CH624554A5 - Method of protecting crops of plants - Google Patents

Abstract

Crops of useful plants are protected against damage by substituted acetanilide herbicides by adding or applying an antidote to the soil. The antidote used is a compound of the formula I. The symbols in formula I have the meanings given in patent claim 1. <IMAGE>

Description

The invention and the preparation of the compounds of the formula I 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, in the course of the reaction, 15 ml of water were modified with a modified Dean-

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

624 554

4th

Stark apparatus disconnected. 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, which contained 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 were separated and the organic phase was 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 = 1.53 64.

Example 6

Preparation of 2-phenyl-3-dichloroacetyl-thiazolidine

5 g of 2-phenyl-thiazolidine were dissolved in 50 ml of acetone and first 3.1 g of triethylamine and then 4.4 g of dichloroacetyl chloride were added dropwise to this solution while stirring at room temperature. 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.

Nd30 = 1.58 36.

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.

Nd30 = 1.5 8 05.

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 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 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 was 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-5-phenyl-oxazolidine

23 ml of a benzene solution containing 5.7 g of 2,2,4-trimethyl-5-phenyl-oxazolidine were mixed with 25 ml of benzene and 3.1 g of triethylamine and kept at room temperature, while 4.4 g of dichloroacetyl chloride were 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 = 1.56 68.

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

624 554

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.

Connection no.

R

RI

R2

R3

R4

Rs

Rs

X

Y

Melting point or Nd:

1

CHC12

m-N02-C6H4

H

H

H

H

H

O

O

1.5590

2nd

chci2

m-N02-C6H4

H

ch3

ch3

H

H

O

O

1.5448

3rd

ch2ci m-NÖ2-C6H4

H

ch3

ch3

H

H

O

O

1.5484

4th

chci2

c6hs

H

H

H

H

H

O

O

1.5490

5

CC13

C6Hs

H

H

H

H

H

O

O

1.5398

6

CHBrCHa c6hs

H

H

H

H

H

O

O

1.5490

7

cci2-ch3

c6hs

H

H

H

H

H

O

O

1.5301

8th

CHBr2

c6hs

H

H

H

H

H

O

O

1.5808

9

CHBrCH2Br c6h5

H

H

H

H

H

O

O

1.5712

10th

CC1 = CC12

c6hs

H

H

H

H

H

O

O

1.5615

11

CHC12

m-ClC6H4

H

H

H

H

H

O

O

1.5550

12th

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

c2h5

H

H

H

O

O

1.5353

19th

cci3

c6h5

H

C2Hs

H

H

H

O

O

1.5310

20th

CHC12

c2hs

H

H

H

c6h5

H

O

O

1.5600

21st

cci3

C2Hs

H

H

H

CA

H

O

O

1.5455

22

CHC12

ch3

ch3

H

h c6h5

H

O

O

1.5438

23

ch2ci ch3

ch3

H

H

c6hs

H

O

O

1.5450

24th

chci2

p-CH3-C6H4

H

H

H

H

H

O

O

1.5440

25th

cc13

p-ch3-c6h4

H

H

H

H

H

O

O

1.5430

26

CHBrCH2Br p-ch3-c6h4

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-C6H4

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-CH3ö-C6H4

H

H

H

H

H

0

O

1.5380

33

CHBrCH2Br m-CH30-C6H4

1

H

H

H

H

H

O

O

1.5688

34

CH2C1

H

H

H

H

H

O

O

1.6030

35

chci2

folci

H

H

H

H

H

O

O

1.5980

624 554 6

Table 1 (continued)

Connection no.

r ri r2

r3

r,

rs r6

x y

Melting point or Nd3c

36

cc13

h h

h h

h o

0

1.5132

37

cc12ch3

h h

h h

h o

0

1.5921

38

ch2ci c6hs h

h h

ch3

h o

0

1.5486

39

chci2

c6hs h

h h

ch3

h o

0

1.5423

40

cela c6h5

h h

h ch3

h o

0

1.5376

41

cc12ch3

c6h5

h h

h ch3

h o

0

1.5530

42

ch2ci c6h5

h ch3

ch3

ch3

h o

0

1.5364

43

chci2

C6hS

h ch3

ch3

ch3

h o

0

1.5343

44

cc13

c6hs h

ch3

ch3

ch3

h o

0

1.5310

45

cc12ch3

c6h5

h ch3

ch3

ch3

h o

0

1.5310

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

c6hs 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

C6HS

H

H

H

H

H

s

0

110-

112 ° C

52

ch2c1

m-ClC6H4

H

H

H

H

H

s

0

1.5925

53

chci2

m-ClC ^

H

H

H

H

H

s

0

1.5805

54

cci3

m-aC6H4

H

H

H

H

H

s

0

1.5940

55

cc12ch3

m-ClC6H4

H

H

H

H

H

s

0

1.5850

56

CH2CH2Br m-CÌC6H4

H

H

H

H

H

s

0

1.5931

57

CHBiCH2Br m-ClC6H4

H

H

H

H

H

s

0

1.6038

58

CH2CH2C1

m-ClC6H4

H

H

H

H

H

s

0

1.5920

59

ch2ci

3,5-Cl2-C6H3

H

H

H

H

H

0

0

1.5748

60

chci2

3,5-Cl2-C6H3

H

H

H

H

H

O

0

1.5663

61

cci3

3,5-Cl2-C6H3

H

H

H

H

H

0

0

1.5613

62

CC12CH3

s ^ -Cl ^ cghs

H

H

H

H

H

0

0

1.5530

63

ch2ci

3,5-Cl2-C6H3

H

H

H

H

H

s

0

1.6041

64

chci2

3,5-Cl2-C6H3

H

H

H

H

H

s

0

1.6038

65

ccu

3,5-Cl2r-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

c6hs

H

0

0

1.5640

68

chci2

H

H

H

H

c6hs

H

0

0

1.5593

69

CC13

H

H

H

H

C6Hs

H

0

0

1.5558

70

CHBr-CH2Br

H

H

H

H

c6hs

H

0

0

1.5738

71

CC12CH3

H

H

H

H

c6hs

H

0

0

1.5433

72

CH2-CH2Br

H

H

H

H

c6hs h

0

0

1.5591

73

CHC12

m-OH-C6H4

H

H

H

H

H

0

0

wax-

good

firmly

74

cci2ch3

m-OH-C6H4

H

H

H

H

H

0

0

1.5453

75

chci2

p-NOy-CgH4

H

H

H

H

H

s

0

1,6008

76

chci2

c6H5

H

c2hs

H

H

H

s

0

1.5352

77

chci2

c6h5

h ch3

ch3

H

H

s

0

1.5366

78

ch2ci ch3

ch3

ch3

h c6hs

H

0

0

1.5021

79

chci2

ch3

ch3

ch3

H

c6hs

H

0

0

126 ° C

80

CC13

ch3

CH3

ch3

H

c6hs

H

0

0

1.5080

81

CH2BrCH2

ch3

ch3

ch3

H

c6h5

H

0

0

1.5051

82

CH2BrCHBr ch3

ch3

ch3

H

c6hs h

0

0

1.5450

83

CH2C1

o-C1-c6H4

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-C1-C6H4

H

H

H

H

H

0

0

1.5794

86

CH2C1

p-Cl-C6H4

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-c6h4

H

H

H

H

H

0

0

1.5814

7

Table 1 (continued)

624 554

Connection no.

R

rJ

r2

r3

89

CC12 = CC1

p-Cl-C6H4

H

H

90

CC12 = CC1

m-ClC6H4

h h

91

CHC12

c6hs h

H

92

CH2BrCHBr c6hs h

H

93

CH2C1

c6hs h

H

94

chci2

3,4-di-ClC6H4

h h

95

C12CH

p-C6H5-OCH3

h h

96

ci2ch o-C1-C6Hs h

H

97

ci2ch m-F-C6H5

h h

98

ci2ch ch3

CH3

CH2OH

99

C12CH

CH,

O

O

r4

Rs r6

X

Y

Melting point or ND3

h h

H

O

0

1.5754

h h

H

S

0

1,6008

h c «h5

H

S

0

1.5653

h c6hs h

S

0

1.5734

h c6hs

N

s

0

1.5723

h h

h s

0

1.5600

h h

h s

0

1.5740

h h

h s

0

97-

102 ° C h

h h

s

0

1.5650

h c6h5

H

0

0

1.5190

h c6h5

H

0

0

1.5070

100

C12CH

CH3

ch3

CH2OCCHCl2

h c6h5

H

O

O

1.5180

101

ch2ci ch3

ch3

ch2oh h

c6h5

h o

O

1.5182

102

chci2

m-Cl-C6H5

H

ch3

h ch3

H

O

O

1.5243

103

CH2BrCHBr m-Cl-C6H5

H

ch3

H

ch3

H

O

O

1.5406

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

ri r2

r3

r4

Rs r6

x y

ch2c1

c6hs h

h h

h h

o s

chci2

c6hs h

h h

h h

o s

cc13

c6h5

h h

h h

h o

s ch2c1

c6hs h

h h

h h

s s

chci2

c6h5

h h

h h

h s

s cc13

c6hs h

h h

h h

s s

ch2c1

ch3

ch3

h h

c6h5

h o

s chci2

ch3

ch3

h h

c6h5

h o

s cc13

ch3

ch3

h h

c6hs h

o s

ch2c1

ch3

ch3

h h

c6h5

h s

s chci2

ch3

ch3

h h

c6h5

h s

s cc13

ch3

ch3

h h

c6hs h

s s

CH2BrCHBr m-Cl-C6H4

H

H

h ch3

H

0

s

CH2BrCHBr c6hs h

h h

ch3

h s

s

CH2BrCHBr ch3

ch3

h h

c6h5

H

0

s

CH2BrCHBr ch3

ch3

h h

c6h5

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 Life-rant, gave representative results. As a result, the weed killing result achieved is commercially acceptable in each individual 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 species can be achieved by adding a compound of formula I or combinations 60 thereof. The plant species that can be protected by this method are not limited to the species listed in the examples.

Substituted acetanilide herbicides are considered to be of a general type. This means that the individual herbicides combined in a 65 class are effective against a large number of plants, whereby no distinction is made between desirable and undesirable species. An effective amount of the herbicidal compound will generally

624 554

8th

applied to the area or plant site where the control is to be carried out. Such herbicides are, for example, 2-chloro-2,6-diethyl-N- (methoxymethyl) acetanilide, 2-chloro-N-isopropyl-acetanilide, N, N-diallyl-2-chloroacetamide and combinations thereof. 5

The term herbicide, as used here, is understood to mean a compound which prevents or alters the growth of vegetation or plants. This suppressing or changing effect includes all deviations from natural development, such as killing, inhibiting, defoliation, drying out, regulating, stunting, population, stimulation, 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 above the surface of the soil.

The compounds of formula I can be used in the form of herbicidal preparations which contain the antidote and a halogenated acetanilide herbicide. The 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

2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide-LASSO 4E -

6.25 g LASSO 4E were diluted in 1000 ml water. 100 ml of this solution was sprayed onto the dishes using a straight-line spray table in such a way that the amount was 2.24 kg LASSO / ha in 7481 water / ha.

b) Antidote 95 mg of each compound to be investigated were dissolved in 15 ml acetone with 1% Tween 20® (polyoxyethylene sorbitan monolaurate), so that when spraying 1V2 ml 40 of this solution per dish (based on half the surface of a dish) applied amount of the test substance corresponds to 5.6 kg / ha.

PES and PPI tank blends 45

The stock solutions (a and b) described above were used to apply the antidote in the groove. As a preparatory step, a soil sample of 0.473 l from each dish was put on the side so that it could be used later

Cover the seeds after treatment with the means to use. 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.

The solution described below was prepared for superficial use before sprouting the seed or for treating the soil before sowing. In order to achieve a concentration of 2.24 kg of 2-chloro-2 ', 6'-diethyl-N-methoxy-methyl-acetanilide / ha, 800 mg of the product 4E were diluted with deionized water. To prepare a combined tank mixture, 4 ml of the acetanilide stock solution and 3 ml of the antidote stock solution (b) were mixed together. To treat the soil before planting, this mixed stock solution was added to the soil sample in a 191 rotating mixer. For superficial application before the seeds sprouted, the same stock solution was spread on the soil after sowing.

The finished treated and seeded trays were placed in a greenhouse on benches where the temperature was maintained between 21 to 32 ° C. The bowls were sprayed with water to ensure good plant growth. The degree of damage was determined 2 and 4 weeks after treatment. Individual trays, which had only been treated with the herbicide, were included in the test series in order to obtain a basis for determining the reduction in damage caused by the herbicidal antidotes.

Table 2 below shows the protective effect in percent for various useful plants which had been treated according to the methods given above. Percentage protection is determined by comparing untreated trays to trays treated with the test compounds of this invention.

10th

IS

30th

9 624 554

Table 2

Treatment methods: IF = in the furrow

PPI = before planting

PES = Superficial treatment before sprouting. Crop type: Milo - (sorghum vulgare) carrot

Shatter cane - SC (Sorghum biocolor) Wild Foxtail - Ft (Setaria viridis) Green Bristle Millet

Carbgrass - CG (Digitaria sanguinalis) Blood Millet Watergrass - WG (Echinochloa crusgalli) Common Chicken Grass

* -% damage ** -% protective effect

Ver

5.6 kg / ha

-IF

PPI (5.6 kg / ha)

PES (5.6 kg / ha)

binding

Tank mix

Tank mix

No.

Milo

SC

Milo

Ft

CG

Flat share

Milo

Ft

CG

Flat share

LASSO

100 *

100 *

50

100

100

100

70

100

100

100

2 Ib / A

1**

70

0

0

0

0

0

0

0

0

0

2nd

20th

0

0

0

0

0

0

0

0

0

3rd

50

0

0

0

0

0

0

0

0

0

4th

60

50

100

0

0

0

70

0

0

0

6

20th

0

0

0

0

0

0

0

0

0

10th

0

0

80

0

0

0

14

0

0

0

11

60

0

60

0

0

0

0

0

0

0

14

0

0

40

0

0

0

0

0

0

0

15

15

0

60

0

0

0

14

0

0

0

18th

0

0

40

0

0

0

14

0

0

0

20th

80

90

100

0

20th

10th

85

0

0

0

21st

15

0

0

0

0

0

0

0

0

0

22

90

90

100

0

0

0

100

0

0

0

23

70

70

0

0

0

0

0

0

0

0

24th

15

0

40

0

0

0

28

0

0

0

27th

0

0

40

0

0

0

0

0

0

0

29

0

0

40

0

0

0

0

0

0

0

32

0

0

40

0

0

0

14

0

0

0

35

30th

0

0

0

0

0

0

0

0

0

42

50

0

20th

0

0

0

0

0

0

0

43

60

0

0

0

0

0

0

0

0

0

46

25th

0

40

0

0

0

14

0

0

0

47

50

0

0

0

0

0

0

0

0

0

48

30th

0

0

0

0

0

0

0

0

0

49

40

0

0

0

0

0

0

0

0

0

50

50

0

40

0

0

0

0

0

0

0

51

30th

0

0

0

0

0

0

0

0

0

52

0

0

40

0

0

0

28

0

0

0

53

50

0

0

0

0

0

0

0

0

0

54

20th

0

0

0

0

0

0

0

0

0

55

60

0

20th

0

0

0

28

0

0

0

56

20th

0

20th

0

0

0

0

0

0

0

57

30th

0

0

0

0

0

0

0

0

0

58

60

0

0

0

0

0

0

0

0

0

59

30th

0

80

0

30th

0

0

0

0

0

63

20th

0

80

0

0

0

14

0

0

0

64

50

0

0

0

0

0

0

0

0

0

65

30th

0

0

0

0

0

0

0

0

0

67

0

0

40

0

0

0

28

0

0

0

68

80

0

0

0

0

0

0

0

0

0

70

40

0

0

0

0

0

0

0

0

0

72

50

0

0

0

0

0

0

0

0

0

73

15

0

60

0

0

0

0

0

0

0

75

40

0

80

0

0

0

65

0

0

0

76

40

0

0

0

0

0

0

0

0

0

77

40

0

0

0

0

0

0

0

0

0

78

5

-

16

0

0

0

20th

0

0

0

79

80

-

50

0

0

0

50

0

0

0

80

20th

-

0

0

0

0

16

0

0

0

624 554

10th

Table 2 (continued)

Ver 5.6 kg / ha - IF PPI (5.6 kg / ha) PES (5.6 kg / ha)

binding tank mix tank mix

No.Milo SC Milo Ft CG WG Milo Ft CG WG

LASSO 100 * 100 * 50 100 100 100 70 100 100 100

2 Ib / A

81

15

-

0

0

0

0

0

0

0

0

83

15

-

0

0

0

0

16

0

0

0

84

60

-

50

0

0

0

50

0

0

0

85

0

-

20th

0

0

0

50

0

0

0

87

50

-

40

0

0

0

67

0

0

0

88

0

-

30th

0

0

0

16

0

0

0

89

30th

-

30th

0

0

0

16

0

0

0

90

30th

-

0

0

0

0

0

0

0

0

91

15

-

0

0

0

0

16

0

0

0

92

40

-

0

0

0

0

0

0

0

0

94

40

50

0

0

0

40

0

0

0

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, emulsifiable concentrates, liquids, moistenable powders, granules or any other suitable form. In the preferred form, a non-phytotoxic amount of a compound which counteracts the damage caused by herbicidal agents is mixed with a selected herbicide and added to the soil before or after sowing. It is obvious that the soil can first be treated 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 of 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.

30th

35

s

Claims (11)

624 554 2nd PATENT CLAIMS 1. Process for protecting plant crops against damage by substituted acetanilide 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 Damage from substituted acetanilide herbicides effective amount of a compound of formula I. R - (I) 11. The method according to claim 1, characterized in that in formula I X is sulfur, Y is oxygen, R is haloalkyl, R i is phenyl, R 2 is hydrogen, R3 is hydrogen, R4 is hydrogen, Rs is hydrogen and R6 is hydrogen. 12. The method according to claim 1, characterized in that in formula I X sulfur, Y oxygen, R haloalkyl, R! Chlorophenyl, .R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, Rs is hydrogen and R6 is hydrogen. R1 R2 wherein X and Y are independently oxygen or sulfur; R haloalkyl; Ri is hydrogen, lower alkyl, phenyl, naphthyl or phenyl substituted by fluorine, one or two chlorine, nitro, methyl, methoxy or hydroxyl; 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; and R6 is hydrogen, with the proviso that at least one of the groups Rj or Rs is a phenyl, substituted phenyl or naphthyl group, or adds to the soil. 2. The method according to claim 1, characterized in that in formula I X mean oxygen, Y oxygen, R haloalkyl, Rt nitrophenyl, R2 hydrogen, R3 hydrogen, R4 hydrogen, Rs hydrogen and R6 hydrogen. 3. The method according to claim 1, characterized in that in formula I X is oxygen, Y oxygen, R haloalkyl, Ri phenyl, R2 hydrogen, R3 hydrogen, R4 hydrogen, Rs hydrogen and R6 hydrogen. 4. The method according to claim 3, characterized in that in formula I R is dichloromethyl. 5. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, R is chlorophenyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, Rs is hydrogen and R6 is hydrogen. . 6. The method according to claim 1, characterized in that in formula I X is oxygen, Y is oxygen, R is haloalkyl, R is lower alkyl, R2 is hydrogen, R3 is hydrogen, R4 is hydrogen, R5 is phenyl and R6 is hydrogen. 7. The method according to claim 6, characterized in that in formula I R is dichloromethyl and Rx is ethyl. 8. 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, Rs phenyl and R6 hydrogen. 9. The method according to claim 8, characterized in that in formula I R is dichloromethyl, Rt is methyl and R2 is methyl. 10. The method according to claim 1, characterized in that in formula 1 X signify oxygen, Y oxygen, R haloalkyl, Ri phenyl, R2 hydrogen, R3 lower alkyl, R4 lower alkyl, R5 lower alkyl and R6. 20th 25th 30th 50 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. Prior 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 specifically directed to a particular crop type. These antagonistic agents have so far 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 halogenated acetani-lid herbicides 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 55 60 65 R - R (I), wherein X and Y independently of one another oxygen or sulfur; R haloalkyl or chloroalkenyl; 3rd 624 554 R] is hydrogen, lower alkyl, phenyl, naphthyl or phenyl substituted by fluorine, one or two chlorine, nitro, methyl, methoxy or hydroxyl; 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 a phenyl, substituted phenyl or naphthyl group, adds it or applies it to the ground. 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; Rj is hydrogen, lower alkyl or phenyl; R2 is hydrogen or lower alkyl; R3 is hydrogen or lower alkyl; R4 is hydrogen or lower alkyl; R5 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, chlorine and bromine as mono-, di-, tri- and tetra-substituents in the straight-chain and in the branched-chain configuration. 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 tri-chlorovinyl. If R 1, R 2, R 3, R 4 and R 5 are 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 formula I can also influence the normal herbicidal activity of the 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 herbicides is maintained, while at the same time their side effects are reduced to the desired crop types. 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 or an effective amount as an antidote” are understood to mean the action which counteracts the normal damaging herbicidal action of the thiocarbamates on the crop 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 in a satisfactory manner. 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, starting from the corresponding oxygen compound, by known methods, for example by treatment with P2Ss in benzene under reflux. By reacting the suitable intermediate with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, the desired product could be obtained. Standard processes such as extraction, distillation or crystallization can be used for working up and purification.