DE2619090A1 - 1.2.6-THIADIAZINONE, THEIR PRODUCTION AND USE - Google Patents

Description

¹ case Cra-52-N

Dr. Ho / sa

CELAMERCK GmbH & Co. KG, Ingelheim am Rhein

1.2.6-Thiadiazinones, their preparation and their

use

The invention relates to 1,2,6-thiadiazinones of the formula

(D,

in the

X chlorine, -0-R ₁ , -SR ₁ , -SO _n -R ₂ or-S-CS-N (R ^) ₂

means, where
R _{1 represents} a straight-chain or branched, saturated or unsaturated aliphatic radical with up to 12 ι carbon atoms, which is represented by 1 to 3 fluorine, chlorine or bromine atoms, by cyano, C ₁ -C ^ -alkoxy, C ₁ - C ^ alkylthio, cycloalkyl with 3 to 6 carbon atoms, phenoxy, -CH-CH ₂ or

0 709846/0166 / ²

-CO-O- (C ₁ -C ^ -alkyl) may be substituted;

or for a cycloalkyl radical with 3 to 6 carbon atoms;

or for a phenyl radical which is replaced by 1 to 3 halogen atoms and / or C ₁ -C ^ -alkyl, C ₁ -C ^ -AIkOXy, C ₁ -C ^ -alkylthio, cyano, trifluoromethyl, formyl, 1 to 2 nitro groups or phenyl may be substituted;

or for naphthyl;

R _{2 is} C ₁ -C ^ alkyl, allyl or cyclohexyl; R _{3 represents} methyl or ethyl;

ri stands for 1 or 2.

The compounds of the formula I are suitable as active ingredients for biocidal agents and are also valuable as intermediates for the production of biocidal substances.

Due to their biocidal effect, those compounds of the formula I should be emphasized in which X is an alkylthio or alkenylthio radical, in particular the compounds with X being methylthio, ethylthio, sec-butylthio, allylthip ^ or chlorine, and also the compounds with X being alkoxy or alkenyloxy radical, ^ finally the compounds in which X is a substituted phenoxy radical.

Individual compounds of formula I have been described (Trav. Chira. 9j5, 270 (1974]). The authors, however, give

no indication of the biocidal effect of the compounds. *) n-butoxy ^

709846/0168

The compound of formula I in which X is chlorine:

N N

(ID,

is known. The other connections can be made out of it of the formula I obtained in a manner known per se by one of the following processes:

1. To prepare compounds in which X is -OR-J ^ or -SR ^, the compounds of the formula II are set with one equivalent of an alcohol of the formula HOR- ^ or a mercaptan of the formula HSR ^ in the presence of an acid acceptor , for example a tertiary amine to. The reaction temperature may be about -20 to + 100 ⁰ C, preferably 0 to 50 ⁰ C. It is expedient to use an inert solvent for the reaction, for example ether, dioxane, tetrahydrofuran, benzene, toluene, ethyl acetate, acetone, and one equivalent of the acid acceptor.

2. Compounds of the formula I in which X is R ^ O- can

surprisingly you also get by making the connection of the formula II, dissolved or suspended in the corresponding alcohol R-, OH, optionally with the addition of Water, with one equivalent of an alkali or alkaline earth hydroxide, hydrogen carbonate or carbonate, preferably Sodium or potassium hydroxide, at temperatures between about 0 and 50 ° C.

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ι 3 · Compounds of the formula I in which X is -SO-R ₀ , are by oxidation of the corresponding compounds

obtained with the group -SR ₀ . This oxidation is expediently carried out with hydrogen peroxide in glacial acetic acid. The oxidation is carried out for preparing the sulfinyl compounds with approximately the calculated amount of hydrogen peroxide in the heat, for example at 90 ⁰ C. For the oxidation to sulfone j are needed stronger oxidizing conditions. j The oxidizing agent is preferably used in excess and the reaction is allowed to proceed at higher temperatures j, for example at about 100 ^° C.

4. Compounds of the formula I in which X is a radical -S-CS-N (R,) 2 can be prepared by reacting 3,5-dichloro-1,2.6-thiadiazin-4-one and alkali salts of dimethyl or diethyl dithiocarbamate are prepared. The implementation is advantageously carried out at room temperature in a solvent such as methanol.

The compounds of the formula I above all have a pronounced herbicidal action; they are especially post-emergence procedure applicable. The application rate is 0.5 to 10 kg per ha. At low dosages, the erfindungsj according to thiadiazinones have a selective effect on dicotyledons, while at higher dosages they also act as total herbicides can be used.

In addition to the herbicidal action, those according to the invention show

Compounds also have a fungicidal effect, e.g. against Phytophtora, Botrytis, Tilletla, a bactericidal effect, e.g. against Xanthomonas, and an insecticidal effect, e.g. against flies.

The compounds of the formula I are formulated in the customary manner for use as biocidal agents. For use as herbicides, they are

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Usual auxiliaries and / or carriers processed into concentrates or ready-to-use preparations,
for example suspension powders, emulsion concentrates, granulates, dusts, ultra-low-volume formulations. The active ingredient content in the ready-to-use preparations is generally between 0.01 and 10 percent by weight, but can also be significantly higher (up to about 80 percent by weight),

Examples of formulations;

a) suspension powder

25 96 active ingredient according to the invention

55 96 kaolin

10 % colloidal silica

9 96 lignosulfonate (dispersing agent)

1 96 sodium tetrapropylene benzene sulfonate (wetting agent)

b) suspension powder

80 96 active ingredient according to the invention

8 96 Calcium Lignosulfonate
5 96 colloidal silica
5 96 sodium sulfate

2 96 diisobutylnaphthalene sodium sulfonate

c) emulsion concentrate

40 96 active ingredient according to the invention
25 96 liquid mixture of aromatic hydrocarbons (e.g. Shellsol A)
25 96 N-methylpyrrolidone

10 96 anion-active emulsifier (e.g. Emuisogen I

40)

The concentrates specified under a) to c) are diluted for use with water to the desired concentration of active ingredient (O ₁ oil up to 10 percent by weight).

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The ingredients in the examples are given in percent by weight. The following examples are intended to provide the Explain the invention in more detail:

example 1

3,5-dichloro-1,2,6-thiadiazin-4-one

15 g (0.063 mol) of 3,4,4,5-tetrachloro-l, 2,6-thiadiazin are mixed with 20 ml formic acid 99 #iger 150 minutes under nitrogen at 40 ⁰ C heated. After cooling, the mixture is poured onto ice, the pale yellow precipitate formed is filtered off with suction, dried and recrystallized from hexane. 8.3 g (72 %) of 3,5-dichloro-1,2,6-thiadiazin-4-one with a p. 82 ^° C. are obtained.

Example 2

3-butylmercapto-5-chloro-1.2.6-thiadiazin-4-one

To a solution of 9.1 g (0.05 mol) of 3,5-dichloro-1,2,6-thiadiazin-4-one and 5.1 g (0.05 mol) of triethylamine in 100 ml of tetrahydrofuran are added at room temperature 4.5 g (0.05 mol) of n-butyl mercaptan were added dropwise to 75 ml of tetrahydrofuran. After stirring for 1 hour, the precipitate formed is filtered off, the filtrate in vacuo. evaporated, the residue taken up in methylene chloride and extracted with water. The organic phase is dried with sodium sulfate and, after the methylene chloride has been distilled off, distilled in a fine vacuum. 9.9 g (90 % of theory) of the title compound are obtained.

^Κ Ρ 0.06 ^{: 112} - ¹¹⁵ ° ^C

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Example 3

5-chloro-3-ethoxy-1.2.6-thiadlazin-4-one To a solution of 9.1 g (0.05 mol) 3,5-dichloro-1,2,6-thiadiazin-4-one in 100 ml of ethanol, a solution of 2.0 g (0.05 mol) of sodium hydroxide in 10 ml of water is added dropwise at room temperature. After stirring for one hour at room temperature, it is concentrated to 1/4 of the volume, the yellow, crystalline precipitate is filtered off with suction, dried and recrystallized from ethanol / water. 7.7 g (80 % of theory) of the title compound with a melting point of 66 ° C. are obtained.

Example 4t

3-chloro-5-methoxl-1.2.5-thiadlazin-4-one

A solution of 4.0 g (0.1 mol ) Sodium hydroxide was added dropwise to 20 ml of water and 50 ml of methanol. The mixture is stirred for one hour at room temperature, and the crystalline precipitate formed is filtered off with suction, washed with water and dried. 15.3 g (86 %) of the title compound with a melting point of 72 ° -73 ° C. are obtained

Example 5:

3-chloro-5-isopropylmercapto-1.2.6-thia diazin-4-one

To a solution of 18.1 g (0.1 mol) of 3,5-dichloro-1.2.6-thiadiazin-4-one in 150 ml of tetrahydrofuran are initially 10.1 g (0.1 mol) of triethylarain with stirring at -10 ° C and then 7.6 g (0.1 mol) of isopropyl mercaptan were added dropwise. It is stirred for 1 hour at room temperature. The educated Triethylamine hydrochloride precipitate is filtered off with suction and the filtrate is evaporated in vacuo. The evaporation residue is dissolved in chloroform, the solution with 2N hydrochloric acid,

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Washed soda solution and water, dried over sodium sulfate and evaporated in vacuo. The residue is distilled in a fine vacuum.

14 g (63 % of theory) of the title compound are obtained as an orange oil.
^K P0.09 ^: 123 - 125 ° C

Example 6:

3-chloro-5-n-butoxy-1.2.6-thiadiazln-4-one

To a solution of 9.1 g (0.05 mol) of 3,5-dichloro-1.2.6-thiadiazin-4-one in 100 ml of n-butanol, 2 g (0.05 mol) are added at 0 ° with vigorous stirring Sodium hydroxide added dropwise to 20 ml of water. After stirring for one hour at room temperature, the butanol phase is separated off and the aqueous phase is extracted with 30 ml of n-butanol. The combined 'butanol solutions are dried over sodium sulfate. The excess butanol is removed in vacuo and the residue is distilled.

7.8 g (71 % of theory) of the title compound are obtained as a yellow oil.

Bp ₀₂ : 110-113 ° C

Example 7

^ Chlor-S-methvlmercapto-i.2.b-thiadiazln-4-one

In a solution of 36.6 g (0.2 mol) of 3,5-dichloro-1,2,6-thiadiazin-4-one and 20 g (0.2 mol) of triethylamine in 200 ml of tetrahydrofuran are at -5 ° C below

Stirring 14.5 g (0.3 mol) of methyl mercaptan passed over the course of 90 minutes. Stirring is continued for 30 minutes at room temperature, the precipitate formed of triethylamine hydrochloride is filtered off with suction and the filtrate is evaporated in vacuo. The solid residue is recrystallized from η-hexane.

709846/0166

This gives 31 g (80% of theory) of the title compound as greenish-yellow crystals of mp. 81 - 82.5 C

Example 8
·

3-chloro-5-allvloxi-1.2.6-thiadiazin-4- one

To a solution of 9.1 g (0.05 mol} of 3,5-dichloro-1,2,6-thiadiazin-4-one and 12 g (0.2 mol) of allyl alcohol in 75 ml of acetone are at -10 ° C under vigorous stirring, 2.0 g (0.05 mol) of sodium hydroxide in 20 ml of water are added dropwise, the mixture is stirred for 1 hour at 0 ° C. and evaporated in vacuo, the residue is washed with water , dried and recrystallized from η-hexane.

9.0 g (88 % of theory) of the title compound are obtained as pale yellowish crystals with a melting point of 51 ° -52 ° C.

Example 9

3-chloro-5-isopropoxy-1.2.6-thiadiazin-4-one

1.2 g (0.05 gram atom) of sodium are dissolved in 150 ml of anhydrous isopropanol. The solution of the alcoholate is added dropwise at 0 ° C. with stirring to a solution of 9.1 g (0.05 mol) of 3,5-dichloro-1,2,6-thiadiazin-4-one in 75 ml of isopropanol. The mixture is kept at 0 ° C. for 1 hour and at 20 ° C. for 24 hours. After distilling off the excess isopropanol in vacuo. the residue is stirred with water, filtered off with suction, washed with water, dried and recrystallized from η-hexane.

Mp. 71-72 ° C.

6.0 g (58 % of theory) of the title compound are obtained

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Example 10;

3-chloro-5-methylsulfinyl-1.2.6-thiadiazin-4-one

To a solution of 9.7 g (0.05 mol) of 3-chloro-5-methylmercapto-1.2.6-thiadiazin-4-one in 100 ml of acetic acid
5.0 ml of 30% H ₂ O _{2 were added} dropwise with stirring. The mixture
is heated to 90 ⁰ C for 1 hour and concentrated in vacuo.
The crystalline residue is recrystallized from methanol. ',

6.1 g (58 % of theory) of lemon-yellow crystals are obtained
Title compound of m.p. 132 "-133 ° C. I

Example 11; i

3-chloro-5-isopropylsulfinyl-1.2.6-thladiazln-4-one

Corresponding to Example 10 from ^ -Chlor-S-isopropylmercapto-, 1.2.6-thiadiazin-4-one and H ₂ O ₂ . \

M.p. 93-94 ° C (from hexane). !

j example 12; 'I.

3 ~ chloro-5-methylsulfonyl-1.2.6-thladiazin-4-one

To a solution of 9.7 g (0.05 mol) of 3-chloro-5-methylmercapto-1.2.6-thiadiazin-4-one in 100 ml of acetic acid
25 ml of 30% H ₂ O _{2 were added} dropwise. The mixture is left for 30 min.
heated to 100 ^° C., ^{cooled to 20 °} C. and poured into 800 ml of ice water. The light yellow crystalline precipitate
is suctioned off, washed with water and dried.

This gives 6.4 g (57% d.Th) title compound, mp. 154 ⁰ C. '

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261 ^ 090

Example 13 ;
^ -Chlor-S-dimethyldithiocarbamoyl-l ^ .e-thiadiazin- ^ one

To a solution of 5.5 g (0.03 mol) of 3,5-dichloro-1,2,6-thiadiazin-4-one in 100 ml of methanol, 5.6 g (0.03 mol) of sodium dimethyldithiocarbamate dihydrate are added in portions with stirring given. After stirring for three hours at room temperature, the mixture is diluted with 250 ml of water. The crystalline precipitate is filtered off with suction and dried. The crude product is in methylene chloride with Hexane added.

3.2 g (40 % of theory) of the title compound crystallize out; M.p. 130-135 ° C.

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709846/0166

■ s *

2619G90

Corresponding to the above examples, the compounds of the following table are also obtained:

-X

Mp. [ ⁰ C] Kp r ° C] / torr

14th -CHn-C ₅ H ₁₁ 15th -0- ^ C ₈ H ₁₇ 16 -0-nC ₁₂ -H ₂₅ 17th -CKn-C ₅ H ₇ 18th -CKn-C ₆ H ₁₃ 19th -0-CH (CH ₅ ) -C ₂ H ₃ 20th -0-CH ₂ -CH (CH ₅ ) ₂ 21 -0-CH ₂ -C = CH 22nd -0-CH ₂ -CH = CH-CH ₅ 23 -0-CH ₂ -CF ₅ 24 -0-CH ₂ -CH ₂ -Cl 25th -0-CH ₂ -CCl ₅ 26th -0-CH ₂ -CN 27 -0-CH (CH ₅ ) -CN 28 -O-CH (CN) -nC ₅ H ₇ 29 -O-tertiC ^ Hg 30th -0-CH ₂ -CH ₂ -OCH ₅ 31 -0-CHp-CH ₂ -SCH ₅ 32 -0-CH ₂ - <1

-O-

-0-CH ₅ -CH-CH.,
^v 0 ' ²

45-48

59-61 158

73-75

77-82 109-111

83 709846/0166 105-107 / 0.1 140-142 / 0.13

94 / 0.1 128-131 / 0.2 110-111 / 0.6

- 120-124 / 0.25 - 88-92 / 0.1 - 133 / 0.15 - 135-138 / 0.2 116-118 - 102-108

No.

35 36

39- ! 40 ■ 41 42 43 44

j 45

46

I. 47

-0-CH ₂ -C-OC ₂ H ₅

0 -0-C (CHJ ₂ -C-OCH ₃

37 -O- <H

-0- <H

-SC ₂ H ₅

-S-Ii-C ₃ H ₇

■ S-CH (CH ₃ ) -C ₂ H ₅

-S-CH ₂ -CH = CH ₂ -S-CH ₂ -CH ₂ -CN

-S -. (H -0-

-0-i Ä -F

48 -O-

Cl

49 -0-

50 -0-

-Cl

-Cl "m.p. [ ⁰ C]

63-67

85

Cl 143

115-117 709846/0166

Kp [° C] / Torr

120-126 / 0.04 - 130-134 / 0.25 - 134-135 / 0.1 55-56 - - - 119-121 / 0.1 - 115 / 0.1 - 110-111 / 0.17 - 119-124 / 0.2 - 172-174 / 0.1 - 145-149 / 0.13 121-123 - 139-141

No,

-X

Ιϊ

Melting point [° C]

Kp [° C] / Torr

53 54

Cl

NO,

Cl

CH,

OCIL

W ^ ^N ° 2

152-154

161-163

137

162-164

143-146 185-186 155-156

182-184 232

126

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Claims (1)

Claims stands for a straight-chain or branched, saturated or unsaturated aliphatic radical with up to 12 carbon atoms, which is represented by 1 to 3 fluorine, chlorine or bromine atoms, by cyano, C ₁ -C ^ -AIkOXy, C ₁ -C ^ - Alkylthio, cycloalkyl with 3 to 6 carbon atoms, phenoxy, -QH- ^ CH ₂ or -CO-O- (C ₁ -C ^ -alkyl) can be substituted; or for a cycloalkyl radical with 3 to 6 carbon atoms; or for a phenyl radical which is replaced by 1 to 3 halogen atoms and / or C ₁ -C ^ -alkyl, C ₁ -C ^ -AIkOXy, C ₁ -C ^ -alkylthio, cyano, trifluoromethyl, formyl, 1 to 2 nitro groups or phenyl may be substituted; / or for naphthyl; 709846/0166 -X- R _{2 is} C ₁ -C ^ alkyl, allyl or cyclohexyl; R, for methyl or ethyl;
j η stands for 1 or 2. r
2y Compounds of the formula I in which X has the same meaning as in claim 1, with the exception of chlorine, methoxy, methylthio, phenoxy, phenylthio. 3. Process for the preparation of the compounds according to claim 2, characterized in that one a) for the preparation of compounds of the formula I in which X is -OR ₁ or -SR ₁ , 3,5-DiChIOr-I ^ .6.-thiadiazin-4-one with about one equivalent of an alcohol . hols R-jOH or a mercaptan R ₁ SH in the presence of an acid acceptor, for example a tertiary amine, in an inert solvent or that one b) for the preparation of compounds of the formula I in which X is -0-R ₁ , the solution or suspension of the 3,5-DiChIOr-I ^ .6-thiadiazin-A-one in the alcohol R ₁ OH, optionally with the addition of water, with one equivalent of an alkali metal or alkaline earth metal hydroxide, hydrogen carbonate or carbonate, preferably sodium or potassium hydroxide, or that one c) for the preparation of compounds of the formula I in which X is -SO _n -R ₂ , a corresponding compound _{where X is -SR 2 is} oxidized or that one d) for the preparation of compounds of the formula I in which X is -S-CS-N (R ₃ ) ₂ , 3,5-dichloro-1,2,6-thiadiazin-4-one with alkali metal salts of dimethyl or diethyldithiocarbomate implements. / 17. 709846/0166 4. Use of compounds of the formula I for combating undesired plant growth. 5. Process for the production of biocidal agents, thereby ge ^! indicates that a compound of the formula I is formulated with conventional auxiliaries and / or carriers. 709846/0168