CH619599A5 - Method of protecting crops. - Google Patents

Abstract

Crops of useful plants are protected against damage by thiocarbamate herbicides by incorporating antidotes into the soil or applying them to the soil. The antidote used is a compound of the formula I <IMAGE> in which X and Y independently of one another denote oxygen or sulphur; R denotes haloalkyl or chloroalkenyl; R1 denotes hydrogen, lower alkyl, phenyl, naphthyl, or phenyl which is substituted by fluorine, nitro, methyl, methoxy or hydroxyl or mono- or disubstituted by chlorine; R2 denotes hydrogen or lower alkyl; R3 denotes hydrogen, lower alkyl, hydroxymethyl, N-methyl-carbamoyloxymethyl or dichloroacetoxymethyl; R4 denotes hydrogen or lower alkyl; R5 denotes hydrogen, lower alkyl or phenyl; and R6 denotes hydrogen; with the proviso that at least one of the groups R1 or R5 is phenyl or a substituted phenyl or naphthyl group.

Description

The invention and the preparation of the compounds of formula 1 are described in more detail in the examples below. Following the preparation examples, there is a table with compounds which were produced by the process specified here. Numbers were assigned to the connections which serve to identify these connections in the explanations below.

example 1

Preparation of 2-m-nitrophenyl-3-dichloroacetyl-oxazolidine

5.8 g of 2-m-nitrophenyl-oxazolidine was dissolved in 50 ml of methylene chloride, which contained 3.5 g of triethylamine. 4.4 g of dichloroacetyl chloride were added dropwise to this solution with stirring, the reaction flask being kept at room temperature by cooling in a water bath. After the addition had ended, the mixture was stirred at room temperature for about 30 minutes, then washed with water, the layers separated and the organic phase dried over anhydrous magnesium sulfate. The solvent was then distilled off under vacuum. 8.6 g of the compound indicated in the title were obtained.

ND30 = 1.5590.

Example 2

Preparation of 2-ethyl-3-dichloroacetyl-5-phenyl-oxazolidine

21.3 ml of a solution containing 5.3 g of 2-ethyl-5-phenyl-oxazolidine was diluted with 25 ml of benzene and 3.1 g of triethylamine were added to the solution. The mixture was cooled to room temperature in a water bath and 4.4 g of dichloroacetyl chloride was added dropwise with stirring. Then stirring was continued for 30 minutes. The solution was washed with water, the layers were separated, the organic phase was dried over magnesium sulfate and the solvent was evaporated under vacuum. 8.7 g of the compound given in the title were obtained as an oil.

ND30 = 1.5600.

Example 3

Preparation of 2,2-dimethyl-3-dichloroacetyl-5-phenyl-oxazolidine

100 g of l-phenyl-2-aminoethanol were dissolved in 250 ml of benzene and 45 g of acetone were added. The mixture was heated to reflux for several hours and during the Reak5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

619 599

4th

15 ml of water were separated using a modified Dean-Stark apparatus. The mixture was cooled and 75 ml of triethylamine was added, and 108 g of dichloroacetyl chloride was added dropwise to the solution while stirring and cooling to room temperature in a water bath. The solution was left for some time. The organic phase was then separated off, washed with water, dried over anhydrous magnesium sulfate and the solvent was evaporated off under vacuum. 170 g of a thick oil were obtained, which then crystallized. The crystal slurry was stirred with ether and 132 g of the compound mentioned in the title were obtained as a white solid substance.

Mp 99.5 to 100.5 ° C.

Example 4

Preparation of 2-a-naphthyl-3-chloroacetyl-oxazolidine

19.9 ml of a benzene solution containing 5 g of 2-a-naphthyl-oxazolidine was combined with 50 ml of benzene and 2.8 g of chloroacetyl chloride. 2.6 g of triethylamine were added dropwise to this mixture with stirring and cooling in an ice bath. After the addition had ended, the mixture was stirred at room temperature for 30 minutes, washed with water, the layers separated and the organic phase dried over magnesium sulfate. The solvent was distilled off under vacuum. 6.7 g of an oil of the compound indicated in the title were obtained as residue.

ND30 = 1.6030.

Example 5

Preparation of 2-phenyl-3-chloroacetyl-4,4-dimethyloxazolidine

21.3 ml of a benzene solution containing 5.3 g of 2-phenyl-4,4-dimethyl-oxazolidine was mixed with 50 ml of benzene and 3.4 g of chloroacetyl chloride. 3.1 g of triethylamine were added dropwise to this solution with stirring and cooling in an ice bath. After the addition, the mixture was stirred for a further 30 minutes, then washed with water, the layers were separated and the organic phase was dried over magnesium sulfate and the solvent was distilled off. 6.5 g of the compound given in the title were obtained in the form of an oil.

ND30 = 1.5364.

Example 6

Preparation of 2-phenyI-3-dichloroacetyl-thiazoIidin

5 g of 2-phenyl-thiazolidine were dissolved in 50 ml of acetone, and first 3.1 g of triethylamine and then dropwise with stirring at room temperature, 4.4 g of dichloroacetyl chloride were added to this solution. The mixture was then left to stand for 30 minutes, poured into water, extracted with methylene chloride, the layers separated, the organic phase dried over magnesium sulfate and the solvent distilled off in vacuo. 7.3 g of the compound shown in the title were obtained in the form of an oil.

ND3Ü = 1.5836.

Example 7

Preparation of 2-m-chlorophenyl-3-dichloroacetyl

thiazolidine

5 g of 2-m-chlorophenyl-thiazolidine were dissolved in 50 ml of benzene and 2.6 g of triethylamine, and 3.7 g of dichloroacetyl chloride were added dropwise to this mixture while stirring at room temperature. This mixture was then left to stand for about 30 minutes, washed with water, the layers separated, the organic phase dried over magnesium sulfate and the benzene distilled off under vacuum. 7.2 g of the compound given in the title were obtained in the form of an oil.

Nd -, () = 1.5805.

Example 8

Preparation of 2- (2 ', 6'-dichlorophenyl) -3-chloroacetyl-thiazolidine

23.5 ml of a solution of 5.9 g of 2- (2 ', 6'-dichlorophenyl) thiazolidine in benzene were added to 25 ml of benzene and 2.8 g of chloroacetyl chloride and the mixture was stirred in an ice bath while 2.6 g of triethylamine were added dropwise. After standing for 30 minutes, the mixture was washed with water, the layers were separated and the organic phase was dried over magnesium sulfate and the benzene was distilled off. 8 g of the compound given in the title were obtained in the form of an oil.

ND30 = 1.6041.

Example 9

Preparation of 3- (3-bromopropionyl) -5-phenyl-oxazolidine

44.7 g of a benzene solution containing 4.5 g of 5-phenyl-oxazolidine were mixed with 3.1 g of triethylamine, and 5.2 g of 3-bromopropionyl chloride were added dropwise to this mixture while stirring at room temperature. After the mixture had stood for about 30 minutes, it was washed out with water, the layers were separated, the organic phase was dried over magnesium sulfate and the solvent was distilled off under vacuum. 6 g of the compound given in the title were obtained in the form of an oil.

ND30 = 1.5591.

Example 10

Preparation of 2,2,4-trimethyl-3-dichloroacetyl-phenyloxazolidine

23 ml of a benzene solution containing 5.7 g of 2,2,5-trimethyl-5-phenyl-oxazolidine was mixed with 25 ml of benzene and 3.1 g of triethylamine and kept at room temperature while 4.4 g of dichloroacetyl chloride was added dropwise were added. After the mixture had stood for 30 minutes, it was washed out with water, the layers were separated and the organic phase was dried over magnesium sulfate and the solvent was distilled off under vacuum. The reaction product, which crystallized, was extracted with ether and precipitated with pentane. 3.9 g of the compound specified in the title were obtained in the form of a solid substance.

Mp 126 ° C.

Example 11

Preparation of 2-p-chlorophenyl-3-dichloroacetyl oxazolidine

22 ml of a solution of 5.5 g of 2-p-chlorophenyl oxazolidine in benzene were mixed with 25 ml of benzene and 3.1 g of triethylamine, and 4.4 g of dichloroacetyl chloride were added dropwise to this mixture at room temperature. The mixture was left to stand for about 30 minutes, then washed with water, the layers were separated and the organic phase was dried over magnesium sulfate and the solvent was distilled off. 8.4 g of the compound given in the title were obtained in the form of an oil.

ND30 = 1.5668.

Example 12

Preparation of 2,5-diphenyl-3- (2,3-dibromopropionyl) oxazolidine

4.5 g of 2,5-diphenyl-oxazolidine were dissolved in 50 ml of methylene chloride, 5 g of 2,3-dibromopropionyl chloride were added to this mixture, and 2.1 triethylamine were added dropwise with stirring and cooling in an ice bath. After standing for 30 minutes, the mixture was washed with water

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

5

619 599

washed out, the layers were separated and the organic phase dried over magnesium sulfate and the solvent distilled under vacuum. 7.1 g of the compound given in the title were obtained in the form of an oil.

ND30 = 1.5734.

In Table 1 below, compounds are listed which have been prepared by the process indicated above. Each connection has been assigned a number which is used to identify it in the following explanations.

Table 1

Connection no.

R

Ri

R2

R3

r4

r5

R *

X

Y

Enamel] or Nd:

1

chc12

m-NÖ2-C6H4

H

H

H

H

H

O

O

1.5590

2nd

chclz m-N02-C6H4

H

ch3

ch3

H

H

O

O

1.5448

3rd

ch2c1

m-N02-C6H4

h ch3

ch3

H

H

O

O

1.5484

4th

chci2

c6h5

H

H

H

H

H

O

O

1.5490

5

cc13

c6h5

H

H

H

H

H

O

O

1.5398

6

CHBrCHa

QHs

H

H

H

H

H

O

O

1.5490

7

cc12-ch3

c6h5

H

H

H

H

H

O

O

1.5301

8th

CHBr2

c6h5

H

H

H

H

H

O

O

1.5808

9

CHBrCH2Br c6h s

H

H

H

H

H

O

O

1.5712

10th

CC1 = CCI2

c6hs

H

H

H

H

H

O

O

1.5615

11

CHC12

m-cicÔHj

H

H

H

H

H

O

O

1.5550

12

CCI3

m-ClC6H4

H

H

H

H

H

O

O

1.5475

13

CH2C1

m-ClC6H4

H

H

H

H

H

O

O

1.5590

14

CH2Br m-ClC6H4

H

H

H

H

H

O

O

1.5720

15

CHBrCH3

m-ClC6H4

H

H

H

H

H

O

O

1.5590

16

CHBr2

m-ClC6H4

H

H

H

H

H

O

O

1.5833

17th

CHBrCH2Br m-ClC6H4

H

H

H

H

H

O

O

1.5718

18th

CHC12

c6hs h

QHS

H

H

H

O

O

1.5353

19th

CC13

QH 5

H

C2H s

H

H

H

O

O

1.5310

20th

CHC12

c2hs

H

H

H

c6h5

H

O

O

1.5600

21st

CCI3

QHs h

H

H

c6h5

H

O

O

1.5455

22

CHC12

ch3

ch3

H

H

c6h5

H

O

O

1.5438

23

ch2ci ch3

ch3

H

H

c6h5

H

O

O

1.5450

24th

chci2

P-CH3-cJHJ

H

H

H

H

H

O

O

1.5440

25th

CCI3

p-CH3-C6H4

H

H

H

H

H

O

O

1.5430

26

CHBrCH2Br p-CHa-QFU

H

H

H

H

H

O

O

1.5627

27th

CC12CH3

P-CH3-C6H4

H

H

H

H

H

O

O

1.5370

28

ch2ci p-CH3-C6H4

H

H

H

H

H

O

O

1.5600

29

ch2ci m-CH30-C5H4

H

H

H

H

H

O

O

1.5570

30th

chci2

m-CH3ö-C6H4

H

H

H

H

H

O

O

1.5557

31

CCI3

m-CH3ö-C6H4

H

H

H

H

H

O

O

1.5479

32

CC12CH3

m-CH30 ~ C6H4

H

H

H

H

H

O

O

1.5380

33

CHBrCH2Br m-CH30-C6H4

I.

H

H

H

H

H

O

O

1.5688

34

CH2C1

© à

H

H

H

H

H

O

O

1.6030

35

chci2

photo

H

H

H

H

H

O

O

1.5980

619 599 6

Table 1 (continued)

Connection no.

R

R,

R2

R3

R4

Rs

R6

X

Y

Melting point or Nd30

36

cc13

h h

h h

H

O

0

1.5132

37

cc12ch3

© à

h h

h h

H

O

0

1.5921

38

ch2ci

QHS

h h

h ch3

H

O

0

1.5486

39

chci2

qhs h

h h

ch3

H

O

0

1.5423

40

CCI3

qhs h

h h

ch3

H

O

0

1.5376

41

cc12ch3

c6hs h

h h

ch3

H

O

0

1.5530

42

ch2ci

Qhs h

ch3

ch3

ch3

H

O

0

1.5364

43

chci2

c6h5

h ch3

ch3

ch3

H

O

0

1.5343

44

cela c6hs h

ch3

ch3

ch3

H

O

0

1.5310

45

cc12ch3

c6hs h

ch3

ch3

ch3

H

O

0

1.5213

46

ch2ci c6hs h

h h

h h

S

0

1.5804

47

chci2

c6h5

H

h h

H

H

S

0

1.5836

48

cc13

c6h5

h h

h h

H

S

0

1.5950

49

cc12ch3

C6hs h

h h

h h

S

0

1.5798

50

CH2CH2Br

C6Hs

H

H

H

H

H

S

0

1.5983

51

CHBrCH2Br

QHs

H

H

H

H

H

S

0

110-112 ° c

52

ch2c1

1t1-CIQH4

H

H

H

H

H

S

0

1.5925

53

chci2

m-ClQH4

H

H

H

H

H

S

0

1.5805

54

CCI3

m-ClQH4

H

H

H

H

H

S

0

1.5940

55

cc12ch3

rn-ClCöH ^

H

H

H

H

H

S

0

1.5850

56

CH2CH2Br m-ClQH4

H

H

H

H

H

s

0

1.5931

57

CHBrCH2Br m-ClC ^ üi

H

H

H

H

H

s

0

1.6038

58

ch2ch2c1

111-CIQH4

H

H

H

H

H

s

0

1.5920

59

ch2ci

3,5-Cl2-QH3

H

H

H

H

H

0

0

1.5748

60

chci2

3,5-Cl2-C6H3

H

H

H

H

H

0

0

1.5663

61

cc13

3,5-Cl2-C6H3

H

H

H

H

H

0

0

1.5613

62

cc12ch3

3,5-Cl2-C6H3

H

H

H

H

H

0

0

1.5530

63

ch2ci

3,5-Cl2-qh3

H

H

H

H

H

s

0

1.6041

64

chci2

3,5-Cl2-qh3

H

H

H

H

H

s

0

1.6038

65

cc13

3,5-Cl2-C6H3

H

H

H

H

H

s

0

1.5962

66

cc12ch3

3,5-Cl2-C6H3

H

H

H

H

H

s

0

1.5908

67

ch2ci

H

H

H

H

QHS

H

0

0

1.5640

68

chci2

H

H

H

H

QHs

H

0

0

1.5593

69

cc13

H

H

H

H

QHS

H

0

0

1.5558

70

CHBr-CH2Br

H

H

H

H

QHs

H

0

0

1.5738

71

cc12ch3

H

H

H

H

QHS

H

0

0

1.5433

72

CH2-CH2Br

H

H

H

H

QHS

H

0

0

1.5591

73

chc12

m-OH-QH4

H

H

H

H

H

0

0

waxy

firmly

74

cci2ch3

m-OH-C6H4

H

H

H

H

H

0

0

1.5453

75

chci2

p-N02-C6H4

H

H

H

H

H

s

0

1,6008

76

chci2

QHS

H

qhs

H

H

H

s

0

1.5352

77

chci2

QHs

H

ch3

ch3

H

H

s

0

1.5366

78

ch2ci ch3

ch3

ch3

H

QHs

H

0

0

1.5021

79

chci2

ch3

ch3

ch3

H

QHS

H

0

0

126 ° c

80

cc13

ch3

ch3

ch3

H

QHs

H

0

0

1.5080

81

CH2BrCH2

ch3

ch3

ch3

H

QHS

H

0

0

1.5051

82

CH2BrCHBr ch3

ch3

ch3

H

QHs

H

0

0

1.5450

83

ch2c1

o-C1-QH4

H

H

H

H

H

0

0

1.5578

84

chci2

o-C1-c6H4

H

H

H

H

H

0

0

1.5595

85

CH2BrCHBr o-Cl — QH4

H

H

H

H

H

0

0

1.5794

86

ch2c1

p-Cl-QH4

H

H

H

H

H

0

0

1.5688

87

chci2

p-Cl-C6H4

H

H

H

H

H

0

0

1.5668

88

CH2BrCHBr p-ci-qh4

H

H

H

H

H

0

0

1.5814

89

cc12 = cc1

p-Cl-QH4

H

H

H

H

H

0

0

1.5754

90

cc12 = cc1

m-ClQH4

H

H

H

H

H

s

0

1,6008

91

chc12

QHS

H

H

H

QHS

H

s

0

1.5653

7

Table 1 (continued)

619 599

Link R Rt R2 R3 Rt R5 R6 X Y Melting point no. Or ND30

92

CH2BrCHBr c6h5

H

H

H

QHS

H

S

0

1.5734

93

CH2C1

QHs

H

H

H

QHs

H

S

0

1.5723

94

chci2

3,4-di-ClQH4

H

H

H

H

H

S

0

1.5600

95

ci2ch p-QHs-OCH3

H

H

H

H

H

S

0

1.5740

96

ci2ch o-Cl-QHs

H

H

H

H

H

S

0

97-102 ° C

97

ci2ch m-f-qh5

H

H

H

H

H

S

0

1.5650

98

ci2ch ch3

ch3

CH2OH O

H

QHs

H

O

0

1.5190

99

ci2ch ch3

ch3

11

CH2OCNHCH3

0

N

QHS

H

O

0

1.5070

100

ci2ch ch3

ch3

II

CH2OCCHCl2

H

QHS

H

O

0

1.5180

101

ch2ci ch3

ch3

ch2oh

H

QHS

H

O

0

1.5182

102

chci2

m-Cl-QH5

H

ch3

H

ch3

H

O

0

1.5243

103

CH2BrCHBr m-Cl-QH5

H

ch3

H

ch3

H

0

0

1.5406

Further examples of compounds which represent the formula for the formulation of herbicidal preparations in-1 correspond, are prepared by the process indicated above and can be used as shown here

R

ri r2

r3

r4

rs r6

x

Y

ch2ci

QHS

H

H

H

H

H

O

s chci2

QHS

H

H

H

H

H

O

s cci3

QHs

H

H

H

H

H

O

s ch2ci

QHs

H

H

H

H

H

S

s chci2

QHs h

h h

H

H

S

s cc13

QHs h

H

H

H

H

S

s ch2c1

ch3

ch3

H

H

QHS

H

0

s chci2

ch3

ch3

H

H

QHs

H

0

s cela ch3

ch3

H

H

QHs

H

0

s ch2c1

ch3

ch3

H

H

QHs h

s s

chci2

ch3

ch3

H

H

QHs

H

s s

cc13

ch3

ch3

H

H

QHs

H

s s

CH2BrCHBr m-Cl-QH4

H

H

H

ch3

H

0

s

CHzBrCHBr

QHs

H

H

H

ch3

H

s s

CH2BrCHBr ch3

ch3

H

H

QHs

H

0

s

CH2BrCHBr ch3

ch3

H

H

QH5

H

s s

The herbicides listed in the tables and elsewhere are used in amounts which effectively prevent the growth of undesirable plants. The quantities used here, which correspond to those recommended by the supplier, gave representative results. Accordingly, the weed extermination result obtained is commercially acceptable in any one case if the specified amount is used.

It is clear that the class of herbicidal agents described here are powerful herbicides that have this effect. The level of herbicidal activity varies from compound to compound, as well as between combinations of specific compounds within each class. Similarly, the level of effectiveness varies depending on the type of plant being treated with the specific herbicidal compound or a combination thereof. Accordingly, a selection can be made from the individual herbicidal compounds or combinations thereof which are suitable for preventing the spread of undesirable plant species in a simple manner. According to the present invention

Damage to a particular crop type can be achieved by adding a compound of formula I or combinations 50 thereof. The plant species that can be protected by this method are not limited to the species listed in the examples.

Thiocarbamate herbicides are considered to be those of a general type. That is, the individual herbicides are effective against a large number of plants, a distinction being made between desirable and undesirable species. An effective amount of the herbicidal compound is generally applied to the area or plant site where the control is to be made. Such herbicides are, for example, EPTC, S-ethyl-diisobutyl-thiocarbamate, S-propyl-dipropyl-thiocarbamate, S-2,3,3-trichloroallyl-diisopropyl-thiocarbamate, S-ethyl-cyclohexylethyl-thiocarbamate, [hexahydro-1H azepine-1-carbamic acid thioethyl ester], S-4-chlorobenzyl-diethyl-65 thiocarbamate and their combinations.

The term herbicide, as used here, is understood to mean a compound which prevents or changes the growth of vegetation or plants. These

619 599

preventing or changing effect includes all deviations from natural development, such as killing. Inhibiting, defoliation, drying out, regulating, stunting, planting, stimulating, dwarfism and the like. “Plants” are understood to mean germinating seeds, seedlings, growing and developing plants, including the roots and the part of the plant standing above the soil surface.

The compounds of the formula I can be used in the form of herbicidal preparations which comprise the antidote and a thiocarbamate herbicide. Such herbicidal preparations were tested in the following way:

Methods for determining the effectiveness The trays required for the growth tests of the useful plants and weed species were filled with loamy, sandy soil. The stock solutions of the herbicidal compounds and the antidotes were prepared as follows:

a) herbicides

S-ethyl-N, N-dipropyl-thiocarbamate (EPTC, EPTAM®)

A. 0.56 kg / ha

670 mg of EPTC 6 E (75.5% content) were diluted with 500 ml of deionized water, so that 2 ml of this solution corresponded to an amount of 0.56 kg / ha per dish.

B. 5.6 kg / ha

6700 mg EPTC 6 E (75.5% content) were diluted with 500 ml of demineralized water, so that 2 ml of this solution corresponded to an amount of 5.6 kg / ha per dish.

S-propyl-N, N-dipropyl-thiocarbamate (VERNAM®)

C. 0.84 kg / ha

95 mg VERNAM® (75% content) were diluted with 100 ml of deionized water, so that 4 ml per bowl of this solution, which was added before planting the soil, corresponded to an amount of 0.84 kg / ha.

D. 1.12 kg / ha

633 mg VERNAM® (75% content) were diluted with 500 ml deionized water so that 4 ml of this solution corresponded to an amount of 1.12 kg / ha per dish.

E. 5.6 kg / ha

633 mg VERNAM® (75% content) were diluted with 100 ml of deionized water so that 4 ml of this solution corresponded to an amount of 5.6 kg / ha per dish.

b) Antidote 95 mg of each compound to be investigated were dissolved in 15 ml of acetone with 1% Tween 20R (polyoxyethylene sorbitan monolaurate), so that when 1V2 ml of this solution was sprayed on per dish (based on half the surface of a dish), the amount applied the test substance corresponds to 5.6 kg / ha.

PES and PPI tank mixes The stock solutions (a and b) described above were used to apply the antidote "in the groove". As a preparation step, a soil sample of 0.473 l from each bowl was placed on the side so that it could later be used to cover the seeds after the treatment with the agents. The earth was leveled before sowing started.

6.4 mm deep longitudinal furrows were drawn into each treated dish before sowing. After sowing, the dishes were separated into two equal parts by means of dividing strips and 1V2 ml of the stock solution b) were sprayed onto the open seeds in the furrows of half the dish. The untreated part of the shell served as a control of the herbicidal action and also made it possible to observe a lateral penetration of the antidote through the soil. The seeds were covered with the untreated 0.473 l soil sample set aside.

The herbicide was initially sprayed onto each individual dish after sowing and treatment with the antidote in the furrow by spraying the required amount of the herbicide stock solution on a straight spray table.

To treat the soil before planting, a stock solution was added to the 19 l rotating mixer in the soil sample. For superficial application before the seeds sprouted, the same stock solution was distributed on the soil after sowing.

Thiocarbamate herbicide selection test with various useful plants De-Kalb XL-44 common maize (Zea mays), sugar beet (Beta vulgaris), small-seeded gray-striped sunflowers (Helianthus annuus), soybean (Glycine max) and oilseed rape (Brassica napus ), Milo = black millet (Sorghum vulgare), seed wheat (Triticum aestivum), green bristle millet (Setaria viridis), rice (Oryza sativa) and multi-row barley (Hordeum vulgare) sown. The seeds were then covered with the 0.473 l soil that had previously been put aside. The dishes were then placed in a greenhouse on benches where the temperature was maintained at 21 to 32 ° C. The earth was sprayed with water to ensure good plant growth. The degree of damage was determined 2 and 4 weeks after treatment. The test included trays which had been treated with the herbicide alone in the amounts indicated, in order to obtain a basis for determining the degree of damage reduction caused by the herbicidal antidotes. The protective effect observed in percent at various representative crops are shown in Table 2. Percentage effectiveness is determined by comparing trays that have been treated with the various antidote compounds to trays that have not been treated.

8th

5

10th

15

20th

25th

30th

35

40

45

50

55

9 619 599

Table 2

Selection test results with various crop plants

Compound Treatment Method Herbicides Protected Percent

Number with antidote kg / ha crop protection effect

1

PPI

EPTC / 0.5

Milo

30th

rice

63

barley

30th

2nd

PPI

EPTC / 5.6

Corn

100 (2 weeks)

3rd

PPI

ETPC / 5.6

rice

63

Corn

100

4th

PPI

EPTC / 0.56

Milo

50

6

PPI

EPTC / 0.56

Milo

40

9

PPI

EPTC / 0.56

rice

100

barley

50

11

PPI

EPTC / 0.56

Milo

50

Corn

100

13

PPI

EPTC / 5.6

Sunflower

67

15

PPI

EPTC / 0.56

rice

100

EPTC / 5.6

Corn

65

16

PPI

EPTC / 0.56

rice

100

EPTC / 5.6

Corn

65

17th

PPI

EPTC / 0.56

rice

100

22

PPI

EPTC / 0.56

Milo

90

EPTC / 5.6

Corn

100

23

PPI

EPTC / 0.56

Milo

67

EPTC / 0.56

rice

55

EPTC / 5.6

Sunflower

30th

28

PPI

EPTC / 5.6

Sunflower

67

31

PPI

EPTC / 5.6

sugar beet

70

33

PPI

EPTC / 0.56

rice

44

EPTC / 0.56

barley

40

34

PPI

EPTC / 0.56

Milo

10th

35

PPI

EPTC / 0.56

Milo

45

36

PPI

EPTC / 5.6

sugar beet

80

38

PPI

EPTC / 5.6

Corn

33

39

PPI

EPTC / 0.56

barley

40

EPTC / 5.6

Corn

55

40

PPI

EPTC / 5.6

Corn

22

41

PPI

EPTC / 5.6

Sunflower

67

41

PPI

EPTC / 5.6

Corn

22

47

PPI

EPTC / 0.56

Milo

75

wheat

67

rice

63

EPTC / 5.6

Corn

100

48

PPI

EPTC / 0.56

Milo

25th

51

PPI

EPTC / 0.56

barley

67

53

PPI

EPTC / 0.56

barley

50

EPTC / 5.6

Corn

100

54

PPI

EPTC / 5.6

Corn

40

57

PPI

EPTC / 5.6

Rapeseed

67

60

PPI

EPTC / 5.6

Corn

100

65

PPI

EPTC / 5.6

Corn

50

67

PPI

EPTC / 0.56

rice

100

68

PPI

EPTC / 0.56

rice

100

70

PPI

EPTC / 0.56

wheat

78

barley

85

rice

100

72

PPI

EPTC / 0.56

rice

85

EPTC / 0.56

barley

85

73

PPI

EPTC / 0.56

barley

50

75

PPI

EPTC / 0.56

rice

85

barley

72

Corn

50

76

IF / 5.6 kg / ha

EPTC / 5.6

Corn

100

77

IF / 5.6 kg / ha

EPTC / 5.6

Corn

50

619 599

10th

Table 2 (continued)

connection

Treatment method

Herbicides

Protected

percent

Number with antidote kg / ha

Crop

Protective effect

VERNAM

VERNAM / 5.6

Corn

60 *% damage

6E

Milo

100

wheat

98

barley

90

2nd

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

50% protection

3rd

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

50

4th

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

11

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

VERNAM / 0.84

Milo

50

18th

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

20th

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

VERNAM / 0.84

Milo

60

22

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

VERNAM / 0.84

Milo

90

23

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

24th

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

84

VERNAM / 0.84

Milo

40

26

IF / 5.6 kg / ha

VERNAM / 0.84

barley

67

35

IF / 5.6 kg / ha

VERNAM / 0.84

Corn

67

VERNAM / 0.84

Milo

40

38

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

50

39

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

VERNAM / 0.84

barley

55

40

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

67

47

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

VERNAM / 0.84

Milo

50

53

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

60

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

100

78

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

50

VERNAM / 5.6

Corn

22

79

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

60

VERNAM / 5.6

Corn

88

80

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

30th

VERNAM / 5.6

Corn

88

81

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

20th

82

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

45 (2 weeks)

83

IF / 5.6 kg / ha

VERNAM / 1.12

barley

50

84

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

40

VERNAM / 5.6

Corn

88

85

IF / 5.6 kg / ha

VERNAM / 1.12

wheat

40

VERNAM / 1.12

barley

45

VERNAM / 5.6

Corn

67

86

IF / 5.6 kg / ha

VERNAM / 1.12

barley

55

VERNAM / 5.6

Corn

78

87

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

50

VERNAM / 1.12

barley

45

VERNAM / 5.6

Corn

67

88

IF / 5.6 kg / ha

VERNAM / 1.12

barley

55

90

IF / 5.6 kg / ha

VERNAM / 1.12

barley

33

VERNAM / 5.6

Soybeans

30th

91

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

36

94

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

23

95

IF / 5.6 kg / ha

VERNAM / 1.12

wheat

44

VERNAM / 1.12

barley

44

VERNAM / 5.6

Corn

100

96

IF / 5.6 kg / ha

VERNAM / 1.12

wheat

67

VERNAM / 1.12

barley

44

VERNAM / 5.6

Corn

37.5

97

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

87.5

98

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

37.5

99

IF / 5.6 kg / ha

VERNAM / 5.6

Corn

75

11

Table 2 (continued)

619 599

Compound Treatment Method Herbicides Protected Percent

Number with antidote kg / ha crop protection effect

100

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

20th

VERNAM / 1.12

barley

22

101

IF / 5.6 kg / ha

VERNAM / 1.12

Milo

20th

VERNAM / 1.12

barley

44

102

IF / 5.6 kg / ha

VERNAM / 6.72

Corn

100

103

IF / 5.6 kg / ha

VERNAM / 1.12

wheat

33

VERNAM / 1.12

barley

33

* Stock solution VERNAM 6E 6.72 kg / ha PPI added 3800 mg / 500 ml water before sowing, so that 4 ml per bowl gives an amount of 6.72 kg / ha.

The compounds of the formula I can be used in preparations which serve to protect crop plants and contain an active herbicidal compound. The preparations of the herbicide and the antidote can be prepared by known methods by intimately mixing and grinding the active herbicidal agents and the antidote with suitable carriers and / or other substances suitable for distribution, if desired with additions of dispersants and with solvents.

The compounds I acting as antidotes and the preparations containing them can be used in any suitable form. Accordingly, the compounds I acting as antidotes can be formulated into emulsifiable liquids, 30 emulsifiable concentrates, liquids, moistenable powders, granules or any other suitable form. In the preferred form, a non-phyto-toxic amount of a compound that counteracts the damage caused by herbicidal agents is mixed with a selected herbicide 35 and added to the soil before or after sowing. It is obvious that the soil can also be treated first with the herbicidal agent and then with the antidote. It is also possible that the seed itself is treated with a non-phytotoxic amount of the compound and the sowing is carried out in a soil which has been treated with herbicidal agents or which has not yet been treated with the herbicidal agent and which has subsequently been treated with the herbicidal agent is treated. The addition of the antidote has no influence on the herbicidal activity of the herbicide.

The amount of the antidote compound can be from about 0.0001 to about 30 parts by weight of the antidote compound, as described here, per part by weight of the herbicidal compound. The exact amount of the antidote is usually determined based on economic considerations regarding the most effective amount to use. It should be mentioned again that a non-phytotoxic amount of the antidote compound is used in the herbicidal preparations described above.

Claims (10)

619 599 2nd PATENT CLAIMS 1. A method for protecting plant crops against damage by thiocarbamate herbicides, characterized in that the soil in which the plants to be cultivated are sown or planted and in which they are to be grown is a non-phytotoxic, as an antidote to the damage effective amount of a compound of formula I by thiocarbamate herbicides 2} 5 : / \ R wherein X and Y independently of one another oxygen or sulfur; R haloalkyl or chloroalkenyl; Ri is hydrogen, lower alkyl, phenyl, naphthyl or phenyl substituted by fluorine, nitro, methyl, methoxy or hydroxyl, or by one or two chlorine; R2 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methyl-carbamoyloxymethyl or dichloroacetoxymethyl; R4 is hydrogen or lower alkyl; R5 is hydrogen, lower alkyl or phenyl; and R6 is hydrogen, with the proviso that at least one of the groups Rt or Rs is a phenyl, a substituted phenyl or naphthyl group, or adds it to the soil. 2. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, R, phenyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, R5 is hydrogen and R5 is hydrogen. 3. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, Rj is chlorophenyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, R5 is hydrogen and R6 is hydrogen. 4. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, R 1 is lower alkyl, R 2 is hydrogen, R3 is hydrogen, R4 is hydrogen, Rs is phenyl and R6 is hydrogen. 5. The method according to claim 1, characterized in that in formula I X is oxygen, Y oxygen, R haloalkyl, Ri lower alkyl, R2 lower alkyl, R3 hydrogen, R4 hydrogen, R5 phenyl and R6 hydrogen. 6. The method according to claim 5, characterized in that in formula I R is dichloromethyl, Rj is methyl and R2 is methyl. 7. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, R is phenyl, R 2 is hydrogen, R3 is lower alkyl, R4 is hydrogen, Rs is hydrogen and R6 is hydrogen. 8. The method according to claim 1, characterized in that in formula I X is oxygen or sulfur, Y is oxygen, R is haloalkyl, Ra is dichlorophenyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, R5 is hydrogen and R6 is hydrogen. 9. The method according to claim 1, characterized in that in formula I X is sulfur, Y is oxygen, R is haloalkyl, R is phenyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, R5 is hydrogen and R6 is hydrogen. 10. The method according to claim 1, characterized in that in formula I X are sulfur, Y oxygen, R haloalkyl, R] phenyl, R2 hydrogen, R3 lower alkyl, R4 hydrogen, R5 hydrogen and R6 hydrogen. It is known that some herbicides, which are immediately toxic to a large number of harmful weeds, are either non-selective or insufficiently selective in their action against crop plants. As a result, some herbicides damage not only the weeds that need to be destroyed, but more or less also the crops. This applies to numerous herbicidal compounds which are commercially successful and commercially available. Such herbicides include certain triazines, urea derivatives, halogenated acetanilides, carbamates, thiocarbamates and the like. Examples of such compounds are found in U.S. Patent Nos. 2 913 327, 3 037 853, 3 175 897, 3 185 720, 3 198 786 and 3,582,314. Damage to crops due to the side effects of herbicides is particularly unpleasant and unfortunate. If the recommended amount of these herbicides is used to treat the soil when controlling broad-leaved weeds and grasses, this can result in considerable malformations and growth disorders and inhibitions in the crop plants. This abnormal growth of crops leads to a loss of yield. The search for good selective herbicides continues. Previous efforts to solve this problem, such as by treating the seed with "hormonal" antagonistic agents prior to sowing, are described in U.S. Patent Nos. 3,131,509 and 3,564,768. The protective agents, such as the herbicides, in these earlier processes are largely specific to a particular crop species. So far, these antagonistic agents have not been very successful. The above-mentioned patents describe the treatment of seeds with compounds of a chemical type different from the type of compound to be used according to this invention. It has now been found that it is possible to protect crops from the harmful effects of herbicides of the Thiocar-bamat type, or alternatively to significantly increase the tolerance of these plants to these herbicides by adding an antidote compound of the formula I to the soil R wherein X and Y independently of one another oxygen or sulfur; R haloalkyl or chloroalkenyl; Rt is hydrogen, lower alkyl, phenyl, naphthyl or phenyl substituted by fluorine, one or two chlorine, nitro, methyl, methoxy or hydroxyl; 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 3rd 619 599 R2 is hydrogen or lower alkyl; R3 is hydrogen, lower alkyl, hydroxymethyl, N-methyl-carbamoyloxymethyl or dichloroacetoxymethyl; R4 is hydrogen or lower alkyl; Rs is hydrogen, lower alkyl or phenyl; R6 means hydrogen, with the proviso that at least one of the groups R 1 or R 5 is phenyl, substituted phenyl or naphthyl group, or adds it to the soil. Certain of the compounds encompassed by the above definition of Formula I are new. These are compounds of the formula I in which X and Y independently of one another oxygen or sulfur; R haloalkyl or chloroalkenyl; Ri is hydrogen, lower alkyl or phenyl; R2 is hydrogen or lower alkyl; R3 is hydrogen or lower alkyl; R4 is hydrogen or lower alkyl; Rs phenyl; and R6 is hydrogen. The various substituents in formula I preferably have the following meaning: If R is haloalkyl, it preferably contains from 1 to 6 carbon atoms, the term halogen in the straight-chain and in the branched-chain configuration meaning chlorine and bromine as mono-, di, tri- and tetra-substituents. Examples of the alkyl part in the preferred embodiment are methyl, ethyl, n-propyl, isopropyl, N-butyl, sec-butyl, 1,1-dimethylbutyl, amyl, isoamyl, n-hexyl and isohexyl. If R is chloroalkenyl, this compound preferably contains from 2 to 4 carbon atoms and at least one olefinic double bond. The chlorine substituents can be present either as mono-, di-, tri- or tetra-substituents such as trichlorovinyl. If Rj, R2, R3, R4 and R5 is lower alkyl, this preferably contains 1 to 4 carbon atoms in a straight or branched chain arrangement, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.- Butyl and the like. The compounds of the formula I can also influence the normal herbicidal activity of herbicides of the thiocarbamate type and other herbicides in such a way that their action becomes more selective. Whatever the mode of action of the compounds of the formula I, their advantageous and desired mode of action is that the herbicidal action of the thiocarbamates is maintained, while at the same time their side effects are reduced to the desired types of useful plants. This advantage and usefulness is explained in more detail in the description below. The terms "compound effective as an antidote to undesirable side effects of a herbicide (English herbicide antidote) or an antidote effective amount" are understood to mean the action which counteracts the normal damaging herbicidal action of the thiocarbamates on the useful plant which the herbicide may otherwise have. Whether this is an antidote, a mechanism-interfering agent, a protective substance or something similar depends on the exact nature of the effect. The nature of the effect can vary, but the desired result is always the result of treating the soil on which the crop grows. So far, there have been no processes which have been able to solve this problem satisfactorily. The compounds of formula I can be prepared by various methods, depending on the starting material. The oxazolidine and thiazolidine intermediates can be obtained by condensing the amino alcohols or mercaptans with a suitable aldehyde or ketone in boiling benzene with constant removal of the water. This method is described by Bergmann et al., JACS 75, 358 (1953). In most cases, the oxazolidine and thiazolidine intermediates were sufficiently pure to be able to be used without intermediate purification. Aliquots of these solutions were then used to prepare the compounds of Formula I. Compounds which have a 3-thioacyl substituent can be obtained from the corresponding oxygen compound by known methods, for example by treatment with P2S5 in benzene under reflux. The desired product could be obtained by reacting the appropriate intermediate with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine. Standard processes such as extraction, distillation or crystallization can be used for working up and purification.