DE3022057A1 - NEW FORMAMINE INSULFIDES AND DISULFIDES AND THIOCARBAMOYLGUANIDINE - Google Patents

Description

PATENT LAWYERS ^ Π? 9 Π R

DH- V. SCHMIED-KOV / ARZIK dr. P. WEiNHOLD · monks . G. DANNENBERG · dr. D. GUDEL-dipu-ino. S. SCHUBERT- Frankfurt

SiECFRLEDSTRASSE β OOOO MONCHEN

TELEPHONE <089> 33S024 + 33SO2S TELEX! S2IS679

SK / SK

Case K.2745 + K.2746

Montedison S * p.A, Foro Buonaparte Milan / Italy

New forniamidine sulfides and disulfides as well as Ihi ο carljamoylguanidine

030051/0903

The present invention relates to new herbicidal compounds, in particular to new formamidine sulfides and -'disulfide and on thiocarbamoylguanidines with high herbicidal Activity, production and use.

In the literature a limited number of Fonaamidindisulfiden is known _r which never herbicidal properties have been awarded. PK Srivastrava et al have ι. for purely academic purposes the following formamidine disulphides are produced in the form of hydrobromides:

N 2HBr

NH S-S NH

(P.K. Srivastrava et al. Tetrahedron Letters 23, 2725, 1968)

^C 6 ^H 5

Jl

λ λ MI

. 2HBr (P.K. Srivastrava et al J. Ind. Chem. Soc. £ 0

yy

^ 2HBr

Uli SS ^ /
CH ₃

(PJ ^. Srivastrava et al. Indian J. Chem. 1_, 354,

⁴³² '

030051/0903

However, there are no analytical data to characterize the three of the above compounds are given, presumably because they are on-; not isolated as free bases because of their instability * Similarly, very few derivatives of the class of thiocarb- j amyl guanidines known. This class of compounds too Herbicidal properties have never been ascribed to them.

mo Held, Gross and Schubert (Zeitschrift der Chemie (1973)) produced the N ¹ , N ¹ -dimethyl-N ² , N ³ -diphenyl-N - / Ν, Ν-dimethylthiocarbamoy! / - guanidine of the formula

H, C-N

³ I.

j her. Srivastrava et al (J.Ind.Chem.Soc. 40, 803 (1963)) ; made derivatives of thiocarbamoylguanidine based on the

Nitrogen atom in the 1-position and ^{niantly substituted on the nitrogen atom of the 2S} thiocarbamoyl group, in the form of the hydrobromides.

The present invention now aims at formamidine disulfides and disulfides of the general formula I and thiocarb-

R. \ N - N ^(S) n / N R. / N 1 - R ι R ^ 1 \ N C - I
Il "1 Il I? Il R - Il Il
S] * - R C. C.
/ \ 2
R. \ ^ N- *
35 . R ¹ !

(D

030051/0903

, ItIf *

- 4 In the above formulas:

j R * is a phenyl group, which is optionally replaced by a or t several halogen atoms, one or more alkyl or,

s haloalkyl groups with 1 to 3 carbon atoms sub- '

can be established:

1 2

! R and R = which can be the same or different: C, .- C-,

12 'P

Alkyl, C ₁ -C 4 alkoxy; or R and R together form

an alkylidene chain with 4 or 5 carbon atoms, which ^is optionally interrupted by heteroatoms; η = 1 or 2

with the proviso * that - if in formula II R = R ² = CH, R is a substituted phenyl group.

'"> The compounds of formulas I and II (even in the case when in formula II R ¹ = R ² = CH, and R = unsubstituted phenyl) have herbicidal activity against both monocotyledons and dicotyledons and can be successful per se or in the form of a suitable preparation for weed control

w , the present invention also relates to the method of controlling weeds using: the compounds of formulas I and II or their preparations.

The inventive preparation of the compounds of formula I and II can be done by the following procedures.

• The compounds of general formula I are produced by oxidation of trisubstituted thioureas (III) in the presence of an organic base (reaction 1) with BiI-

j3o formation of the compounds of formula I in which η = 2 (Disulfides); the corresponding ones are obtained from these by desulfurization in the presence of triphenylphosphine (reaction 2) Sulphides. The same compounds (monosulfides) can also be prepared by reacting a trisubstituted one Thiourea (III) with the appropriate imidoyl chloride (IV) in the presence of a hydrogen halide

• acid-binding "base (reaction 3):

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I ■

SR ¹ R

11 / oxidation \

1) R-NH-C-N r-r-r-r> N

\ ini-cxel

(ill) ^ r ²

2) (I, n = 2) + (C ₆ H ₅ ) ₃ P -> (i, _n = i) +

Cl R ¹ I.

3) (III) + RN = CN (IV) (I, _n = 1) f

\ 2 I.

R i

K-

Reaction 1 takes place by oxidizing the thiourea |

(II) in the presence of an organic base and in a |

: inert solvent. Suitable oxidizing agents are '

eg halogen atoms such as bromine and iodine (Br ₂ , I ₂ ) »while a |

tertiary amine, such as triethylamine or tributylamine, as an orga- j

niche base can be used. Excellent yields I.

obtained by using methylene chloride (CH ₂ Cl ₂ ) ^; | ⁼

or chloroform (CHCl,) as a solvent. Among the above j

the conditions described, the reaction occurs with room \

at temperature and in a very short time. After the end of the reaction,]

the mixture washed with water and dried, and that;

^: Solvent is evaporated. The product obtained can;

j used per se or made from non-polar solvents- |

be crystallized. I.

; Reaction 2 is expediently carried out by reacting equimola- |

(obtained from reaction 1) rer amounts of disulfide and tri- t

: phenylphosphine in diethyl ether at about ⁰ ° C. The obtained · "■

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Triphenylphosphine sulfide precipitates and is filtered off at the end of the reaction. The reaction mixture is customary Treated manner, and the formamidine sulfide thus obtained is by recrystallization from a hydrocarbon cleaned.

Reaction 3 leads directly to formamidine sulfides without prior. previous production of the corresponding disulfides. The reaction takes place in an aprotic solvent and in the m being a hydrohalic acid binding base. An advantageous process for carrying out the above reaction consists in adding a solution of the thiourea derivative (II) and a slight excess of base (tertiary amine) in methylene chloride to a solution of imidoyl chloride (III) in the same solvent. The mix ^! is stirred at room temperature, and the reaction takes place j in a short time. The product is obtained in the usual way.!

The compounds of formula II are prepared by reacting a foramidine sulfide or disulfide (i) with a catalytic amount of a strong, anhydrous acid ^f (reaction 4):

η R

Jl Il

Il

C.

(S)

NO

(D

(ID

Reaction 4 is preferably carried out by adding a catalytic amount of a sufficiently strong acid Formation of the basic groups of the sulfide or disulfide of the formula I to form a solution of the latter in an aprotic one Solvents such as chloroform (CHCl ^). As a strong acid, an anhydrous hydrohalic acid or a trihaloacetic acid is suitable. The reaction rate

030051/0903

thing depends on the nature of the connection to be implemented of formula I also depends on the amount of acid used. With amounts of acid of 0.1 equivalent per mole of the compound of the formula 1, reaction 4 proceeds at room temperature within a few minutes to completion. After Reaction, the chloroform solution is washed with a saturated aqueous sodium bicarbonate solution (NaHCO ^) and then dried. The solvent is evaporated in vacuo, yielding the corresponding compound of the formula II is obtained as a residue which is purified by recrystallization.

The process for preparing the compounds of Formula I and II can be summarized by Scheme 1 below

become: Scheme 1

SR ¹

R-NH-C-N

(III) R ²

Oxidizing agent

(n = 2)

Cl

^(C 6 ^H 5> 3 ^P

base

(n = 1)

(III) + R-N = C-N '

(IV)

The compounds of the formula ϊ and II listed in the following Table 1 are according to the processes described above manufactured:

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CO the O ι 1 R. R.
N N π NO C. R. \
1 I /
-N N
I. Ui NO
I. links
Formulas Ii ij I ₂
R. Table 1 L. I ₂
R. I.
R. I2
R. 1 / ^ (p
-N (ι) and T R. Il
S.

(II)

O O cn

ο co ο

formula Verb.
No. π R. R. 2
R. elements
Q /
yQ
ber. iranalysis;
found (1)
NMS (<jf, ppm) (.2 /
F.} Cc IRicm "") approximate
formula
Mol. Wt. I. 1 1 4-CH -CH
3 64 I
3 7 IC H ''
3 7 C 72.05 72.45 7.3-6.5 (m) 1610; 1590 CHNS
28 42 4 H 9.07 8.78 4-3.4 (q) 1360-1370 N 12.00 10.35 2.3 (s) 466.74 1.07-0.97 (0) I. 2 2 4-Cl-C H
6 4 CH CH
3 C 50.58 50.28 CHNS Cl
18 20 4 2 2 H 4.72 4.56 N 11/13 13.01 427.42 I. 3 2 4-Cl-C H
64 -CH -CH -Q-CH -CH -
2 2 2 2 C 51.66 51.66 CHNS 0 Cl
22 24 4 2 2 2 H 4.73 4.71 150-152 N 10.95 06/11 511.50

oo

CO O NJ ro ο cn

IiI I 4 * i

■ (I (If ■ * i

I Cf f t I # ι

If tt it t t

-9- ou ^ zui I. C H N S Cl
24 28 4 2 2
507.55 -CH - (CH) -CH -
2 2 3 2 C H N S Cl
24 26 4 2 "4.
576.44 - ² H3- ^C (* HO) - * H0- C H N S Cl
26 34 4 2 4
608.53 o ¹⁰
.1 C H N SCl
24 26 4 4
544.38 133-136 - HO- (HO) - HO- 4-Cl-C H
64 Kt
CJ
• rt O" 1590-1560
1370-1110 3,4-Cl -C H
2 6 3 105-107 Cl 136,138 rsi 130-132 3,4-Cl -C H
2 6 3 5473
4.S6
9.46 IO CJ C 52.95
H 4.81
N 10.29 CV O -β
ίο ι / τ- τ-
»" T ^ - 49.07
4.41
9.42 - 50.32
5.46
8.21 CO - C 56.79
H 5.56
M 04/11 C 50.00
'' H 4.55
N 9.72 ?, S cw
t- ίο σ »
IO
L> -31 -se. -

03D051 / 0903

• · 4 9

Il 1

■ Cf

f ItM

if β ν ι «

- 10 -

1*

(O

u> IO

G

ζ *

.ίο

IS 7

■ ~ ti

O Oi

• ·

co ίο

IO

T-

IO Γ4
τ- «Ο

3 pp

τ- * ΟΪ

· «* Ιο

IO IO

t ^ «5 ο *

ΙΛ τ-

Sr * cv co «5 o *

IO T-

UXZ

S «, SP

3 *

030051/0903

O U) O O

12th 1 4-C1-C H
6 4 -CH - <Ci! ) -CH -
2 2 3 2 '-C ₃ H ₇ CH ₅ Tabel 1 continuation t 146-151 1695-1590 C Ii N SCl
24 28 4 2 I. C 60.62 62.87 1575-1370 H 5.93 5.84 475.49 13th 1 4-Cl-C H
64 I
3 7 -CH -CH -O-CH -CH-
2 2 2 2 CH N 11.78 9.67 1600-1590 CHN SCl
26 36 4 2 I [ C 61.77 63.49 1570-1360 H 6.78 6.90 159-165 505.56 14th 2 3,4-Cl -CH
- 2 63 N 08/11 9.33 7.35-845 (6H, m) CHNSQ Cl
22 22 4 2 2 4 I. CH 2.73 (i2H, a) C 45.52 44.63 123-125 580.38 H 3.82 3.68 15th 2 3,4-Cl -CH
2 6 3 CH
3 N 9.65 9.4 CHNS Cl
18 18 4 2 4 I. C 43.54 43.68 69-71 H 3.62 3.55 495.8 16 1 3,4-Cl -CH
2 6 3 N 11.26 11.15 CHN SCl
1B18 4 4 I. C 46.57 48.86 95-97 H 3.9 4.00 464.25 N 07/12 10.95

Table 1 continued

O CJ O

ο co ο

ι 17th 1 CH
6 5 CH CH
3 ι I
3 7 C 66.22 66.2 7.4-6. 6 (1 OH, m) 100-102 1620.1585 j
CHNS
18 22 4 H 6.79 6.8 2.68 (12H, s) 1300.750 CH ₃ N 17.16 17.25 690 326.47 I. 19th 2 CH
6 5 CH CH
3 -CH -
3 2 C 60.3 60.45 1610.15SS, CHK 3
18 22 4 2 H 6.2 6.2 2.9 (12H, s) 56-60 1260,1100, lC H
3 7 N 15.65 15.65 920,830, 357.47 114-119 765.698 I. 19th 2 4-CH -CH
3 6 4 I
3 7 C 67.42
H 8.49 67.53
8.72 CHNS
28 42 4 2
498.30 N 11.23 11.32 oil I. 20th 2 3-CF-CH
3 6 4 CH S 12.96
N 11.33 12.46
11.39 oil CHFNS
20 20 6 4 2
494.51 I. 21 2 3-CF-OH
3 6 4 -CH - (CH
2 2 S 11.16 10.23 CH FNS
26 28 6 4 2 N 9.75 9.73 111-112 574.58 I. 22nd 2 3-CF-CH
3 6 4 I
3 7 S 10.57 10.67 CHFNS
28 36 6 4 2
606.72

CJ O N)

N> CD Crt

ro

O CO O O

ο co ο

Table 1 continued

• 23 1 3-CF-C H
3 6 4 CH CH
3 I
3 7 F 21.01
N 10.33 20.10
11.22 2.65 (s) 96-Ί00 1600.1590 CHNFS
20 18 4 6 I. 1575.1370 oil 1320.1210 462.45 24 1 3-CF-C H
3 64 -CH - (CH) -CH -
2 2 3 2
I. CH FNS
26 26 6 4
542.58 1 25th 1 3-CF-C H
3 64 NC H
3 7 130-133 1605.1565, I. 1
I. 1370.1360, 1320,1255, 1220

00 O

N> N) O

cn

Q CO O

Verb. - 27 R. R. Table I. ' 2
R. continuation % found (1)
NNRfcf ^ ppm) (2)
F. J ( ⁰ C) ⁽³ > 1
IR (om) approximate
formula formula No. 3,4-Cl -C H
2 6 3 CH CH Elemental analysis e 46.08 Mol. Wt. Il 26th % ber. 3.76 1SS-127 C H N SCl
18 18 4 4 C 46.57 11.81 28 C H
6.5 CH
3 CH H 3.88 66.55 7.53-6.6 (iOH, m 1625.1590,
1300 463.8 Il N 08/12 6.85 2.9 (6H, s) 1080, 765, CHNS
18 22 4 C 66.2 119-120 695 29 H 6.8 17.2 2.53 '(6H, s) 4-CH-C H
3 6 4 -CH -CH -0-CW -CH -
2 2 2 2 65 “E 326.47 π N 17.15 6.95 C H N SO
24 30 4 2 C 65.72 13.01 142-145 4-CII -C H
3 64 -CH - (CH) -CH -
2 2 3 2 H 6.89 68.98 438.59 Il N 12.74 7.68 193-197 CHNS
26 34 4 C 71.85 12.82 H 7.88 434.65
I. N 12.89

Table 1 continued

ο co ο ο cn

σ co ο us

Il 30th 4 "CH -C H
3 6 4 CH CH CH C 67.7S 66.99 170.5- C Il N S
20 26 4 H 7.39 7.33 17?., 5 N 8/15 16.1 354.52 Il 31 4-Cl-C H
64 CH CH C 54.8 * 54.46 CHN SCx
18 20 4 2 H 5.1 4.97 161-163 N 14.17 14.22 396.36 π 32 4-Cl-C H
6 4 -CH - (CH> -CH -
2 2 3 2 C 60.62 60.62 CHN SCl
24 28 4 2 H 5.93 5.99 186-189 N 11.78 11.83 475.49 Il 33 4-Cl-C H
6 4 -CH -CH - (3-CH -CH -
2 2 2 2 C 55.12 53.29 C H N SO Cl
22 24 4 2 2 H 5.04 4.86 189-194 N 11.69 11.22 479.41 Il 34 3-CF-C H
3 6 4 -CH -CH - (D-CH -CH -
2 2 2 2 N 10.25 9.86 174-175 546.52 F 20.86 20.66 Il 35 3-CF-C H
3 6 4 CH ₃ S 6.93 6.72 oil 462.45

VJI

CO O K) hO O

cn -j

Table 1 continued

Il 36 5-CF-CH
3 64 -CH (-CH J -CH -
2 2 3 2 S 5.91 5.59 1 142-148 542.58 Il 37 ! 5.4-Cl -CH
2 6 3 -CH -CH -CI-CH -CH -
2 2 2 2 C 48.19 47.29 CHN 0 Cl
22 22 4 2 4 H 4.04 3.96 153-155 548.32 N 10.21 9.99 Il 38 5.4-Cl-CH
2 6 3 -CH - (CH) -CH -
2 2 3 2 C 52.95 52.08 156-1 60 CHN SCl
24 26 4 M 4.61 4.75 N 10.29 10.03 544.38

I CO CD

Ill III

- 3 ϋ 2 2 U b 7

- 17 The compounds of the formulas I and II have a high herbic

activity against both monocotyledons and di-

cotyledons. The following table 2 gives activity data j 5 of some representative, obtained according to Example 5!

bonds, the herbicidal activity against the following

Weeds was tested:;

Monocotyledons

A = Echinochloa crusgalli ία B = Avena fatua

C = Lolium italicum;

D β Sorghum spp. '

E * = Setaria glauca

F = Digitaria sanguinaliä j

is G = Alopecurus myosuroides j

H = Panicum dichotomiflorum \

I * Festuca pratense

J = Bromus sterilis {

K s = Poa annua,

Dicotyledons L = Stellaria media M β Ipofflea purpürea N = Vigna sinensis 0 = Rumex acetosella P = Galinsoga parviflora Q = Convolvolus sepium R = "ariensis S" = Geranium dissect T = Sida spinosa U - Brassica V = Gypsophila muralis W χ = Galium aparine

The herbicidal activity data given in Table 2
j were from 0 = no herbicidal activity, growth of the plant J35 ze as in the control, to 4 = death of the plant or

complete cessation of growth, assessed.

03 0051/0903

ο ο cn

CO

Table 2

Verb, no. treatment dose Monocotyl edonen I. J K L. M. N Di c otvledonen P. Q R. S. T U V W. (see.
Tab.i) leader
trailing (kg / ha) ABCD EFGH 4th 4th
4th 4th
4th 4th O 4th 4th
4th 4th
4th 4th
4th 4th i ² trailing 6th
2 · 4th 4 4 4 4th 4th 4th
4th 4th 4th ] 11 leader
trailing 2 4 4 4 4 4 4 4 4 4th 3 3 4th 4th
4th 4th
4th 4th I 1 ⁵ trailing
H 6th
6th 3 4th 4th 4th 4th 4th 4th 4th 4th 4th 4th
4th 1 6
■ 17 N 6th
■ 6 2 2 4 4 4 4 4 4th 3 3. 4th 3 2 4th 4th 2 20th leader
trailing 2 /
1 4th
4th 4th
4th 4th 4th 4th 4th 4th
4th 26th leader 6th
6th 2
4 4 4 4 4 4
4 4 4 4 4th 3 3 4th A. 35 trailing 6th A 's 2 4th 4 3

00 1

CO

α rs: κ;

he

I ■ 1 I I I

Τ ^ Γ ~. JÜ22TT57—

Depending on the particular compound, the best herbicidal effectiveness is achieved by applying before or after, i.e. before or after the weeds have sprouted from the ground. The herbicidal compounds according to the invention are! also selective for crops such as wheat, corn, soybeans and cotton.

For agricultural purposes, the active compounds per se or preferably in the form of suitable preparations, which consist of one or more compounds of the formula I as an active ingredient and one or more carriers. Suitable preparations include wettable powders, liquid pastes, granular formulations, etc.

Suitable carriers are - depending on the type of preparation ZtB. Silicic acid, kaolin, diatomaceous earth, bentonite, pumice stone, organic solvents, water, etc. The preparation can also contain other additives, such as surface-active agents, j Emulsifiers, thickeners, etc. include. A list of i carriers and additives can be found in McCutcheons, Detergents; and Emulsifiers, North American and International Eds. 1977, Annual. McCutcheoi »Publ. Co., Glen Rock, New Jersey, USA. j These preparations are produced in the usual way.

If necessary, the preparations can also convert other active ingredients such as fertilizers, insecticides or fungicides! grasp. On the ground to be dispensed amount of active \ ingredient (compound of Formula I or II) depends on; various factors, such as the environmental conditions, the type of crop to be protected, the type of preparation and the particular active ingredient. Usually, amounts of the compounds of formula I or II provide between; 1 and 6 kg / ha, preferably about 2 to 3 kg / ha, good results in weed control.

The following examples illustrate the present invention.

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t * * I

- 20 -

Example I ^

11 2

Production of N, N -dimethyl-N -phenyl-formamidine-

disulfide (Compound No. 18 From Table 1; Reaction 1)
5 A solution of 5 * 2 g of iodine in 100 ml of chloroform was added dropwise with stirring to a solution of 5 g (0.0277 mol)

N, N-dimethyl-N »-phenylthiourea and 7.5 ml of triethylamine j

added in 50 ml of chloroform. The encore continued, '

until the iodine color persisted in the reaction mixture. j ίο After 15 minutes the stirring was stopped, the reaction mixture was repeatedly washed with water (750 ml) and

dried with anhydrous NapSOr. After removing the ^:

Solvent gave a yellow oil which after Umkri- i Installation from n-hexane gave 4 g of the above product.

is example 2 ^!

112 f

Production of N, N -dimethyl-N -phenylformamide-;

sulfide (compound no. 17 of table 1; reaction 2)!

A solution of 350 mg of that prepared in Example 1. N ¹ , N ¹ -dimethyl-N ² -phenylformamidine disulfide in 2 ml of diethyl!

20 ether was mixed with 256 mg. Triphenylphosphine be j

acts, while from the outside by means of a water / ice bath j

was cooled. After the reaction has ended (after about 3 hours) I

a white precipitate of triphenylphosphine sulfide was removed by filtration at ^{0 ° C.} The solvent was
^; 25 removed under vacuum and the crystallized from η-hexane

! The residue yielded 112 mg of the free from impurities,

! desired product. !

j Example 3_ ^!

ι Production of N, N -dimethyl-N -phenylformamide sulfide [

! so (compound no. 17, table 1; reaction 3)!

f A solution of 0.9 g of N, N-dimethyl-N ¹ -phenylthiourea 'I; and 2 g of phosgene (COClJ in methylene chloride was 8 hrs
I stirred room temperature. After removing the solvent

! under vacuum, the residue (ImidoylLchlorid) in a \ "was 35 solution of 0.7 ml of triethylamine and 20 ml of anhydrous

: Dissolved methylene chloride. \

1 ^;

i ι

y y

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A solution of 0.9 g of N, N-dimethyl-N'-phenyltbiourea and 0.7 inl of triethylamine in 20 ml of methylene chloride was added dropwise to the above-mentioned solution with stirring at room temperature. After stirring for 8 hours, the reaction mixture was washed with water, dried with anhydrous sodium sulfate and the solvent was removed in vacuo. The residue was crystallized from petroleum ether and gave 1.4 g of the desired product in a yield of 86 %. . ίο Example 4

i Preparation of N ¹ , N ¹ -dimethyl-N ² , N ⁵ -diphenyl-N ⁵ - / (N, N- } dimethyl) -thiocarbamoylT-guanidine (compound no. 27! from table 1; reaction 4}

43 ml of trifluoroacetic acid were added to a solution of 2 g of fts (5.58 × 10 "× ⁵ mol) of the N ¹ , N ¹ -Dinjethy3> i N -phenylformamidinedisulfide obtained in Example 1 in 200 ml of chloroform.

^: The reaction mixture was left at room temperature for 15 minutes

; left to stand, then with a saturated NaHCO 3 solution

washed and dried with anhydrous sodium hydroxide. After j 20 evaporation of the solvent in vacuo, the back; was recrystallized from 70:30 n-hexane / benzoil and gave 1 »3 S of the desired product in a yield of 71 SG.

Example 5_

2s determination of herbicidal activity

Some pots of 10 cm top diameter and 10 cm in height, containing a sandy soil were sown with one of the above [mentioned weeds. ^{The amount of water necessary for 1} good sprouting of the seeds was added to each pot. i3o The pots were divided into three groups. The first group I was not treated with a herbicide and served as a control. The second group was treated one day after sowing with "an aqueous-acetone dispersion (20% by volume / vol.) Of a compound of the invention, tivity i to the herbicidal j 35-forward-act to determine the third group was 15. Days after sowing, had already reached as the small plants a. ι height of 5 to 10 cm (which depended on the respective ¹ j type), with a wäösrig-acetonic Disperion (20%, ι Vol./VoI) a compound of the invention for determination !

030051/0903

• St ■ ■ «<

1 11 * 1 lit

t ti S t: 'I

a II

the herbicidal follow-up activity "treated. ι

All pots were placed in a conditioned environment; Temperatures between 15 to 24 ° C, a relative humidity | activity of 70 Ji ₉ a photoperiod of 12 hrs and one;

Light intensity of 2500 lux observed. Every second day
All pots were watered uniformly in order to ensure sufficient moisture for the plants to grow well.

The controls were carried out 28 days after the treatment to determine the vegetative status of the plants, the j Results were evaluated in the manner described above.! §

is The above-mentioned radicals have the following meaning, for example:
R = phenyl group, which optionally contains 7mft Tf 2 or 3 halogen atoms, such as F, Cl, Br or J, alkyl groups with 1
up to 3 carbon atoms, such as methyl, ethyl, propyl,
Isopropyl, or halogenated derivatives of these compounds

? q fertilize with one or more

Halogen atoms, e.g. 1, 2 or 3 halogen atoms such as F, j

Cl or Br _{1 are} substituted, such as CF ^; '

'R and R = alkyl or alkoxy groups with 1 to 3 carbon

material atoms (definition see above); you can also '■

an alkylene group such as - (CH ₂ ) ^ - or (CH ₂ ) "form ^: al © interrupted by a heteroatom such as O or S.

can be. ■

030051/0903

Claims (1)

Claims 1. + compounds of the general formulas; S. Il Il R ¹ -: (S) - R (D R ¹ -N NCNR (H) in which R s is a phenyl group, which is optionally replaced by an or several halogen atoms, one or more alkyl or haloalkyl groups with 1 to 3 carbon atoms substituted can be R ¹ and R ² which can be identical or different: C ₁ -C, J ₁ -C, alkoxy; or R and R ² together form ' Alkyl, C ₁ - an alkylidene chain with 4 or 5 carbon atoms, which is optionally interrupted by heteroatoms; η * 1 or 2 with the proviso that - if in formula II R = R = CR, R means one substituted phenyl group. I25 2.- compounds according to claim 1, characterized in that '■ that η = 1 in formula I. ί 3 · compounds according to claim 1, characterized in that 'That η = 2 in formula I. 4. Compounds according to claim 1 with the formula II. 5. Compounds according to claims 1 to 4, characterized in that R * and R, which can be the same or different, are each C ₁ -C alkyl. 030051/0903 I I E »Ι 6.- compounds according to claim 1 to 4, characterized 1 2
draws that R and R together make up the group 5 or form the group -CH ₂ -CH ₂ -O-CHp-CH ₂ . 7.- Process for making connections
according to claim 1, characterized in that a trisubstituted thiourea of the formula:
I 10 cn Ϊ V. ! 12 ^r2 j in which R, R and R have the meaning given in claim 1 is have: 1) with an oxidizing agent in the presence of a base 'and an inert solvent to form a Compound of formula I, in which η = 2, treated [ delt; j 20 2) a compound of the formula I (with η = 2) with triphenyl phosphine in dimethyl ether at about O ⁰ C to form a
Compound of the formula I, in which η = 1, treated ί delt and; [3) a compound of the formula I (in which η = 1 or 2 ■ i is 25) with a strong, anhydrous acid in one; \ aprotic polar solvent at room temperature j treated, whereby a compound of formula II ι j receives, ! wherein the above steps i) to 3) according to the following schemes • run like this:: j S R i ii / II / oxidation \\ R - MH - C - H '-—— ΐ> T fn = 2) "mnrcex ~ - .... 2) I (η = 2)> I (η = 1) 3) I (η = 1 or 2) ii (above reaction k) 030051 / 0S03 - 3 - 3Ü22057 8.- The method according to claim 7, characterized in that step 1) with bromine (Br ") or iodine (Jp) as the oxidizing agent he follows. j 9 »- method according to claim 7, characterized in that j Stage 3) with a hydrocalic acid or trihaloacetic acid takes place as a strong anhydrous acid. ! to 10, - Move n «c-. Claim 7, characterized in that that in stage '-.) and 3) methylene chloride (CH ^ Cl ^) or chloro-; form (CHGI ^; used as solvent. \ 11.- Method of making connections t _ • is according to claim 1, formula i, in which η = 1, thereby j marked that a trisubstituted thiourea • of the formula: ! R-NH-CN ^ ₀ (III) ; » ^V R ^ - 1 2 ' in which R, R and R have the meaning given in claim 1 : have, in the presence of a slight excess of a 1 2b organic base and in an inert solvent with an imidoyl chloride of the formula: i V ¹ R ¹ .1-N = CN ^ ο (IV) ■ \ R ^ 1 2
j 3o in which R ₇ R and R have the meaning mentioned in claim 1 I tung is implemented (reaction 3 above). ' : Λ O - Zlrf-wiT-wt * » Λ Λ λ c ΌνίοηίίΜβΨ öv ^ -i-VkoT 4 - /% * ^ <Λ>^> i <r» -v * nwfo c · * ^^> * - » ^ ^ -ί - ^ *. ^. _t r b. «- iivA vAUAVLvu *. j. <- * ^ »_ * Λ. ν »w ^ y \ / i.« Ι / ΜΜ4. wv «* vi. 'vwo.wE VUU4. uw vXiU Oa ₁ J ₁ IC : or more compounds according to claim 1 as active ; 3b component, if necessary with the usual carrier and Additives.
j The patent attorney: / i 030051 / 09O3