JPS6056710B2 - Synthesis method of imidazole dithiocarboxylic acid allyl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing imidazole dithiocarboxylic acid allyl ester, and specifically relates to a method for synthesizing imidazole dithiocarboxylic acid allyl ester, and more specifically, a compound having the structural formula R [wherein R2 is a hydrogen atom or a methyl group, an ethyl group, an undecyl group, a heptadecyl group] a residue selected from the group consisting of R and phenyl;

represents a hydrogen atom or a methyl group. It is characterized by carrying out a condensation reaction between imidazoledithiocarboxylic acid shown in ] and allyl halide.

Structural formula 5-℃H2-CH:℃H2 R, [However, in the formula, R2 and R4 are the same as above.

] This relates to a method for synthesizing imidazoledithiocarboxylic acid allyl ester shown in the following. It is known that imidazole dithiocarboxylic acid and its alkali metal salt, which are the starting materials for the method of the present invention, can be easily obtained in high yield from the corresponding parent imidazole and carbon disulfide, as shown in the following reaction formula. This has already been discovered by the present inventors.

(Refer to Japanese Patent Application Laid-Open No. 57-17696) When the starting material imidazole dithiocarboxylic acid and allyl halide are subjected to a condensation reaction, the dithiocarboxylic acid allyl ester hydrogen halide salt is first produced according to the following reaction formula, The desired allyl ester is then obtained by reacting the hydrogen halide salt with a hydrogen halide acceptor. Further, when the starting material imidazoledithiocarboxylic acid and allyl halide are subjected to a condensation reaction in the presence of a hydrogen halide acceptor, the target allyl ester can be obtained according to the following reaction formula.

Further, when the starting material, an alkali metal salt of imidazole dithiocarboxylic acid, is subjected to a condensation reaction with an allyl halide, the target allyl ester can be obtained according to the following reaction formula.

The starting imidazoledithiocarboxylic acid alkali salts 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, an alkali metal salt of the dithiocarboxylic acid is first produced, and this is used as it is as a starting material for allyl ester synthesis. I can do it. The dithiocarboxylic acid easily forms a salt with the basic ion B4, and as shown in the reaction formula below,
Since the dithiocarboxylic acid B salt is provided, the B salt can also be used as a starting material.

Those used as basic ions B4 are Lil, Na
4, K8, Call, Ball, Mgll, Zn48,
Cu44, Mn48, CO844, Ni4l, Fel4
4, Hg84, Sn44, Pbll, NH,4, organic ammonium ion, etc.

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 disadvantageous compared to the use of sodium and potassium salts. I can't think of any particular advantage.

The halogenated receptor used in the present invention is of a very general type, and any receptor can be used as long as it reacts with hydrogen halide to give a neutralized salt.

They are as shown below. NH3, NH4OH,
LiOH, NaOH, KOH, Ca(0H)2, Ba(
0H)2, Mg(0H)2, Li2CO3, Na2CO
3, K2CO3, CaCO3, BaCO3, MgCO3
, CH3COOHNa, CH3COOK, Et3N and tertiary amines such as pyridines, quaternary ammonium hydroxides (eg TritOnB9) and the like.

The allyl halides used in the present invention include allyl chloride,
Among allyl bromide and allyl iodide, allyl iodide is considered to be too expensive and less practical than the former two.

Considering the reaction between active hydrogen in the solvent and allyl halide, it can theoretically be used in the reaction.

It is thought that it is desirable for the solvent to have no active hydrogen, but experimental results show that such predictions are not necessarily accurate, and that solvents such as water and alcohol can also be used satisfactorily. Therefore, restrictions regarding solvents are not considered to have much significance. Representative solvents suitable for the practice of this invention are water, methyl alcohol, ethyl alcohol, dimethyl formamide, dimethyl sulfoxide, acetonitrile, pyridine, acetic acid, acetone, and the like. The reaction of the present invention is exothermic. Therefore, in the case of large-scale synthesis, cooling is required at the start of the reaction, but in the case of small-scale synthesis, no special cooling is necessary. 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 2 hours. A reaction temperature of 80° C. or higher is not particularly required.

A temperature of 80C or less is sufficient.

In order to slow down the heat generation, it is desirable to drop allyl halide into 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 under normal pressure, there is no need to apply additional pressure.

Imidazole dithiocarboxylic acid or its alkali metal salt, allyl halide and nobegen! Regarding the molar equivalent relationship of the hydrogen hydride acceptor, 1 molar equivalent or more than 1 molar equivalent of allyl halide and acceptor may be used per 1 molar equivalent of the starting material dithiocarboxylic acid or its salt.

However, it is uneconomical and meaningless to use them in excessive quantities. 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 dicarboxylic acid allyl esters obtained by the method of the present invention are useful as agricultural chemical intermediates and pharmaceutical intermediates.

Next, the properties of the starting material and the target product will be illustrated.

1 Imidazole dithiocarboxylic acid sodium salt [Both have high melting points and it is difficult to indicate the melting point based on normal melting point measurements.

Instead, Rf in TLC (Silica G, EtOH) is displayed. ] Imidazole-4-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na, B.T.B), 0.45~
0.60 (visual observation) 2-methylimidazole-4-dithiocarboxylic acid Na salt Rf: 0.0 (derived from Na, B.T.
B color), 0.50 to 0.60 (visual observation) 2-ethylimidazole-4-dithiocarboxylic acid Na salt Rf: 0.0 (B
．． T. B), 0.63-0.77 (visual observation) 2-undecylimidazole-4-dithiocarboxylic acid Na salt Rf: 0
．． 0 (B.T.B), 0.57 to 0.70 (visual) 2-
Sodium heptadecyl imidazole-4-dithiocarboxylate
Salt Rf: 0.0 (B.T.B), 0.63 to 0.75 (
Visual observation) 2-phenylimidazole-4-dithiocarboxylic acid Na salt Rf: 0.0 (B.T.B), 0.52 to 0.
66 (visual observation) 4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (B.T.B), 0.44~
0.58 (visual observation) 2.4-dimethylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (B.T.B),
0.55-0.68 (visual observation) 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0
(B.T.B), 0.60-0.73 (visual observation) 2-undecyl-4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (B.T.B), 0.78-0.
90 (visual observation) 2-phenyl-4-methylimidazole-5-dithiocarboxylic acid Na salt Rf: 0.0 (B.T.B
), 0.62 to 0.74 (visual observation) Each of the above Na salts exhibits strong νc=s absorption at 950 to 1030c1-1.

2 Imidazole dithiocarboxylic acid Imidazole-4-dithiocarboxylic acid: Reddish brown crystals.

neutral. M. p. 157-159°C.

Slightly soluble in water, methanol, chloroform, acetone, and acetic acid. DMF1DMSO,. Easily soluble in NaOH aqueous solution.

Rf: 0.45-0.60 (visual observation). νW-1:143
8 (second absorption), 1025 (first absorption). NMR (DM
SO-d(.): δ8.80, DllH; 7.7&Dl
lHr! 4ass: m/El44 (M two, 111 (M-
SH), Seki (imidazole), 44 (:C=S) 2-methylimidazole-4-dithiocarboxylic acid: reddish brown crystals.

neutral. M. p. 187-188°C.

Slightly soluble in water, methanol, chloroform, acetone, acetic acid, acetonitrile, and pyridine. DMSO,. DMF,.
Easily soluble in NaOH aqueous solution. Rf: 0.50 to 0.60 (visual observation). ν11: 1607 (3rd absorption), 1210 (1st
absorption), 1040 (third absorption). NMR (DMF-D7
): δ7.75, SllH; 2.67, S. ．． 3HMa
ss: m/El58 (M, 125 (M+-SH), 8
1, 7 to 44(:C=S)2-ethylimidazole-4
-Dithiocarboxylic acid: Reddish brown crystals.

neutral. M. p. 137-139°C.

Slightly soluble in water, chloroform, and acetic acid. methanol, DMSO
、． Easily soluble in NaOH aqueous solution. Rf: 0.64-0.77
(Visually). νUr. l: 1605 (second absorption), 104
5 (first absorption). Nr! 1R (DMSO.-D6): δ
7.70, SllH; 2.87, Q. ．． 2H; 1.2 sleep T. ．． 3HOMass: m/El72M, 139(M
8-SH), 9-442-undecylimidazole-4-dithiocarboxylic acid: brown crystals. neutral. M. p. l
16-119°C.

Slightly soluble in water, chloroform and cold acetic acid. Soluble in methanol, acetone and hot acetic acid. DMSO. ．． Easily soluble in DMFlNaOH aqueous solution. Rf: 0.70 to 0.81 (visual observation). νduck′.
1:1602 (4th absorption), 1205 (3rd absorption), 1
042 (first absorption). Nr! 4R (CF3COOH):
δ7. Part, SllH; 3.10, t1? ;1.88,M
、． Sha11.30, Mll6H; 0.87, M. ．． 3H
OMass: m/E298 (M+), 265 (M+-S
H), 2, 223s442-heptadecyl imidazole-4-dithiocarboxylic acid: brown crystals.

neutral. M. p. lO7! -112℃.

Slightly soluble in water, chloroform, and cold acetic acid. Soluble in DMSO. R
f: 0.63 to 0.75 (visual observation). νUr. l:160
0 (first absorption), 1525 (third absorption), 1040 (second absorption). NMR (DMSO-D6): δ7.70, S
llH; 2.80, M,. 2H; 1.65, m1? ;1
．． 22, Ml28H; 0.85, M,. 3HOMass
: m/EM+ not appearing, 348 (M+-H2S), 317, 307, 30eK442-phenylimidazole-4-dithiocarboxylic acid: brown crystals.

Mild acidity. M. p. 154-157°C.

Slightly soluble in water, methanol, chloroform, acetic acid, and acetone. DMSO. ．． Easily soluble in NaOH aqueous solution. Rf: 0.52
~0.66 (visual). νU′. 1:1615 (second absorption), 1215 (first absorption), 1040 (first absorption). N
MR (DMSO-D6): δ8.33. ~7.92, M
．． ．． 2H; 7.92, SllH; 7.76-7.30s
m,. 3H0Mass: m/E22O (M, 187 (
M+-SH), 14 days, 10 days, 77.4-Methylimidazole-5-dithiocarboxylic acid: Reddish brown crystals.

neutral. M. p. 159-161°C.

Slightly soluble in water, methanol, chloroform, and acetic acid. DMSO
．． ．． Easily soluble in NaOH aqueous solution. Rf: 0.47-0.60
(Visually). VU'-1: 1590, 1375 to 144,
1265s (second absorption), 1020 to 112, 92\8
8001720 to 6. NMR (DMSO-4): δ8.
60, SllH; 2.62, S. s3HOMass:m
/El58 (M, 125 (M+-SH), 81, 7 Mr. 442.4-dimethylimidazole-5-dithiocarboxylic acid: red crystals. M.p.l 87-189°C.

Slightly soluble in water, methanol, ethanol, chloroform, and acetone. Soluble in acetic acid. DMF. ．． Easily soluble in DMSO. Rf
: 0.57 to 0.70 (visual observation). ν611:1615(
2nd absorption), 1025 and 990 (1st absorption). NMR
(CF, COOH) δ2.77, S,. 3H:2.7
to S. ．． 3HOMass: m/El72 (M, 139
(M+-SH), 95s422-ethyl-4-methylimidazole-5-dithiocarboxylic acid: reddish-purple crystals.

neutral. M. p. 177-179°C.

Slightly soluble in water, methanol, ethanol, and acetone. Soluble in acetic acid. DMF1 Easily soluble in DMSO. Rf: 0.60~0.
70 (visual). νU′. 1:1615 (second absorption), 1
013 (first absorption). NMR (DMSO-D6): δ2
．． 80sq. 2H: 2.60, Ss3H: 1.23N
t,. 3H. ．． Mass: m/El86 (M, 153
(M+-SH), 1092-undecyl-4-methylimidazole-5-dithiocarboxylic acid, red solid.

basic. M. p. Unable to measure due to high moisture absorption.

Soluble in water, methanol and ethanol. Rf: 0.70~
0.80 (visual). νU′. 1:1512 (first absorption)
, 1378 (second absorption), 1000 (third absorption). Ma
ss: m/E3l2 (M, 279 (M+-SH), 2
47(M+-HS2) 23602-phenyl-4-methylimidazole-5-dithiocarboxylic acid: Reddish brown crystals.
M. p. 165-168°C.

Slightly soluble in water, methanol, ethanol, acetone, chloroform, t-butanol, and benzene. Soluble in acetic acid and methyl cellosolve. DMF. ．． DMSO. ．． Soluble in NaOH aqueous solution. Rf: 0.65-0.78. νUr. l:16
25 (third absorption), 1603, 1540, 1485, 1
215 (second absorption) 1040 (first absorption). NMR(C
F3COOH) δ8.00, ~7.50, M. ,5H
:2.89,S,. 3H Or! 4ass:m/E234
(M+), 201 (M+-SH), 1 Seki, 10 ton 77.
3 Target imidazo-4-dithiocarboxylic acid-allyle.

Stell structural formula” 1-yun, child − −ーー゜ −゜“ −
゜゜゜Physical propertiesOrange crystal.

neutral. M. p. 139-141°C (acetone) Soluble in methanol, ethanol, acetone, acetic acid, dimethyl sulfoxide, and chloroform. Poorly soluble in water. TLC (Silica G..CHCl3/MeOH=10/1V0I:, ratio)
RfO. 3O~0.40νU'. 1:1634 (νC=
C), 1438 (third absorption), 1100 (fourth absorption) 1
045 (first absorption, νC=S), 989 (δCH=),
920 (4th absorption, δCH=), 822 (2nd absorption)
4NMR (CF, COOH): δ
8.80, SllH (2nd position proton); 8.03, Sl
lH (proton at 4th position); 6.08-5.27, M. ．． 3
H (vinyl); 4.13, D. ．． 2H (methylene) Ma
ss:m/El84(M+), 169(M+-CH2-
H), 16 to 151 (M+-S-H), 12 巳 11 飄 1
11 (Im+CS), taste 64.44 (CS) 2-methylimidazole-4-dithiocarboxylic acid monoallyl ester "-]) Structural formula N..7NHS Orange crystals.

neutral. M. p. 144-146℃ (acetone), MeO
H,. Soluble in EtOH, acetone, acetic acid, CHCl3, and benzene. Poorly soluble in water. L°C (mentioned above): RfO. 44-0
．． 54v5'. 1:1632(νC=C), 1522(
3rd absorption), 1395 (4th absorption), 1065 (4th absorption), 1020 (1st absorption, νC=S), 991 (δC
H=), 915 (δCH=), 847 (second absorption) NM
R(CF3COOH) δ7.90, SllH (4th position)
;6.10~5.23sm. ．． 3H (vinyl); 4.1
0, D, . 2H (methylene); 2.80. ．． s,. 3H
(Methyl) Mass: m/El98(M+), 183(
M+-CH2-H), 165 (M+-S-H), 157
(Im+CSS), 125 (1m+CS), 44 (CS
) 2-ethylimidazole-4-dithiocarboxylic acid allyl ester 11X Mi-NiNHS Orange crystal.

neutral. M. p. lO7-109°C (acetone). MeO
HlEtOHl Acetone, AcOH, . Soluble in CHCl, toluene, DMSO.

Poorly soluble in water. L°C (mentioned above): RfO. 55~0.65vU
″.1:1635 (νC=C), 1516 (second absorption)
, 1117 (4th absorption), 1087 (3rd absorption), 10
45 (first absorption, νC=S), 984 (δCH=), 9
21 (δCH=), 828 (fifth absorption) NMR (CF3
COOH) δ7.90, SllH (4th position); 6.13
~5.23. m. ．． 3H (vinyl); 3.15, Q, .
2H (methylene); T. to 1.5. 3H (methyl) Mas
s: m/E2l2(M+), 197(M+-CH2-H
), 179 (M+-S-H), 139 (Im+CS),
127, 12 tons 44 (CS) 2-undecylimidazole-4-dithiocarboxylic acid-allyl ester --]
″＼ Structural formula N-, NHS Yellow-orange crystal.

neutral. M. p. 75-78°C (acetone). MeOH,
．． EtOHl acetone, AcOH. ．． CHCl3, CH
3CNl toluene, DMSO. ．． Soluble in DMF.

Poorly soluble in water. TLC (supra): RfO. 7O~0.80ν
18fL'. 1:1636 (νC=C), 1520 (third absorption), 1118 (second absorption), 1060 (first absorption, νC=S), 975 (δCH=), 900 (δCH=
), 825 (4th absorption) NMR (CF3COOH)
δ7.92, SllH (4th position): M to 6.00 to 5.2
、． 3H (vinyl); 4.12, D. ．． 2H (methylene); 3.12, T. ．． 2H (α-methylene); 1.92
, Br. ．． 2H (β-methylene); 1.3 AtsushiBrll6
H (polymethylene); 0.88, Tl3H (terminal methyl) Mass: m/E338 (M, 305 (M+-S-
H), 297 (Im+CSS), 296 (297-H)
, 265 (Im+CS), 44 (CS) 2-heptadecyl imidazole-4-dithiocarboxylic acid allyl ester --T~\ Structural formula N. -NHS Orange crystal.

neutral. M. p. 8l~85°C (acetone) MeOH. ．．
EtOHl acetone, CHCl3, AcOHl toluene, DMSO. ．． Soluble in DMF. Poorly soluble in water. TLC (supra): RfO. 72-0.811469 (4th absorption), 1
120 (second absorption), 1066 (first absorption, νC=S)
, 972 (δCH=), 900 (δCH=), 83 fight 5
Absorption) NMR (CF3COOH) δ7.90, Sll
H (4th place): 6.00-5.200, M. ．． 3H (vinyl) 4.30,. d, s2H(-S-CH2-);3.
10, Tl3H (α-methylene); 1.90, Br. ．．
2H (β-methylene); 1.3λBrl28H (polymethylene); T. to 0.9. ．． 3H (methyl) Mass: m
/E422(M+), 407(M+-CH2-H), 3
89 (M+-S-H), 380 (Im+CSS), 34
9(Im+CS), 347,...4t(CS)2-
Phenylimidazole-4-dithiocarboxylic acid allyl ester structural formula 1\Ia111Orange crystals.

neutral. M. p. ll7-119lC(acetone)MeO
H. sEtOHl acetone, CHCl3, AcOHl toluene, DMSO. Soluble in sDMF.

Poorly soluble in water. TLC (supra): RfO. 65~0.75v
U'-1: 1635 (νC=C), 1510 (4th absorption), 1136 (1st absorption), 1100 (5th absorption), 1
000 (second absorption, νC=S), 980 (δCH=),
930 (δCH=), 714 (third absorption) NMR (CF
3COOH) δ&10, SllH (4th place), 8.0
0-7.60, M,,5H (phenyl); 6.10-5
．． 30, M,. 3H (vinyl); 4.20. sd. ．． 2
H (methylene) Mass: m/E26O (M+), 24
5 (M+-CH2-H), 227 (M+-S-H), 1
87 (Im+CS), 104 (Ph-C=NH) 77,
6g. 44(CS) 4-methylimidazole-5-dithiocarboxylic acid allyl ester Structural formula 0H・1"--"4
〉.

MeOH,. EtOHl acetone, AcOH. ,CHC
Soluble in l3, benzene, CH3CN.

Poorly soluble in water. Tada (mentioned above): RfO. 32~0.42νu
'． 1:1639 (νC=C), 1500 (5th absorption)
, 1430 (4th absorption), 1382 (3rd absorption), 10
47 (first absorption, νC=S) 985 (δCH=), 92
5 (δCH=), 837 (second absorption) NMR (CF3C
OOH) δ8.62, SllH (2nd place); 6.20~
．． Go to 5.3 M. ．． 3ll (vinyl); 4.17, D. ．．
2H (methylene); 2.87, S, . 3H (methyl) M
ass: m/El98 (M+), 183 (M+-CH2
-H), 165 (M+-S-H), 157 (Im+CS
S), 125 (Im+CS), 44 (CS) 2,4-dimethylimidazole-5-dithiocarboxylic acid allyl ester structural formula orange crystals.

neutral. M. p. l48-150℃ (acetone) MeOH
、． EtOHl acetone, AcOH,. CHCl3, soluble in benzene.

Poorly soluble in water. TLC (supra) RfO. 46~0.56νU
r. l: 1638 (νC=C), 1523 (second absorption)
, 31113 (fifth absorption), 1075 (first absorption, νC
=S), 998 (third absorption, δCH=), 920(δC
H=), 834 (4th absorption) NMR (CF3COOH)
δ6.10-5.30, M,. 3H (vinyl); 4.
13, D. ．． 2H (methylene) 32.80ss. ,3
H (2-position methyl): 2.73. s1 target (4th methyl) M
ass: m/E2l2(M+), 197(M+-CH2
1H), 179 (M+-S-H), 171 (Im+CS
S), 139 (Im+CS), 44 (CS)
42-Ethyl-4-methylimidazole-5-dithiocarboxylic acid allyl ester structural formula rl-J,,
Blue H\Orange crystal.

neutral. M. p. l27-129℃ (acetone) MeOH
lEtOHlacetone, AcOHlCHCl3, CCl
, Soluble in benzene, toluene, DMSO1DMF.

Poorly soluble in water. TLC (supra): RfO. 5O~0.60ν
Duck R. l: 1638 (νC=C), 1525 (first absorption), 1395 (second absorption), 1047 (first absorption, νC
=S), 1025 (third absorption), 985 (δCH=),
915 (δCH=), 845 (4th absorption) NMR (CF
3COOH): δ6.20-5.20, M,. 3H (vinyl): 4.03sd,. 2H(-S-CH2-)2.
71, Q. 2H (α-methyl); S to 2.6, . 3H (
4-position methyl); T to 1.3, . 3H (terminal methyl) Ma
ss: m/E226 (M, 193 (M+-S-H),
185 (Im+CSS), 153 (!m+CS) 2-undecyl-4-methylimidazole-5-dithiocarboxylic acid allyl ester 113] = 2\, Fukizo style,, NIIS orange crystal.

neutral. M. p. 86～屹℃(acetone)MeOHlEt
OHL acetone, toluene, AcOH,. CHCl3,
Soluble in DMSO, DMF. Poorly soluble in water. TLC (mentioned above)
:RfO. 7O~0.80Vur. 1:1631 (νC
=C), 1520 (first absorption), 1390 (second absorption)
, 1049 (first absorption, νC=S), 1020 (third absorption), 980 (δCH=), 910 (δCH=), 84
4 (4th absorption) NMR (CF3COOH): δ6.00
~5.10, M,. 3H (vinyl): 4.20, D, .
2H(-S-C-)3.10, T. ．． 2H (α-methylene): 2.87, Sl3H (4-position methyl): 1.97
, Br. ．． 2H (β-methylene): 1.40Nbr11
6H (polymethylene) 0.97, Br,. 3H (terminal methyl) Mass: m/E352 (M two, 337 (M+-
CH2-H), 319 (M+-S-H), 311 (Im
+CSS), 310 (311-H), 279 (Im+C
S), 44(CS) 2-phenyl-4-methylimidazole-5-dithiocarboxylic acid allyl ester structural formula N
YNH゛Orange crystal.

neutral. M. p. l57~15Cfc(EtOH)MeO
H,. EtOHl Acetone, CHCl3, AcOHl
Toluene, CH3CNlDMSO, . Soluble in DMF, sparingly soluble in water. TLC (supra): RfO. 65~0.75νU
'． 1:1635 (νC=C), 1520 (4th absorption)
, 1482 (4th absorption), 1392 (3rd absorption), 10
51 (second absorption, νC=S), 980 (δCH=), 9
23 (δCH=), 840 (first absorption) NMR (CF3
COOH) δ8.00~7.63, m1 station; 6.2
0-5.30, M. ．． 3H (vinyl); 4.19, D,
．． 2H (methylene); 2, 屹, S, . 3H (methyl) M
ass: m/E274 (M, 241 (M+-S-H)
, 201 (Im+CS), 189, 104 (Ph−C=
NH), 77, 44 (CS) Example 1 A reaction vessel equipped with a reflux condenser was mounted on a magnetic stirring hot plate, and 0.03 mol (4
．． 3f1), calcium hydroxide 0.015 mol (1.1
After 0.03 mol (2.3 fI) of allyl chloride was added all at once at room temperature while stirring, the system was heated and refluxed for 2 hours.

The internal temperature during reflux was 70°C. After cooling the system, the contents were filtered, the filtrate was dried to dryness under reduced pressure, and the dried product was briefly boiled with 30 ml of water, then cooled, the insoluble crystals were collected by filtration, and the filtered crystals were reconsolidated with acetone to obtain a crude product. Target object (M.p.l27-1
35°C; TLC (silica G1 chloroform/methanol 10/1 volume ratio, 12 colors) RfO. 3O~0.40
, 0.80-0.83 (very thin)) was obtained in 3.5y (yield: 8%). Example 2 A part of the crude target product of Example 1 was taken and made into a hot acetone solution, the hot solution was treated with activated carbon, the crystals that precipitated when cold were collected from the filtrate, and the hot acetone solution of the filtered crystals was further dissolved. The activated carbon treatment was performed once more, and the crystals precipitated when cold were collected from the filtrate by filtration, and the filtered crystals were reconsolidated with acetone to obtain the previously identified sample (M.
9-141°C).

Example 3 A system consisting of 0.03 mol (5.9 f) of 2-methylimidazole-4-dithiocarboxylic acid potassium salt, 20 ml of methanol, and 0.03 mol (3.6 V) of allyl bromide was cooled with three ice cubes. Then, after keeping it at 20-25℃ for 2 hours, it was dried under reduced pressure, and the dried product was washed with 30ml of water and then recondensed with acetone to obtain the crude target product (M.p.l 38-145℃).
; TLC (equivalent to Example 1) RfO. 46-0.56) was obtained in 4.3y (yield 72%).

Example 4 2-methylimidazole-4-dithiocarboxylic acid 0.0
3 mol (4.7y), 2 ml DMFl and 0 allyl chloride
．． A system consisting of 03 moles (2.3 V) of 40
After being kept at ~45°C and then at 70-75°C for 1 hour, it was cooled and concentrated under reduced pressure to give a candy-like residue.

The residue was extracted with 30 ml of methanol, the extract was made ammoniacal, and then dried under reduced pressure.
After boiling briefly with water, the water layer was decanted, the insoluble residue was reconsolidated with acetone, and the crude target product (M.p.l.
35-142°C, published (corresponding to Example 1) RfO. 45~
0.55) was obtained (2.4 g (yield 40%)). Example 5 A portion of the crude target product of Example 4 was treated as in Example 2 to obtain the identified sample (M.p.I. 44-146 DEG C.).

Example 6 0.03 mol (5.2 fI) of 2-ethylimidazole-4-dithiocarboxylic acid, 0.0 potassium carbonate
15 mol (2.1y), 12 ml of water and 0.1 y of allyl chloride.
A system consisting of 03 moles (2.3・') of 4 components was heated for 1 hour at 40
~45°C, then kept at 70-75°C for 1 hour, cooled, decanted the aqueous layer, extracted the residue with 20 ml of acetone, dried the extract, and reconstituted the dry matter with acetone. The crude target product (M.p.lO2 ~ 106°C: L°C (described above)) RfO. 55-0.65) (3.3g (yield 52%)
) got it.

Example 7 A part of the crude target product of Example 6 was taken and made into a hot acetone solution, the solution was treated with activated carbon, the crystals that precipitated when cold were collected from the filtrate, and the filtered crystals were reconsolidated with acetone. An identification sample (M.p.lO 7-109°C) was obtained.

Example 8 2-undecylimidazole-4-dithiocarboxylic acid 0
．． 03 mol (8.9f), sodium hydroxide 0.03 mol (1.2y), ethanol 12ml and allyl chloride 0
．． A system consisting of 03 moles (2.3 y) of 4 members was heated for 2 hours at 70
The system was maintained at ~75°C, then cooled, the system was filtered, the filtrate was concentrated under reduced pressure, the toluene solution of the residue was passed through a bed of activated clay, the permeate was dried under reduced pressure, and the dried product was reconsolidated with acetone. Crude target material (M.p. 7l~76℃; η℃ (previously) RfO.7O~
0.80, 0.80-0.85 (very thin)) to 5.3
y (yield 52%) was obtained.

Example 9 A portion of the crude target product of Example 8 was treated as in Example 7 to obtain an identified sample (M.p. 75-78°C).

Example 10 0.01 mol (3.8') of 2-heptadecyl imidazole-4-dithiocarboxylic acid, 0.005 mol (4) of calcium carbonate. 5y), a system consisting of 2 ml of DMF1 and 0.01 mol (0.8 f) of allyl chloride was kept at 70-75°C for 2 hours, then cooled, the system was filtered, the filtrate was concentrated under reduced pressure, and the residue was dissolved in 30 ml of water. The aqueous layer was decanted, the residue was reconstituted with acetone, and the crude target product (M.p. 6O~75C; TLC (previously)) was obtained by cooling.
．． 65-0.72 (very thin), 0.72-0.81)
3.5y (yield: 82%) was obtained.

Example 11 A portion of the crude target material of Example 10 was treated as in Example 2,
An identification sample (M.p. 8l~85°C) was obtained.

Example 12 0.03 mol (6.6y) of 2-phenylimidazole-4-dithiocarboxylic acid, 0 triethylamine
．． A system consisting of 0.03 mol (3.0 f1) ethanol 20 ml and allyl chloride 0.03 mol (2.31) was heated for 2 hours 7
The system was kept at 0-75°C and then cooled, the system was concentrated under reduced pressure, the residue was boiled with 30 ml of water, cooled, the aqueous layer was removed, the residue was dissolved in chloroform, and the solution was added to the activated clay layer. The filtered liquid was dried under reduced pressure, and the dried product was reconsolidated with acetonitrile to obtain the crude target product (M.P.ll3-11rc; TL
C (supra) RfO. 65-0.75) was obtained in 4.1y (yield 52%). Example 13 A part of the crude target product of Example 12 was reconstituted twice with acetone to obtain an identified sample (M.p.ll7-11CfC).

Example 14 4-methylimidazole-5-dithiocarboxylic acid 0.03 mol (4.7f), 28% aqueous ammonia 0
．． 03 mol (1.8 V), 20 ml of water and 0 allyl chloride
．． A system consisting of 03 moles (2.3y) was heated for 2 hours at 20-30
After maintaining the temperature at 45°C, the precipitated crystals were collected by filtration and reconsolidated with acetone to obtain the crude target product (M.p.l 45-155°C: Tada (supra) Rf
O. OO~0.15 (very thin), 0.32~0.42
) was obtained in an amount of 3.6 fI (yield 60%).

Example 15 4-methylimidazole-5-dithiocarboxylic acid 0.0
2 ml of 3 mol (4.7y) DMF1 and 0.0 ml of allyl chloride.
A system consisting of 0.03 mol (2.3f) was heated at 40-45°C for 1 hour.
After keeping at 70-75°C for 1 hour, it was cooled, the system was concentrated under reduced pressure, the residue was extracted with 30 mt of methanol, the extract was made ammoniacal, and then dried under reduced pressure to dryness. The product was boiled with 30 ml of water, cooled, the aqueous layer was removed, and the residue was reconstituted with acetone to obtain the crude target product (M.p.
l49-155°C; η°C (supra) RfO. OO～0.1
5 (extremely thin), 0.32-0.42) was obtained by 2.3f (yield 39%).

Example 16 A portion of the crude target product of Example 15 was treated as in Example 2 to obtain an identified sample (M.p.l 59-161°C).

Example 17 A system consisting of 0.03 mol (4.7 f) of 4-methylimidazole-5-dithiocarboxylic acid, 12 ml of pyridine and 0.03 mol (2.3 f) of allyl chloride was kept at 40-45°C for 2 hours and then cooled. , subjected to vacuum concentration,
The residue was boiled with 30 ml of water, cooled, the aqueous layer was removed, and the residue was reconsolidated with acetone to obtain the crude target product (M.p.l2
5-140°C: TLC (mentioned above) RfO. 32-0.42
, 0.80-0.82 (extremely thin)) at 2.5 V (yield 42%).

Example 18 0.03 mol (5.2 y) of 2.4-dimethylimidazole-5-dithiocarboxylic acid, 0.03 mol (4.1 y) of sodium acetate, trihydrate, 20 ml of water and 0.03 mol (2 y) of allyl chloride. The system consisting of .3V) was kept at 40-45°C for 3 hours, then cooled, the precipitated crystals were collected by filtration, the filtered crystals were extracted with 30ml of acetone, and the extract was filtered (at this time, unreacted Thiocarboxylic acid 3.1f1 recovered), the filtrate was dried, the dried product was reconsolidated with acetone, and the crude target product (M.p.l 35-143°C; TLC (supra) RfO.
2O~0.23 (extremely thin), 0.44~0.54) was obtained in 1.8y (yield 28%, corrected yield 70%).

Example 19 A system consisting of 0.03 mol (5.2 V) of 2.4-dimethylimidazole-5-dithiocarboxylic acid, 2 ml of DMFL and 0.03 mol (2.3 f) of allyl chloride was heated at 40 mol for 1 hour.
After keeping the temperature at ~45°C and then at 70-75°C for 1 hour, the system was cooled and filtered, the filtrate was dried under reduced pressure, and the dried product was extracted with 30 ml of methanol to make the extract ammoniacal. The dried product was boiled with 30 ml of water and then cooled. The aqueous layer was removed and the residue was reconstituted with acetone to obtain the crude target product (M.p.l 34-142C; TLC (previously)) RfO. ．．
3.3f (yield 52%) of lO~0.14 (very thin), 0.44~0.54) was obtained.

Example 20 A part of the crude target product of Example 19 was dissolved in hot acetone and treated with activated carbon, and the crystals precipitated when cold were collected from the filtrate by filtration, and then reconsolidated once with acetone to obtain an identified sample (M.p. .l48～
150°C).

Example 21 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid 0.03 mol (5.6y), magnesium carbonate 1
．． 5y1 water 20ml and allyl chloride 0.03 mol (2.
The system consisting of 3y) was kept at 40-45°C for 5 hours, then cooled, the precipitated crystals were collected by filtration, and the filtered crystals were extracted with 30ml of acetone (at this time, unreacted dithiocarboxylic acid 1 .7y was collected), the extract was dried, and the dried product was reconstituted with acetone to obtain the crude target product (M.p.12O~12rC;
TLC (supra) RfO. 2O~0.52 (extremely thin),
0.52-0.62) was obtained by 3.5 f (yield 51%, corrected yield 72%).

Example A system consisting of 0.03 mol (5.6') of 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid, 2 ml of DMF1 and 0.03 mol (2.3y) of allyl chloride was kept at 40-45°C for 1 hour. , then another hour 70-75
After cooling, the system was concentrated under reduced pressure. The residue was dissolved in 30 ml of methanol to make the methanol solution ammoniacal, and then dried under reduced pressure. The dried product was boiled with 30 ml of water, then cooled, and the aqueous layer was removed. The residue was reconstituted with acetone to obtain the crude target product (M.p.l 22-127°C; L°C (as above) RfO.
5O~0.60) was obtained in an amount of 2.9y (yield 43%).

Example 23 A portion of the crude target product of Example n was taken and reconstituted twice with acetone to obtain an identified sample (M.p.l 27-129°C).

Example 24 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid 0.03 mol (5.6 f), potassium hydroxide 0.
A system consisting of 0.03 mol (1.7 f), 2 ml of DMSOl, and 0.03 mol (2.3 f) of allyl chloride was heated for 20 hours at 20 ml of allyl chloride.
After keeping the temperature at ~25°C, it was concentrated under reduced pressure, and the residue was boiled with 30 ml of water, cooled, the aqueous layer was removed, and the residue was reconstituted with acetone to give the crude target product (M.p.ll 9-126°C; TLC(
(mentioned above) RfO. 2O~0.52 (very thin), 0.52
~0.64) was obtained by 3.6 f (yield percentage).

Example 25 0.03 mol (9.4 y) of 2-undecyl-4-methylimidazole-5-dithiocarboxylic acid, 0.015 mol (1.6 f) of sodium carbonate, 12 ml of ethanol, and 0.03 mol (2.3 y) of allyl chloride. After keeping the system at 40-45°C for 2 hours, the system was cooled and filtered, the filtrate was concentrated under reduced pressure, the residue was dissolved in toluene, the toluene solution was passed through a bed of activated clay, and the passed liquid was dried under reduced pressure. The dried product was reconsolidated with acetone to obtain the crude target product (M.P. 75 ~ ℃; TLC
(Supra) RfO. 7O~0.80) in 4.3g (yield 4
0%) got it.

Example 26 A portion of the crude target product of Example 25 was taken and reconstituted twice with acetone to obtain an identified sample (M.p. 86-97C).

Example 272-Phenyl-4-methylimidazole-5
-dithiocarboxylic acid 0.03 mol (7y), sodium carbonate 0.015 (1.6y), acetonitrile 20ml
A system consisting of 0.03 mol (2.3 y) of allyl chloride was kept at 70 to 75°C for 2 hours, then cooled and filtered, the filtrate was dried, and the dried product was reconsolidated with toluene to obtain the crude target. Things (M.
p. l42-149 Re-C; TLC (supra) RfO. 5O
~0.57 (very thin), 0.65-0.75) 4.4
y (yield percentage) was obtained.

Example 28 A portion of the crude target product of Example 27 was taken, a hot ethanol solution thereof was treated with activated carbon, the crystals that precipitated when cold were collected from the filtrate, and the filtered crystals were treated in the same manner one more time. Then, the crystals thus obtained were re-solidified with ethanol and used as an identification sample (
M. p. 157-159°C) was obtained.

Example 29 4-methylimidazole-5-dithiocarboxylic acid 0.0
3 mol (4.7y), sodium acetate trihydrate 0.03
mol (4.1y), acetic acid 12ml and allyl chloride 0.0
The system consisting of 3 mol (2.3y) was kept at 70-75°C for 2 hours, then the system was cooled and filtered, the liquid was concentrated under reduced pressure, the residue was boiled with 30ml of water, and after cooling the aqueous layer was removed. The residue thus obtained was recondensed with acetone to obtain the crude target product (
M. p. l42-150°C; TLC (supra) RfO. 3
4-0.45) was obtained in 3.1y (52% yield).

Example 30 2. Consists of 0.03 mol (5.2y) of 4-dimethylimidazole-5-dithiocarboxylic acid, 0.015 mol (1.6 fI) of sodium carbonate, 20 ml of acetone and 0.03 mol (2.3 V) of allyl chloride. After the system was refluxed for 3 hours (inner temperature 56-59'C), it was cooled and filtered (
At that time, 0.5f of unreacted dithiocarboxylic acid was recovered)
, dry the p solution, reconsolidate the dried product with acetone to obtain the crude target product (
M. p. 138-146 C; TLC (supra) RfO.
42-0.54) to 3.7y (yield ratio %, corrected yield 64
%) Got.

Claims (1)

[Claims] 1 Structural formula ▲ Numerical formulas, chemical formulas, tables, etc. The residue R_4 represents a hydrogen atom or a methyl group. ] There are structural formulas characterized by the condensation reaction of imidazole dithiocarboxylic acid and allyl halide ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R_2 and R_4 are the same as above. ] A method for synthesizing imidazole dithiocarboxylic acid allyl ester. 2. The method for synthesizing imidazoledithiocarboxylic acid allyl ester according to claim 1, wherein imidazoledithiocarboxylic acid and allyl halide are subjected to a condensation reaction, and dehydrohalogenation is carried out using a hydrogen halide acceptor. 3 Forming a salt of imidazole dithiocarboxylic acid and subjecting it to a condensation reaction with allyl halide Claim 1
The method for synthesizing imidazoledithiocarboxylic acid allyl ester described in .