JPS62145B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for synthesizing an imidazole dithiocarboxylic acid ester compound, and specifically relates to a method for synthesizing an imidazole dithiocarboxylic acid ester compound.

[However, in the formula, R ₂ represents a hydrogen atom or a residue selected from the group consisting of a methyl group, an ethyl group, an undecyl group, a heptadecyl group, and a phenyl group, and R ₄ represents a hydrogen atom or a methyl group. ]

An imidazoledithiocarboxylic acid compound represented by the general formula R ₅ -Z [wherein R ₅ is a residue selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, and a lauryl group, and Z is a halogen Represents an atom or 1/2SO ₄ group. ] General formula characterized by causing a condensation reaction of an alkylating agent represented by

[However, in the formula, R ₂ , R ₄ and R ₅ are the same as above. ]

This relates to a method for synthesizing an imidazole dithiocarboxylic acid ester compound shown in the following. The imidazole dithiocarboxylic acid compound and its alkali metal salt, which are the starting materials for the method of the present invention, are:
As shown in JP-A-57-17696, it can be easily obtained in high yield from the corresponding parent imidazole and carbon disulfide. When the starting material imidazole dithiocarboxylic acid and the alkylating agent are subjected to a condensation reaction, a hydrogen halide salt or monoalkyl sulfate of the dithiocarboxylic acid ester is first produced, and then the hydrogen halide salt is formed according to the reaction formula shown below. Alternatively, the desired dithiocarboxylic acid ester can be obtained by reacting a monoalkyl sulfate with a hydrogen halide acceptor or a monoalkyl sulfate acceptor. Further, when the starting material imidazole dithiocarboxylic acid and an alkylating agent are subjected to a condensation reaction in the presence of a hydrogen halide acceptor or a monoalkyl sulfate acceptor, the target dithiocarboxylic acid ester is obtained according to the following reaction formula. Further, when the starting material alkali metal imidazole dithiocarboxylic acid is subjected to a condensation reaction with an alkylating agent, the target dithiocarboxylic acid ester can be similarly obtained according to the following reaction formula. The starting alkali metal salts of imidazoledithiocarboxylic acids are primarily sodium and potassium salts. When imidazole and carbon disulfide are reacted in the presence of an alkali hydroxide to synthesize imidazole dithiocarboxylic acid, the alkali metal salt of the dithiocarboxylic acid is first produced, so it can be used as it is as a starting material for the synthesis of imidazole dithiocarboxylic acid ester. It can be used as Since the dithiocarboxylic acid easily forms a salt with the basic ion B to give the dithiocarboxylic acid B salt as shown in the reaction formula shown below, the B salt can also be used as a starting material. What is used as basic ion B?
Li, Na, K, Ca, Ba, Mg,
Zn, Cu, Mn, Co,
Ni, Fe, Hg, Sn, Pb,
These include NH ₄ and organic ammonium ions. As mentioned above, the dithiocarboxylic acid easily forms various salts with various metal ions, but the use of these metal salts as starting materials is economically more economical than the use of sodium and potassium salts. I don't think it's a good idea. The hydrogen halide acceptor or monoalkyl sulfate acceptor used in the present invention is of a very general type and is one that reacts with hydrogen halide or monoalkyl sulfate to give a neutralized salt. You can use anything. They are as shown below. _NH3 , _NH4OH , LiOH, NaOH, KOH, Ca
(OH) ₂ , Ba(OH) ₂ , Mg(OH) ₂ , LiCO ₃ ,
Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , BaCO ₃ , MgCO ₃ ,
Tertiary amines such as CH ₃ COONa, CH ₃ COOK, Et ₃ N and pyridines, quaternary ammonium hydroxides (eg Triton B) and the like. The alkylating agent used in the present invention is an alkyl halide and a dialkyl sulfate, and the type of alkyl group can be from a lower alkyl group to a higher alkyl group with various carbon numbers, and the type of halogen atom can be can be a chlorine atom, a bromine atom or an iodine atom. Representative alkylating agents are shown below. Methyl iodide, ethyl iodide, propyl chloride,
Propyl bromide, propyl iodide, butyl chloride, butyl bromide, butyl iodide, lauryl chloride, lauryl bromide, dimethyl sulfate, diethyl sulfate, etc. Considering the reaction between the active hydrogen in the solvent and the alkylating agent, theoretically it would be desirable for the solvent used in the reaction to be one that does not have active hydrogen.
Experimental results do not necessarily confirm such predictions;
It has been found that solvents such as water and alcohol can also be used satisfactorily. Therefore, restrictions regarding solvents are considered not to have much significance. Representative solvents suitable for the practice of this invention are water, methyl alcohol, ethyl alcohol, dimethyl formamide, dimethyl sulfoxide, acetonitrile, acetone, acetic acid, pyridine, and the like. The reaction of the present invention is exothermic. Therefore, in the case of large-scale synthesis, cooling is required at the beginning of the reaction, but
In the case of small-scale reactions, there is no need for additional cooling. After the reaction has progressed to a certain extent, the heat generation weakens, so heating is necessary. This is a method of temperature control when shortening the reaction time is taken into account. In this case, the reaction temperature may be maintained between room temperature and about 80°C. The reaction in this case is completed within about 5 hours.
A reaction temperature of 80°C or higher is not particularly required. A temperature below 80℃ is sufficient. To relieve fever,
It is desirable to gradually add the alkylating agent to the reaction system. It is of course possible to conduct the reaction for a long time under ice cooling or at room temperature unless shortening the reaction time is taken into account. The reaction apparatus must be equipped with a stirrer and a reflux condenser, but since these reactions proceed at normal pressure, there is no need to apply additional pressure. Regarding the molar equivalent relationship of imidazole dithiocarboxylic acid or its alkali metal salt, alkylating agent, and hydrogen halide acceptor or monoalkyl sulfate acceptor, 1 molar equivalent per 1 molar equivalent of the starting material dithiocarboxylic acid or its salt. or 1
More than molar equivalents of alkylating agent and receptor may be used. However, it is uneconomical and meaningless to use them in gross excess. Isolation and purification of the target product is carried out according to conventional methods.
Specific aspects thereof will be described later in Examples.
Further, the implementation mode of this reaction will also be described later in Examples. Various imidazole dithiocarboxylic acid ester compounds obtained by the method of the present invention are useful as agricultural chemical intermediates and pharmaceutical intermediates. Next, the properties of the target product synthesized by the method of the present invention will be illustrated. Imidazole-4-dithiocarboxylic acid ethyl ester structural formula Physical properties Orange crystal. neutral. mp140-143℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (Silica G, _CHCl3 /MeOH=10/1 volume ratio, _I2 color development): Rf0.33-0.43. ν ^KBr cm ₋₁ :1058 (first absorption, νc=s). NMR (CF ₃ COOH): δ8.76, d, 1H, (proton at 2nd position); 8.02, d, 1H (proton at 4th position);
3.50, q, 2H (methylene proton of ethyl group). Mass: m/e172 (M ⁺ ), 144 (M ⁺ −CH ₂ CH ₃ +
H), 111 (M ⁺ _{-SCH2CH3 )} . 2-Methylimidazole-4-dithiocarboxylic acid ethyl ester Structural formula Physical Properties Red-orange crystal. neutral. mp115-117℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (mentioned above): Rf0.45~0.55. ν ^KBr cm ₋₁ :1072 (first absorption, νc=s). NMR (CF ₃ COOH): δ7.87, s, 1H (4-position proton); 3.47, q, 2H (methylene proton of ethyl group); 2.78, s, 3H (2-position methyl proton); 1.44, t, 3H (methyl proton of ethyl group). Mass: m/e186 (M ⁺ ), 158 (M ⁺ −CH ₂ CH ₃ +
H), 125 (M ⁺ _{-SCH2CH3 )} . 2-Methylimidazole-4-dithiocarboxylic acid butyl ester Structural formula Physical properties Orange crystal. neutral. mp107~110℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (mentioned above): Rf0.40~0.50. ν ^KBr cm ₋₁ :1075 (second absorption, νc=s). NMR (CF ₃ COOH): δ7.85, s, 1H (4-position proton); 3.49, t, 2H (α-methylene proton of butyl group); 2.78, s, 3H (2-position methyl proton); 1.97-1.33 , m, 4H (β and γ-methylene protons of butyl group); 1.00, t,
3H (terminal methyl proton of butyl group). Mass: m/e214 (M ⁺ ), 181 (M ⁺ -S-H),
158 (M ⁺ −CH ₂ CH ₂ CH ₂ CH ₃ +H), 125 (M ⁺ −
SCH ₂ CH ₂ CH ₂ CH ₃ ), 44 (:C=S). 2-Methylimidazole-4-dithiocarboxylic acid lauryl ester Structural formula Physical properties Orange crystal. neutral. mp104-108℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Insoluble in water. TLC (mentioned above): Rf0.50~0.60. ν ^KBr cm ₋₁ : 1068 (fourth absorption, νc=s). NMR (CF ₃ COOH): δ7.85, s, 1H (4-position proton); 3.49, t, 2H (α-
methylene proton); 2.74, s, 3H (2H methyl proton); 1.86, m, 2H (β-methylene proton of lauryl group); 1.34, m, 18H (middle methylene proton of lauryl group); 0.89,
m, 3H (terminal methyl proton of lauryl group). Mass: m/e326 (M ⁺ ), 293 (M ⁺ -S-H),
158 (M ⁺ −CH ₂ (CH ₂ ) ₁₀ CH ₃ +H), 125 (M ⁺
-SCH ₂ (CH ₂ ) ₁₀ CH ₃ ), 44 (:C=S). 2-ethylimidazole-4-dithiocarboxylic acid ethyl ester structural formula Physical properties Orange crystal. neutral. mp108~110℃ (Acetone. Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Slightly soluble in water. TLC (mentioned above): Rf0.50~0.60. ν ^KBr cm _-1 : 1084 or 1048 (Third absorption, νc=s)
. NMR (CF ₃ COOH): δ7.88, s, 1H (4-position proton); 3.48, q, 2H (methylene proton of mercaptoethyl group); 3.14, q, 2H (2
methylene proton of ethyl group); 1.49, t,
3H (methyl proton of mercaptoethyl group); 1.44, t, 3H (methyl proton of 2-position ethyl group). Mass: m/e200 (M ⁺ ), 172 (M ⁺ −CH ₂ CH ₃ +
H), 139 (M ⁺ _-SCH2CH3 ), 44 (:C= _S ). 2-Undecylimidazole-4-dithiocarboxylic acid ethyl ester Structural formula Physical properties Orange crystal. neutral. mp80-83℃ (acetone).
Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Insoluble in water. TLC (mentioned above): Rf0.70~0.80. ν ^KBr cm ₋₁ :1068 (third absorption, νc=s). NMR (CF ₃ COOH): δ7.85, s, 1H (4-position proton); 3.46, q, 2H (methylene proton of ethyl group); 3.09, t, 2H (α-methylene proton of 2-position undecyl group); 1.90, m,
2H (β-methylene proton of undecyl group at 2-position); 1.43, t, 3H (methyl proton of ethyl group); 1.32, m, 16H (intermediate methylene proton of undecyl group at 2-position); 0.88, m, 3H (2
terminal methyl proton of the undecyl group). Mass: m/e326 (M ⁺ ), 298 (M ⁺ −CH ₂ CH ₃ ),
297 (M ⁺ −CH ₂ CH ₂ +H), 293 (M ⁺ −S−
H), 265 (M ⁺ _-SCH2CH3 ), 44 (:c= _S ). 2-heptadecylimidazole-4-dithiocarboxylic acid ethyl ester Structural formula Physical Properties: Yellow-orange crystals. neutral. mp90-93℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Insoluble in water. TLC (mentioned above): Rf0.75~0.85. ν ^KBr cm ₋₁ :1072 (third absorption, νc=s). NMR (CF ₃ COOH): δ7.85, s, 1H (4-position proton); 3.46, q, 2H (methylene proton of ethyl group); 3.09, t, 2H (α-methylene proton of 2-position heptadecyl group); 1.90, m,
2H (β-methylene proton of heptadecyl group at 2-position); 1.44, t, 3H (methyl proton of ethyl group); 1.32, m, 28H (intermediate methylene proton of heptadecyl group at 2-position); 0.88, m, 3H
(Terminal methyl proton of heptadecyl group at 2-position). Mass; m/e410 (M ⁺ ), 382 (M ⁺ −CH ₂ CH ₃ +
H), 381 (M ⁺ −CH ₂ CH ₃ ), 349 (M ⁺ −
_{SCH2CH3 )} . 4-Methylimidazole-5-dithiocarboxylic acid methyl ester Structural formula Physical properties Orange crystal. neutral. mp194-196℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (mentioned above): Rf0.36~0.46. ν ^KBr cm ₋₁ : 1058 (first absorption, νc=s). NMR (CF ₃ COOH): δ8.58, s, 1H (proton at 2nd position); 2.91, s, 3H (methyl proton of mercaptomethyl group); 2.87, s, 3H (methyl proton at 4th position). Mass: m/e172 (M ⁺ ), 157 (M ⁺ −CH ₃ ), 125
(M ⁺ _−SCH3 ). 4-Methylimidazole-5-dithiocarboxylic acid ethyl ester Structural formula Physical Properties Red-orange crystal. neutral. mp185-187℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (mentioned above): Rf0.40~0.50. ν ^KBr cm ₋₁ :1061 (first absorption, νc=s). NMR (CF ₃ COOH): δ8.61, s, 1H (2nd position proton); 3.53, q, 2H (methylene proton of ethyl group); 2.87, s, 3H (4th position methyl proton); 1.49, t, 3H (methyl proton of ethyl group). Mass: m/e186 (M ⁺ ), 158 (M ⁺ −CH ₂ CH ₃ +
H), 125 (M ⁺ _-SCH2CH3 ), 44 (:C= _S ). 2,4-dimethylimidazole-5-dithiocarboxylic acid propyl ester Structural formula Physical properties Orange crystal. neutral. mp127-129℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Poorly soluble in water. TLC (mentioned above): Rf0.42~0.52. ν ^KBr cm ₋₁ : 1065 (νc=s). NMR (CF ₃ COOH): 3.47, t, 2H (α-methylene proton of propyl group); 2.79, s, 3H
(2nd position methyl proton); 2.71, s, 3H (4th position methyl proton); 1.83, m, 2H (β-methyl proton of propyl group); 1.10, t, 3H
(methyl proton of propyl group). Mass: m/e214 (M ⁺ ), 172 (M ⁺ −CH ₂ CH ₂ CH ₃
+H), 139 (M ⁺ -SCH ₂ CH ₂ CH ₃ ), 44 (:C
=S). 2-Ethyl-4-methylimidazole-5-dithiocarboxylic acid ethyl ester Structural formula Physical properties Orange crystal. neutral. mp130-132℃ (acetone). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, carbon tetrachloride, toluene, benzene and DMSO. Poorly soluble in water. TLC (mentioned above):
Rf0.56~0.66. ν ^KBr cm ₋₁ : 1055 (νc=s). NMR (CDCl ₃ ): δ3.33, q, 2H (methylene proton of mercaptoethyl group); 2.70, q, 2H
(methylene proton of 2-position ethyl group); 2.59,
s, 3H (4-position methyl proton); 1.36, t,
3H (methyl proton of mercaptoethyl group); 1.27, t, 3H (methyl proton of 2-position ethyl group). Mass: m/e214 (M ⁺ ), 186 (M ⁺ −CH ₂ CH ₃ +
H), 181 (M ⁺ -S-H), 153 (M ⁺ -
_{SCH2CH3 )} . 2-Phenyl-4-methylimidazole-5-dithiocarboxylic acid ethyl ester Structural formula Physical properties Orange crystal. neutral. mp162-165℃ (EtOH). Soluble in methanol, ethanol, acetone, acetic acid, chloroform, toluene and DMSO. Insoluble in water. TLC (mentioned above): Rf0.65~0.75. ν ^KBr cm ₋₁ : 1068 (second absorption, νc=s). NMR (CF ₃ COOH): δ7.97-7.60, m, 5H
(phenyl proton); 3.54, q, 2H (methylene proton of ethyl group); 2.91, s, 3H (4
1.50, t, 3H (methyl proton of ethyl group). Mass: m/e262 (M ⁺ ), 234 (M ⁺ −CH ₂ CH ₃ +
H), 201 (M ⁺ −SCH ₂ CH ₃ ), 104, 77, 44. Example 1 A reaction vessel equipped with a reflux condenser was mounted on a magnetic stirring hot plate, and 0.03 mol (4.3 gr) of imidazole-4-dithiocarboxylic acid, 0.015 mol (1.1 gr) of calcium hydroxide, and 20 ml of water were charged. Then, 0.03 mol (4.7 g) of ethyl iodide was added all at once to room temperature with stirring, and the system was kept at 60 to 70°C for 2 hours, the precipitated crystals were collected, and the crystals were recrystallized with acetone to give a crude Target [mp130-140℃; TLC (Silica G, chloroform/methanol = 10/1 volume ratio, I ₂ color development)
Rf0.33~0.4] (3.8g of dithiocarboxylic acid yield
73.6%). Example 2 The hot acetone solution of the crude target product in Example 1 was treated with activated carbon, and the crystals precipitated when cold were collected. mp140-143℃). Example 3 0.03 mol (4.7 g) of 2-methylimidazole-4-dithiocarboxylic acid, 0.015 mol (2.1 g) of potassium carbonate, 20 ml of water and 0.03 mol (4.7 g) of ethyl iodide.
After keeping the system consisting of the four components in g) at 50-70°C for 2 hours, the aqueous layer was decanted to obtain a candy-like substance, and the candy-like substance was reconsolidated with acetone to obtain the crude target product [mp107-115
3.8 g (yield based on dithiocarboxylic acid: 68.1%) of Rf 0.45-0.55] was obtained. Example 4 The hot acetone solution of the crude target product in Example 3 was treated with activated carbon, and the crystals precipitated when cold were collected, and the collected crystals were re-consolidated with acetone to obtain the identified sample (mp115-117). ℃) was obtained. Example 5 A system consisting of 0.03 mol (4.7 g) of 2-methylimidazole-4-dithiocarboxylic acid, 0.03 mol (2.5 g) of sodium acetate, 20 ml of acetic acid, and 0.03 mol (4.7 g) of ethyl iodide was heated for 3 hours. After keeping the temperature at 70℃, the precipitated crystals were separated, the liquid was dried to dryness under reduced pressure, and the dried product was washed with water and reconsolidated with acetone to obtain the crude target product [mp107-115℃; TLC (previous) Rf0.45-0.55 ]
1.7g (yield based on dithiocarboxylic acid: 30.4%) was obtained. Example 6 A system consisting of 0.03 mol (4.7 g) of 2-methylimidazole-4-dithiocarboxylic acid, 0.03 mol (1.7 g) of potassium hydroxide, 20 ml of water, and 0.03 mol (4.1 g) of n-butyl bromide. After keeping the water at 75-80℃ for 3 hours, the aqueous layer was decanted to obtain a candy-like substance, the candy-like substance was washed with water to remove precipitated crystals, and the collected crystals were reconsolidated with acetone to obtain the crude target product. [mp92~109℃;
4.5 g (yield 70.0% based on dithiocarboxylic acid) of TLC (described above) Rf 0.40-0.50] was obtained. Example 7 The crude target material of Example 6 was treated as in Example 4,
The previously identified sample (mp 107-110°C) was obtained. Example 8 A system consisting of 0.03 mol (4.7 g) of 2-methylimidazole-4-dithiocarboxylic acid, 0.03 mol (1.2 g) of sodium hydroxide, 20 ml of ethanol, and 0.03 mol (7.5 g) of n-lauryl bromide was prepared. 3
After heating under reflux for an hour (liquid temperature 80°C), the system was cooled.
The precipitated crystals were collected, washed with water, and then reconsolidated with acetone to obtain the crude target product [mp104-108℃; TLC
8.2 g (83.8% yield based on dithiocarboxylic acid) of Rf0.50-0.60] was obtained. Example 9 The crude target product of Example 8 was treated as in Example 4 to obtain the identified sample (mp 104-108°C). Example 10 0.03 mol (5.2 g) of 2-ethylimidazole-4-dithiocarboxylic acid, 1.5 g of magnesium carbonate, water
After keeping the four-part system of 20 ml and 0.03 mol (4.7 g) of ethyl iodide at 60-70°C for 2 hours, the aqueous layer was decanted to obtain a candy-like substance, and the candy-like substance was reconstituted with acetone. and crude target [mp103~109℃; TLC
4.0 g (62.3% yield based on dithiocarboxylic acid) of Rf0.50-0.60] was obtained. Example 11 The crude target material of Example 10 was treated as in Example 4,
The previously identified sample (mp 108-110°C) was obtained. Example 12 0.025 mol (7.5 g) of 2-undecylimidazole-4-dithiocarboxylic acid, sodium hydroxide
A system consisting of 0.025 mol (1.0 g), 20 ml of ethanol, and 0.025 mol (3.9 g) of ethyl iodide was
After keeping the temperature at 60 to 70℃ for an hour, the contents were dried under reduced pressure.
After washing the dried product with water, reconsolidate with acetone to obtain the crude target product [mp77-82℃; TLC (mentioned above) Rf0.70-0.80].
7.0 g (85.9% yield based on dithiocarboxylic acid) was obtained. Example 13 The crude target material of Example 12 was treated as in Example 4,
The previously identified sample (mp 80-83°C) was obtained. Example 14 0.015 mol (5.7 g) of 2-heptadecyl imidazole-4-dithiocarboxylic acid, calcium carbonate
0.0075 mol (0.75 g), dimethylformamide 20
ml and 0.015 mol (2.3 g) of ethyl iodide were kept at 65-70°C for 4 hours, the precipitate was separated, the liquid was concentrated under reduced pressure, and the ammoniacal methanol solution of the residue was dried under reduced pressure. After solidifying and washing the dried product with water, reconsolidate with acetone to obtain the crude target product [mp85-90
℃; TLC (mentioned above) Rf0.60~0.75 (very thin),
0.75-0.85] (yield 91 for dithiocarboxylic acid)
%) Got. Example 15 The crude target material of Example 14 was treated as in Example 4,
The previously identified sample (mp 90-93°C) was obtained. Example 16 0.03 mol (4.7 g) of 4-methylimidazole-5-dithiocarboxylic acid, 0.03 mol (1.2 g) of sodium hydroxide, 20 ml of water and 0.03 mol (4.3 ml) of methyl iodide
After keeping the system consisting of the four components in g) at 40°C for 2 hours, the precipitated crystals were collected, and the collected crystals were reconsolidated with acetone.
Crude target [mp185-192℃; TLC (see above)
2.2 g (42.6% yield based on dithiocarboxylic acid) of Rf0.36-0.46] were obtained. Example 17 The crude target material of Example 16 was treated as in Example 4,
The previously identified sample (mp 194-196°C) was obtained. Example 18 A system consisting of 0.03 mol (4.7 g) of 4-methylimidazole-5-dithiocarboxylic acid, 20 ml of acetone, and 0.03 mol (3.8 g) of dimethyl sulfuric acid was heated under reflux for 5 hours (inner temperature 57°C). The contents were concentrated under reduced pressure, the residue was extracted with methanol, the extract was made basic with aqueous ammonia, and then dried under reduced pressure. The dried product was washed with water and reconstituted with acetone to obtain the crude target product ℃; TLC (mentioned above) Rf0.05~0.10
(very thin), 0.36-0.46] was obtained (yield 34.9% based on dithiocarboxylic acid). Example 19 0.03 mol (4.7 g) of 4-methylimidazole-5-dithiocarboxylic acid, 0.03 mol (2.0 g) of 25% aqueous ammonia, 20 ml of water and 0.03 mol (4.7 g) of ethyl iodide
After keeping the system consisting of the four components in g) at 60-70℃ for 2 hours, the precipitated crystals were collected, and the collected crystals were recrystallized with acetone to obtain the crude target product (mp175-184℃; TLC (described above)).
3.2g of Rf0.35~0.40 (very thin), 0.40~0.50]
(yield 57.3% based on dithiocarboxylic acid). Example 20 The crude target material of Example 19 was treated as in Example 4,
The previously identified sample (mp 185-187°C) was obtained. Example 21 A system consisting of 0.03 mol (4.7 g) of 4-methylimidazole-5-dithiocarboxylic acid, 20 ml of pyridine, and 0.03 mol (4.7 g) of ethyl iodide was kept at 65 to 70°C for 3 hours, and then The contents were dried under reduced pressure,
After washing the dry matter with water, it was reconsolidated with acetone to obtain the crude target product [mp175-183℃; TLC (mentioned above) Rf0.35-0.40
(very thin), 0.40-0.50] (3.2 g (yield based on dithiocarboxylic acid: 57.3%)). Example 22 0.03 mol (5.2 g) of 2,4-dimethylimidazole-5-dithiocarboxylic acid, 0.015 sodium carbonate
After keeping the system consisting of mol (1.6 g), methanol 20 ml, and n-propyl chloride 0.03 mol (2.4 g) at 60 to 65°C for 3 hours, the precipitated crystals were separated, and the liquid was dried under reduced pressure. The solid substance was reconsolidated with acetone to obtain the crude target product [mp114-121℃; TLC (mentioned above) Rf0.05-0.10
(very thin) 0.42-0.52] (yield 31.1% based on dithiocarboxylic acid) was obtained. Example 23 The hot acetone solution of the crude target product of Example 22 was treated with activated carbon, and the crystals precipitated when cold were collected from the solution obtained, to obtain the above-mentioned identified sample (mp 127-129°C). Example 24 0.03 mol (5.6 g) of 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid, 12 ml of dimethylformamide and 0.03 mol (4.7 ml) of ethyl iodide
After keeping the system consisting of the three components in g) at 70°C for 2 hours, the contents were dried under reduced pressure, and the dried product was reconsolidated with acetone.
Hydroiodide salt of target product [mp153-157℃;
TLC (mentioned above) Rf0.00 (acidic substance), 0.56 to 0.66]
7.0g (yield based on dithiocarboxylic acid: 68.2%) was obtained. The ammoniacal methanol solution of the hydroiodide salt was dried under reduced pressure, and the dried product was washed with water and reconsolidated with acetone to obtain the crude target product [mp127-130°C; TLC (mentioned above) Rf0.56-0.66]. 3.0g (46.7% yield based on dithiocarboxylic acid) was obtained. Example 25 The crude target product of Example 24 was reconsolidated twice with acetone,
The previously identified sample (mp 130-132°C) was obtained. Example 26 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid sodium salt 0.03 mol (6.3 g),
20 ml of ethanol and 0.03 mol of ethyl iodide (4.7
After keeping the system consisting of the three components in g) at 65 to 70°C for 4 hours, the contents were dried under reduced pressure, and the dried product was washed with water and reconsolidated with acetone to obtain the crude target product [mp 127 to 131°C;
4.2 g (65.4% yield relative to sodium dithiocarboxylic acid salt) of TLC (described above) Rf0.56-0.66] was obtained. Example 27 0.03 mol (5.6 g) of 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid, 12 ml of dimethylformamide and 0.03 mol (4.6 g) of diethyl sulfate
After keeping the system consisting of the three components in g) at 50 to 70°C for 2 hours, the contents were concentrated under reduced pressure, the ammoniacal methanol solution of the residue was dried under reduced pressure, the dried product was washed with water, and then reconsolidated with acetone. , coarse object (mp125~130
3.6 g (yield based on dithiocarboxylic acid: 56.1%) of Rf 0.56-0.66] was obtained. Example 28 2-phenyl-4-methylimidazole-5-
After keeping a system consisting of 0.03 mol (7.0 g) of dithiocarboxylic acid, 0.015 mol (1.6 g) of sodium carbonate, 20 ml of acetonitrile, and 0.03 mol (4.7 g) of ethyl iodide at 60 to 70°C for 3 hours, the contents was dried under reduced pressure, and the dried product was washed with water and then reconsolidated with ethanol to obtain the crude target product (mp150-158℃; TLC (see above)
3.0g of Rf0.47~0.57 (extremely thin), 0.65~0.75]
(yield 38.2% based on dithiocarboxylic acid). Example 29 The hot ethanol solution of the crude target product in Example 28 was treated with activated carbon, the resulting liquid was dried under reduced pressure, the dried solid was reconsolidated twice with ethanol, and the acetone solution of the crystals was poured into an activated clay layer. The filtered liquid was dried under reduced pressure, the dried solid was reconsolidated with ethanol, and the identified sample (m.
p.162-165℃).

Claims (1)

[Claims] 1 General formula [Formula] [In the formula, R ₂ is a hydrogen atom or a residue selected from the group consisting of a methyl group, an ethyl group, an undecyl group, a heptadecyl group, and a phenyl group, and R ₄ is a Represents a hydrogen atom or a methyl group. ] An imidazole dithiocarboxylic acid compound represented by the general formula R ₅ -Z [wherein R ₅ is a residue selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, and a lauryl group, and Z is a Represents a halogen atom or 1/ _2SO4 group. ] Characterized by carrying out a condensation reaction with an alkylating agent represented by the general formula [Formula] [However, in the formula, R ₂ , R ₄ and R ₅ are the same as above. ] A method for synthesizing an imidazole dithiocarboxylic acid ester compound. 2. Claim 1: A condensation reaction between an imidazoledithiocarboxylic acid compound and an alkylating agent, and dehydrohalogenation or monoalkyl sulfate removal using a hydrogen halide acceptor or monoalkyl sulfate acceptor.
A method for synthesizing an imidazole dithiocarboxylic acid ester compound described in . 3. The method for synthesizing an imidazole dithiocarboxylic acid ester compound according to claim 1, wherein the imidazole dithiocarboxylic acid compound and an alkylating agent are subjected to a condensation reaction in the presence of a hydrogen halide acceptor or a monoalkyl sulfate acceptor. 4. The method for synthesizing an imidazoledithiocarboxylic acid compound according to claim 1, wherein an alkali metal salt of the imidazoledithiocarboxylic acid compound and an alkylating agent are subjected to a condensation reaction.