CH627916A5 - Herbicide - Google Patents

Description

The invention relates to herbicidal compositions, characterized in that they contain compounds of the formula I.

r,

-y-chch2-z (i)

wherein R the same or different substituents from the

Group halogen, CF3, CH3 or C2H5;

R: = same or different substituents from the

Group consisting of halogen and CF3; R2 = H or (CrC4) -ASkyl;

n = the numbers 1 or 2;

nt = zero, 1, 2;

X and Y = O or S;

Z = -OH, -SH,

R4 \

-nc;

K

-O-CO-N:

-F, -Cl, -Br, -J, -OCO-OR3

RÒ

R /

-0-S02-N;

R4 \

v

-o-co-r6,

R5 = H or (C1-C4) alkyl; or

R4 and R5 together with the nitrogen atom form a saturated heterocyclic ring with 2 to 5 C atoms, which may be interrupted by O, S or the rest of the formula NR'5, in which R'5 has the meaning of R5

Has;

R6 = a radical of the formula R3 or phenoxy- (C2-C3) alkyl, which is optionally substituted 1 to 3 times in the phenyl ring by F, Cl, Br and / or -CH3;

10 R, = H, (Ci-C4) alkyl or Kat®; and

Kat® the cation of an inorganic or organic

Base mean, in addition to formulation auxiliaries and carriers.

15 Alkyl, alkenyl and alkynyl radicals mentioned in R3 to R can be straight-chain and branched.

Among the radicals mentioned above are preferably:

20 (R) n - up to 2 -Cl, -Br and -CF3, where these radicals can be the same and different, in particular 4-C1, 2,4-Cl, 2-Cl-4-Br, 4-CF3 and 2-Cl-4-CF3; na = OoderCRj) ,! = Cl or Br in 2-position to Y;

25th

R2 - CH3;

X, Y = oxygen;

Z = -OH, -Cl, -Br, the rest of the formula II in which (R) n and nj have the meanings mentioned; furthermore the groups

30th

35

O

R.

-O-C-NC ', R4 = H, (C] -C4) alkyl, phenyl,

r /

Halophenyl, methylphenyl or trifluoromethylphenyl; and

R *

as stated;

40 -0-S02-R3 with R3 = CH3, phenyl, methylphenyl or

Chlorophenyl;

-o-so2-r6, -o-so3-r7

-0-S03-R7 with R7 = (CrC4) alkyl or Kat®;

or the rest of the formula II

-o-co-i-ho- x-0

(R.) In.

(R)

n

45

O

(Ii)

R, =

R, =

-0-C-R6 with Re = (CrCg) alkyl, (Cj-CJ-chloroalkyl, phenoxy (C2-C3) alkyl, which is optionally substituted in the phenyl radical by 1 to 50 2 halogen atoms and / or methyl groups, (C2-C5) Alkenyl or phenyl, which may be replaced by -Cl, -Br, -N02, -CH3,

(CrCi2) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cycloalkenyl, (C3-C8) alkynyl, phenyl or benzyl, the radicals mentioned also being halogen, CF3, NO2, CN , (CrC4) alkyl, (CrC4) alkylthio, (CrC4) alkoxy, -OH, -NH2, (QC ^ alkylamino, di - (CrC6) alkylamino and / or (CrCG) alkoxycarbonyl) may be substituted;

H, (CrC4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclohexyl, (CrC4) alkoxy or phenyl, which may be replaced by halogen, CF3, N02, CN, (C1-C4) alkyl, (Cj-CJalkylthio, (CrC4) alkoxy, OH, NH2, (CrC6) alkylamino, DHQ-QJalkylamino and / or (Cj-Cg) alkoxycarbonyl;

55

60

-CF3 or -OCH3 is mono- or disubstituted; and

Kat®: Na +, K :, NH4 +, M Ca ++, H3N + C2H5, H3N + CH2-

+/— \

CH2OH, H3N + CH3, HN + (C2H5) 3, NH2 0 or HN + (CH2CH2OH) 3.

Compounds in which Z is -OH, -0-C0-NH2 or -0-C0-R6 are particularly preferred due to their biological properties.

The compounds of the formula I can, starting from phenoxyphenols of the formula

627916

4th

y-h

(R)

or corresponding phenolates can be prepared in a number of ways known to the person skilled in the art. Thus, the compounds of formula III with those of formula r2 I

B-C-CH2-Z (IV)

I.

H

where B is halogen or a sulfoester group, for example 2-bromo-propane, 2-bromo-1-chloropropane or 2-bromo-propanol, optionally in the presence of acid-binding agents, are reacted in a manner known per se and then by in the organic Reactions customary in chemistry, in particular by esterification of the propanols obtained in this way, are converted into further compounds of the formula I.

Various methods can be used for the preparative preparation of the compounds of the formula I, some of which will be described below and in the examples.

1) Alcohols of the formula I (Z = OH) can, as described above, by reacting compounds of the formula III with halogen alcohols of the formula IV, by saponification of the corresponding haloalkyl compounds (Z = halogen) or by reducing corresponding esters of the carboxylic acids Formula II can preferably be obtained with metal hydrides such as lithium aluminum hydride. For R2 = H, alcohols of the formula I can also be obtained by reacting a compound of the formula III, preferably its alkali metal salt, with ethylene oxide.

2) Halogen compounds of the formula I (Z = Hal) can be prepared by reacting the corresponding alcohols with halogenating agents such as thionyl chloride.

3) Mercaptans of the formula I (Z = SH) are obtained, for example, from the corresponding halogen compounds of the formula I (Z = Hal) by reaction with metal hydrogen sulfides, preferably alkali hydrogen sulfides or xanthates or by reaction with thiourea and subsequent alkaline cleavage the resulting isothiu-ronium salts.

4) Esters are prepared, for example, by reacting alcohols of the formula I (Z = OH) in the presence of acid-binding agents (bases) by reacting with the corresponding acid halides, preferably acid chlorides or acid anhydrides, preferably in inert organic solvents, or else by direct esterification of the components in the presence of acidic catalysts and use of suitable solvents which form azeotropes with water or in the presence of water-binding agents. Suitable acid halides (chlorides) are those of monobasic acids such as alkane carboxylic acids, benzoic acids, benzenesulfonic acids and others. are used, but also those of polybasic acids such as carbonic acid, sulfuric acid, dicarboxylic acids, in which the other acid group (s) e.g. are esterified or amidated, e.g. by ester residues OR6 or amide residues

R4n,

nc;

r5- '

In particular, carbonic acid amides can be obtained by reacting compounds of the formula I (Z = OH) with corresponding carbamic acid halides in the presence of acid-binding agents or by reacting with isocyanates of the formula R4NCO.

5) Amines of the formula I (Z = NR4R5) are obtained by reacting corresponding halides (chlorides) of the formula I [Z = Hal (Cl)] by reaction with amines HNR4R5 in a manner known per se.

The base bodies of the formula III can be prepared in a manner known per se, for example analogously to the processes in DE-OS 1 668 896 and 2 433 067.

The compounds of formula I used according to the invention have a broad spectrum of activity against harmful grasses, but are tolerated by dicotyledonous crop plants and by various types of cereals and can therefore be used for the selective control of harmful grasses in crop plants.

The agents according to the invention generally contain the active compounds of the formula I in an amount of 2-95% by weight. They can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the usual preparations.

Wettable powders are preparations which are uniformly dispersible in water and which, in addition to the active ingredient, contain a wetting agent, in addition to a diluent or inert substance, e.g. polyoxyethylated alkylphenols, polyoxyethylated oleyl or stearylamines, alkyl or alkylphenyl sulfonates and dispersants, e.g. sodium lignosulfonate, 2,2'-dinaphthylme-than-6,6'-disulfonic acid sodium, dinaphthylmethane disulfonic acid sodium or oleylmethyl tauric acid sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Buta-nol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics and addition of a nonionic surfactant, for example a polyoxyethylated alkylphenol or a polyoxyethylated oleyl or stearylamine, are obtained.

Dusts are obtained by grinding the active ingredient with finely divided, solid substances, e.g. Talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Sprayable solutions, as are often sold in spray cans, contain the active ingredient dissolved in an organic solvent, next to it is e.g. a mixture of chlorofluorocarbons as blowing agent.

Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, poly-acrylic acid sodium or mineral oils on the surface of carriers such as sand, kaolinite, or granulated inert material. Suitable active substances can also be produced in the manner customary for the production of fertilizer granules - if desired in a mixture with fertilizers.

In the case of herbicidal compositions, the concentrations of the active compounds in the commercial formulations can vary. In wettable powders, the active ingredient concentration varies e.g. between about 10% and 95%, the rest consists of the formulation additives given above. In the case of emulsifiable concentrates, the active substance concentration is approximately 10% to 80%. Contain dusty formulations

5

to

15

20th

25th

30th

35

40

45

50

55

60

65

5

627916

mostly 5-20% of active ingredient, sprayable solutions about 2-20%. In the case of granules, the active ingredient content depends in part. depends on whether the active compound is liquid or solid and which granulation aids, fillers etc. are used.

For use, the commercially available concentrates are optionally diluted in the customary manner, e.g. for wettable powders and emulsifiable concentrates using water. Dust-like and granulated preparations and sprayable solutions are no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity, etc. the required application rate varies. It can fluctuate within wide limits, e.g. between 0.1 and 10.0 kg / ha of active substance, but is preferably between 0.5 and 5 kg / ha.

The active compounds according to the invention can be combined with other herbicides and soil insecticides.

Formulation examples

Example A:

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol (10AeO) as emulsifier.

Example B

A wettable powder easily dispersible in water is obtained by:

25 parts by weight of active ingredient

64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleylmethyl taurine as

Mixes wetting and dispersing agents and grinds them in a pin mill.

Example C

A dusts are contained by

Mix 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and crushed in a hammer mill.

Example D

Granules are e.g. from about 2-15 parts by weight of active ingredient 98-85 parts by weight of inert granule materials, such as Atapulgite, pumice stone and quartz sand.

Production Examples Example 1

2- [4 '- (2 ", 4" -dichlorophenoxy) phenoxy] propanol

28.6 g (0.75 mol) of lithium aluminum hydride are placed in 2 liters of absolute ether. While stirring, 354.3 g (1 mol) of ethyl 2- [4 '- (2 ", 4" -dichlorophenoxy) phenoxy] propionate dissolved in 500 ml of absolute ether are added dropwise so that the reaction mixture is kept at the boil. After the addition, the mixture is stirred at boiling temperature for 1 hour. After adding one liter of water and one liter of 10% sulfuric acid, the ethereal phase is separated off and the aqueous phase is extracted twice with 300 ml of ether each time. The combined ether phases become with

Washed and dried water until neutral. After the ether has been stripped off, the remaining residue is distilled under vacuum. After distillation, 303 g (96.7% of theory) of 2- [4 '- (2 ", 4" -dichlorophenoxy) -phenoxy] -propanol of Kp0il: 181 ° C.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

627916

The following were produced analogously:

6

Example No.

Compound of formula I.

Kp. (° C)

Cl-

Br- '

CHa-0-C-CH2-0H

f

H

çh3

-o-c-chj, -oh »

H

168-172 / 0.05 torr

164 / 0.02 torr f5c-

—0—

CHg

-o-c-chjj-oh t

H

140 / 0.05 torr

H * C-

häc fsc-

-0-

ch3 -o-c-ch2-oh t

H

çh3

O-c-ch2-oh

1

H

çh3

o-c-ch2 -oh

H

156 / 0.07 torr

165 / 0.02 torr

133 / 0.02 torr

Example 8

2- [4 '- (4 "-T rifluoromethylphenoxy) phenoxy] -1-chloropropane

31.2 g (0.1 mol) of the alcohol obtained in Example 4 are placed in 150 ml of toluene with 7.9 g (0.1 mol) of pyridine and cooled to -5 ° C. 13.1 g (0.11 mol) of thionyl chloride are added dropwise to the mixture in such a way that the temperature does not exceed 10 ° C. After the addition, stirring is continued for 1 hour, the temperature is slowly increased to 110 ° C. and held there for 2 hours. It is cooled, about 150 ml of 20% hydrochloric acid are added and the mixture is stirred for an hour. The toluene phase is separated off and the aqueous phase is extracted twice with 100 ml of toluene. The combined toluene extracts are washed neutral with water and dried. Toluene is distilled off and the remaining residue is distilled. After distillation, 31.3 g (94.6% of theory) of 2- [4 '- (4 "-trifluoromethylphenoxy) phenoxy] -1-chloropropane of KpL2: 182 ° C., which solidifies after 4 days and has a melting point of 38 ° -39 ° C.

45

50

55

60

f3c

CHS -0-C-CH2 -Cl t

H

65

The following were produced analogously:

7

627916

Example No.

Compound of formula I.

Kp. (° C)

10th

ch3 -o-c-chg -cl h

çh3

■ o-c-cha-cl t

H

159 / 0.05 torr

170 / 0.08 torr

11

ch3

-o-c-ch2-ci t

H

Example 12

Benzoic acid <2- [4 '- (4 "chlorophenoxy) phenoxy] prop-l-yl> ester

23 g (0.083 mol) of the alcohol obtained in Example 2 are dissolved with 9.3 g (0.092 mol) of triethylamine in 50 ml of toluene and within 15 minutes to a solution of 11.7 g (0.083 mol) which is at room temperature. Benzoyl chloride was added dropwise in 150 ml of toluene. After the addition, during which the solution warms to about 40 ° C., the mixture is stirred for 2 hours and washed twice with 200 ml of water 25 to remove triethylamine hydrochloride. The toluene phase is dried, toluene is distilled off. Drying the residue yields 31.4 g (99% of theory) of benzoic acid <2- [4 '- (4 "-chlorophenoxy) phenoxy] - prop-l-yl> ester, which after 3 days becomes solid and has an mp of 68.5 ° C.

30th

The following were prepared analogously using the corresponding acid component:

Example No.

Compound of formula I.

nD / Fp. CC)

13

cl-

chg 0

-0-c-cho -0-m>

i h

-Cl nD24'5: 1.5874

14

Cl

-0-

chg o

-0-c-ch2-0-c h cl

Mp .: 43-44

15

cl-

16 cl

-0-

Cft,

ch3 0

-o-c-chl -o-c i

H

0 ch.

3 w

-0-c-cho-o-c-c-o-

t i h h no.

nD24'5: 1.5857

nD23: 1.5844

17th

18th

19th

20th

21st

22

23

24th

25th

26

27th

8th

Compound of formula I.

Cl

Cl-

ch3 0 ch3

-0-c-cho-o-c-c-o

I «

h h ch3 0 ch3 • o-c-ch2-0-c-ç-0 H H

-Cl

-CFa

Cl-

Cîk 0

O-c-ch2 -o-c- (ch2) 8 -ch3

H

Cl- (

> -0

ch3 0 ■ o-c-ch2 -o-c-ch2 -ch2 -ch3

H

Cl «

Cl-

CHS 0 -0-C-CH2 -o-c-ch2 -Cl h

çh3

-0-C-CHo -0-c-i 2

h ch3 0 -o-c-cho -o-c-

i h

ch3 0 -0-c-ch2-0-c-

ch3 0 -o-c-ch2 -o-c-

-n0a

-cho,

H

-Cl ciclici

ÇH3 O ■ o-c-ch2 -0-c-

-c1

28

29

30th

31

32

33

34

35

36

37

38

9

Compound of formula I.

cl-

cl-

cl-

cl-

cl-

cl-

c1

, c1

Cl -0-

ch3

-0-c-cii2 -

I.

h ci ^ öc- ° -O-0tcH2-

0-c-ch2 -ch2 -chjj ch,

0

If

-0-c-ch2 -0-c- (ch2) 8 -cha

I.

H

-Cl

-Cl

-cfa fa

-0-

ch3

-o-c-ch.

H

0

, -o-c-ch3

f8c-

-cha

627916

10th

Example No. Compound of Formula I.

nD / FP. (° C)

39

F * C - (()) - 0-

CHg 0

-0-C-CH2-0-C-H

-Cl nD24: 1.5490

40

F * C - (()> - 0-

-c1

nd24: 1.5553

41

f8c-

-O-

CHa 0

-0-C-C «2 -0-C-CHa Cl H

nd24: 1.5190

42

f3c-

-0-

ch,

L3

0

■ o-c-ch2-o-c-c = ch h cn nD24: 1.5755

43

44

f * c - (() \ - 0

f8c - (()> - 0-

ch3 0 ch3 ■ o-c-ch2 -o-c-c-o- <

h h

CH3 0 CH3

-0-C-CHo -O-C-C-O-

i t

H H

> -0

Cl -0-

_Cl mp: 38-40

-Cl nD23: 1.5568

45

f3c-

-0-

ch3 0 ch3

-o-c-ch2-o-c-c-o-

t f h

H

—0— “) -cfg Mp .: 67-70

46

FsC-d)) - 0-

chg 0

-o-c-ch2 -o-c-ch2 -ch2 -ch3

H

nD23: 1.5008

47

48

fsc-

c1 -0-

CH.

fsc - (()) - 0 - <(j) -0-c-CH2-0-c- (ch2) 8-ch3

i

H

CH3 0 • O-C-CHg-O-C-

i

H

nD23: 1.4911

nD23: 1.5485

49

Hs C - <()) - 0

CH3 O

-0-C-CH2 -O-C-H

nD23'5: 1.5730

11

627916

Example No.

Compound of formula I.

nD / Fp. (° C)

50

-0-

CHS -O-C-CPL,

i

H

-o-S-Q ^ cx

Bp 148 ° / 0.02 torr

CHS 0 Cl

! H "

15

20th

Example 51

2,2-dichloropropionic acid <2- [4 '- (2 ", 4" -dichlorophenoxy) - phenoxy] -prop-l-yl> ester

31.3 g (0.1 mol) of the alcohol obtained in Example 1 are concentrated with 21.5 g (0.15 mol) of dichloropropionic acid, 50 ml of chloroform and 1 ml. H2S04 boiled under reflux for 6 hours. The water of reaction formed is distilled off azeotropically. The mixture is cooled and washed three times with 60 ml of water, neutralized with bicarbonate solution, washed with 100 ml of water, dried and distilled to dryness. The remaining oily residue is distilled under vacuum. After distillation, 39.1 g (91% of 25% of theory) of 2,2-dichloropropionic acid <2- [4 '- (2 ", 4" -dichlorophenoxy) phenoxy] prop-1 are obtained -yl> -ester from Kp0 05: 204 ° to 206 ° C; nD23: 1.5602.

30th

Cl - (()> - 0 - ((.)) - 0-C-CH2 -0-C-C-CHs

H Cl 35

The following were produced analogously:

Example No. Compound of Formula I.

nD / Kp (° C)

52

53

Cl-

Br-

-0-

, C1 -0-

CHg 0 Cl -0-C-CH2 -O-C-C-CH,

I I

H Cl

CHjs 0 Cl -O-C-CHg-O-C-C-CHjs H Cl nD23: 1.5525

54

55

F * C-

F * C

~ 0-i

Cl

CH3 0 Cl ■ 0-C-CH2 -O-C-C-CH;

I I

H Cl

5

CHg 0 Cl -O-C-CHg -O-C-C-CH ^ H Cl

Bp 193-97 / 0.1 torr nD23: 1.5225

627916

12

Example 56

l-Methylaminocarbonyloxi-2- [4 '- (2 "-chloro-4" -trifluoromethyl-phenoxy) -phenoxy] -propane

15 g (0.043 mol) of the alcohol obtained in Example 7 are kept at 100 ° C. for 7 hours with 6.3 g (0.11 mol) of methyl isocyanate and 1 ml of triethylamine in 150 ml of toluene. The mixture is cooled, washed with 100 ml of water, dried and toluene is distilled off in vacuo.

The remaining residue is dried at 100 ° C under vacuum. After drying, 17.1 g (98.5% of theory) of l-methylaminocarbonyloxy-2- [4 '- (2 "-chloro-4" - trifluoromethylphenoxy) phenoxy] propane of mp 64 are obtained ° -65 ° C.

10th

CHH

0-

0

II

0-c-cho-0-c-nh-ch,

f

H

The following were prepared analogously (see table):

Example No. Compound of Formula I.

%, / Fp. (° C)

57

Cl «

-0 «

CHg 0

■ 0-c-ch2-o-c-nh-ch3 h

Mp .: 76-77

58

Cl-

-0 "

CHs

0

II

0-C-CH2-0-C-NH-C8 Rf (n)

H

nd24: 1.5488

59

Cl

-0-

ch3 0 • o-c-ch2-o-c-nh-h

Mp: 68-69

60

61

62

63

Cl-

Cl- <

Cl-

Cl-

ch3 0

-0-c-cho-0-c-nh-

t h

CHg

0

II

-0-c-ch2-o-c-nh-

ch3 0

■ 0-c-ch2 -0-c-nh-

ch3 0

-o-c-ch2 -o-c-nh-ch3 h

-Cl

-Cl

Fp .: 76

nD24: 1.6006

nd24: 1.5935

nd24: 1.5690

64

65

66

67

68

69

70

71

72

73

74

13

Compound of formula I.

ch.

0

ti

-ö- ° -o-

Br "O_0 ~

■ 0-c-ch2 -o-c-nh- (cgh?) N h ch8 0 0-c-ch2 -0-c-nhcha h

CH3 0 -0-C-CH2 -O-C-NH- (C3 H?) N H

CH3 0 0-C-CH2-O-C-NH

ch3

0

0-C-CH2-0-C-NH-

H

-Cl f3c-

-0-

ch3 0 • o-c-ch2 -o-c-nh-ch3

f

H

f3c

-0-

ch3 0

■ O-C-CHg -0-C-NH-C3H7 (n) 1

h f «c

-0-

CH3 0 -0-C-CH2 -O-C-NH

f * c-

-0-

CH3 0 ■ 0-C-CH2 -O-C-NH H

-Cl ch3 0

■ o-c-ch2 -o-c-nhch3

i h

ch3 0

-0-c-ch2 -o-c-nh-

627 916

14

Example 75

l-Dimethylaminocarbonyloxi-2- [4 '- (2 ", 4" -dichlorophenoxy) phenoxy] propane

25 g (0.08 mol) of the alcohol obtained in Example 1 are refluxed with 21.5 g (0.2 mol) of dimethylcarbamic acid chloride and 20 g (0.198 mol) of triethylamine in 150 ml of toluene until no more starting material is found in the thin-layer chromatogram see is. The mixture is filtered hot, washed with 150 ml of water after cooling and dried. Toluene is distilled off under vacuum. The remaining residue is purified by column chromatography over aluminum oxide until neutral with ethyl acetate as the eluent. After distilling off the ethyl acetate, 26.6 g (86.4% of theory) of 1-dimethylamino-carbonyloxy-2- [4 '- (2 ", 4" -dichlorophenoxy) -phenoxy] -propane with nD24: 1 are obtained , 5609.

10th

15

ch3 0

-0-c-ch2-o-c-n (ch3) 2 h

20th

The following were produced analogously:

Example No. Compound of Formula I.

76

77

CHg

I.

0

II

-0-C-CHg -O-C-N (CHg) 2 H

CHg 0

• 0-C-CH2-O-C-N (CHg) 2 H

78

FSC

ç * 0 ■ 0-C-CH2 -O-C-N (CHg) 2

t

H

Analysis:

€

H

N

calc .:

59.5

5.3

3.7

found:

59.4

5.2

3.4

Example 79

l-ethoxycarbonyloxy-2- [4 '- (2 ", 4" dichlorophenoxy) phenoxy] - 50 propane

31.3 g (0.1 mol) of the alcohol obtained in Example 1 are boiled with 15.9 g (0.105 mol) of ethyl a-chlorocarbonic acid and 16.6 g (0.12 mol) of potassium carbonate in 100 ml of acetone 55. There is a slight elimination of carbon dioxide. After 18 hours, the salt fraction is filtered off and acetone is distilled off. The residue is purified by column chromatography using aluminum oxide and ethyl acetate as the eluent. The eluent is distilled off and the residue is dried under vacuum. After drying, 18.5 g (48% of theory) of l-ethoxycarbonyloxy-2 - [4 '- (2 ", 4" -dichlorophenoxy) -phenoxy] -propane with nD24: 1.5516.

15

627916

Example 80

Methanesulfonic acid <2- [4 '- (4 "-trifluoromethylphenoxy) phenoxy] prop-l -yl> ester

25 g (0.08 mol) of the alcohol obtained in Example 4 are dissolved in 10.1 ml (0.1 mol) of triethylamine in 50 ml of toluene and within 10 minutes in a solution of 9.2 g (0.08 mol ) Dropped methanesulfonyl chloride in 140 ml of toluene. After the addition, the mixture is stirred for 2 hours and washed three times with 150 ml of water each. It is dried and toluene is distilled off under vacuum. Drying the remaining residue under vacuum gives 29 g (92.7% of theory) of methanesulfonic acid <2- [4 '- (4 "-trifluoromethylphenoxy) phenoxy] -pro-1 -yl> ester.

fso

-0-

CHs

O-C-CHjj-O-SOjj-CHss t

h io

15

20th

Analysis: calculated: found:

C 52.3% C 52.0%

H 4.4% H 4.3%

The following were produced analogously:

8.2% 8.0%

25th

Example No. Compound of Formula I.

nD / Fp. CO

81

FjrC-

ÇH3

-O-C-CHg-O-SOji nD23'5: 1.5412

82

Cl-

, c1

83

Cl ch5

-o-c-ch2-o-so2-

h ch

0-c-ch2-0-s02

T

H

Cl

Mp .: 56-58

84

h5 ch5

-o-c-ch2-o-so2 h

Example 85

1-N-Piperidino-2- [4 '- (2 ", 4" -dichlorophenoxy) phenoxy] propane

27.5 g (0.083 mol) of the chloride obtained in Example 10 are kept at 150 ° C. for 10 hours in an autoclave with 150 ml of piperidine. After cooling, it is taken up in 400 ml of methylene chloride and washed neutral with water. Methylene chloride is distilled off and the remaining residue is dried under vacuum. After drying, 28.5 g (90.4% of theory) of 1-N-piperidino-2 - [4 '- (2 ", 4" -dichlorophenoxy) -phenoxy] -propane are obtained; nD22: 1.5688.

60

65

ÇH3

-o-c-ch2-n \

h ny '

627916

The following were produced analogously:

16

Example No. Compound of Formula I.

86

87

88

89

90

CI

OC

CI "

-O-

-o-c-ch2-n \

h ny— '

^ r ~ \

-O-C-CHg -N \ H ^ - '

CHS / - -O-C-CHg-N H ^ -

CHS,

»/ -O-C-CHg-N

H ^ —I

CH.

-O-C-CHg-N I H N '

nD23: 1.5597

C H F calc .: 66.5 6.4 15.0 found: 66.0 6.2 15.0

nD23'5: 1.5208

Example 91

l-aminocarbonyloxy-2- [4 '- (4 "trifluoromethylphenoxy) phenoxy] propane

31.2 g (0.1 mol) of the alcohol obtained in Example 4 were initially charged with 13 g (0.2 mol) of sodium cyanate in 200 ml of methylene chloride, to which 24 g of trifluoroacetic acid were added dropwise with stirring. After the addition, the mixture is heated to boiling (about 2 days) until starting material can no longer be detected by thin layer chromatography. It is cooled and stirred into 400 ml of water, the organic phase is separated off and washed neutral with water. Methylene chloride is distilled off, the remaining residue is recrystallized from ethanol / water. After recrystallization, 27.2 g (80.4% of theory) of l-aminocarbonyloxy-2- [4 '- (4 "-trifluoromethylphenoxy) -phenoxy] -propane with mp. 80 ° -82 ° C.

The following are produced analogously:

Example No.

40

92

45

93

50

55

F * C-

CH3 0 -0-C-CHg-0-C-NH2 h

95

60

CH3 0 • OC-CHg-O-C-NHj, H

94

Br-

F5C-

CH3 0 -0-C-CH2-0-C-NH2 H

CH3 0 -O-C-CHg-O-C-NHjj H

CH,

0

ti

-0-C-CH2-0-C-NH2 H

65

Example 96

Sodium 2- [4 '- (4 "-trifluoromethyleneoxy) phenoxyJ-propyl sulfate

13.4 g (0.115 mol) of chlorosulfonic acid are carefully mixed with approx. 15 ml of diethyl ether, cooled to -10 ° C. and added dropwise with 31.2 g (0.1 mol) of 2- [4 '- (4 "-trifluorme- thyl-phenoxi) -phenoxi] -propanol- (l)

17th

627916

Addition, the temperature is held for 2 hours and then warmed to room temperature. The ether is removed in vacuo and a solution of 9 g (0.225 mol) of sodium hydroxide solution in 50 ml of water is added dropwise to the free acid thus obtained. The salt precipitates immediately upon addition; it is suctioned off, washed well with water and then dried. 36.6 g (95.7% of theory) of sodium 2- [4 '- (4 "-trifluoromethylphenoxy) phenoxy] propyl sulfate of mp 235.50 (dec.) Are obtained.

10th

F_C

Oo -O "

CH,

I J

-CH-CH_-0-S0? Na9

15

The following connections can be made analogously:

example

Mp (° C)

97

98

ch3

• o-c-chg-0-s03 h H

ch.

i s

■ 0-c-ch. H

, -0-s0sh

99

100

f «c br-

-o-so3h

-0-s0, h

101

102

103

Br

Cl

çh3

■ 0-c-ch2!

H

çh3 ■ 0-c-ch. H

-0-S0sNa

1 -0-SO * Well

çh5

■ 0-c-chg -0-s03 Na h

226-7 (dec.)

104

F * C

çh3

• O-C-CHg. H

■ 0-s03 k

206-209 (dec.)

627916

18th

example

Mp (° C)

105

106

107

Cl

Cl

Br—

—0—

Cl

Cl

-0 '

ÇHs ■ 0-C-CHg-SH

i

H

CHS

• 0-C-CHo -SH »

H

çh3

-o-c-ceg-sh t

H

108

109

f * c «

frc

Cl

CHS

-0-c-ch2-sh h

çh3 ■ o-c-ch2-sh

I 2

H

110

111

112

elei ch3 p j- \

■ O-C-CHg-0-SO3 NH2 O h ^ -

ch3

■ o-c-chg- o-sof NH0 O t 3 v 2 /

H \-'

ch3

t © ©

■ O-C-CHg - O-SO3K

H

136-137 ° (Z.)

127-128 ° (Z.)

215 ° (Z.)

113

F3C

—0—1

chs © \

■ 0-c-ch2-o-so, nh 0

H 3 ^

112-113 ° (Z.)

114

F C -, 3rd

-0- <

Ìh3 e ©

■ O-C-CI ^> - so3NH4

H

137 ° (Z.)

19th

The following compounds were also prepared analogously to Example 12:

627916

Example nD or Kp (° C)

, C1

115

116

117

118

Cl-

Br frc-

F «C-

, C1

■■ ö "

CH3 o ^ CH2 ■ O-C-CH «-0-C-CH I H \ CH2

Cl

CH5 0

-O-C-CHg-0-C!

H

CIL

i

0

it

-0-C-CH2-0-C-CH = CH2 -0-C-CH2 -O-C-CH «C J

1 \

H N CH_

nd24: 1.5645

Kp 220 ° / 0.05 mm

Bp 17070.003 mm

Kp 170 ° / 0.02 mm

119

120

FSC-

FSC-

—0—

—0—

respectively.

/, ch2

-ch - c chg ch3 0 ^

-0-C-CHp-0-C-CH H NCH2

Cl

CH.

s

0 CIL

• 0 ~ C-CH2 -0-C-CH-0 - H

-cl nD25: 1.5142

nD42'5: 1.5452

121 F3C

• 0—

CH3 0

-0-C-CH, -0-C-CH-CH3

T t

H Br '

n «22: 1.5202

627 916 20

Furthermore, the following compounds can be produced by the processes described:

as under example

Cl-

ch3

-o-c-ch2-oh

Cl

—0— <

^ ch3 -o-c-ch2-oh t

r, -, h cl

-0-

çh3

-o-c-ch2-oh

Br h

cl-

-0-

çh3

-o-c-ch2-óh t

ch.

h cl-

cl-

cl-

c1

f3c-

-0

h3c

Cl -0-

c1

h * c

/

ch3

-o-c-ch2-oh t

H

çhs

-o-c-ch2-oh t

cl h

-0-c-cho-oh

çh3

-o-c-ch2-oh t

H

Qch3

-o-c-ch2-oh c1h

21st

627916

as under example

FsC-

fsc-

ch3

-o-c-chg-oh r *

Cl ck,

-o-c-ch2-oh t 2

Cl h

frc

-0-

hsc

çhs

-o-c-ch2-oh

T

H

Br-

-0-

ch3

-0-c-ch2-0h m H

Br

-0 ~

ch3

-o-c-ch2-oh

Br »

B:

-0-

ch3

-o-c-ch2-oh »

H

Br h * c ch5

-o-c-chg-0h t *

H

Cl

-0-

c1

ch.

-0-c-ch2-cl

I.

H

Cl- (

> -0

Cl ch,

t

-0-c-ch2-cl

Cl-

—0—1

çh3

-o-c-ch2-ci t

Br h

627916

22

as under example cl-

cha

-o-c-ch2-ci ch ^

cl-

ch3

-o-c-ch2-ci »

H

ÇH3

-o-c-ch2-ci t

H

çh3

-o-c-ch2-ci

Br *

çh3

-o-c-ch2-ci t

h f * c

-0-

ch3

-o-c-ch2-cl ci *

f3c

-0-

f, c- <

"ch3

-o-c-ch2-Cl cl h f * c h3c ch3

-o-c-chg-cl h

Br-

-0-

çh3

-o-c-ch2-ci

Cl h

23

627916

as under example

Br-

Br

çhs

-0-c-ch2-cl

Br

Cl

H

ch,

-c-c-ch2-c1! ^

Cl

H

Br-

ch3

-0-c-ch, -cl i

h cl-

-0-

CH,

0

• 0-c-ch2-0-c-ch3

12

cl-

CH3 0

• O-C-CHg - O-C-CHg -CH; H

3rd

12

cl—

-0-

ch,

0 CHa ti i

■ O-C-CHg-0-C-C-H

t 2 t

H

CH,

12

Cl-

-0-

ch,

0

-O-C-CHg -0-C-CH = CHg H

12 or 51

627916

24th

as under example

ch3 0 ycez

-0-c-ch, -0-c-ch I t \ I

h xch2

CH,

0

Cl

■ 0-C-CH2-0-C-CH2-0-H

-Cl

12

12

Cl ch,

0

• 0-C-CH2 -O-C-CHg -o-k

12th

ci ca,

o h.

■ 0-c-ch2-0-c-ch2-h

-Cl

12th

Cl «

ch,

0 ch,

f x3 v

-0-c-ch2-0-c-ch-0-h

-Cl

12th

ch3 0 ch3 ■ o-c-ch2 -o-c-ch-o-

H

-Cl

12

Cl-

h3c ch3 o ch3

■ 0-c-ch2 -o-c-ch-o- 'h

-Cl

12

ch3 0

-0-c-ch2-0-c (ch2) 3 "h

-Cl

12th

ch3 0

-0-c-ch2-0-c (ch2) a-h

-Cl

12

Cl-

CHS 0 Hs C \

■ 0-C-CH2-0-C (CH2) 3-0-

-c1

12th

25th

627916

as under example

Cl-

CH, 0 CH ~

-Br

12th

12th

12th

12 or 51

12 or 51

12

12

12

12

12

12th

627916

26

as under example.

Cl »

XI

ch3 0 -o-c-ch2-o-c (ch2) 3-o-

-Cl

12

Cl-

Cl-

Cl-, C1

Br- ^

Br-.

Br-.

Br-.

Br-

Br-.

Cl -0-

c1 -0-.

CH?

-0-C-CH2-0-C (CH2) s-

k

CH,

H3C.

0

-o-c-ch2-o-c (ch2) 3-0-

H

CH,

0 CH,

it »

Clv

-0-C-CH2 - 0-C-CH-0-.

!

H

Cl -0-

c1 -0-

c1 —0—

Cl -0-

CH,

0

-0-C-CH2-0-C-CH3 H

0

f ^ 1 / T \

"°" C "CH2" CH =

CH,

0 u

-Cl

-Cl

-Br

-0-C-CH2-0-C-CH2-CH2-CH5 H

CH3 0 -O-C-CHg-0-C (CH2) 8-CH, H

0 / CH3

«I! /

ch3

-o-c-chg-0-c-ch i

H

CH,

\?H.

O

-O-C-CHg-0-C-CH = CHg H

CHS 0 -O-C-CHg -0-C-CH = CH-CH3 H

12

12

12

12

12

12

12

12

12 or 51

12 or 51

27th

627916

as under example

Br-

CH3 0 Qpj

! II ^ - ^ n3

■ o-c-ch, -o-c-ch = c ^

h xch>

ch3 0

• 0-c-ch2-o-c-ch-chj

«2!

h Br ch3 0

.0-c-ch2-o-c-ghclj

T

h ch,

0

u

.ch,

■ 0-c-ch2-0-c-c-h t \

h \ ch5

ch3 0 ■ o-c-ch2-o-c-

h ch,

0

Cl

.0-c-ch2-0-c- <h

-Cl

-Cl

12

12

12

12

12

12

12

Br-

ch5 0

-o-c-chg-o-c-h

-ch,

12

-ÎJ Cv

0

o-c-ch, -o-c-ch, -0-

t h

-Cl

12

12

12

627916

28

as under example

Br-

0

■ O-C-CHg-

c1

0

1!

h3c

-o-c-ch2-o-

0 ch3

■ 0-c-ch-0-

0 ch:

ti i

.o-c-ch-0-

0 ch3hsq

«I

. o-c-ch-0-

0

II t

■ o-c-ch-0-

0

-0-c (chg) s-

0

-0-c (ch2) 3-0-

CHk

-Cl Cl

-Cl

-Cl

-Cl

-Cl

-ch,

-Cl

-Cl h, c

0

-c-ch2-0-c (ch2) 3-0-h

0 chs

It I

■ 0-c-ch-0-

0 ch3

ii t

■ 0-c-ch-0-

-c1

-Cl

-Cl

12

12

12

12

12

12

12

12

12

12

12

29

627916

as under example

Br—

Br ei

"O-1 Cl

CH,

0 ch,

f 13 w Yia3

0-C-CH2 -0-C-CH-0-

i 2

H

CH3 0 CH3 • O-C-CHg - 0-C-CH- 0-

H

Br. -0 ~

-C1

-CF.,

12

12

f3c-

CH,

0

-0-C-CH. - 0-C-CH, -CH,

t

H

12

Fr C

f3c-

-0 "

-0-

CH3 0 ^ CH3

-0-C-CH, -0-C-CH »\

H ACH

ch3

0

it

-0-c-ch2-0-c-ch = CH-CH3

ch3 0

■ 0-0 -0-C-CH2-0-C-CHCl

12

12 or 51

12

F, C

f5c frc

—0—

CH3 0 CH3 -0-C-CH2-0-C-CH-0-

ch3 0 ch3h3q

-o-c-ch2-o-c-ch-

H

ch3 0 ch3

-0-c-ch2-0-c-ch-

i h

H3c

-Cl

-Cl

-CH,

12

12

12

fäc-

f, c-

CH,

0

II

-o-c-ch2-o-c (ch2), - o-

i

H

c

CH,

-o-c-ch2-o-c (ch,) 3-0-

1

H

-Cl

-Cl

12

12

627916

30th

as under example

FSC-

ch3 0 hsc -o-c-ch2-o-c (ch2) a-0-

i h

-cl

12

f3c - (()) - o-

ch3 0 ch3 ■ o-c-chg-o-c-c-o-

H

H

-Br

12

Cl

-0-,

ch3 0 -0-c-ch2-0-c-ch3

cl h

12

cl

-0 '

ch3 0 -o-c-ch2-o-c-ch2-ck2-ch3

Cl H

12

cl

-0.

ch,

0

i ii

-0-c-cho-o-c-ch = c:

t

H

-ch3

'ch,

12

ch,

i3 0

t II

-0-c-cho-0-c-cho-ch,

i h

12

cl

CH,

0

-O-C-CHg -0-8

Cl t

H

12

Cl «

CHS 0 -0-C-CH2-O-C-CHg Cl

Br H

12

cl chs 0 -0-c-ch2-0-c-chclj ch3 ^

12

cl-

ch3 0 ch3

-0-c-ch2 - 0-c-ch- 0-

T

TT h

-cl

12

31

627916

as under example

Cl-

ch,

0 ch,

-O-C-CHg-O-C-CH-O

—0—

-cf,

12

Cl «

ch3 0 -o-c-chg-0-c-ch2 h ch, »

0

II

-O-C-CHg-0-C-CH3

ch3 0

-o-c-chg-0-c-ch, h

12

12

12

Cl

Cl hsc ch3 0

-o-c-chg-0-c-h

-Cl

12

f * c-

-0-

CH

l3

C.

O-C-CHg-0-C-CH3 H

f, c-

-0-

ch3 0 ^ chz

-o-c-chg-0-c-ch »\

c1 h xch3

12

f, c

-0-

ch3 0 -o-c-chg-0-c-ch = c:

M 8

cl h

'CHS • CH,

12

f3c ch3 0

-O-C-CHg -O-C-CHg -CHg -CHS ■ Br H

12

f3c

-0-.

ch3 0

o-c-chg-0-c!

r H

-CH,

12

627916

32

as under example

F * C-

-0-

C1 CHg 0

-0-C-CH2-0-C-CH8 Cl »

12

FSC-

-0-

h3c ch3 c

-0-c-ch2-0-c-ch, h

12

F * C

-0-

h3c ch3 0 -o-c-ch2 -o-c-ch2 -ch2 -ch3

H

12

F * C

ch3 0 nu

I II ^ tt3

■ 0-c-cho-0-c-ch = c.

h cife

12

For C

—0—

h5c ch3 0 ■ o-c-ch2-o-c-chcib t

H

12

CH,

0 h

u i

-0-c-chp-0-c-c-ch,

t h

i

Br

12

FRC

h3c ch3 0

-0-C-CHo -0-C-

t

H

-Cl

12

f, c ch3 0 ch3

O-c-ch2-o-c-ch-

i h

-Cl

12

Br>

-0-

ch3 o

-o-c-ch2-o-c-ch3

Cl "

12

Br-

-0-

CH3 0 -O-C-CHo-0-C-CH = C ^

t ^ \

C1H

ch,

ce,

12

33

627916

Biological Examples Example 1

Seeds of grass were sown in pots and the preparations according to the invention formulated as wettable powder were sprayed onto the surface of the earth in various dosages. The pots were then placed in a greenhouse for 4 weeks. The result of the treatment (also in the following examples) was determined by a rating according to the scheme by Bolle (newsletter of the German Plant Protection Service 16, 1964, 92-94):

10th

thylphenyl) ether] and mecoprop [2- (4'-chloro-2'-methyl-phenoxy) propionic acid]. The results summarized in Table I show that the claimed compounds are more effective on grasses on average than the two comparative herbicides. The claimed compounds according to Examples 2, 9, 10, 12, 13, 14, 15, 21, 26, 27, 28, 36, 37, 38, 39, 40, 41, 42, 58 also showed a similar activity against grasses. 60, 61, 62, 64, 69, 70, 72, 75 and 81.

TABLE I

Weed ratings for pre-emergence treatment

Value number

Harmful effects in% of weeds crops

1

100

0

2nd

97.5

to

<100

> o to

2.5

3rd

95

to

<97.5

> 2.5

to

5

4th

90

to

<95

> 5

to

10th

5

85

to

<90

> 10

to

15

6

75

to

<85

> 15

to

25th

7

65

to

<75

> 25

to

35

8th

32.5

to

<65

> 35

to

37.5

9

0

to

<32.5

> 67.5

to

100

Fluorodifen [4-nitrophenyl- (2'-nitro-4'-trifluorme-

15 Example No.

Dosage (kg / ha A.S.)

AL

Plant species SA LO

EC

1

2.5

2nd

1

1

2nd

0.6

3rd

2nd

1

2nd

20 4

2.5

1

1

1

1

0.6

1

1

1

1

8th

2.5

1

1

2nd

1

0.6

2nd

2nd

2nd

2nd

25 22

2.5

3rd

1

1

1

0.6

4th

2nd

2nd

2nd

30th

2.5

1

1

1

1

0.6

3rd

2nd

1

1

30th

29

2.5

2nd

1

1

1

0.6

3rd

1

1

1

24th

2.5

4th

2nd

2nd

2nd

35

0.6

5

4th

3rd

2nd

63

2.5

4th

3rd

1

3rd

0.6

4th

5

4th

5

71

2.5

1

1

1

1

40

0.6

2nd

1

1

1

80

2.5

2nd

2nd

1

1

0.6

5

3rd

3rd

3rd

Fluoro-

2.5

7

1

1

4th

45 difen

0.6

8th

5

8th

8th

Meco

2.5

4 '

3rd

5

3rd

prop

0.6

7

6

8th

7

50 AL = Alopecurus myosuroides

SA = Setaria lutescens

LO = Lolium multiflorum

EC = Echinochloa crus-galli

Example II

55 grass seeds were sown in pots and grown in the greenhouse. 3 weeks after sowing, the preparations according to the invention formulated as wettable powder were sprayed onto the plants in various dosages and, after 4 weeks in the greenhouse, the effects of the preparations were rated. Here too, fluorodifene and mecoprop served as comparative herbicides. The claimed compounds were somewhat less effective in this application process than in the pre-emergence process described in Example I, but they were 65 more effective against grasses than the two comparison agents (Table II). The claimed compounds according to Examples 2, 10, 24, 36, 37, 39 and 41 also showed a similar activity against grasses.

627 916

34

TABLE II

Weed ratings for post-emergence applications

example

dosage

Plant species

No.

(kg / ha A.S.)

AL

SAT

LO

EC

1

2.5

5

1

1

1

0.6

8th

2nd

1

1

4th

2.5

1

1

1

1

0.6

2nd

1

2nd

1

8th

2.5

1

1

2nd

1

0.6

2nd

2nd

2nd

22

2.5

8th

3rd

2nd

1

0.6

9

3rd

5

30th

2.5

3rd

2nd

2nd

1

0.6

9

4th

3rd

1

29

2.5

2nd

1

1

1

0.6

7

2nd

2nd

71

2.5

4th

1

1

1

0.6

6

2nd

6

1

Fluoro-

2.5

8th

2nd

6

4th

difen

0.6

8th

3rd

8th

6

Meco

2.5

8th

7

8th

8th

prop

0.6

9

8th

9

9

Example III

Seeds from a large number of crop plants were placed in pots. Some of the pots were placed in a greenhouse for germination and emergence for 2 to 3 weeks and treated with substances according to the invention after the plants had developed 2 to 3 real leaves; the other pots were immediately sprayed in the same manner as in Example 21.

The result was found 4 to Al / 2 weeks after treatment, it is shown in Table III. In detail, the results show that almost all dicotyledons

Cultivated plants in the highest dosage (2.5 kg / ha) tolerated the preparations according to the invention very well both in the pre-emergence and post-emergence process; since the effective dosage is approximately 0.6 kg / ha, the active compounds according to the invention are therefore well selective in these crops.

TABLE III

Pre- and post-emergence effect on crops, doses 2.5 and 0.6 kgfhaA.S.

example

1

preem. 2.5 0.6

2nd

preem. 2.5 0.6

2nd

postem. 2.5 0.6

4th

preem. 2.5 0.6

4th

postem. 2.5 0.6

barley

2 1

1

1

1 1

wheat

2 1

-

-

3rd

1

- -

4 1

sugar beet

1 1

3rd

2nd

2nd

1

3 1

2 1

spinach

1 1

3rd

1

1

1

2 -1

1 1

to sunbathe

flower

1 1

1

1

1

1

1 1

1 1

salad

3 1

1

1

1

1

3 1

2 1

Rapeseed

1 1

2nd

1

1

1

2 1

2 1

White cabbage

1 1

3rd

1

2nd

1

2 1

3 1

cauliflower

1 1

2nd

1

1

1

2 1

1 1

cucumber

1 1

1

1

5

1

3 1

5 1

soy

1 1

1

1

1

1

3 1

2 1

alfalfa

1 1

2nd

1

3rd

1

1 1

2 1

Bush bean

1 1

3rd

1

3rd

1

3 1

1 1

pea

1 1

2nd

1

1

1

2 1

1 1

Field bean

1 1

1

1

1

1

1 1

1 1

Flax

1 1

2nd

1

1

1

1 1

2 1

cotton

2 1

1

1

3rd

1

1 1

2 1

tomato

1 1

2nd

1

3rd

1

1 1

2 1

tobacco

2 1

1

1

4th

2nd

1 1

4 2

celery

1 1

1

1

1

1

1 1

1 1

carrot

1 1

1

1

1

1

1 1

1 1

Example IV

Seeds of maize and rice and of some grass weeds occurring in these crops were sown in pots and germinated in the greenhouse for 3 weeks. The preparations according to the invention formulated as wettable powder and the comparative agents were then sprayed onto the plants in different dosages and the effect of the preparations was determined after 4 weeks.

The following compounds were used as comparison means:

A = 2- [4 '- (2 ", 4" -dichlorophenoxy) -phenoxy] -propionic acid

re-methyl ester (DT-OS 22 23 894) B = 2- [4 '- (4 "chlorophenoxy) phenoxy] propionic acid iso-

butyl ester (DT-OS 22 23 894) C = 2- [4 '- (4 "-trifluoromethylphenoxy) phenoxy] propionic acid methyl ester (DT-OS 24 33 067)

The claimed compounds showed a significantly better tolerance in maize and / or rice than the comparative herbicides. At the dosages that do not or only slightly damage the crop plants, they were extremely effective against the weeds tested. The comparison compounds, on the other hand, were not selective in maize and rice.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

35

627916

TABLE IV

Credit score for post-emergence treatment

Crop

Dose zen weed binding (kg / ha) maize rice EV SA

1

2.5

6

3rd

1

1

0.6

3rd

3rd

1

2nd

0.15

1

1

5

3rd

2nd

2.5

6

7

1

1

0.6

2nd

3rd

2nd

1

0.15

1

2nd

6

2nd

4th

2.5

8th

-

1

1

0.6

3rd

-

1

1

0.15

1

-

6

8th

22

2.5

-

3rd

1

-

0.6

-

1

1

0.15

-

1

6

A

2.5

8th

8th

1

!

0.6

7

7

1

1

0.15

6

6

3rd

1

B

2.5

9

8th

1

1

0.6

9

7

1

1

0.15

8th

4th

2nd

7

C.

9

-

1

1

9

-

1

1

9

-

3rd

1

Example V

In a further experiment, compounds 8, 46, 117 and 91 were treated with comparative compound C post-emergence in accordance with Example I.

The results shown in Table V show that the claimed compounds are superior to the comparative agents in crop tolerance (compound 8) or, with equally good tolerance to soybeans, show no advantage in comparison with the tested grasses.

TABLE V

Credit score for pre-run treatment

connection

Dose (kg / ha)

Crop barley wheat soybean

AL

Grasses DI SA

EC

8th

2.5

1

1

1

2nd

__

1

1

0.6

1

1

1

4th

-

2nd

4th

0.15

1

1

1

7

-

5

5

46

2.5

-

-

1

1

1

1

1

0.6

-

-

1

2nd

1

1

2nd

0.15

-

-

1

3rd

1

2nd

91

2.5

-

-

1

1

1

1

1

0.6

-

-

1

1

1

1

1

0.15

-

-

1

1

1

2nd

117

2.5

-

1

1

1

1

1

0.6

-

-

1

1

1

1

1

0.15

-

-

1

1

3rd

C.

2.5

9

9

1

1

1

1

1

0.6

9

9

1

1

2nd

1

2nd

0.15

8th

5

1

5

6

4th

4th

■ DI = Digitaria sanguinalis

Example VI

The effectiveness of further compounds according to the invention in the pre-emergence is shown in the following table.

TABLE VI

Rating results in pre-emergence treatment against important grasses

connection

dose

Effect against grasses

(kg / ha)

AL

EC

SAT

DI

2nd

2.5

1

1

1

_

0.6

2nd

1

3rd

-

3rd

2.5

2nd

1

1

-

0.6

3rd

1

3rd

-

7

2.5

1

1

1

1

0.6

3rd

1

2nd

1

13

2.5

2nd

1

1

-

0.6

3rd

1

3rd

-

14

2.5

2nd

1

1

-

0.6

4th

3rd

-

15

2.5

2nd

1

2nd

-

0.6

3rd

3rd

-

12

2.5

1

1

-

-

0.6

3rd

-

-

16

2.5

-

1

1

-

0.6

-

1

3rd

-

17th

2.5

-

1

1

-

0.6

-

4th

-

20th

2.5

-

1

1

-

0.6

-

3rd

3rd

-

21st

2.5

3rd

2nd

3rd

-

0.6

3rd

3rd

4th

-

24th

2.5

-

2nd

2nd

_

0.6

-

3rd

4th

-

26

2.5

-

2nd

3rd

-

0.6

-

3rd

4th

-

27th

2.5

-

3rd

-

-

0.6

-

4th

-

-

28

2.5

_

2nd

3rd

-

0.6

-

3rd

3rd

-

31

2.5

3rd

3rd

2nd

-

0.6

4th

3rd

3rd

-

32

2.5

2nd

1

1

-

0.6

4th

4th

4th

-

33

2.5

1

1

1

1

0.6

4th

1

2nd

1

34

2.5

-

1

-

-

0.6

-

3rd

-

-

35

2.5

-

3rd

-

-

0.6

-

4th

-

-

36

2.5

1

1

1

1

0.6

3rd

1

1

1

37

2.5

-

1

1

1

0.6

-

1

1

2nd

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

38

39

41

43

45

48

47

46

52

54

56

58

61

62

63

64

69

70

72

75

v

36

Dose (kg / ha)

Effect against grasses AL EC SA DI

connection

Dose (kg / ha)

Effect against grasses AL EC SA DI

2.5

_

1

1

1

5 78

2.5

2nd

1

0.6

-

2nd

1

1

0.6

-

3rd

3rd

-

2.5

1

1

1

1

79

2.5

2nd

2nd

2nd

0.6

2nd

2nd

2nd

1

0.6

4th

4th

4th

2.5

2nd

1

1

-

O

00 ©

2.5

1

2nd

_

0.6

3rd

1

1

-

0.6

-

3rd

3rd

-

2.5

1

1

1

_

81

2.5

2nd

1

0.6

2nd

2nd

1

-

0.6

-

2nd

-

2.5

2nd

1

1

-

15 82

2.5

_

1

1

0.6

3rd

4th

3rd

-

0.6

-

2nd

-

2.5

2nd

2nd

2nd

_

91

2.5

1

1

1

1

0.6

4th

6

4th

-

0.6

1

1

1

1

2.5

1

1

1

_

20 117

2.5

1

1

1

1

0.6

3rd

2nd

-

-

0.6

1

1

1

1

2.5

1

1

1

1

118

2.5

1

1

1

_

0.6

2nd

2nd

1

1

0.6

2nd

1

-

2.5

3rd

3rd

2nd

_

25 121

2.5

1

1

0.6

4th

4th

4th

-

0.6

2nd

2nd

1

-

2.5

1

1

1

_

119

2.5

1

1

1

_

0.6

1

2nd

1

-

0.6

3rd

2nd

1

2.5

30th

-

3rd

-

-

116

2.5

3rd

3rd

1

_

0.6

-

5

-

-

0.6

4th

4th

-

2.5

-

1

3rd

-

115

2.5

3rd

1

1

_

0.6

-

2nd

4th

-

0.6

4th

2nd

1

_

35

2.5

-

2nd

2nd

-

96

2.5

2nd

2nd

1

1

0.6

-

3rd

4th

-

0.6

3rd

4th

2nd

1

2.5

-

4th

1

-

101

2.5

1

1

4th

-

0.6

-

5

2nd

-

40

0.6

3rd

2nd

5

-

2.5

4th

3rd

3rd

-

113

2.5

2nd

1

1

,

0.6

4th

5

5

-

0.6

3rd

2nd

2nd

-

2.5

-

2nd

2nd

_

114

2.5

1

1

1

_

0.6

3rd

4th

-

45

0.6

3rd

2nd

2nd

-

2.5

-

3rd

2nd

-

104

2.5

2nd

1

1

0.6

-

4th

3rd

-

0.6

3rd

2nd

2nd

-

2.5

-

1

1

_

110

2.5

1

2nd

2nd

_

0.6

-

2nd

2nd

-

50

0.6

3rd

2nd

3rd

-

2.5

1

1

1

_

111

2.5

3rd

3rd

2nd

-

0.6

4th

1

2nd

-

0.6

4th

4th

3rd

-

2.5

-

2nd

2nd

_

112

2.5

4th

3rd

2nd

0.6

-

3rd

3rd

-

55

0.6

4th

4th

3rd

- -

1

Claims (3)

627916 2. Herbicidal composition according to claim 1, characterized in that it contains compounds of the formula I in which (R) n = 1 to 2 chlorine or bromine atoms or CF3 groups, where these radicals can be the same or different; n4 = 0 or (R ^ n = Cl or Br in the 2-position to Y; l R2 = CH3; X, Y = oxygen; Z = -OH, -Cl, -Br, the rest of the formula II in which (R) n and% have the meanings given above; furthermore the groups O II -o-C-NC /, r4 = H, (Cj-C4) alkyl, phenyl, Rs Halophenyl, methylphenyl or trifluoromethylphenyl; and R5 as specified in claim 1; -0-S02-R3 with R3 - CH3) phenyl, methylphenyl or Chlorophenyl; -0-S03-R, with R, = (C1-C4) alkyl or Kat®; O II -0-C-R6 with Re = (CrC9) alkyl, (C1-C4) chloroalkyl, phenoxy (C2-C3) alkyl, which is optionally substituted in the phenyl radical by 1 to 2 halogen atoms and / or methyl groups, (C2-C5) -Alkenyl or phenyl, which is optionally mono- or disubstituted by -Cl, -Br, -N02, -QH3, -CF3 or -OCH3; and Kat®: Na K +, NH4-, H Ca-, H2N + (CH3) 2, H2N + (C2HS) 2, J \ H3N + CH2CH2OH, HN + (C2H5) 3, fH2 0 or HN (CH2CH2OH) 3 mean. 3. Herbicidal composition according to claim 2, characterized in that in the compounds of formula I. (R) n = 4-chloro, 2,4-dichloro, 2-chloro-4-bromo, 4-trifluoro methyl or 2-chloro-4-trifluoromethyl; n, = zero; R2 = CH3; and X, Y = oxygen and Z has the same meaning as in claim 2. 4., herbicidal composition according to claim 2, characterized in that in the compounds of the formula I Z = -OH, -Cl, -Br; the rest of the formula II [wherein (R) n and% have the meanings as in claim 3]; furthermore the groups r; \ -O-CO-Nd j, -0-S03-Kat® and-0-C0-Rg Rr 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 2nd PATENT CLAIMS 1. Herbicidal agents, characterized by their content of compounds of the formula I. (R) wherein R the same or different substituents from the Group halogen, CF3, CHS or C2H5; Rj = identical or different substituents from the Group consisting of halogen and CF3; R2 = H or (CrC4) alkyl; n = the numbers 1 or 2; n, = zero, 1, 2; X and Y = O or S; Z = -OH, -SH, r; \ -NcT}, -F, -Cl, -Br, -J, -OCO-OR, Rs r; \ -o-co-ncT; r; \ -o-so2-nc), -o-co-r8, R »' -O-SO2-R6, -O-SO3-R, or the rest of the formula II -o-co-ch-y- (R) R3 = (Cj-C12) alkyl, (C3-C8) cycloalkyl, (C2-C10) alkenyl, (C5-C6) cycloalkenyl, (C3-C8) alkynyl, phenyl or benzyl, the radicals mentioned also being halogen, CF3 , NO2, CN, (CrC4) alkyl, (Ci-Qalkylthio, (CrC ") alkoxy, -OH, -NH2, (CrC6) alkylamino, di - (C1-CGJ-alkylamino and / or (C1-C6) alkoxycarbonyl can be substituted; R4 = H, (CrC4) alkyl, (C2-C4) alkenyl, cyclopentyl, cyclo-hexyl, (CrC4) alkoxy or phenyl, which may be replaced by halogen, CF3, N02, CN, (C1-C4) alkyl, (CrC4) Alkylthio, (CrC4) alkoxy, OH, NH2, (QQ) -alkylamino, DHQ-QJalkylamino and / or (C ^ Cg) -alkoxycarbonyl; R5 = H or (Ci-C4) alkyl; or R4 and R5 together with the nitrogen atom form a saturated heterocyclic ring with 2 to 5 C atoms, which can be interrupted by O, S or the rest of the formula NR'g, in which R's has the meaning of Rg; R6 = a radical of the formula R3 or phenoxy- (C2-C3) alkyl which is optionally substituted in the phenyl ring 1 to 3 times by F, Cl, Br and / or -CH3; R, = H, (C1-C4) alkyl or Kat®; and Kat® is the cation of an inorganic or organic base, in addition to formulation auxiliaries and carriers. 3rd 627916 means (R) “, rij, R2, X, Y, R4, R5 and R6 have the same meanings as in claim 3 and Kat © Na +, K +, NH4 + or NHg p means.