JP2003055334A - Method for producing carbonyl group-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a carbonyl group-containing compound can simply be produced in high yield and high purity. SOLUTION: This method for producing the carbonyl group-containing compound comprises reacting a thiocarbonyl group-containing compound with a metal salt which is chemically bonded to sulfur atom to enable formation of a metal sulfide and water. The thiocarbonyl group-containing compound is preferably represented by the general formula (I) (X1 is oxygen atom, sulfur atom or -N(R2 )-; X2 is carbonyl group or a single bond; R1 and R2 are each independently hydrogen atom or a monovalent nonmetal atomic group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a carbonyl group-containing compound, and more particularly to a method for easily producing a thiocarbonyl group-containing compound in high yield and high purity.

[0002]

2. Description of the Related Art Carbonyl group-containing compounds, particularly carbonyl group-containing compounds having the structure of the following general formula (I), are used as dyes and sensitizing dyes for optical recording media. These compounds have been synthesized by various synthetic methods so far. However, for example, JP-A-62-1957
In the method described in JP-A-5-140130, a quaternary ammonium salt is used as a synthetic intermediate, so that strict reaction conditions are required. And the yield was not sufficient. In addition, the following general formula (I
In the synthesis of the compound represented by I), it was difficult to obtain 95% or more of the product due to the formation of by-products.

[0003]

[Chemical 3]

(X ₁ is an oxygen atom, a sulfur atom or --N (R
₂ )-, X ₂ is a carbonyl group or a single bond, and R _{1 to} R ₄
Are each independently a hydrogen atom or a monovalent non-metallic atomic group).

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for easily producing a carbonyl group-containing compound in high yield and high purity.

[0006]

As a result of intensive studies, the present inventors have found that a metal salt activates a sulfur atom on a thiocarbonyl group, and have completed the present invention.

That is, the present invention is as follows. (1) A method for producing a carbonyl group-containing compound, which comprises reacting a thiocarbonyl group-containing compound with a metal salt capable of chemically binding to a sulfur atom to form a metal sulfide and water. (2) The carbonyl group-containing compound is represented by the following general formula
The method for producing a carbonyl group-containing compound according to (1) above, which has the structure (I).

[0008]

[Chemical 4]

(X ₁ is an oxygen atom, a sulfur atom or --N (R
₂ )-, X ₂ represents a carbonyl group or a single bond, and R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group). (3) A compound represented by the following general formula (II) having a purity of 95% or more.

[0010]

[Chemical 5]

(X ₁ is an oxygen atom, a sulfur atom or --N (R
₂ )-, and R _{1 to} R ₄ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.

The method for producing the carbonyl group-containing compound of the present invention is considered to be based on the reaction formula shown below.

[0013]

[Chemical 6]

That is, by reacting a sulfur atom, which is an active site of a thiocarbonyl group-containing compound as a starting material, with a metal salt capable of chemically interacting with each other and forming a metal sulfide after elimination, and water. The carbonyl compound can be easily obtained in high yield and high purity.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below, and other objects, advantages and effects of the present invention will become apparent. As the thiocarbonyl group-containing compound which is the starting material of the present invention, a compound having a structure represented by the following general formula (III) is preferably used.

[0016]

[Chemical 7]

(X ₁ is an oxygen atom, a sulfur atom or --N (R
₂ )-, X ₂ represents a carbonyl group or a single bond, and R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. )

The general formula (III) will be described in detail.
R ₁ is a hydrogen atom or a monovalent non-metallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic group. It represents a group heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

A preferred example of R ₁ will be specifically described. Examples of preferred alkyl groups have 1 carbon atom
Straight chain, branched, and cyclic alkyl groups from 1 to 20, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1- Methylbutyl group,
Isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-
A norbornyl group can be mentioned. Among these, straight-chain with 1 to 12 carbon atoms and 3 carbon atoms
Branched from 1 to 12, and 5 to 10 carbon atoms
Up to cyclic alkyl groups are more preferred.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group excluding hydrogen is used, and preferred examples are a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, Alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N- Diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N -Arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group,
N'-alkylureido group, N ', N'-dialkylureido group,

N'-arylureido group, N ', N'-
Diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ',
N'-dialkyl-N-alkylureido group, N ',
N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N
-Arylureido group, N ', N'-diaryl-N-
Alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-
N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N- Aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group,
Acyl group, carboxyl group,

Alkoxycarbonyl group, aryloxyca
Rubonyl group, carbamoyl group, N-alkylcarbamoy
Group, N, N-dialkylcarbamoyl group, N-ary
Rucarbamoyl group, N, N-diarylcarbamoyl
Group, N-alkyl-N-arylcarbamoyl group, ar
Kirsulfinyl group, Arylsulfinyl group, Alky
Group, arylsulfonyl group, sulfo group (-
SO₃H) and its conjugate base group (hereinafter referred to as sulfonato group and
A), alkoxysulfonyl group, aryloxysulfo
Nyl group, sulfinamoyl group, N-alkylsulfina
Moyl group, N, N-dialkylsulfinamoyl group, N
-Arylsulfinamoyl group, N, N-diaryls
Rufinamoyl group, N-alkyl-N-arylsulf
Inamoyl group, sulfamoyl group, N-alkylsulfate
Amoyl group, N, N-dialkylsulfamoyl group, N
-Arylsulfamoyl group, N, N-diarylsul
Famoyl group, N-alkyl-N-arylsulfamo
Ile group, phosphono group (-PO ₃H₂) And its conjugate bases
A group (hereinafter referred to as a phosphonate group),

Dialkylphosphono group (--PO ₃ (alkyl)
_2), diaryl phosphono group (-PO ₃ (aryl) _2), alkyl aryl phosphono group (-PO ₃ (alkyl) (ary
l)), monoalkyl phosphono group (-PO ₃ H (alkyl))
And a conjugate base group thereof (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono group (—PO ₃ H (ary
l)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy oxy Group (-OPO ₃ (alky
l) ₂ ), a diarylphosphonooxy group (--OPO ₃ (ary
l) ₂ ), an alkylarylphosphonooxy group (-OP
O ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (- OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, heteroaryl group, alkenyl group and alkynyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group,
Examples thereof include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group and a phosphonatophenyl group.

The heteroaryl group includes nitrogen, oxygen,
A monocyclic or polycyclic aromatic ring containing at least one of sulfur atoms is used, and examples of particularly preferable heteroaryl groups include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, and phenoxy. Thazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indole, indazole, purine, quinolizine, isoquinoline, phthalazine, naphthyridine, quinazoline, cynoline, pteridine, carbazole, carboline, Phenanthrine, acridine, perimidine, phenanthroline,
Examples thereof include phthalazine, phenalzazine, phenoxazine, furazan, phenoxazine, and the like, which may be further benzo-fused and may have a substituent.

Further, examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like, and examples of the alkynyl group include ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO—) include hydrogen, and the above alkyl groups and aryl groups. Among these substituents, a halogen atom (-F, -Br, -Cl,
-I), alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N
-Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphono group Examples thereof include an oxy group, a phosphonatoxy group, an aryl group and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Examples thereof include straight-chain alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of the substituted alkyl group preferable as R ₁ obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group and 2
-Chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl Oxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-
Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N
-(Sulfophenyl) carbamoylmethyl group,

Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group,
N-tolylsulfamoylpropyl group, N-methyl-N
-(Phosphonophenyl) sulfamoyloctyl group,
Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group Group, phosphonatooxybutyl group, benzyl group, phenethyl group, α
-Methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group,
Examples thereof include a 1-propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group and a 3-butynyl group.

Specific examples of the aryl group preferable as R ₁ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Yes, as a specific example, a phenyl group,
Examples thereof include a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of the substituted aryl group preferable as R ₁ include those having a monovalent non-metal atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the above-mentioned aryl group. Examples of preferable substituents include the above-mentioned alkyl groups, substituted alkyl groups, and the substituents described above for the substituted alkyl groups. Specific examples of preferred substituted aryl groups include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. , A hydroxyphenyl group,
Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group,

Acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group,
Carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group,
N- (methoxyphenyl) carbamoylphenyl group, N
-Methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N- Tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group,
Diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, Examples thereof include a 2-methylallylphenyl group, a 2-methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group and a 3-butynylphenyl group.

X ₁ is an oxygen atom, a sulfur atom or --N (R
₂ )-, and specific examples of R ₂ include those shown above as specific examples of R ₁ . X
₂ represents a carbonyl group or a single bond. Also, X ₁ , X ₂
It is also possible to form a ring structure via a non-metal atom bonded to. When X 1 and X ₂ of the general formula (III) form a ring structure together with the carbon atom bonded to them, as the thiocarbonyl group-containing compound of the above general formula (III) containing a ring,
For example, those shown in the following (A), (B), (C) and (D) can be cited.

[0034]

[Chemical 8]

As the thiocarbonyl group-containing compound which is the starting material of the production method of the present invention, the above-mentioned (A),
A compound obtained by a dehydration condensation reaction of the compound shown in (B), (C) or (D) and an aromatic aldehyde is preferably used.

Containing a thiocarbonyl group used in the present invention
As a metal salt that can be chemically bound to the sulfur atom of a compound
Is a metal salt capable of forming a metal sulfide with a sulfur atom.
Can be used. Sulfurization of compounds containing thiocarbonyl groups
As an example of a metal of a metal salt that can chemically bond with a yellow atom
Is Al, Au, Ag, Hg, Cu, Zn, Fe, Cd, Cr, Co, Ce, B
i, Mn, Mo, Ga, Ni, Pd, Pt, Ru, Rh, Sc, Sb, Sr, M
Examples thereof include metal salts such as g and Ti. Also metal salt
The counter anions of F, Cl, Br, I, NO₃, SO_Four, N
O₂, PO_Four, CH ₃CO₂Etc. can be mentioned.

Specific examples of metal salts include AgBr, AgI, Ag
F, AgO, AgCl, Ag₂O, Ag (NO₃), AgSO _Four, AgNO₂, Ag₂Cr
O_Four, Ag₃PO_Four, Hg₂(NO₃)₂, HgBr₂, Hg₂Br₂, HgO, HgI₂, H
g (NO₃)₂, Hg (NO₂)₂, HgBr₂, HgSO_Four, Hg₂I₂, Hg₂SO_Four, Hg
(CH₃CO₂)₂, AuBr, AuBr₃, AuI, AuI₃, AuF₃, Au₂O₃, Au
Cl, AuCl₃, CuCl, CuI, CuI₂, CuF₂, CuO, CuO₂, Cu (NO
₃)₂, CuSO_Four, Cu₃(PO_Four)₂Is mentioned. In addition, Iohara
Most preferred metal salt in terms of easy interaction with the child
For, a silver salt can be used.

The thiocarbonyl group-containing compound used in the present invention forms a complex by reacting with the above-mentioned metal salt capable of chemically binding to the sulfur atom, but the metal sulfide is eliminated to form a carbonyl group. Add water to convert.
In addition, in the method for producing a carbonyl group-containing compound in the present invention, in order to increase the reaction rate, it is preferable to add a base after adding water as described above. This is considered to have the effect of suppressing the reaction from being brought into an equilibrium state and being delayed by the acid generated in the reaction system. Examples of the base used in the present invention include organic bases such as pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), and inorganic bases such as potassium carbonate and sodium hydrogen carbonate. Either is fine.

The reaction solvent in the reaction of the present invention is
Any solvent that can dissolve a metal salt that can chemically interact with a sulfur atom can be suitably used, and acetonitrile is preferable.

In the reaction of the present invention, a metal salt capable of chemically interacting with a sulfur atom is added in an amount of 0.5 to 10 mol, preferably 1 mol, based on 1 mol of a starting material containing a thiocarbonyl group.
Mol to 3 mol, water 1 mol to 3 mol, base 0.5 to 1
It is carried out by using 0 mol, preferably 1 mol to 3 mol. Further, the reaction of the present invention is carried out at a temperature of usually 0 to 150 ° C, preferably 20 to 100 ° C, though it varies depending on the kind of compound and solvent used. After completion of the reaction, a solvent that does not dissolve the unreacted metal salt is added, the precipitated unreacted metal salt and the metal sulfide generated by the reaction are filtered off, and when the product is a crystal, the filtrate is added to water. It can be obtained as crystals. When the product is a liquid, it can be obtained by extraction with an organic solvent such as ethyl acetate or diethyl ether and water. The obtained crude product can be obtained as a highly pure product by refining using recrystallization, reslurry, column chromatography and the like.

The production method of the present invention usually proceeds at room temperature, and since a side reaction and a by-product hardly occur, a product of high purity can be obtained. Particularly, it is effective in the production of the compound represented by the following general formula (II).

[0042]

[Chemical 9]

The general formula (II) will be described. R _1, X ₁ in the general formula (II), R _1, X ₁ in the aforementioned general formula (I)
The ones described in are listed. Examples of R ₃ and R ₄ include those described for R ₁ in the above general formula (I), which can be bonded to each other to form an aliphatic or aromatic ring.

The carbonyl group-containing compound produced by the production method of the present invention can be used as a dye for an optical recording medium, a sensitizing dye for a photopolymerizable composition and the like.

[0045]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto. [Example 1] 10 g of silver nitrate and 500 ml of acetonitrile
The following 3-ethyl-5,5-dimethyl-
5.0 g of 2-thioxo-4-oxazolidinone (formula 1)
Was added and stirred for 0.5 hour. Next, 0.5 g of pure water was added dropwise and stirred for 1 hour, 6.2 g of triethylamine was added dropwise, and the mixture was further stirred for 1 hour. After completion of the reaction, add acetone to 500 m
1, and the precipitated silver salt was filtered off using Celite, 1000 ml of water was added to the filtrate, and the mixture was extracted 3 times with ethyl acetate. After the solvent was distilled off, the residue was purified by column chromatography to obtain 3.7 g of the following carbonyl group-containing compound (formula 2) (yield 82%). Identification was performed by ¹ H-NMR.

[0046]

[Chemical 10]

In the same manner, the following (formula 3) to (formula 32)
A carbonyl group-containing compound represented by was synthesized.

[0048]

[Chemical 11]

[0049]

[Chemical 12]

Example 2 3.4 g of silver nitrate was dissolved in 300 ml of acetonitrile, 4.0 g of a thiocarbonyl group-containing compound represented by the following formula 33 was added, and the mixture was stirred for 0.5 hours. Next, 0.1 g of water was added dropwise, and the mixture was stirred for 1.5 hours, then 2.2 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, add 400 ml of acetone,
The precipitated silver salt was filtered off using Celite, and the filtrate was washed with water 100
It was added to 0 ml. The precipitated crystals were collected by filtration and then reslurried in methanol to give the following carbonyl group-containing compound (formula 3
3.0 g of 4) was obtained (yield 92%). Identification was performed by ¹ H-NMR.

[0051]

[Chemical 13]

Example 3 1.7 g of silver nitrate was dissolved in 20 ml of acetonitrile, 2.0 g of a thiocarbonyl group-containing compound represented by the following formula 35 was added, and the mixture was stirred for 0.5 hours. Next, 0.3 g of water was dropped and after stirring for 1.5 hours,
1.0 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After completion of the reaction, 30 ml of acetone was added, the precipitated silver salt was filtered off using Celite, and the filtrate was added to 100 ml of water. The precipitated crystals were collected by filtration and then reslurried in methanol to obtain 1.7 g of the following carbonyl group-containing compound (formula 36) (yield 89%). Identification was performed by ¹ H-NMR.

[0053]

[Chemical 14]

In the same manner, the following (Equation 37) to (Equation 5)
A carbonyl group-containing compound represented by 4) was synthesized.

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

Example 3 3.5 g of silver nitrate was dissolved in 50 ml of acetonitrile, 4.0 g of a thiocarbonyl group-containing compound represented by the following formula 75 was added, and the mixture was stirred for 1 hour. Next, 1.0 g of water was added dropwise and stirred for 1.5 hours, 2.5 g of triethylamine was added dropwise, and the mixture was further stirred for 1.5 hours. After the reaction was completed, 100 ml of acetone was added, the precipitated silver salt was filtered off using Celite, and the filtrate was added to 150 ml of water. The precipitated crystals were collected by filtration and reslurried in methanol to give the following carbonyl group-containing compound (formula 76).
5 g was obtained (yield 90%). Identification was performed by ¹ H-NMR.

[0060]

[Chemical 19]

Example 4 8.0 g of copper nitrate was dissolved in 800 ml of acetonitrile, 7.4 g of the thiocarbonyl group-containing compound represented by the above formula 77 was added, and the mixture was stirred for 0.5 hours. Next, 0.2 g of methanol was dropped and after stirring for 1.5 hours, 5.0 g of triethylamine was dropped and further stirred for 1.5 hours. After completion of the reaction, add 700 m of acetone
Then, the precipitated silver salt was filtered off using Celite, and the filtrate was added to 2000 ml of water. The precipitated crystals were collected by filtration and then reslurried in methanol to obtain 5.9 g of the following carbonyl group-containing compound (formula 78) (yield 83%). ¹ H-NMR
It was identified by.

[0062]

[Chemical 20]

In the same manner, the following (Equation 79) to (Equation 8)
A carbonyl group-containing compound represented by 8) was synthesized.

[0064]

[Chemical 21]

Comparative Example 1 2.8 g of a thiocarbonyl group-containing compound represented by the above formula 89 and 1.4 g of potassium carbonate
To the mixture, 100 ml of acetonitrile was added, 1.6 g of methyl iodide was added dropwise with stirring at room temperature, and the mixture was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was poured into 300 liters of water, and the precipitated crude crystals were collected by filtration and recrystallized with ethyl acetate to give the following carbonyl group-containing compound (formula 9).
0) was obtained (g yield 55%). Identification was performed by ¹ H-NMR.

[0066]

[Chemical formula 22]

[0067]

EFFECT OF THE INVENTION According to the production method of the present invention, a carbonyl group-containing compound can be easily synthesized in high yield and high purity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 275/06 C07C 275/06 333/10 333/10 C07D 263/44 C07D 263/44 401/04 401 / 04 413/06 413/06 F-term (reference) 4C056 AA01 AB01 AC02 AD01 AE03 AF05 BA03 BB08 BC02 4C063 AA01 BB03 CC29 CC52 DD08 DD14 EE10 4H006 AA02 AC56 AC57 BE60 BE62 BJ50 BV72 RA12

Claims (3)

[Claims] 1. A process for producing a carbonyl group-containing compound, which comprises reacting a thiocarbonyl group-containing compound with a metal salt capable of chemically bonding to a sulfur atom to form a metal sulfide and water. 2. The method for producing a carbonyl group-containing compound according to claim 1, wherein the carbonyl group-containing compound has a structure represented by the following general formula (I). [Chemical 1] (X ₁ is an oxygen atom, a sulfur atom or -N (R ₂₎ - a, X ₂
Represents a carbonyl group or a single bond, and R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group). 3. A compound represented by the following general formula (II) having a purity of 95% or more. [Chemical 2] (X ₁ is an oxygen atom, a sulfur atom or -N (R ₂₎ - a, R ₁
To R ₄ each independently represent a hydrogen atom or a monovalent non-metallic atomic group.