JPH03236369A - Production of sulfenamide derivative - Google Patents

Abstract

PURPOSE:To readily and quickly obtain a compound useful as a fog restrainer for silver halide photograph in high yield by treating an amide-type compound with sodium hydrogenate and iodine and reacting with dithiocarbamate. CONSTITUTION:An amide-type compound expressed by formula I(R<1> is aryl, heterocycle group, alkyl, dialkylamino or alkoxy) is dissolved in a suitable solvent (e.g. THF) and sodium hydrogenate is added, then stirred at room temperature, thus iodine is further added and stirred. Next, dithiocarbamate expressed by formula II(R<2> and R<3> are lower alkyl, formable of a ring with bonding; M<+> is metallic cation) in an amount of 1-1.2 equiv. to iodine is added to the system and resultant system is stirred at room temperature for 1-2hr to afford the aimed compound expressed by formula III. 1-0.75 equiv. sodium hydrogenate and 0.75-0.5 equiv. iodine are used to 1 equiv. of the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing sulfenamide derivatives, more specifically, after treating an amide type compound with sodium hydride and iodine, it is treated with a dithiocarbamate. This invention relates to a method for producing sulfenamide derivatives simply, rapidly, and in good yields by reaction. (III)) and its analogs, N-acyl-8-thioaroylsulfenamide, etc., are produced by aroylation or acylation reaction of the corresponding N-unsubstituted sulfenamide. (Special Publication No. 62-41712, Special Patent Application No. 1983)
3-219738).

However, the raw material N-unsubstituted sulfenamide has a stability problem, and the acyl group or aroyl group (substituent R1 in general formula (III) below) of the sulfenamide derivative synthesized by this method The types were limited.

(Problems to be Solved by the Invention) The present invention provides a method for producing a wide variety of sulfenamide derivatives using a dithiocarbamate in a simple, rapid manner and in good yields, which overcomes the drawbacks of the above-mentioned conventional methods. The purpose is to provide

(Means for Solving the Problems) The above object of the present invention is achieved by the general formula % (in the formula, R1 represents an aryl group, a heterocyclic group, an alkyl group, a dialkylamino group, or an alkoxy group). After treating the amide type compound represented by sodium hydride and iodine, the compound of the general formula (wherein R'', R'' represents a lower alkyl group, R'',
R' may be combined to form a ring, and M+ represents a metal cation. ) (wherein R', R'' and R3 have the same meanings as above).

) This was achieved by the method for producing a sulfenamide derivative represented by:

In the method of the present invention, specific examples of R in the above general formula (I) include phenyl group, p-anisyl group, p-)lyl group,
p-chlorophenyl group, 2-thienyl group, 3-pyridyl group, 2-furyl group, t-butyl group, n-butyl group, methyl group, dimethylamino group, diethylamine group, diisopropylamino group, methoxy group, ethoxy group, Examples include impropoxy group. This R' may have a substituent that is inactive in the reaction. General formulas (n) and (II
Examples of the R"R"N group in I) include dimethylamino group, diethylamino group, diisopropylamino group, morpholino group, piperidino group, and the like. General formula (Ir)
Examples of the Mo inside include Na'', R4, Ag+, and the like.

In the method of the present invention, the reaction solvent is preferably an anhydrous ether, such as tetrahydrofuran or dioxane. Further, as the sodium hydride, either an anhydride or an oil suspension (C50 to 60%) can be used.

In the method of the present invention, the reaction is carried out by first dissolving the amide type compound represented by the general formula (I) in a suitable solvent, adding preferably 1 to 0.75 equivalents of sodium hydride, and more preferably 0.75 equivalents of sodium hydride at room temperature. Stir with After the generation of hydrogen gas has stopped, preferably 0.7 for the amide type compound.
Add 5 to 0.5 equivalents, more preferably 0.5 equivalents of iodine, and stir further. Finally, the dithiocarbamate represented by the general formula (n) is preferably 1 to 1 to 1 to iodine.
Add 1.2 equivalents, more preferably 1.2 equivalents, about 1 to 2
Stir for an hour. The completion of the reaction can be determined by the discoloration of the reaction solution. The reaction temperature is usually room temperature, but
The reaction can also be accelerated by heating if necessary. For post-treatment after completion of the reaction, first, the mixture is poured into water, extracted with methylene chloride, and separated and purified by column chromatography and recrystallization.

The reaction in the method of the present invention can be expressed by the scheme below.

R” R” NC3S-M” R”＼ R” S O The structure of the obtained sulfenamide derivative was confirmed by comparing known compounds with standard products, and for new compounds by infrared absorption spectra and nuclear magnetism. resonance spectrum,
This can be carried out using mass spectrometry or elemental analysis.

(Effects of the Invention) According to the method of the present invention, the reaction proceeds rapidly under relatively mild conditions, and sulfenamide derivatives can be obtained in good yields. The raw materials and reaction reagents used are both inexpensive and easy to handle, and in post-treatment, inorganic components and unreacted raw materials can be effectively removed by extraction. In addition, by appropriately selecting an amide type compound represented by formula (I), 7. Aa, □derivative,, □ftW□3.
□Can enter.

Sulfenamide derivatives produced by the method of the present invention, and 1, 4. obtained by cyclodehydration thereof.
Both 2-dithiazolium salts are used as fog suppressants for silver halide photography (Japanese Patent Application No. 530-1982).
No. 73, Japanese Patent Application No. 1-94149). Also, 1,4.2
-Dithiazolium salts are intermediate raw materials for various sulfur-containing, nitrogen-containing heterocyclic compounds, and are useful compounds in organic synthesis.

Furthermore, this reaction is not limited to amide-type compounds, but can also be applied to primary or secondary amines, and thiolate can be used instead of dithiocarbamate, and can be used as a general synthesis method for sulfenamide. It can be applied to the synthesis of various compounds.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 225 mg (3 mmol) of methyl carbamate was dissolved in 12 mmol of anhydrous tetrahydrofuran, and 108 mg (2,25 mmol) of sodium hydride (50% oil suspension) was dissolved.
mmol) was added, and after hydrogen generation stopped, the mixture was further stirred for 5 minutes. After adding 381 mg (1.5 mmol) of iodine and stirring for 5 minutes, 46 mg of silver diethyldithiocarbamate was added.
1 mg (1.8 mmol) was added and stirred for 30 minutes.

Add water and extract with methylene chloride. At that time, insoluble matter was filtered off. After distilling off the solvent, it was treated with silica gel column chromatography and recrystallized from pentane-ether, resulting in a melting point of 6.
White crystals of N-methoxycarbonyl-8- at 67°C
Diethylthiocarbamoylsulfenamide 291mg
(yield 87%).

H-NMR (CDC1, TMS) δ=1.29
(6H, t, J=7.5Hz).

3.79 (3H, s), 3.4-4.2 (4H, br
), 6.35 (br, 5) IR (KBr, cra-
') 322g (NH), 1735 (C:0) Elemental analysis (%) Measured value C; 37.82 H; 6.27 N
; 12.50S; 28.73 Calculated value C; 37.82 H: 6.35 N
; 12.60S ; 28.85 Example 2 Methyl carbamate 2.04g (27.2mmol)
was dissolved in 35% of anhydrous tetrahydrofuran, and in the same manner as in Example 1, 0.98 g (2
0.4 mmol), iodine 3.45 g (13.6 mmol)
1) and 3.02 g (16.3 mmol) of sodium morpholine-N-dithiocarboxylate were sequentially added and stirred for 2 hours. After the post-treatment in the same manner as in Example 1, white crystals of N-methoxycarbonyl-5-(morpholine-N-
2.50 g (78
%) was obtained.

'H-NMR (CDC1,, TMS) δ=3.7-
3.8 (4H, m).

3.9-4.1 (4H, m), 3.80 (3H, s)
, 6.22 (br, s) C-NMR (CDC1,,
TMS) δ=50.37.53.56.65.67
゜156.87.198.51 Example 3 121 mg of benzamide instead of methyl carbamate
Sodium hydride (0.75 mmol), iodine (0.5 mmol) were used in the same manner as in Example 1, except that (1a + mol) was effectively dissolved in anhydrous tetrahydrofuran.
l), silver diethyldithiocarbamate (0,5 mmo
1) were added one after another and stirred for 1 hour. Thereafter, the same post-treatment as in Example 1 was carried out to obtain 71 mg of white crystalline N-benzoyl-3-diethylthiocarbamoylsulfenamide (53%
) was obtained.

Specimen (Bull, Chem, Sac, Jpn,
59.2017 (1986)).

Example 4 122 mg of nicotinic acid amide instead of benzamide (
The reaction and post-treatment were carried out in the same manner as in Example 3, except that 1 mmol) was dissolved in 4 ml of anhydrous tetrahydrofuran. carbonyl)-
3-diethylthiocarbamoylsulfenamide 50m
g (37%) was obtained.

'H-NMR (CDC1, MS) δ=3.3
1 (6H, t, J=7.5Hz).

3.5-4.2 (4H, br,), 7.3-7.5 (
LH,m), 8.2-8.4(LH,m)CTh, 7
-8.8 (IH, m), 9.2-9.3 (IH, II
I) MS (m/z) 269 (M""), 116
(Et2NC5"") Example 5 88 mg of N,N-dimethylurea instead of benzamide
The reaction and post-treatment were carried out in the same manner as in Example 3, except that N-dimethylthiocarbamoyl (1 mmol) was dissolved in anhydrous tetrahydrofuran 4d.
8-diethylthiocarbamoylsulfenamide 19m
g (16%) was obtained.

H-NMR (CD (1:1., TMS) δ=1.3
0 (6H, t, J=7.5Hz).

3.09 (6H, s), 3.5-4.2 (4H, br
), 6.10 (br, 5) IR (KBr, cm-'
) 3228 (NH), 1651 (C=0) MS (
m/z) 235 (M"") 116 (Et2NC3"
″) Example 6 Pivalic acid amide 10101rn instead of benzamide
The reaction and post-treatment were conducted in the same manner as in Example 3, except that 1 mmol) was dissolved in anhydrous tetrahydrofuran, and the melting point was 145.5-146.5°C (benzene)
White crystals of N-pivaloyl-S-diethylthiorubamoylsulfenamide 5' 1 mg (41%)
I got it.

'H-NMR (CDC1, TMS) δ=1.3 (
6H, t).

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼………………(I) (In the formula, R^1 is an aryl group, a heterocyclic group, an alkyl group,
Indicates a dialkylamino group or an alkoxy group. ) After treating the amide type compound represented by sodium hydride and iodine, the general formula ▲ has mathematical formulas, chemical formulas, tables, etc. ▼…………(II) (In the formula, R^2 and R^3 are lower Indicates an alkyl group, R^
2. R^3 may be combined to form a ring, M^+
indicates a metal cation. ) There are general formulas, mathematical formulas, chemical formulas, tables, etc., which are characterized by reaction with a dithiocarbamate represented by have the same meaning.) A method for producing a sulfenamide derivative represented by