DE1940032C - Substituted N phenyl succinimides, process for their preparation and their use as fungicides - Google Patents

Description

The invention relates to new substituted N-phenylsua: imides of the general formula I

R ₁

H ₁ C-C '

in which R _{1 and R 2 are} identical or different and represent a hydrogen atom, an alkyl radical having 1 to 3 carbon atoms, a benzyl group, a phenyl group or a chlorophenyl group, Rj represents a hydrogen or halogen atom or a methyl group and X is a halogen atom . with the proviso that X denotes a fluorine, bromine or iodine atom when R ₁ , R ₂ and R _{3 are} hydrogen atoms.

The following compounds, the structural formulas of which are given in Table I, are preferred:

have cyclized to succinimide by heating with elimination of water.
'5 Preferred starting compounds are, for. B.

N- (3 ', 5'-dichlorophenyl) -3-methyl- (II)

succinimide
N- (3 ', 5'-dichlorophenyl) -3,3-dimethyl- (III) succinimide

N-l.lAS-TrichlorphenyO-succinimide (IV)

N- | 3'.5'-dichloro-4'-methyl-phenyl) - (V)

succinimide
N- (3 ', 5'-dichlorophenyl) -3-phenyl- (Vl)

succinimide
N- (3'.5'-dichlorophenyl) -3- (2 "-chlor- (VII)

phenyl) succinimide
N- (3'.5'-dibromophenyl) -3-phenyl- (VIII)

succinimide
N- (3'.5'-dichlorophenyl) -3-benzyl- (IX)

succinimide
Ni.V.S'-DichlorphcnyDO-methyl- (X)

3-phenyl succinimide
N- (3.5-dibromophenyl) succinimide (Xl)

and
N - (. V.4 ', 5'-Trichlorphcny!) - (XII)

3.3-dimethylsueinimide

The [invention also relates to a method for Preparation of the substituted N-phenylsuccinimides of general formula I. The process is thereby characterized in that substituted Bcrnstcinsäurcincnoanilidc of the general formulas XIII or XIV

N - (. V, 5'-dichlorophenyl) -

2 (or 3) methyl succinic monoamide

N- (3 .S'-dichlorophenyl) -2.2 (or 3,3) dimethyl succinic monoamide

N- (3,4,5-trichlorophenyl) succinic monoamide

N- (3,5-dichloro-4'-methyl-phenyl) succinic monoamide

N- (3 ', 5'-dichlorophenyl (-2 (or 3) -phenylsuccinic monoamide

N- (3'.5'-dichlorophenyl) -2 (or 3) - (2 "-chlorophenyl succinic monoamide

N- (3 \ 5'-dibromophenyl> -

2 (or 3) -phenylsuccinic monoamide

N- (3 ', 5'-dichlorophynyl) -

2 (or .ll-benzylsuccinic monoamide

N- (3'.5'-dichlorophenyl) -2-methyl-2-phenylsuccinic monoamide

N- (3'.5'-dichlorophenyl) -3-methyl-3-phenylsuccinic monoamide

N-l.'i.i-Dibromphcnyn-succin-

monoamid

and

N- (3'.4'.5'-trichlorophenyl | -
2.2 (or } 3) dimethyl succinic monoamide

C COi) II

CII, COMI

C CONIl

!!, coon

iXllh

(XIV) (Ma) (IHa)

(IVa)

(Va)

(VIu)

(Vila)

(Villa)

IIX a)

(Xa)

(Xa)

(XIa)

in which R ,. M ₁ , R, uiul X the preliminary Hedeu-According to the founding process, the substituted N-methylsuccinimides can be prepared from the corresponding hydrostic acid monounilides by a simple ratio of about 170%. Before / ugl, however, the reaction at 100 C untc

Stir in the presence of a dehydrating agent

fio such as fissure anhydride, Acclykhlorid, Phosphorus pcntachloride or phosphorus oxychloride, preferably wcisi Acetic acid hydride made, the ge

wish substilui ■ nc N-phenylsuccinimide in high Yield is obtained. The response time is cheating

'' 5 this lull about I hour.

The invention also relates to the use of substituted N-phenylsuceinimides in general Formula I as a fungicide or in a fiingicidal agent

I 940 032

They can be used either neat or together with an inert carrier in any conventional manner, e.g. B. in I ¹ Or m of dusts, wettable powders, oil sprays, sprays, J'abletten, Emulsifiable concentrates or in Torrn of Ciranulaia be used. Furthermore, the substituted N-phenylsuucinimides of the l-.rligation can be used in combination with other compounds, e.g. H. together with Blasticidin-S, Kasugamycin, PoIypxin, Pentachlorbenzaldoxim, -1,2,3,4,5,6-HeXaChIOrcyclohexan, 3,5-Diehlorphenylmaleimid, 3,5-Dichlorphenylsuccininiid, S ^ -Dichlorphenylitaconsäureimid, OO-diethyl -S-benzyl-thiophosphoric acid ester. O - ethyl - SS - diphenyl - dithiophosphoric acid. O-butyl-S-benzyl-S-ethyl-dithiophosphoric acid ester, OO - dimethyl - O - (3 - methyl - 4 - nitrophenyl) - thiophosphoric acid ester. S - [1,2 - bis - (ethoxycarbonyl) ethyl] - O, C) - dimethyl - dithiophosphoric acid ester. 0.0 - Dimethyl - S - (N - methyl - carbamoylmethyl) - «iithiophosphoric acid ester, OO - diethyl - O - (2 - isopropyl - 6 - methyltityl - 4 - pyrimidinyll - thiophosphate. 3.4 - Dimethylphenyl - N - methyl - carbamate. Zinc ethylene bis dithiocarbamate, N - trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide, N - (II, 2.2-tetrathlorälhylthio) -4-cyclohexcn-1,2-dicarboxyimide and F.iscn-methylarsonal can be used in all Combinations do not impair the effectiveness of the individual compounds. As a result, it is possible to control several diseases and infestations with harmful insects at the same time, whereby, depending on the combination, synergistic effects could be established 'henylsua.mimide in combination with other, especially agricultural chemicals. ? .. B. llerbiciden, Ncmatociden and Mitleiden, or be used together with fertilizers.

The substituted N-phenyl succinimides show one excellent effectiveness z. B. against Piricularia ory / ac. Pellicularia sasakii, Cochliobnlus miyabeanus. Seleruthinia sclerotiorum and Sphaerothcca fuliginea. the arable and agricultural crops attacked. In addition, they are well suited for combating Aspergillus niger. The connections are but hardly harmful to animals and plants.

So far there are no T'ungieide with a similar width biocidcm spectrum and known with such activity

The examples explain the invention.

Examples I to 11
1 Preparation of substituted N-phenyl succinimides

line Mixture of 0.1 mol of a substituted succinic acid monoanilide of the general Tormein NIII or NIV. 50 g of acetic anhydride and I.Og anhydrous nairium acetate was placed in a 100-nil vicr neck flask Stirred at 90 to 100 ° C. for 1 hour. Subsequently, acetic acid and acetic anhydride distilled off under reduced pressure; the residue is washed with water and dried, and the desired substituted N-Piknylsuccinimide is obtained relatively pure and in high yield. The pure product is obtained by recrystallization from alcohol.

line Table I.

™ -rf- r **> ^ r U r- 'r- ^a , _. - r \ r ι t / " Y. - r ι r .O - ^ r r ι β - ~ _t V. <r \ T r- T 3 - ^X

_

sz

'd

X. ■ χ.

KortNct / unt!

IVa

Va

Via

Vila

villa

Substituted N-Phcmlsuccinimide Structural formula (no.)

C!

ί;

H ₂ C-CH, C-C

H ₂ CC _n

HX- C ^/

SI ο

Il

y, - HC - C

H, C - C

yy

O O

- HC-C _x

. ·

HX - C ^y

Ii ο

Il

- HC-Cx HX —C ^/

Il

Cl

N-

. ■? - ei

I! Cl O O j! Cl

N-

Cl

Cl

Ci

Cl

Cl

Br

Br

Fl Cl

yield

("oil

(IV) i IS6 to 187.5

(V) 161 to 162! 91

(VI)! ICO to 101 I 94

(VII) 152.5 to 153.5

(VIII) I 124.5 to 127.5

98

Elcmentarar.alysc tX = halogen I. C (% l H <% l N (% |! X (", .ι

! i ICl)

calculated: 43.12 2.17 5.03 38.19

j Found: 43.25 2.07 i 4.81! 37.80

calculated: 51.18
found: 51.24

3.51
3.36

calculated: 60.02
found: 60.50

3.46
3.28

calculated: 54.19
cc found: 54.36

2.84
3.00

calculated: 46.97
found: 47.04

2.71
2.58

5.43
5.45

(Cl)

27.47 27.66

4.37
4.12

(ClI

22.15

21.99

3.95
3.80

(ClI 29.99

29.77

(BrI

3.42; '.9.07 3.31! 38.93

example

Output connection

X IXa

Xa

XIa

Il XIIa

Structural formula iNr.)

^ - CH, -HC - C,

H, C C

H ₁ CO

H, C - C

i | ο

Ij

HX · ■ - C _x H, CC- ''

Il I!

C) C)

IKC C

_N -.

CH ₃
CH /

C - C

l-ortset / un »

Substituted N-Phcmisuccinirmii

F I Cl

ι Auibcuk

I "n I

ElementaranaK ^ e (X = halogen) C'l ".. l ι Hl'Ol I N ('" ,,!

(IXl: 112 to 113.5

90

(X)

111 to 112.5 '93

(XI) ■ 15X.5 to 159.5: 96

(XlI): IXI to 1X2

94

calculated: 61.10
»Found: 61.68

3.92
4.04

calculated: 36.07 2.12 i 4.21 found: 36.21 2.IX i 4.35

X <"■«

I (CD

4.19 j 21.22

4.19 i 20.87 - »

61.09 3. ¹ > 2 4.19 (CIl calculated 60.X I. 3.91 4.05 21.22 ■ el'unden: 04/21

(Br)

48.00

48.11

47.01 I. 4.57 ' (Cl) calculated: 46.74 3.29: 4.58 34.69 izeTunden: 3.15 34.60

O CjJ N)

Manufacturing blocking agents

Those marked with a number in the examples Connections can be found in Table I. ,.

Example 12 Dust

3 parts of compound IV and 97 "I hurry tone werft-η carefully mixed and powdered. Da, dust- (means contains 3 "η of the active compound and can be used #directly.

Example 13

. In

Dusty medium

4 'file of compound VIII and 96 loile talc ! »Earth carefully mixed and powdered. The jam helnitlel contains 4 "n of the active compound and can be used directly. ^ o

Example 14 Wettable powder

50 file of the connection \. 5 parts of a network 2 ;, (by means of the alkylbenzenesulfonate type and 45 parts l ') iatomaceous earths are carefully mixed and powdered. For use, the powder is mixed with water diluted and sprayed.

Example 15 FEmulgierbart.-s concentrate

10 I speed of connection IX. 60 parts of dimethylformamide. 20 parts of dioxane and 10 parts of an emulsifier of the Polyoxyäthylcn-Alkylphcnoltyp are mixed into an emulsifiable concentrate. For use, the concentrate is diluted with water and sprayed.

• P

example
granules

16

File the compound X. 93.5 parts clay and file a binder based on polyvinyl alcohol are carefully powdered and mixed together. After kneading with water it becomes the mixture granulated and dried. The granules are used directly for application

Example 17
Combined dust

2 parts of the compound III. 1.5 parts of Pcntachlorhenzaldoxime. 1.5 parts of O-n-butyl-S-ethyl-S-benzyldithiophosphoric acid ester and 95 I eile lon are carefully mixed and powdered. The dust ciiiittcl contains 5% active compounds and can be used directly.

Example IX
Combined dust

2 parts of the compound VI I. 1.5 file O-n-butyl-S-eth \ l-S-benzyl-dithiophosphoric acid ester. 2 file (). () - 1) methyl - < > - (3 - methyl - 4 - nitrophenyl thiophosphoric acid ester. 1.5 file 3.4- Dimethylphenvl-N-mcihvl-earhamat and 93 I rush ions are carefully mixed and powdered. Contains dust 7% active compounds and can be used directly.

The following test examples show the excellent biocidal effect of the mixed body N-phenyl succininides.

Test example 1
Control of Piricularia oryzae

Rcispfianzcn the variety Waseasahi are in flower pots from 9 cm in diameter to the 3-leaf stage drawn and then each with 100 mg pot of the compounds listed in Table II each in a 3.0 iger concentration. After a lay the plants are with a Spore suspension of Piricularia oryzae inoculated and sprayed. After 5 layers the number of Infested sites counted. As can be seen from Table II, the substituted N-prynylsuccinimides are of the invention much more effective than the known comparison compounds.

Table U

connection

Λη / ahl der Rdiillstclicn
per 10 blues

Ii

IV

ν

VIII

Xl

Cl Il

N I * |

c cn (!!, cn cn,

9
Il

I ¹ M

llckaimlc

hstirhiiiiliim;

(1

IQS

Cl

C. Il r'ortset / ung I.
j connection I.
C. O ii
C. * l ίΊΙ, C. O

Λη / ahl of the cases per IO sheets

Cl

: ίι I (V7

Not treated

• Back-up network connection

I'est-Hcispicl 2 ikkan ^ lun ^ onCochhoiolusnuyaheanus

Reispllan / eti (Ilt variety Wasjasahi are placed in wooden pots \ nn ⁽ ) cm Oiirehm.-sscr up to the 4-Hhiü- ν ^ς stage and with each H '. Ml' cup of a tviil.ingen suspension of the in Ί ahelle Il aufgoführten V erbiiulungen each in a concentration \ 100 on sprayed ppm. After a l'ai · expectant-n ti te ..flan / cn with a S _P orensuspens.on% on C ochhobiilus mivabeanus inoculated and sprayed. 3 tepid thereafter As can be seen from Table III , the new substituted N-phenylsiicemimides are actually more effective than the known counterparts.

Table III

\ crhintluni! Λη / iihl iIlt Hcl.1llM1.lltn pn

III

Vl

VII

VIII

IX

Xl

CH,

Π! .Ι

Il

c cn,

l "

c cn c ₄ n "- iso

15th

·) Known comparison compound.

13 14

continuation

Binding ι number of letters per sheet

C - CH

C] - ' N! Ι *' 103

CC - ■ " .-Cl
O

'■■ • kIii treated ^l ) p

I est example ^
Inoculation on Pellicularia sasakii

V ei plants of the Kinmaze variety are in Wagner infestation mdex 0:

1 '-arrow au-porcelain to a height of 50 to no teasing on the leaf surface.

6 * i _rn iie / ngen. The leaves of the individual plants - infestation index 1:

«I-jnuel '.'. Earth inoculated with Pellicularia sasakii. After switching, signs of network formation are

• On the next day, the plans are each with 10 ml I opf 2? Jen watched on the horn surface

Finer undengen kmuKn> n of the infestation index 2 in Table IV:

led connections each in a concentration by less than 3 cm 1st irolJe (1st tang

Irv.Mon -on 200 ppm bc ^ pr. '. Ht. After 7 days, observations are made on the surface of the leaf.

The size of each infestation point is measured. where for Bcfallindex V

the evaluation learn the following for the application 3 ° I lick more than 3cm (irölie are aiii

comes. observed the leaf surface.

The extent of damage is determined by the relationship

Σ (infestation index number of stencils)

Degree of inclination) = ■ - - ϊ, ^ Γ '"" —ι- <? ~ <"-.''^'

^c Number of stems examined χ 3

definitely.

As can be seen from Table IV, the new substituted N-phenyl succinimides are significantly more effective than the known comparative compounds.

Table IV

μ Sih.ktiiuineviuMiuli

11 4.2

III 22.7

IV 2ß

V 18.6

VI 17.4

VII 1S.8

VIII l ^l ) .3

XI 6.2

XII 11.7

C!

- NHSO, CH, C1 *>

Cl

Hekannlc VcrclciclKvcrhjndunc

78.5

IQS?

continuation

Cl

Cl

Cl

- -N

C -CH ₂

C-CH-CH,

t ^; O

CH

- NI connection CH ₂ CH ·) = -CH, Injury ^ Cl ICOOC, 11 ₅ 71.7 I.
Cl - N Cl
I. O
Il
c - cu, KX) c cu
ll

KK)

100

Cl

I ** O N C ( Ή beh O I.
CC andell. . . • egg 117 ' not

100

I 5.5 KM)

·) Known comparison

* l iliiruk'lslii / ι'κΐιηιιιΐ)! iüi a Χ (Ι'Ίι | (.ί ·> bend / ha ι es l'uKci

MιΜκιηκΊh> l.irsin-HiS- (IiIIHlInI-Il11lnociirb.iiiiiil. /inkiliiiH'llnl-dilliiiKiirhiiin.il

Tesl game 4 Vaccination of Sphacrothcca fuliginea

pumpkin plants of the Hcian Kogiku variety Jelly buttons with a diameter of 12 cm! until to 4-Hlall-Staditim and each time with I l'opf'CiiH'r suspension of the listed in Table V : ncti compounds each sprayed at a concentration of 5 (M) ppm, one day later Jen die! '(Lances with a spore suspension inoculated and sprayed by Sphacrothcca Tuliginca.

After IO lay the damage level will be mii four top millers of each plant determined by measuring the I lick.

Iiir each connection represents the value in the last Column of table V the result from a Vcr-

& 5 suchsrcihc with 7 pots. As from Table V As can be seen, the N-phenylsuccinimides substituted according to the invention are considerably more effective than the known comparative compounds.

O I 77! 09AfU-H9

17th

Tändle V

connection

III

IV

V

VI

IX

Xl

Cl

j

<f -NHSOjCH ₂ CI *)

Cl
Cl

Cl

is

CH,

L.

Γ '

CH.,

- N

C CH -CH., -

ί! ο

C CH,

C CW CH,

Ii ο

C CH

18th

7.4 1 (1.3

5.7

4.6 11.2

4.3

37.5

33.7

38.9

50.1

42.7

CC <'' Cl

1! ■ "

Not hchiindi-lt

*) Known «revaluation.

lesl · Example 5 Hiocl's spectrum

The growing Aspergillus niger is examined according to the dilution method. The values> 200 tumsver / öperndu liinliuö in table Vl unge- and> 1000 mean, duO at a concentration given compounds on different plants of 200 or 1000 ppm no effect of disease-causing and bacteria are based on thlet will be able to

Verhiiuliing

Piricularia üryzae

CoL'hliobolus mijabeainis ....

Allernaria kikuchiana

Pellicularia sasakii

Pythium aphanidermatum ....

Pclliciilaria filanienlosa

C'orticium rolfsii

Bolrvlis cinerea

Selerotinia seleroliorum

Alternaria mali

<ilomerclla ciniiulata

Xanihomonas ory / ae

Aspcrgilliis niuer

I 940 032

Table V!

ti

Cl

20th

,, uloilicm ι Ii k iin / L η I [al κ hi Ippinl

Il

C CII,

S!

c- cn

C)

III) 40

• η

40 2 (K) 2 (K)

2 (K)

40

40

40

40

'Π.

CII,

(ClI, (C II,

, -200 2 (M)

-> 2 (M) 2 (M) 2 (M) 200 2 (M) 200

> 2 (K) -2 (M) -2 (K) KK) O

HcNpicl

\ Ί.τΙιΐΡΐ '' ιιπμ

Cl

O · N Cl

Cl

CH,

O O

CH,

Cl

C! 'Ο, -CI

O O

.11, ⁿ . J

l'h \ lotoxi / il: tlcn

Kcispfliin / cn

(Wascas.ilnl

AkulL * Orale Inxi / ii.ii

hci K.illcn LI). ,, Ιιπμ kui

15 (K)

1500

15 (K)

> 15 (K)

example

connection

Cl

O, · N

Cl

Br

Br

I,

O O

_o \ _N

(Ί

ⁿ Ilen,

θ 'N ^C

C, ^

Mr

ν O N

Mr

Kp
(Waseusaliil

22nd

KUrhispfian / cn
(llcian Kngikul

Akulc: iir.ilt I nxi / i near Kallun

LU ,,, (mg Κμΐ

>! 500

> 1500

15 (K)

15 (K)

I MK)

> 15 (K)

2300

continuation

Rice plants (Waseasahi)

Phylotoxicities

Pumpkin plants (Heian Kogiku)

Acute Oral ToxicillS

for rails LD ₅₀ (mg / 1 (g)

15500

control

(Farmaco Ed. Sience, Vol. 22 (1967). Pp. 781 to 785)

1500

Remarks:

- - No l'lntouixmtüi

Very low phyt: Moxi / iliit.

(- Light Phuouui / itiit Jf = Maliice Ph.uoio Vitiit tu- = Sliirkc Phvl.M.txmliil.

The connections according to the invention do not show any or very little phytotoxicity.

Claims (7)

Patent claims: I. Substituted N-phenylsuccinimides of the general formula I. R, O R ₂ - C - C (I! in which R ₁ or R _{2 are} identical or different and represent a hydrogen atom, an alkyl radical having 1 to 3 carbon atoms, a benzyl group, a phenyl group or a chlorophenyl group, R _{3 represents} a hydrogen or halogen atom or a methyl group and X a halogen atom with the proviso that X is a fluorine, bromine or iodine atom when R ₁ , R ₂ and R _{3 are} hydrogen atoms. 2. N- (3,5'-dichlorophenyl I-B-methylsuccinimide. 3. N- (3 .5 '-dichlorophenyO ^ α-dimethylsuccinimide. 4. N- (3,5-dibromophenyl) succinimide. 5. N-pAS-trichlorophenyl succinimide. 55 6. A method for producing the connector according to claim 1, characterized in that dai substituted succinic acid monoanilides dei general formulas XIII or XIV R, R ₂ -C-COOH CH ₅ CONH R, R ₂ -C-CONH CH ₂ COOH in which R ₁ , R ₂ , R ₃ and X have the aforementioned meaning, cyclized to succinimide by heating with elimination of water. 7. Use of the compounds according to claim 1 as a fungicide. 109 684/31: ι η c Ί