JPS5843965A - 2-imino-6h-2,3-dihydro-1,3-thiazine derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The 2-imino-6H-2,3-dihydro-1,3-thiazine derivative of formulaI[R<1> is lower alkyl or phenyl; R<2> is H or lower alkyl; R<3> is lower alkyl, lower alkenyl, lower alkoxy(lower alkyl), phenoxy(lower alkyl), benzyl, cycloalkyl, furfuryl, or tetrahydrofurfuryl; R<4> is phenyl, alpha-naphthyl, or benzoyl]. EXAMPLE:2-Phenylimino-3-methyl-6-phenyl-6H-2,3-dihydro-1,3-thiazine. USE:Useful as a herbicide. It can be applied by soil treatment and foliar treatment, and is effective to a wide variety of weeds such as annual or perennial gramineous weeds, broad-leaved weeds, etc. grown in paddy rice field and plowed land. PROCESS:The compound of formulaIis prepared by reacting the 1-azabutadiene derivative of formula II with the isothiocyanate of formula III.

Description

Detailed Description of the Invention This invention is based on the general formula [wherein R1 is a lower alkyl group or a phenyl group (one or two hydrogen atoms of the phenyl group are a halogen atom, a lower alkyl group, or a nitro group)] B2 represents a hydrogen atom or a lower alkyl group; R3 represents a lower alkyl group, a lower alkenyl group, a lower terkoxy lower alkyl group, a phenoxy lower alkyl group (one of the hydrogen atoms of the phenoxy group); Or two:
It may be substituted with a lower alkyl group or a halogen atom. ), a benzyl group (one or two hydrogen atoms of the benzyl group may be substituted with a lower alkyl group or a halogen atom), a cycloalkyl group, a furfuryl group, or a tetrahydrofurfuryl group: R4 is Represented by a phenyl group (one or two hydrogen atoms of the phenyl group may be substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group), an α-naphthyl group, or a benzoyl group. Novel 2-imino-
A 6H-2,3-dihydro-1,3-thiazine derivative and a method for producing the same are provided.

The inventors have discovered an industrially useful 1.3-
We conducted intensive research with the aim of obtaining thiazine derivatives. As a result, a novel 2-imino-6H-2,3-dihydro-1,3-thiazine derivative represented by the general formula (wherein R+, R2, R1, and R4 each have the same meaning as above) The 2-imino-6H-2,3-dihydro-1,3-thiazine derivative of this invention was successfully synthesized by a new manufacturing method and was incorporated into this invention. It has both soil treatment ability and foliage treatment ability, and is effective against a wide range of weeds such as annual and perennial grass weeds and broad-leaved weeds that occur in paddy fields and fields.

The 2-imino-6H-2,3-dihydro-1,3-thiazine derivative in this invention is produced by a novel linear reaction. Note that R' in the linear equation, R2゜R3
, R4 each have the same meaning as above.

2 (1) In the reaction of the l-7 zabutadiene derivative represented by the general formula (1) and the isothiocyanate represented by the general formula (I[), benzene, toluene, dioxane, etc., in an inert solvent, 0 =-1,50℃, preferably 20-100℃
By carrying out the reaction at a temperature of 0.5 to 30 hours, a 2-imino-6H-2,3-dihydro-1,3-thiazine derivative represented by the general formula .

Next, examples of the manufacturing method according to the present invention will be given.

Example 1. Synthesis of 2-phenylimino-3-methyl-6-7enyl-6H-2,3-dihydro-1,3-thiazine (compound No. 1 in Table 1 below) N-methyl-4
- phenyl-1-azabutadiene 0.725F (5 mmol) and phenylisothiocyanate) o, 675r (5 mmol)
mmol) in dry benzene at 80° C. for 2 hours. After the reaction, benzene was distilled off, pure cine was removed by silica gel column chromatography, and the resulting crude crystals were recrystallized from ether to obtain the target product, 2-phenylimino-3-methyl-6-7enyl. 6H-2,3-dihydro-1,3-thiazine 1.29F was obtained.

”O-N, M, R, measured value (C!DOj3/TM
8) δ (ppm) 39.3; 43.5; 10
2.7; 122.3; 123.2127.9~
133.3; 140.7'; 149.2 Example 2.2-Phenylimino 3-improvyl-6-phenyl-6H-2,3-dihydro-1,3-thiazine (Compound number in Table 1 below) Synthesis of Compound 2) N-'l Sopropyl-4-phenyl-1-Asaphtadiene O, 565F (5 mmol) and Phenylthiocyane) O, 675F (5 mmol) were heated at 80°C for 20 hours in dry benzene 5-. did. After the reaction, benzene was distilled off, impurities were removed by silica gel column chromatography, and the obtained crude crystals were recrystallized from ether to obtain the target product, 2-phenylimino-3-improvir-6.
-Phenyl-6H-2,3-dihydro-1,3-thiazine 1.05f was obtained.

”O-N, M, R, measurement value (cDat3/TMS
) δ (ppm) 20.3; 21.1; 42.8; 47
．． 2; 104.1122.2; 122.9; 1
27.0-128.6; 140.7; 149.5 Example 3.2-benzoylimino-3-isopropyl-
Synthesis of 6-phenyl-6H-2,3-dihydro-1,3-thiazine (compound No. 6 in Table 1 below) Ne7-. ) 0.815F (5 mmol) was reacted in dry benzene at 20°C for 20 hours. After reaction.

Benzene was distilled off, and n-hexane was added for purification.

The target product, 2-benzoylimino-3-improbyl-6-phenyl-6H-2,3-dihydro-1,3-thiazine 1.65F, was obtained.

13C-N, M, R measurement values (c+oc2./TM
s) δ (ppm) 20.3; 20.8; 41.
3; 49.7; 10B, 9; 125.6-139
．． 1; 163.2; 174. .

Example 4.2-α-naphthylimino-3-isobutyl-
Synthesis of 6-phenyl-6H-2,3-dihydro-1,3-thiazine (Compound No. 8 in Table 1 below) N-isobutyl-4-phenyl-1-azabutadiene 3
．． 7t (Q,,02 mol) and α-naphthylthiocyane=)3.5F (0.02 mol) were dissolved in toluene 15-
It was dissolved in After that, it was heated at 100°C for 1 hour.

After the reaction, the product was purified by column chromatography,
2.92 kg of a yellow liquid of the target product, 2-α-naphthylimino-3-isobutyl-6-phenyl-6H-2,3-dihydro-1,3-thiazine, was obtained.

'll Example 5-2-p-chlorophenylimino-3-
Ethyl-6-phenyl-6H-2,3-dihydro-1β
-Synthesis of thiazine (compound No. 11 in Table 1 below) N-ethyl-4-phenyl-1-azaphtadiene 3.2
F (0.02 mol) was dissolved in benzene 20- and p-chlorophenylthiocyanate) 3.4F at room temperature.
After adding (0.02 mol), reflux was performed for 3 hours while stirring. After the reaction, the product was purified by column chromatography, and the target product, 2-p,-chlorophenylimino-3-ethyl-6-7enyl-6H-,2,3-dihydro-1,3-thiazine, was purified to a pale yellow color. 3.2 tons of crystals were obtained.

Example 111A Example 6.2-p-xylophenylimino-3-
n-propyl-6-0-chlorophenyl-6H-2,3
-dihydro-1,3-thiazine (see Table 1 below).

Synthesis of compound No. 16)
2 mol) was dissolved in benzene lO- and heated under reflux for 2 hours. After the reaction, the product was purified by column chromatography to obtain the target product, 2-p-chlorophenylimino-3.
-n-propyl-6-〇-chlorophenyl-6H-2,
3-dihydro-1,3-thiazine yellow-orange liquid 2.59
I got it.

Example 7.2-Phenylimino-3-p-methylbenzyl-6-phenyl-6H-z, 3-) HiF o-1,
3-thiazine (compound No. 21 in Table 1 below)
Synthesis of N -p-)f Rubenzyl-4-phenyl-1-azaphtadiene 4.79 (0.02 mol) Tophenylthiocyanate 2.7 t (0.02 mol) was added to dioxane 1
5- and heated at 80°C for 3 hours. After the reaction, the product is purified by column column chromatography to obtain the desired product, 2-phenylimino-3-p-methylbenzyl-
4.12 of a yellow liquid of 6-phenyl-6H-2,3-dihydro-1,3-thiazine was obtained.

Example 8.2-m-chlorophenylimino-3-cyclohexyl-6-methyl-6H-2,3-dihydro-1,
3-thiazine (compound No. 24 in Table 1 below)
Synthesis of N-cyclohexyl-4-methyl-1-azaphtadiene3. Of (0.02 mol) in benzene 15m7! 3.4 F (0.02 mol) of m-chlorophenylisothiocyanate was added to the mixture at room temperature, heated under reflux for 2 hours, and then left at room temperature for 16 hours.

After the reaction, the product was purified by column chromatography to obtain the target product, 2-m-chlorophenylimino-3-
2.62 g of a yellow-orange liquid of cyclohexyl-6-methyl-6H-2,3-dihydro-1,3 thiazine was obtained.

Example 9.2-7 enylimino 3-(2;4'-dichlorophenoxy)ethyl-5-methyl-6-ethyl-
6H-2,3-dihydro-1,3-thiazine (Part 1 below)
Table, Synthesis of Compound No. 26) N-(2', 4'
~Dichlorophenoxy)ethyl-3-methyl-4-ethyl-1-azabutadiene 2.9f (o, o 1 mol) and phenyl isothiocyanate 1.4y (0,01 mol) are dissolved in benzene 1 Offl/ The mixture was heated under reflux for 5 hours.

After the reaction, the product was purified by column chromatography,
The target product, 2-phenylimino-3-(44'-dichlorophenoxy)ethyl-5-methyl-6-nityl-6
A yellow brown liquid 1.1f of H-2,3-dihydro-1,3-thiazine was obtained.

Example 10. 2-p-:yfluorophenylimino-3-cyclohexyl-6-methyl-6H-2,3-dihydro-1,3-thiazine (Table 1 below, compound number 2
Synthesis of compound 9).

N-7 Chlohexyl-4-methyl-1-azabutadiene3. Of (0.02 mol) and p-fluorophenyl isothiocyane) 3.1F (0.02 mol) were dissolved in benzene 15- and heated under reflux for 1 hour.

After the reaction, the product was purified by column chromatography.
．． The target product, 2-p-fluorophenylimino-3-
A yellowish brown liquid 1.3F of cyclohexyl-6-methyl-6H-2,3-dihydro-1,3-thiazine was obtained.

Table 1 lists examples of the novel 2-imino-6H-2,3-dihydro-1,3-thiazine derivatives of the present invention, which were prepared according to the above examples, along with their physical properties and yields. Note that the compound numbers in Table 1 are referred to in the following description.

Table lContinued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Next, the 'H-N, M, R analysis results of each compound disclosed in Table 1 are shown in Table 2. List.

Table 2 Continuation of Table 2Continuation of Table 2Continuation of Table 2Continuation of Table 2Continuation of Table 2Next, reference examples showing the herbicidal activity of the compounds of the present invention will be given.

Reference example: A 10,000-are Wagner pot was filled with Ubejo fl (alluvial clay loam), and the upper layer was lightly covered with soil containing seeds of chinensis and annual Cantonese weeds (kikashigusa, chickweed, azalea, horsetail, and cypress). After that, transplant the paddy rice seedlings (variety: Nipponbare) at the two-leaf stage and add water to the water depth of 3.
It was assumed that the crn was flooded. Next, a wettable powder obtained by uniformly mixing and pulverizing 50 parts by weight of the compound of the present invention, 48 parts by weight of kaolin, and 2 parts of Neobelenx Powder (trade name: manufactured by Kao Atlas Co., Ltd.) was added to the active ingredient (of the present invention). Pipette the drug diluted with water so that the concentration of the compound (compound) is 1,000 ppm to make the amount of active ingredient 50 ppm per 1 ar.
Drop it evenly so that it becomes 2.

It was maintained in a glass room with an average temperature of 25°C. Three weeks after the chemical treatment, the herbicidal effects of each test compound were investigated.

The results are shown in Table 3.

In addition, the herbicidal effects in Table 3 were based on the following criteria.

5: Complete withering 4: Big good luck 3: Medium good luck 2: Small damage 0: Harmless (normal growth) Table 3 Special liver applicant Ube Industries, Ltd.

Claims (1)

[Claims] (In, general formula [wherein R1 is a lower alkyl group or may be substituted).1. R2 represents a hydrogen atom or a lower alkyl group, BS is a lower alkyl group, a lower alkenyl group, a lower alkoxy lower alkyl group, a phenoxy lower alkyl group (1″ of the hydrogen atom of the phenoxy group:) t or 2 are lower alkyl ), benzyl group (one hydrogen atom of benzyl group may be substituted with
One or two of them may be substituted with a lower alkyl group or a halogen atom. ), cycloalkyl group, furfuryl group or tetrahydrofurfuryl group a'
FL4 represents a phenyl group (one or two hydrogen atoms of the phenyl group may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group), an α-naphthyl group or a benzoyl group. ] A 2-imino-6H-2,37 dihydro-1,3-thiazine derivative. (2), a l-azabutadiene derivative represented by the general formula (υ 2 (1) ri°-°-9-83 R' -CH and a general formula (f
f) R4-N=C=S (If) 2-imino-6H-2,3-dihydro-1 of the general formula (NO) is reacted with an isothiocyanate represented by
, 3-thiazine derivative manufacturing method. However, in each of the above general formulas, R1 is a lower primary alkyl group or a phenyl group (one or two hydrogen atoms of the phenyl group may be substituted with an atom, a lower alkyl group, or a nitro group). R2 represents a hydrogen atom or a lower alkyl group, R3 represents a lower alkyl group,
Lower alkenyl group, lower alkoxy lower alkyl group, phenoxy lower alkyl group (one of the hydrogen atoms of the phenoxy group
One or two may be substituted with a lower alkyl group or a halogen atom. ), a benzyl group (one or two hydrogen atoms of the benzyl group may be substituted with a lower alkyl group or a halogen atom). Represents a cycloalkyl group, furfuryl group or tetrahydrofurfuryl group; B4 is a phenyl group (one or two hydrogen atoms of the phenyl group may be substituted with a halogen atom, a lower alkyl group or a +4 lower alkoxy group); ), α-su7tyl group or benzoyl group.