DE2257052C3 - Imidothiocarbonic acid esters, process for their preparation and their use as microbicides - Google Patents

Description

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

3. N-3-pyridyl-imidodithiocarbonic acid-S-cyclohe \ yl-S'-p-tert-butylbenzyl ester.

4. N-3-pyridyl-imidothiocarbonic acid-O-.V-meihvlcyclohexyl-S-i tert-butylbenzyl-estcr.

5. NO-pyridyl-imidothiocarbonic acid-O ^ '- meihyleyclohexyl-S-p-tert.-butylbenzyl-ester.

6. Process for the preparation of the imidothiocarbonic acid esters according to claim 1, characterized in that that one either

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

NIICX-R S

(11)

The invention relates to new hyoid thiocarbon acids of the general formula I.

V-N = C

X-R

'SCH, -:' -C CW,
CH ₁

in which X is an oxygen or sulfur atom and R is also one or more methyl "Ruppcn" substituted cycloalkyl radical with 4 to ! θ means carbon atoms.

The invention also relates to a process for the preparation of the imidolhiocarbonic acid eggs of general Formula 1. which is characterized. that one either

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

35 ■■ N

-NHC-X R

in which X and R are as defined above, with 1 to 2 mol of a halide the all-pure formula III

V-CH, -

CM.,

C CH,
CH.,

in which X and R are as defined above, with 1 to 2 mol of a halide of the common form! St.

Y CH, - ··· ■

CH,

C CH ₃ CH,

45

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

1 mol of N-3-pyridyl-dilhioearbamic acid p-tert-butylbenzyl ester with I to 2 mol of a halotienide of the general formula V

Y R

(V)

in which N 'and R have the abovementioned meaning have, in the presence of 1 to 1.5 moles of an alkali or metal alkali metal hydroxide. an alkali metal alcoholate or a tertiary amine in known per se Way.

7. Use of the imidol gum eggs according to claim 1 as microbicides.

in the Y a chlorine. Bromine or iodine atom
indicates, or

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

Y R

in which Y and R have the meanings given above, in the presence of I to 1.5 mol of an alkali metal or alkali metal hydroxide. like NaOH. KOH and Ca (OH) ,. an alkali metal alcoholate. as well. NaOC ₂ II, and KC) CH ,, or a tertiary amine, such as N (CH,) ,. N (C \ H _S ) _, and (CH.,) INC "H ,. implemented in a manner known per se.

The reaction is preferably carried out in a solvent like methanol. Ethanol. Tetrahydrofuran. Dioxane. Dimethyl sulfoxide or dimethyl formamide accomplished. The added basic compound

ho serves to neutralize the hydrogen halide formed during the reaction. One can proceed like this then the basic compound is first added to the solution of the I hiocarhamidic ester and then the halogen compound is added or the aibamic acid ester solution with the halogen compound first added and then the basic compound is added. The implementation will be milder Operating conditions. z. B. by stirring for 1 to 4 hours

of the reaction mixture at temperatures of is α ι ι-- λ- ■ ·. ■ .. ^N "^ ·

κ- HKi γ Hiirrhi.i-riihi-1 R _f . V, ~ "Examples of compounds of the general form

^bls "™ carried out. Reaction temperatures are RY

,, -. η Π to λθ C sini before / M "» M-jrV. o.,., ", i :.

Implementation is the reaction mixture ir. Water in CH

Pour in excess, and the separating 5 _

Crystals or the oily layer are removed by filtni- r \\ --c- ^ —r \\ (\

tion b / w. by extraction with a water-insoluble "' - - =, ^Lt1 ^ ^LI

borrowed organic solvents such as benzene. Toluene CFl

Ethyl acetate. Diethyl ether, hexane or octane! ^J

isolated. _I0 ".

As starting compounds in the process'

Variants Λ and B used N-3-pyridylthiocarb- CH-C- / -THRr

Amates can be obtained using different methods. ³ / "'. =, -'"

such as the following reaction; - CH

show equations. _IS - '

/ CH,

^NC ^ + RXH--. · '-NHC-XR _NN CH, c CHJ

^: s

IC)

j H - Br II - I

NHCS R

N ^ N _s ² 5 (H,

IDl _CHr i

NHC SM Y X - ■. N S. R -f NH; C. X - S. HCl Nl R. N f R ' f- a IC ¹ I.
S.

'- MY

25th

CIi, H - Cl and

Base I

30 CW, CII ₁

Examples of compounds of the general formula

-Ba *, F, ^{C1 CXR}

35

S ■
are

In these equations, R. X and Y have the meanings given above. R 'has the dike ⁽ " ^{Λ C} "' ^f "<meaning like R or means the Res! The general formula 'j ,,; ,, _{() (} . ₍ .,

CH, ■ C CH, ° ^{m S} CU. ^S.

45 _ς

CU, ^S

\ 1 means an alkali metal ion or a tertiary one

Amine. Il. occi n

The following are specific examples of the in 50 ^; () ((I

the above reaction schemes listed S '

general formula given. Ol ^ -μ S

Examples of compounds of the general formula *

RX !! are

₅₅ H SCCI H SCCl Ii SC (I

11 H OH H on _s SS

CW ₁ and OH

60 () ((I.

H "II II _{() | l} I, _OI ,

(jj, The Imidothiokohlensaureesler of the general

65 Formula I are valuable microbiota. those in the arable

; and horticulture can be used with IrIoIg.

" ^S " ^{UIK |} "i They allow safe and environmentally friendly

^ H fighting various plan / s illnesses.

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 plant diseases. Botrytis cinerea. Sclerotinia red and similar vegetable diseases. They also work against powdery mildew in various plants such as pumpkins. Beans. Tobacco. Egg fruits. Strawberries. Sugar peas. Roses, berry pods, apples, pears, peaches. Grapes. Chestnuts. Alders and cereals.

The examples explain the preparation of the invention Links.

example 1

20 N-.VPvridylimido-thiocarbonic acid-CM'-methyl-

cyclohexyl-S-p-tert-butylbenzyl-cster (Compound No. 5). Process variant (A)

In a lot of 5.6 iifO.1 mol) potassium hydroxide in KX) ml of methanol at 15 C 25.1 g (0.1 Mo!) 4 '- N - 3 - pyridyl - thiocarbamic acid - O - 4 - methylcyclohexyl ester solved. This solution is mixed dropwise at 15 to 20 ° C. with 22.7 g (0.1 mol) of p-tert-butylbenzyl bromide offset. The reaction mixture is then left to stand at 25 ° C. for 3 hours. Here-

Table I.

The reaction mixture is poured into 400 ml of ice-cold water, and the oily layer is extracted with 200 ml of ethyl acetate. The extract is washed once with 200 ml of water. After drying the extract over sodium sulfate, the solvent is evaporated under reduced pressure. This gives 33.9 g (85.5 ¹ O theory one: blaßeelben oil information on the physical properties of the resulting product linden fell in Table I..

Example 2

N-.VPyridylimido-dithiocarbonic acid-S-cv dohe- ■;,! -

S'-p-tert-butyibenzyl-esier (Compound No. Wi.

Process variance (B)

31.6 u (0.1 mol) N-3-pyridyl-dithiocarbamic Acid p-tert-butyl benzyl esters become 11 at 10 C one from 2.3 g of metallic sodium and WOm Methanol produced sodium methylate solution is dissolved. This solution is at room temperature mi 23.1 sz (0.11 mol) of Cydohxyli ^ id added. Receive tcne "solution is Ϊ hour at 30 C" and 2 hours! left to stand at 50 C. The reaction mixture according to Example 1 is then processed further One uses "! 3.3 g of a yellow oil (71" "of the theory! The physical properties of this product can be found in Table I.

The remaining Yerhin listed in Table 1 fertilize are prepared according to Example 1 and 2.

connection

Structural formula

yield

I "o I refractive index resp.
Melting point.
Bcmerkui.ücn

Klemcntaranahse I "..)

SCH,

CH,

-CCH ₁ CH ₁

Travel variance ³ ' 1.5703

calculated
found

71.64 7.67 7th wl
71.61 7.64 7.5 (1st

N C

SCH,

CH,

CH,

C VW, CH,

Process variant IBl

71.0 I-. 7S to 74 C

calculate!
uelunden

72.20 7.42
71.43 7.41)

7 " ¹ p

N C

SCH.

CH, C ί \\,

Procedural variable (ΛΙ

40 .:

.5622

calculate!
found

1 2.67
72.5X

P. 15
X.30

7.06
¹ JX

X.OX K.0I

S (H,

(H,

C (H ₁ CH,

Veifahrcns-Viuiiinle (Bt

76.6 if ' I.56S2

calculated 72.67 χ. 15th
»Find 72.Xl X. (l ')

7.06
7.IS

\ er Slnikliirl'ormel

Howl lii et Ihiiil '^ -
iiulcx h / w
Melting point.
Remarks

I linen! .Ir.in.il \ ^ c I "η ι

Il N

N C

SfH.

C] L. C. H, Vc ilahrcn ^ - C. H ₁ \ .1! ianlc (Al C. S 5. ( H,

Ii 1.55V

calculated
• jcfuiulen

i7 S. I 5 ".0 / i S. (IS 13 p.31 7. (H S.Ill

N C

SCH.

(H, CH,

C <- \\ _x

CIl ₁

\ crliihren - \ al Killte I IiI

Sl.! herechncl 73.11, p.3d d.S2 ".SI • jefuiKlcn 73.32 p.45 d.7l 7. (, 3

N C

SC

Ul,

CH ₁ CH. Cu ₁

\ ari.inic (Al

SM.7 hercchnel "3.11 p.3d d.H2 tx finds 73. (11 X. 21 d.ys

CH,

N C

SCH,

CH, ClI,

- C CH ₁

CH ₁

\ ariame I Bi

7 "> i. 1 1S hi-I 19 C calculate!

73.11 p.3d d.S2 73.ΙΠ p.4O d. ') 2

N C

SCH.

C H, ClI,

C (H,

CH ₁

\ orl.ihrcii · .- \ .tn; inlc IAi

SS.7 127.5 C

hcredmct
! icfuntien

P.3S

left left

d.72

N C

SCH.

(H ₁

( CW, CH,

\ erf.your. · .- \, inanle (Bl herechnel W. 24 7th no ucfuiulen 6P.41 7.57

Ki.HS lh. IS

N C

SCH.

CII, C (H,

Seduce · - lananle ι Al bei et lind
found

11 s - -

i'i S. " ⁷ Il

Table I (Fortset / imu)

10

connection
No.

Structural formula

Howl

("ill

lirechuiigsiiule \ b / u. Melting point. ilenierkuMLien

N f CH ₁

SCH .. - c CH ₁

Implementation variants

light yellow iil

H '■ "■ 1.55M)

N C

SC I

πι,

C CU,
CH,

example

Process variance Hi)

saiilenehronialogr.iphischc Cleaning: on silica gel mn n-He \ on acetone 120: as Luufmillcl

ii: '' 1.5756

After the agar dilution method, the activity of the compounds listed in Table II -c determined on various microorganisms harmful to plants. "~

Table II

Connection uni; No.

Microorganisms

minimum growth inhibiting concentration (ppm)

Cm Ak Ck

Xo

• N S

N'- 'S

C O

100 100 5 (K) 500 500 5 (K) 500 5 (X) 500 HK) 500

<KX)

<100

6-Meih \ l-quinoxaline-2.3-cve! .- dithiol carbonate

^ m = Cochliobolus mnabeanus.

Ak = Alternana kikuehiana.

Cjc = Glomerella cingulata.

Xo = Xanthomonas orv? Ae

on, on, powdery mildew infested Kürhispflan / cn Cucumber seedlings of the cultivar Kaga Aonagafushm'ri are grown in flower pots until the cotyledons have developed sufficiently. Those in the form of Emulsifiable concentrates present Testver-500 500 500 500 5 (X) 5 (X) 500 500 500 500 500 500 500

> 1000

<5 () 500 <50 500 <50 <50 <50 <50 <50 500 50 500 <50 500 500 5 (X) 5 (X) 500 <50 500 500 500 <50 500 <50 500

>

200

^h ' ^{S / U cil1cr}

_nc r Menc tTuVT ™ ¹ n * ^an ' ^icß . ^cnd . Sprühnis ^ le au? i? L ^pr ° ^Blumcnt0 P ^fm " ^cin 'hours Jh Jf" sprays. 24 u, i

S _P ore _nsus nen ^ ^ u ^ ^PflanZC " ^{infected with} ™ ' ^porensus P ^cns ' ° n of Sphaeroteca fuliainea

11th

12th

The temperature is kept at 2 ° C. during this process. I 5 thaws later becomes the infection stage of one leaf examined. The degree of damage is calculated according to the following calibration:

.,. . ,. (Infection index · Blatlan / ahl) .....

Damage rate ("") = -,,.. ...... · 100.

· ■ Number of examined leaves ■. ">

The infection index ranges from 0 (no infection of the leaves b / w. No infectious spots) to 5 (complete Infestation of the leaf surfaces).

The preventive effect of the test compounds on plant diseases is illustrated by the following equation definitely:

.. .... .... / ', Degree of damage during treatment \. ,,,.

Contraceptive effect = 11- "-. ■■ -. _c . . ..-.: - ■ - · -,,. ,,. - 1 ■ 100.

V Degree of damage without treatment /

The results are shown in Table III.

From Table III it is apparent that the compounds of the invention has a significantly better effect than the / \ comparative purposes employed commercially available fungicide. In addition, it can be seen that the compounds of the invention are effective even at extremely low concentrations.

Table IU

Connection University: No.

VV ikstoffkon / cnl ration SchadmuntiMirad Contraceptive effect lppml (%) 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 0.0 100.0 50 0.0 : oo, o 50 0.0 100.0 50 3.0 97.0 50 0.0 100.0 50 16.0 «4.0 50 0.0 100.0 50 19.0 81.0 50 0.0 100.0 50 0.0 100.0

C =

50

32.0

68.0

untreated

100.0

0.0

Connection \ r.

Example 5 Table IV

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 according to the method of

Litchfield & WiIcoxon definitely. The results are summarized in Table IV.

Oral ukule

LD ₅ T ^JI " (mg kg)

> 3000> 3000

> 3000 2500- 30C

Fort set / un μ

Compound no Oi.ilc, ikiiu-

lnM / itat. I IV ,,

Ιιιιμ kr I

5th - 3000

6> 3000

7> 3000 S> 3000 9 > 3000

H)> 3000

1 1> 3000

12> 3000

^H J ^cf if 'i: ^ o 2500

From Table IV it can be seen that the compounds of the invention have an extremely low level Γοχί / ität they show about acidic substances.

Claims (1)

Patent claims: 1. Imidothiocarbonic acid esters of the general Formula I. X-R XY-N = C CH, ^N SCH, - '■''."—C-CH, (1)