DE2257052B2 - I midothiocarbonic acid esters, process for their preparation and their use as microbicides - Google Patents

Description

X-R

_N = C

NS,

// V

CH ₃

C-CH ₃ (1) CH ₃

N '

CH ₃
-CH ₃ (!)

CH

in which X is an oxygen or sulfur atom and R is optionally one or more Means methyl group-substituted cycloalkyl radical with up to 10 carbon atoms.

2. N-3-pyridyl-imidothiocarbonic acid-O-'l'-me-Ihylcyclohexyl-S-p-tert-butylbenzyl-ester.

3. N-3-pyridyl-imidodithiocarbonic acid-S-cyclohexyl-S'-p-tert-butylbenzyl-ester.

4. N-S-Pyridyl-imidothiocarbonic acid-O-S'-methylcyclohexyl-S-p-tert-butylbenzyl-ester.

5. N-3-pyridyl-imidothiocarbonic acid-O-2'-methylcyclohexyl-S-p-tert-butylbenzyl-cster.

6. A process for the preparation of the imidothioic acid esters according to claim I, characterized in that that one either

(A) 1 mole of a thiocarbamic acid ester of the general Formula II

in which X is an oxygen or sulfur atom and R is optionally one or more methyl groups ~ substituted Cycloalkylresl with 4 to 10 carbon atoms means.

The invention also relates to a process for the preparation of the imidothioic acid esters of the general Formula I, which is characterized in that either

(A) 1 mol of a thiocarbamic acid ester of the general formula II

X-R

C,

X-R

(II)

35

in which X and R are as defined above, with 1 to 2 moles of a halide of the general formula III

in which X and R are as defined above, with 1 to 2 moles of a halide of the general formula III

(111)

in which Y is a chlorine, bromine or iodine atom, or

(B) 1 mole of N-3-pyridyl-di-thiocarbamic acid c-p-tert-butylbenzyl ester with 1 to 2 moles of a halide of the general formula V

(HI)

45 YR

in which Y is a chlorine, bromine or iodine atom, or

(B) 1 mol of N - 3 - pyridyl - dithiocarbamic acid p-tert-butylbenzyl ester with 1 to 2 moles of a halide of the general formula V

Y-R

(V)

55 in which Y and R have the meaning given above, in the presence of 1 to 1.5 mol of an alkali or alkaline earth _{metal hydroxide such as NaOH, KOH and Ca (OH) 2} , an alkali metal alcoholate such as NaOCH ₃ , NaOC ₂ H ₅ and K OCH ₃ , or a tertiary amine, such as N (CH ₃ ) ,, N (C ₂ H ₅ J ₃ and (CH ₃ J ₂ NC ₆ H ₅₎ in a manner known per se.

in which Y and R have the meaning given above, have, in the presence of 1 to 1.5 moles of an alkali or alkaline earth metal hydroxide, an alkali metal alcoholate or a tertiary amine in a manner known per se.

7. Use of the Imidothiokohiensäureester according to claim 1 as microbi / .ide.

The reaction is preferably carried out in a solvent such as methanol, ethanol, tetrahydrofuran, dioxane, dimethyl sulfoxide or dimethylformamide. The basic compound added serves to neutralize the hydrogen halide formed during the reaction. One can proceed in such a way that first the solution of the thiocarbamic acid ester with the basic compound is added and then the halogen compound is added, or the carbamic acid ester solution is first mixed with the halogen compound and then the basic compound is added. Implementation is under mild conditions. / .. B. by stirring for 1 to 4 hours

of the reaction mixture at temperatures from - 15 to +100 ¹ C. Reaction temperatures of 0 to 30 ° C. are preferred. After the reaction has ended, the reaction mixture is poured into excess water, and the crystals which separate out or the oily layer are filtered or extracted with a water-insoluble organic solvent such as benzene, toluene. Ethyl acetate, diethyl ether, hexane or octane.

isolated.

N-3-pyridyllhiocarbamates used as starting compounds in process variants A and B. can be prepared by various methods such as the following reaction equations demonstrate.

Examples of compounds of the general formula R ~ Y are

fV ^NCS

-Y-H ► Γ

+ R-XH

-NHC-X-R

(C)

NHCSM

NH,

+ RY - *

+ Cl- C - X-

I!
s

-X-R

CH ₃ * ~ ^ -CH ₂ Cl CH ₃ -C- f /
CH ₃ CH ₃ f ~ '') - CH ₂ Bi CH ₃ -C ^ CH ₃ CH ₃ ^ ~ y-cn ₂ \ CH ₃ -C- ' /
CH, H V- Br

IrNHCS-R '

II "s

MY (D) CH,

Cl and

R + base CH ₃

+ HCl base (Ii)

35 examples of compounds of the general formula Cl-C-X-R

i! s

In these equations, R, X and Y have the meanings given above. R 'has the same Meaning as R or denotes the remainder of the general formula

CH ₁

-CH, -

// X

C CH ₃ \ CH ₃

45

M represents an alkali metal ion or a tertiary amine.

The following are specific examples of those listed in the above action schemes general formulas given.

Examples of compounds of the general formula R - X - H are

OH

Oll

OH

55

60

-OH

OH

Il OH CII.,

are
CH ₃ CH,
I. r \
H
γ ... / < H H V-OCCI < I.
CH ₃ OCCl ^S
Ii I!
S. ; ^a ( ^H v-occi
CH ₃ CH ₃ ^s H
\, - N- O (
/ > SCCl < H V-SCC'I
Ij \ /! > - OCCl
Il H II '!
SS Il
S. and ': OCCl S. Ϊ s
CH ₃ ^S

H; —SH

and

Il

-SH The iniidothiocarbonic acid esters of the generali lciimel I are valuable microbicides that are found in the field

and (iartenbau can be used with I-.rfole They allow a safe and environmentally friendly inoculation of various plant diseases

In addition, the compounds have extremely low toxicity to warm-blooded animals.

The invention thus also relates to the use of the imidothiocarbonic acid esters of the general formula I as microbicides.

For example, the compounds of the invention have potent activity against piricularia oryzae, Pellicularia sasakii and similar rice plant diseases, Botrytis cinerea, Sclerotinia rot and similar vegetable diseases. They also work against powdery mildew in various plants such as pumpkins, beans, tobacco, eggplant, strawberries, sugar peas, Roses, berry pods, apples, pears. Peaches, grapes, chestnuts, alders and cereals. '5

The examples illustrate the preparation of the compounds according to the invention.

example 1

20th

N-S-pyridylimido-thiocarbonic acid-CM'-methyl-

cyclohexyl-S-p-tert-butylbenzyl ester (Compound No. 5), process variant (A)

In a solution of 5.6 g (0.1 mol) of potassium hydroxide in 100 ml of methanol, 25.1 g (0.1 mol) of 4 '- N - 3 - pyridyl - thiocarbamic acid - O - 4' - methylcyclohexyl ester are obtained at 15 ° C solved. 22.7 g (0.1 mol) of p-tert-butylbenzyl bromide are added dropwise to this solution at 15 to 20 ^{° C.} The reaction mixture is then left to stand at 25 ° C. for 3 hours. Here-

Table I.

the reaction mixture is ice-cooled in 400 ml Pour in water, and the oily layer becomes mn 700 ml of ethyl acetate extracted. The extract is washed once with 200 ml of water. After drying the extract over sodium sulfate the solvent evaporated under reduced pressure. One receives 33.9 g (85.5% of the Thcoriel one pale yellow oil. Information about the physical Properties of the product obtained can be found in Table 1.

Example 2

N-3-Pvridyiimido-dithiocarbonic acid-S-cyclohexyl-

S'-p-tert-butylbenzyl ester (Compound No. 10).

Process variant (B)

M 6 a (0 l mol) N - 3 - pyridyl - dithiocarbamic acid p-tert-butylbenzyl ester are dissolved at id C in a sodium methylal solution prepared from 2.3 g of metallic sodium and 100 ml of methanol 11 Moll cyclohexyl iodide is added. The resulting solution is left to stand for 1 hour at 30 ° C. and 2 hours at 50 ° C. The above reaction mixture is then processed further as in Example 1. 23.3 g of a yellow oil (71% of the 1 heonei The physical properties of this product can be found in Table I.

The other compounds listed in Table I are prepared according to Examples 1 and 2.

link

Structural formula

Howl

Refractive index or
Melting point.
Remarks

Llementary Analysis (%)

N = C

NS,

CH,

/ -C-CH ₃ CH,

Procedural variance (A)

85.5 n'f 1.5703

calculate! found

71.69 7.67 7. «) x.711 71.61 7.69 7.5 (1 X.7 '

^ Vn = C

NS,-

ν Η>

CH.,

/ -C-CH ₃ CH,

CH ₃

Process variance (B)

71.0 I-. 7X to 79 C

calculated found

72.20 7.92 7.32
71.93 7.90 7.25

O

CH ₃

SCH, - <'/ -C'-CH,

Procedure '1.5622 calculated 72.67 8.15 7.06 8.08 variant (Al found 72.58 8.30 7.18 8.01

90.2

CU _x

N - C

NS,

CH,

C (II,

cn,

^v 'eifahrensvarianlc (Bl

76.6 1.5652

calculated
found

72.67 X. 15 7.116
72.Xl X. (N MX

• Iziing

Structural formula

Howl

Refractive index h / u.
Sehmel /. Point.
Remarks

Klemcntai analysis ("oil

ο -; ' η ) -cn,

N-C CII.,

NS,-

CII.,

Process variant (Al

85.5

πί '1.5597 calculated 72.67 8.15 7.06 8.08

found 72.33 8.31 7.03 8.10

CH ₃

N-C '

NS,

CH ₃ CH ₃

"V-C-CH,

CH,

Process variant (B)

81.1

"'■■' 15336 calculated 73.11 8.36 6.82 7.81

uefundcn 73.32 8.45 6.71 7.63

o— <η y-cH,

NS,-

CH ₃

CH ₃

Process variant (A)

89.7

'■ " 1.5530 calculated 73.11 8.36 6.82 7.81

found 73.01 8.21 6.98 7.90

N - ■■ = C

SC

<H

CH, CH, CH,

Process variant (B)

72.3

1 ^; . I18bisll9 C calculated 73.1! 8.36 6.82 7.81 found 73.03 P.40 6.92 7.X7

] - N = C

NS,-

Process variant c (Al

8S.7

1- ". 126.5 to
127.5 C

calculated 73.52 K.56 h.Wt 7.55 Findings 73.43 8.3X 6.72 7.6f

NS

V N-C

Process variant (B)

ir "'1.5830 calculated 69.29 7.60 7.03 16J

found 68.91 7.57 7.25 16.

VN - = - C

■ 'N ■' '

'sh, -if

Process variant IA)

75.6

1.5562 calculated 73.91 8.75 6.39 7.3

found 73.59 8.70 6.45 7.3

50? 522 /

Table 1 (continued)

10

link

Formula

Howl Refractive index h / w. Melting point Ι'ΊιΙ Remarks

ι-N - = - C

SCH, - '(

S -

NS,

cn., Procedure s- 3 light yellow ul C. CH, Viiriiinlc (A) η "' 1.55W) Xl CH., CH, Traversing column chromatographyc f- f Ί 1 variant (B) Cleaning at Kicsclgel with V 11 ₁ _ η-hexane acetone (20: I) CH., (i5 as a solvent n: "- 1.575ft Bc i s ρ i e 1

After the agar dilution method, the activity of the compounds listed in Table II against various plant-damaging microorganisms determined.

Tabel

Connection no.

Microorganisms

minimal growth inhibiting concentration (ppm)

Ak

Gc

100 500 <5 () 500 KXI 500 <50 5 (K) 500 500 <50 <50 5 (X) 500 <50 <5 () 500 500 <50 5 (X) 5 (X) 500 50 500 5 (X) 500 <50 500 500 500 5 (X) 5 (X) 500 5 (X) 5 (X) 5 (X) KX) 500 <50 5 (X) 500 5 (X) 5 (X) 5 (K) <KX) 5 (X) <50 500 <KX) 5 (X) <50 5 (X)

^{c = o}

t-methyl-quinoxal.n-l.Vcycl.-dithiol- > KMXI> KM) O> 5 (X) 2 (X)

carbon at

Cm = Cochlioboliis miyabcanus.

Ak = Altcrnaria kikuchiana.

Gc = Glomcrclla cingulala.

Xo - Xanthomonas oryzac.

Example 4 bonds are made with water up to a certain

linfluii on pumpkin plants infested with powdery mildew: th concentration and then in

Gurkcns ^: imlin «c of the variety Kaüa Aonauafushinari 6 _{5 in} an amount of 10 ml per flower pot with a

are sprayed onto the plants in flower pots until the l-nt spray gun is sufficient. 24 and

development of the cotyledons. The in the form of 4S hours later the plants will be with a

The concentration of the present test ver- spore suspension of Sphaeroteca fuliginea nilized.

11

12th

The temperature is kept at 28 ° C. during this process. The infection stage of the individual leaves becomes 15 days later examined. The degree of damage is calculated using the following equation:

~~ (infection index · number of leaves)., ".

Degree of damage (%) = f ~,,,. , .— ηϊ-ν. c '■ ^ ^ ^ Number of leaves examined 5

The infection index ranges from 0 (no infection of the BUitlci or no infectious spots) to 5 (complete egg Infestation of the blank surfaces).

The preventive effect of the test compounds on Pancreatic diseases is given by the following equation certainly:

., ..., ..... (. Degree of damage during treatment \

Preventive effect = 11 - ^ - , ~ _r - ■ „-; —-. = -r -—-—? - 1 · 100.

\ Degree of damage without treatment /

The results are shown in Table Uli.

From Table HI it can be seen that the compounds of the invention have a much better effect than the zi Commercially available fungicide used for comparison purposes. It can also be seen that di Compounds of the invention are already effective at extremely low concentrations.

Tabel

Connection no.

Effective factor concentration Degree of damage Contraceptive effect (ppm) (%) (%) 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 3.0 97.0 50 0.0 100.0 50 16.0 84.0 50 0.0 100.0 50 19.0 81.0 50 0.0 ! 00.0 50 0.0 100.0

untreated

50

32.0

100.0

68.0

0.0

Example 5 Determination of the acute toxicity in rats

Test animals: Commercially available male rats.

Mode of Administration of Test Compound: The test compounds become emulsifiable in the form Concentrates administered orally in doses of 0.2 ml 10 g body weight. Observation time: 7 days.

LD ₅₀ : The values are determined using the Litchficld & Wilcoxor. certainly. The results are shown in Table IV.

Table IV

Connection no.

2
3
4th

Oral aVule

Toxicity.

LD ₅₀

(mg / kg)

> 3000> 3000> 3000 2500-30

continuation

Compound No. Oral Acute

To.M / .ilät.

ι n, "

I me kgl

5> 3 (KX)

6> 30 (M)

7> 3 (K) O K> 3 (XX) 9> 3000

10> 3000

11> 3000

12> 3000

13> 3000

2500

It can be seen from Table V that the compounds according to the invention have an extremely low level Have toxicity to mammals.

Claims (1)

Patent claims: I. Imidothioic acid esters of the general formula I X-R The invention relates to new imidothiocarbonic acid esters of the general formula I.