess of base relative to chromium?
Bases play an important role in this reaction
It is thought that aromatic carbon
It seems that the conversion reaction hardly proceeds. On the other hand, the method of the present invention comprises
And alkali metal iodide, alkaline earth metal iodide
Selected from uranium and onium iodide compounds
Compounds are used, these compounds, the usual
Under the reaction conditions, the cation moiety cannot perform a redox reaction
Or no metal components
Things. [0013] Such a combination of palladium and iodide
Aromatic hydroxylation also occurs in catalyst systems consisting of
By oxidative carbonylation of the compound with carbon monoxide.
Thus, the present inventors have found that aromatic carbonates are produced.
Led to the present invention. The palladium used in the present invention or
Is a palladium compound and contains palladium as a component
Anything may be used, for example,
Pd black; Pd-C, Pd-Al_TwoO_Three, Pd-Si
O_Two, Pd-TiO_Two, Pd-ZrO_Two, Pd-BaS
O_Four, Pd-CaCO_Three, Pd-asbestos, Pd-ze
Supported parasites such as olites and Pd-molecular sieves
Catalysts: Pd-Pb, Pd-Se, Pd-Te, P
d-Hg, Pd-Tl, Pd-P, Pd-Cu, Pd-
Ag, Pd-Fe, Pd-Co, Pd-Ni, Pd-R
h or other alloys or intermetallic compounds;
A gold or intermetallic compound supported on a carrier as described above
; PdCl_Two, PdBr_Two, PdI_Two, Pd (N
O_Three)_Two, PdSO_FourInorganic salts such as Pd (OCOC
H_Three)_TwoAnd organic acid salts such as palladium oxalate; Pd
(CN)_TwoPdO; PdS; M_Two[PdX '_Four], M
_Two[PdX '₆Palladium salts represented by the formula (M is
X 'represents an alkali metal or ammonium ion
Represents a nitro group or a cyano group or a halogen);
[Pd (NH_Three)_FourX '_Two, [Pd (en)_TwoX '
_TwoAmmine complexes of palladium (X ′ is as defined above)
Has the same meaning, en represents ethylenediamine); P
dCl_Two(PhCN)_Two, PdCl_Two(PR_Three)_Two, P
d (CO) (PR_Three)_Three, Pd (PPh_Three)_Four, PdC
l (R) (PPh_Three)_Two, Pd (C_TwoH_Four) (PP
h_Three)_Two, Pd (C_ThreeH_Five)_TwoComplex compounds such as
Metal compounds (Ph represents phenyl, R represents an organic group
Pd (acac)_TwoChelating ligands such as
Complex compounds (acac is acetylacetone)
Are preferably used. These palladium catalysts can be used alone.
Can be used, or a mixture of two or more
You can also. The alkali gold used in the present invention
As the genus iodide and the alkaline earth metal iodide,
For example, lithium, sodium, potassium, rubidium
, Cesium, beryllium, magnesium, calcium
, Strontium, barium, radium, etc.
Substances, specifically, lithium iodide, sodium iodide
, Potassium iodide, rubidium iodide, cesium iodide
, Beryllium iodide, magnesium iodide, iodide
Calcium, strontium iodide, barium iodide,
Compounds of a single metal such as radium iodide with iodine;
Potassium iodine chloride, rubidium iodine chloride, iodine chloride
Cesium iodine, Cesium iodine bromide, Potassium iodine bromide
, Cesium iodide bromide, rubidium iodine bromide, etc.
Of polyalkali metal compounds containing iodine
Which is preferably used. The onium iodide used in the present invention
A compound is a compound that contains an element with a lone pair of electrons.
The lone pair of electrons or protons
Elements in a lone pair form a common element
It has become a cation by increasing its valence by one.
Having an iodine anion as a counter ion.
You. As such an onium iodide compound
Is an ammonium iodide compound ([R¹R^TwoR^ThreeR^FourN
⁺] I^-), A phosphonium iodide compound ([R¹R^TwoR
^ThreeR^FourP⁺] I^-), An arsonium iodide compound ([R
¹R^TwoR^ThreeR^FourAs⁺] I^-), Stibonium iodide
Compound ([R¹R^TwoR^ThreeR^FourSb⁺] I^-), Iodine oki
Sonium compounds ([R¹R^TwoR^ThreeO⁺] I^-), Iodide
Sulfonium compound ([R¹R^TwoR^ThreeS⁺] I^-), Yo
Oxysulfonium compounds ([R¹R^TwoR^ThreeS
⁺(O)] I^-), Selenonium iodide compound ([R¹
R^TwoR^ThreeSe⁺] I^-), Telluronium iodide compound
([R¹R^TwoR^ThreeTe⁺] I^-), Stannoid iodide
Compound ([R¹R^TwoR^ThreeSn⁺] I^-), Iodide
Donium compound ([R¹R^TwoI⁺] I^-)
It is. Where R¹, R^Two, R^Three, R^FourIs hydrogen or fat
Selected from an aliphatic group, an aromatic group, an alicyclic group, and an araliphatic group.
And each may be the same, or
In some cases, a ring containing an element having a lone pair of electrons
May be included. Of course, such an oni
A compound having two or more
Or even on the main or side chain
It may be a polymer containing a polymer group. Such an onium iodide compound is
Hydrogen or organic iodine compounds and the corresponding amino compounds
(Including ammonia) or nitrogen-containing compounds, phosphites
Compounds, arsine compounds, stibine compounds, oxylation
Compound, sulfide compound, sulfoxide compound,
Easily by reaction with sulfide compounds, telluride compounds, etc.
That are produced outside the reaction system.
May be used, or they may be generated in the reaction system.
Good. Of course, it may be manufactured by other methods
It is produced in the reaction system by another method.
You may. Of these, preferred are ammonium iodide
Compound, phosphonium iodide compound, iodide
Sonium compounds and sulfonium iodide compounds
Particularly preferred are ammonium iodide compounds and
It is a phosphonium iodide compound. The ammonium iodide compounds have the corresponding nitrogen-containing properties.
Reaction of nitrogen compounds with hydrogen iodide, nitrogen-containing compounds and iodide
Organic iodine compounds such as alkyl or aryl iodides
It can be easily obtained by reacting with
Examples of the nitrogen-containing compound such as ammonia,
Amines such as primary, secondary and tertiary amines
, Hydroxylamines, hydrazines, hydrazones
, Amino acids, oximes, imide esters, amino acids
And various nitrogen-containing heterocyclic compounds. Like
As the hydrogen iodide salt of a new nitrogen-containing compound, ammonia
Ammonium iodide, which is a salt with aniline, diphenyi
Salts of aromatic amines such as ruamine and triphenylamine
, Methylamine, ethylamine, hexylamine,
Octylamine, dimethylamine, trimethylamine, di
Ethylamine, triethylamine, dibutylamine,
Lipropylamine, methylethylamine, dimethylethyl
Ruamine, dibutylmethylamine, tributylamine,
Aliphatic such as ethylenediamine and hexamethylenediamine
Amine salts; cyclopropylamine, cyclohexyl
Alicyclic amines such as amines and N-methylcyclohexylamine;
Min's salts; benzylamine, N-methylbenzylamido
, N, N-diethylbenzylamine, dibenzylamido
Salts of araliphatic amines such as pyridine, piperidine, piperazine
, Morpholine, pyridine, quinoline, hexamethylene
Tetramine, oxazole, thiazole, imidazo
, Triazole, henzotriazole, diazavisic
Salts of nitrogen-containing heterocyclic compounds such as loundecene; dimethyl
Amide salts such as luacetamide and N-methylpyrrolidone
And the like are used. Also, a quaternary ammonium iodide compound
Are tetramethylammonium iodide,
Laethylammonium, tetrabutylammonium iodide
Trimethylethylammonium iodide
Quaternary aliphatic iodides such as tildibutylammonium
Ammonium compounds; N, N, N-trimethyl iodide
Quaternary amines such as cyclohexyl ammonium
Ammonium compounds; tetrabenzylammonium iodide
And aromatic fats such as trimethylbenzylammonium iodide
Aliphatic quaternary ammonium iodides; N-iodide,
N, N-trimethylphenylammonium, N, N iodide
Aromatic, such as N, N-triethylphenylammonium
Quaternary ammonium iodides; N-methyl iodide
Pyridium, N-ethylquinolinium iodide, iodide
N, N-dimethylpiperidinium, N, N-dimethyl iodide
Heterocyclic quaternary iodides such as thilimidazolium
Nitride compounds and the like are preferably used. In addition,
A polymer containing a monium group in the main chain or side chain
For example, those having the following main structural units
It is preferably used. [0022] Embedded image[0023] Embedded imageWhere R¹, R^Two, R^ThreeHas the same meaning as above,
R^FiveRepresents a divalent organic group. As the phosphonium iodide compound, for example,
For example, tetramethylphosphonium iodide, tetraethyl iodide
Tylphosphonium, tetrabutylphosphonium iodide, etc.
Symmetrical Tetraalkylphosphonium Iodides
And ethyltrimethylphosphonium iodide, die iodide
Asymmetric tetraiodide such as tyldimethylphosphonium
Alkyl phosphonium compounds; tetraphenyl iodide
Phosphonium, tetra (p-tolyl) phosphonium iodide
Symmetric tetraarylphosphonium iodide compounds
: (Α-naphthyl) triphenylphosphonium iodide
Unsymmetrical Tetraarylphosphonium Iodide Compounds
Substances; methyltriphenylphosphonium iodide, iodide
Alkylaryl such as phenyltrimethylphosphonium
Mixed forms of phosphonium iodide compounds;
Tetraaralkylphospho iodide such as benzylphosphonium
Nium compounds and the like are preferably used. As the arsonium iodide compound, for example,
For example, tetramethylarsonium iodide, tetraethyl iodide
Symmetrical tetraalkyl iodide such as tylarsonium
Rusonium compounds; methyltriethylarsoni iodide
Asymmetric, such as chromium, dimethyldiethylarsonium iodide
Tetraalkylarsonium iodides in the form of iodine; iodine
Tetrate iodide such as tetraphenylarsonium iodide
Laarylarsonium compounds; methyltrif iodide
Enyl arsonium, ethyl triphenyl arso iodide
And phenyltrimethylarsonium iodide
Alkyl Arylium Iodide Compounds
Are preferably used. Also, as a sulfonium iodide compound
Is, for example, trimethylsulfonium iodide,
Triethylsulfonium, methyldiethylsulfonium iodide
Symmetric or asymmetric alkylsulfonides such as um
Compounds such as triphenylsulfonium iodide
Arylsulfonium iodide compound; dimethyl iodide
Nylsulfonium, methyldiphenylsulfonium iodide
Alkylarylsulfonium compounds such as
Bicyclo- (2,2,1) -heptane-1-sulfur iodide
Cyclic sulfonium such as honium and thiopyrylium iodide
Compounds and the like are preferably used. In addition, phosphoiodide
Group or sulfonium iodide group
Polymers contained in the main chain or side chain are also suitably used.
However, such polymers include, for example,
Those having a main structural unit are exemplified. [0027] Embedded image (Where R¹, R^Two, R^ThreeHas the same meaning as above) In the method of the present invention, these iodine compounds are one kind.
Can be used alone or as a mixture of two or more
It can also be used. The aromatic hydroxy used in the present invention
As a sil compound, a hydroxyl group is directly attached to an aromatic group.
No matter what is connected,
Good. For example, phenol; clay sol (each isomer),
Xylenol (each isomer), trimethylphenol (each
Isomers), tetramethylphenol (each isomer), ethyl
Phenol (each isomer), propyl phenol (each
Alkylphenols such as
Knol (each isomer), ethoxyphenol (each isomer)
Various alkoxyphenols such as chlorophenol
(Each isomer), bromophenol (each isomer), dichloro
Phenol (each isomer), dibromophenol, etc.
Halogenated phenols; methylchlorophenol (each
Isomers), ethyl chlorophenol (each isomer), methyl
Rubromophenol (each isomer), ethyl bromopheno
Alkyl and halogen-substituted phenols such as phenols;
formula [0029] Embedded image [Wherein, A is a mere bond, or -O-, -S-, -S
O_Two-, -CO-, -CH_Two-, -C (R_Two)-(R is
Represents a divalent group such as a lower alkyl group) and an aromatic ring
Represents a halogen, an alkyl group, an alkoxy group, an ester
Substituted by a substituent such as a group, amino group, cyano group, etc.
May be. ] Various substituted phenols represented by
Toll (each isomer) and various substituted naphthols;
Roxypyridine (each isomer), hydroxycoumarin (each
Isomers), hydroxyquinoline (each isomer)
B) Aromatic hydroxyl compound; hydroquinone, resor
Syn, catechol and their alkyl substitution or
Aromatic dihydrides such as halogen-substituted dihydroxy compounds
Roxy compounds; Formula [0031] Embedded image Wherein A is as described above, or the aromatic ring is halo
Gen, alkyl group, alkoxy group, ester group, amide
Substituted by a substituent such as a group or a cyano group
It may be. ) An aromatic dihydroxy compound represented by the formula:
And polyvalent phenols such as pyrogallol and phloroglucin
And the like are used. In addition, the aromatic hydroxyl group
Group contains the main or side chain of the polymer
May be used. From aromatic dihydroxy compounds
Gives an aromatic polycarbonate. Such fragrance
The hydroxyl group may be only one kind or two or more kinds.
They can be used in combination. Preferred among these are aromatic hydroxyls
The compound is an aromatic monohydroxy compound,
And various substituted phenols are preferred. Especially preferred
Ino uses diphenol carbonate with phenol.
This is the case of manufacturing. Diphenyl carbonate is organic
React with dihydroxy compound to produce polycarbonate
It is also important as a raw material for
As a raw material to produce the corresponding isocyanates
Is an industrially important compound that can also be used
It is. The molecular oxygen used in the present invention is a pure acid
Containing air or oxygen, and may be air,
Air or other gases that do not interfere with the reaction to pure oxygen, even if
Inert gas such as nitrogen, argon, helium, carbon dioxide
It may be diluted with a gas. In some cases,
Hydrogen, carbon monoxide, hydrocarbons, halogenated hydrocarbons
It may contain a gas such as hydrogen. In addition, carbon monoxide is also highly pure carbon monoxide.
Or nitrogen, argon, helium, carbon dioxide, charcoal
Adversely affect the reaction of hydrogen chloride, halogenated hydrocarbons, etc.
It may be diluted with another gas that is not used. Monoacid
Carbonized carbon is 0.1 to 300 kg / cm in partial pressure^Two, Preferably
Is 1 to 200 kg / cm^TwoUsed in the range. The reaction of the present invention is carried out by an aromatic monohydroxy compound.
For example, in the case of a product, the following reaction formula (I)
Is represented by Embedded image In carrying out the method of the present invention, aromatic arsenic is used.
If the droxyl compound also serves as a solvent, no other reaction
There is no need to use a solvent, and in this case
Is one of the preferred embodiments, but in some cases
It is possible to use a solvent that does not adversely affect the reaction
Wear. Such solvents include, for example, benzene,
Aromatic hydrocarbons such as ruene, xylene and mesitylene
Chlorobenzene, dichlorobenzene, trichlorobe
Benzene, fluorobenzene, chlorotoluene, chlorna
Halogenated aromatic coal such as phthalene and bromnaphthalene
Hydrogens: chlorohexane, chlorocyclohexane,
Lichlorotrifluoroethane, methylene chloride, chloropho
Halogenated aliphatic hydrocarbons such as lum and carbon tetrachloride
Or halogenated alicyclic hydrocarbons; acetonitrile,
Nitriles such as zononitrile; sulfolane, methyls
Sulfonic acids such as ruphorane and dimethyl sulfolane;
Trahydrofuran, 1,4-dioxane, 1,2-dimethyl
Ethers such as toxicethane and anisole; aceto
, Methyl ethyl ketone, acetophenone and other ketones
Esters such as ethyl acetate and ethyl benzoate;
N, N-dimethylformamide, N, N-dimethylacetate
Toamide, N-methylpyrrolidone, hexamethylphospho
And amides such as luamide. The amount of the catalyst used in the present invention is
But the palladium-containing component may be an aromatic hydroxy
0.0001 to 50 mol%, preferably
More preferably, it is in the range of 0.01 to 10 mol%. Also, Yo
Iodine compounds are usually used for the amount of palladium used.
0.01 to 1000 times mol, preferably 0.1 to 100 times
The range is twice as high. In the method of the present invention, the reaction is usually carried out at 30 to 3
Carried out at a temperature in the range of 00 ° C., preferably 80 to 250 ° C.
You. The reaction pressure is 0.1 to 500 kg / cm^Two, Good
Preferably 1-250 kg / cm^TwoThe range of the reaction
The time depends on the reaction system, catalyst system and other reaction conditions
However, it is usually in the range of several minutes to several hours. In addition, the present invention
The reaction can be carried out batchwise, or the reaction components can be supplied continuously.
Implemented in a continuous system where the reaction solution is continuously extracted while feeding
it can. [0040] Next, the present invention will be described in more detail by way of examples.
Although described, the invention is not limited to these examples.
Not. (Example 1) A 200 ml stirring type autoclave was
28.2 g (0.3 mol) of phenol, Pd (acac)
_Two0.612 g (2 mmol), tetrabutyl iodide
1.85 g (5 mmol) of ammonium
After replacing with carbon oxide, carbon monoxide is reduced to 70 kg / c
m^TwoAnd then 30 kg / cm of air^TwoAnd pressurize
100kg / cm^TwoI made it. 100 to 10 with stirring
After reacting at 5 ° C for 7 hours, the mixture was cooled, released, and the contents were filtered.
And the filter cake is washed with tetrahydrofuran.
Gas chromatography and high-performance liquid chromatography
As a result of the analysis, diphenyl carbonate was 1.5%.
g (7 mmol) was found to be formed. this
Corresponds to a yield of 4.6% based on the phenol used,
The selectivity was 89%. Example 2 Pd (acac)_TwoInstead of
Except for using 0.212 g (2 mmol) of Pd-black,
The reaction was carried out in the same manner as in Example 1, and as a result,
Nyl carbonate is 3.9% yield based on phenol.
It was found that it was formed at a selectivity of 90%. Example 3 Instead of Tetrabutylammonium Iodide
Use 0.75 g (5 mmol) of sodium iodide
The reaction was conducted in the same manner as in Example 1 except that
Phenyl carbonate yield 4.1 based on phenol
% And a selectivity of 85%. Example 4 Pd (acac)_TwoInstead of
(PhCN)_TwoPdCl_TwoExcept using (2 mmol)
Was reacted in the same manner as in Example 1, and as a result
Phenyl carbonate yield of 3.7% based on phenol,
It turned out that it formed with selectivity 88%. Example 5 Instead of Tetrabutylammonium Iodide
Except for using 1.32 g (5 mmol) of barium iodide
Was reacted in the same manner as in Example 1, and as a result
3.5% yield of carbonate based on phenol, selected
It turned out that it formed at a rate of 84%. Example 6 (PhCN)_TwoPdCl
_Two0.5 g (1.3 mmol), cesium iodide 1.3
g (5 mmol) and the same method as in Example 1.
Phenol oxidative carbonylation reaction
Of course, diphenyl carbonate is 3.1 based on phenol.
% And selectivity of 82%. (Example 7) Parachlorophenol instead of phenol
Example 1 except that 38.6 g (0.3 mmol) was used.
The reaction was carried out in the same manner as
Nyl) carbonate yield based on parachlorophenol
It turns out that it forms with 3.3% and selectivity 78%.
Was. Example 8 Instead of phenol, paracrete
Except that 32.4 g (0.3 mmol) of sol was used.
As a result of carrying out the reaction in the same manner as in Example 1, di-para
Yield of 3.6% based on paracresol,
It turned out that it formed with a selectivity of 82%. (Examples 9 to 14) of tetrabutylammonium iodide
Instead of using various iodine compounds (7 mmol) instead
Is the oxidative power of phenol by the same method as in Example 1.
Table 1 shows the results of the rubynylation reaction. (Ph is
Represents a phenyl group. ) [0045] [Table 1]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07B 61/00 300 C07B 61/00 300 (72) Inventor Tomoya Watanabe 3-3-1, Utsudori, Kurashiki-shi, Okayama Prefecture Asahi Kasei Industry Co., Ltd. (56) References JP-A-1-165551 (JP, A) JP-A-4-257546 (JP, A)

Claims (1)

(57) [Claims] a) at least one selected from palladium and a palladium compound; and b) at least one iodine compound selected from an alkali metal iodide, an alkaline earth metal iodide and an onium iodide compound. A process for producing an aromatic carbonate, which comprises reacting an aromatic hydroxyl compound with carbon monoxide and molecular oxygen. 2. The method according to claim 1, wherein the onium iodide compound is an ammonium iodide compound, a phosphonium iodide compound, an arsonium iodide compound, or a sulfonium iodide compound. 3. 3. The method according to claim 1, wherein the aromatic hydroxyl compound is an aromatic monohydroxy compound. 4. The aromatic monohydroxy compound is phenol,
The method according to claim 3, wherein the aromatic carbonate to be produced is diphenyl carbonate.