JPS5896077A - 2,4,6-substituted-1,3,5-s-triazine compound and its preparation - Google Patents

Abstract

PURPOSE:To prepare the titled novel compound useful as an agent for suppressing the premature vulcanization of rubber, etc. by reacting an N-substituted-N- cyclohexylbenzothiazole-2-sulfonamide compound with trithiocyanuric acid or a specific triazine compound. CONSTITUTION:An N-substituted-N-cyclohexylbenzothiazole-2-sulfonamide compound of formulaI[R1 is alkyl, cycloalkyl, benzyl, trichloromethyl, phenyl, substituted aryl of formula II (Y is halogen, lower alkyl, etc.), or naphthyl]is made to react with trithiocyanuric acid or a 2-substituted-4,6-dimercapto-1,3,5-S-triazine compound of formula III (R2 is primary or secondary alkylamino, alkoxy, phenoxy, anilino, etc.) in an inert solvent. USE:Activating agent for rubbers, stabilizer for rubbers and plastics, pharmaceuticals, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention represents a compound of the general formula [wherein R>ma-SS R1 or R2]. R1 is.

Alkyl group, cycloalkyl group, benzyl group, trichloromethyl group, phenyl group, general formula OY (where Y is hawagen, lower alkyl group, nitro group).

Power! Represents a levoquine group, represents a substituted ary group and a naphthyl group represented by ). R2 is primary or secondary
alkylamino group, alkoxy group, phenoquine group, anilino group, toluidino group, diphenylamino group, N-alkyl-N-arylamino group.

1st. or secondary @cycloalkylamino group.

2゜4.6- represented by alicyclic amino group, benzylamino group, naphthylamino group and -N) (represents two groups)
Substituted-1,3,5-3-) lyashiso compounds and their production methods (=).

The 2,4,6-substituted-1,3,6-8-) riazine compound according to the present invention can be used with sulfur or a sulfur-based vulcanizing agent or with vulcanization (
Early addition of natural and synthetic rubber containing foot additives.
The effect of suppressing the flow is extremely large.

Moreover, it can be expected to be effective as a rubber activator, a rubber or plastic stabilizer, a medicine, an agricultural chemical, a fungicide, a rust preventive, a lubricating oil additive, etc. Below are 2 and 4 related to the present invention.
A method for producing a 6-substituted-1,3,5-5-triazine compound will be explained.

S.S.R.

■ (In the formula, R1 and R2 are the same as above.) Above (1
) and (2) are synthesized by the following method. (Patent Application No. 1983-65040) (In the formula, R1 is the same as above. X is halogen,
base indicates a base. ) The reactions of formulas (1) and (2) proceed easily even at room temperature, but the reactions are completed in a short time when carried out under reflux of the solvent.
Methanol is used as a solvent for this reaction.

Acetone, chloroform, dimethylformamide.

Any inert solvent may be used, such as tetrahydrofuran, benzene, toluene, n-hexane, and trichloroethylene.

2. New and current features according to the present invention. 4. Examples of 6-substituted-1,3°5-5-) riazine compounds are shown below.

2.4.6-tris(methyldithio)-1,3゜5-5
-Triazines. 2,4.6-)Lis(ethyldithio>
-1,3,5-5-) riazine. 2°4.6-)lis(n-propyldithio)-1,3°5-5-triazine. 2,4.6-) Lis (isopropyldithio) -1
,3,5-5-) riazine.

2.4.6-) Lis(n-butyldithio)-1°3.5
-5-) Reazine. 2,4,6-tris(isobutyldithio)-1,3,5-5-) riazine. 2,4.6-
-) Lis(Secondary-butyldithio)-1,3,5-
3,-) riazine. 2,4゜6-tris (turnyary)
butyldithio)-1°3.5-5-triazine. 2,4
．． 6-tris(n-octyldithio)-1,3,5-3
−) riazine. 2,4.6-)lis(n-doacyldithio)-L 3. 5-3-) riazine. 2-dibutylamino-4,6-bis(cyclohexyldithio)-1,
3,5-5-') riazine, 2-dibutylamino-4
,6-bis(phenyldithio)-1,3°5-3-)lyasiso. 2-anilino-4,6-bis(tolyldithio)
-1,3,5-3-) riazine. 2-Ani! J/-4
,6-bis(P-chlorophenyldithio') -1,3
,5-3-) riazine.

2-anilino-4,6-bis(trichloromethyldithio)-1,3,5-5-)riazine. 2-cyclohekynylamino-4,6-bis(benzyldithio)-1,3,
5-5-) riazine. 2-Zinkurohekin! Rareamino-4,6-bis(,isopropyldithio)-1,3,5
-8-) Reazine. 2-benzylamino-4,6-(m
-carboquinphenyldithio) -1,3,5-3-)
Reazin. 2-piperidino-4,6-bis(n-11quinrudithio)-1,3,5-5-triazine. 2-Amino-4,6-bis(n-butyldithio)-1,3゜5
-3-) Reazine. 2-dicyclohequinylamino-4,
6-bis(cyclohexyldithio) -1゜3.5-5
−) riazine. 2-diphenylamino-4,6-bis(
2.4.6-substituted-1゜3.5-5-) such as naphthyldithio)-1,3,5-8-triazine! Examples include J azine compounds.

The present invention is not limited to the following.

Next, two 2,4.6-substituted-1,3゜5-3 according to the present invention
- A method for producing a triazine compound will be specifically described with reference to Examples.

Example 1. , 2, 4. 6-Tris(isopropyldithio) 1. 3. 5-5-) Synthesis of riazine 300 equipped with thermometer, stirrer, 1 dropping funnel, and condenser
m/? trithiocyanuric acid 7.5%
9 (0,042 mol), tetrahydrofuran 120r
rLe was charged and dissolved, then 'N-isopropylthio N-cyclohexylbenzothiazole-2-sulfonamide 529 (0,141 mol) was added and stirred for 60 minutes under reflux (71-73°C). -The solvent was distilled off under reduced pressure.

Add 100% methanol to the obtained yellow pickles.

The undissolved bone was suction filtered at 40°C and dried at 50°C to 60°C to obtain 30.569 (yield 8148%) of N-cyclohequinolbenzothiazole-2-sulfonamide 6n.
p160-160.5°C) was obtained.

The filtrate was cooled, and the precipitated pale yellowish white crystals were suction filtered and dried. mp 53.6-55.0°C 2. 4.
6-tris(isopropyldithio)1,3.5-5-triazine 16.37F (yield 97.47%) was obtained.

This crystal was dissolved in acetone and subjected to column chromatography [adsorbent Nijirikaglu C-200 (manufactured by Wako Pure Chemical Industries, Ltd.)]
]. The elemental analysis values of the obtained white crystals are as follows.

Analysis value C: 35.96%, H: 5.18%, N: 10
．． 42%.

S: 47.50% Calculated value (as Cl2H21H3S6) C: 36.0
9%, H: 5.26%, N: 10.52%.

S: 48.12% Implementation%l 2. 2-Butylamino-4,6-bis(・
isopropyldithio) 1. 3. 5-9-) Synthesis of riazine Example 1 (2) 2-dibutylamino-4,6-dimercabuto 1. 3. 5-5-triazine 122 (0,
・944 mol) and N-isopropylthio-N-cyclohequinrubeni/futhiazole-2-sulfonamide 36f
7 (0,097 mol) in 200 mm β of ethanol at 22 to 25° C. for 3 hours, and the by-produced N-cyclohexylbenzothiazole-2-sulfonamide was filtered.

After concentrating the filtrate under reduced pressure, 1]-hequinane 100- was added,
After extracting and filtering the small pupil crystals and concentrating the filtrate again,
2-dibutylamino-4,6-
17.44P (yield: 93.9%) of white crystals of bis(isopropyl ditheo)-1°3.5-3-) riazine was obtained.

Melting point 536-550°C (methanol recrystallization) Elemental analysis value C: 48.23%, H near, 81%, N: 13.13
%.

S: 30.32% Calculated value (as C17H32N4 S4) C: 48
．． 57%, H near, 60%, N: 13.30%.

S: 30.47% Example 3 An example of a synthetic 1-Daki invention according to Example 1 is shown below.

2-dibutylamino-4,6-bis(phenyldithio)
-1,3,5-5-) Reazine: White crystal, melting point 57
．． 0 to 59.0°C 2-dibutylamino-4,6-bis(n-dodecyldithio)-1,3,5-8-) riazine: White crystal melting point
33.5-345°C 2-dibutylamino-4,6-bis(cyclohexyldithio)-1,3,5-5-) riazine: white sticky substance 2.4.6-)lith(n-dodecyldithio) -1, 3,
5-3-11 Azine: Pale yellow sticky substance 21 4+ 6
) Lis(cyclohequinrudithio)-1,,3,5-
5-) Riazine: white crystals, melting point 660-708°C Test Example 1, the formulations in Table 1 were tested using a 6″s x 1i test roll.
After kneading at 50±5° C., the scorch prevention effect of the nine products of the present invention and the influence on the vulcanization rate were comparatively tested. JISK
The results of the Mooney Scorch test at 135° C. according to J.D.-6300 (1974) are shown in Table 2. 160°
The Curelast meter test results for C are shown in Table 3. The test conditions for the key last meter are as follows.

Testing machine: JSR type Ki, Last meter, Dice: ±2
mm, swing width: ±3. Induction period: t1o (min.

seconds), vulcanization time: too (minutes 9 seconds), standing L speed: R
(minute 2 seconds), estimated vulcanization time: T = 2 too −
ttO (minutes 9 seconds) was adopted.

Table 1 Mixture 5 BR1500 100 parts by weight Zinc Flower 5
2 〃 〃 〃Stearic acid
1〃l〃process oil
10〃ll carbon black (ISAF)
50〃IN vulcanization accelerator CM* 0
．． 7-1 sample 05 or 1.0* N-cyclohexynerubenzothiazyl-2-
Sulfenamide Table 2 Mooney Scorch (ML 1135°C) From the test results shown in Table 2, it was found that all the products of the present invention had extremely high scorch prevention effects.

Table 3: Curelast meter test 160°C From the above test results, two induction periods (txo) of the product of the present invention are longer than those of the blank or comparative sample.

A 2-amino substituted compound such as 2-dibutylamino-4,6-bis(isopropyldithio)-1,3,5-3-)riazine has a short vulcanization rise (R) time. It was also found that the maximum torque value was also large.

Patent jaw man Sanshin Chemical Industry Co., Ltd.

Claims (1)

[Claims] (1) General formula [wherein R represents -S S R1 or R2, R1
is an alkyl group, a cycloalkyl group, a benzyl group, a trichloromethyl group, a phenyl group, a substituted aryl group represented by the general formula 0Y (where Y represents a halogen, a lower alkyl group, a nitro group, or a carboxyne group), and a naphthyl group. 5. R2 is a primary or secondary alkylamino group, alkoxy group, phenoxy group, anilino group, toluidino group, diphenylamino group, N-alkyl-N-arylamino group, primary or secondary cycloalkylamino group , alicyclic amino group, pesodylamino group, naphthylamine group and -N3 (represents 2 groups).
A 2,4,6-substituted-1,3,5-5-) riazine compound represented by (2) 21416-substituted-1,3,5- according to claim <1), which is 21 41 6 ) lis(isopropyldithio)-1,3,5-3-)riazine
2. 8-F lyazine compound, <3) 2-di'butylamino-4,6-bis(isopropyldithio>-1,3,5-5-1-riazine) according to claim (1). 4; 6-substituted-1,3,5-3-) riazine compound. (4)) Lithiocyanuric acid or the general formula (in the formula,
R2 is a primary or secondary alkylamino group, an alkoxy group, a fenoquine group, an anilino group, a toluidino group, I
, 7 phenylamino group, N-alxy N-arylamino group, first, @ or Z 2 , fl ry fuchlorokylamino group, alicyclic amino group. benzylamino group, naphthylamino group and -N[(2
represents a group. ) 2-substituted-4,6-dimercap)-1,3,5-3-) riazine compound represented by the general formula [wherein R1 is an alkyl group or a cycloalkyl group. Besodyl group, trichloromethyl group, phenyl group. It represents a substituted aryl or naphthyl group represented by the general formula +Y (where Y represents a halogenated lower alkyl group, a nitro group, or a carboxyne group). ] N Am N
General formula consisting of reacting -cyclohexylpepthiazole-2-sulfonamide compound in an inert solvent [wherein R represents -5SR1 or R2]. R1 is an alkyl group, a cycloalkyl group, a benzyl group, a trichloromethyl group, a phenyl group, a substituted aryl group represented by the general formula OY (wherein Y5 represents a halogen, a lower alkyl group, a nitro group, or a carboxyne group), and naphthyl. represents a group. R2 is a primary or secondary alkylamino group, alkokene group, phenoxy group, anilino group, toluidino group, diphenylamino group, N-alkyl-N-arylamino group, primary or secondary cycloalkylamino group , a ring amino group, a benzylamino group, a naphthylamino group, and a group of 12 groups, 2, 4. 6=method for producing a substituted-1,3,5-5-triazine compound,