CH619925A5 - Process for the preparation of 2-substituted benzanilide. - Google Patents

Description

The present invention relates to a process for the preparation of 2-substituted benzanilides which are suitable as germicidal and pesticidal agents for agriculture. In particular, the invention relates to an improved, industrially feasible method for producing 2-substituted benzanilides with high purity 40 by reacting 2-substituted alkyl benzoate with aniline or an aniline derivative.

2-Substituted benzanilides show strong germicidal effects and a broad spectrum of activity against pathogens of various plant diseases. In particular, they are effective for preventing various plant diseases, such as rice sheath disease (Pellecularia sukaki), bacterial rice leaf disease, leaf blight disease, cucumber anthracnosis, white bean stem rot, Alternaria leaf tan (blotches) of the apple trees, apple mildew, so called phoma rot, the orange, Barley rust, coffee rust or rust disease of ornamental plants or vegetable brandy, grain brandy, rhizoctonia and Fusarium soil diseases, wheat brandy or the like. Furthermore, these agents are also suitable for seed disinfection.

55 It is known that benzanilides, which have no substituent on the benzene nucleus of the benzoyl group, by reacting alkyl benzoate, which has no substituent on the benzene nucleus, with aniline in the presence of an alcoholate, e.g. B. of sodium methylate in an organic solvent 60 with azeotropic distillation of the alcohol formed as a by-product. According to Richard J. De Feo et al., Journal of Organic Chemistry, vol. 28, p. 2915 (1963) and US Pat. No. 3,462,486, benzanilides can be prepared by reacting ethylbenzoate with an aniline in benzene 65, with as a by-product Ethyl alcohol is formed. This is distilled off under azeotropic conditions in the presence of solid sodium methylate. This reaction follows the following reaction equation:

3rd

619 925

O

- oc2h5 + h2n

NaOCH3

In order to carry out a condensation reaction of an alkyl carboxylate with an aniline smoothly, it is necessary to remove the alcohol formed as a by-product from the reaction system. It was therefore considered optimal to use an organic solvent which can be distilled off azeotropically with the alcohol formed. For this reason, benzene has been used as an organic solvent. However, it is difficult to produce the 2-substituted benzanilides in a high yield by this conventional method. It is particularly difficult to react 2-substituted benzanilides with aniline in high yield by reacting 2-substituted alkyl benzoate which has a substituent ortho to the alkoxycarbonyl group. With this method, N-alkylbenzamides are easily formed as by-products, and it is difficult to completely prevent the formation of this by-product. This results in contamination of the 2-substituted benzanilide formed with the by-product, so that the effectiveness of the 2-substituted benzanilide as a pesticide is adversely affected.

The inventors have attempted to improve the conventional method so that the formation of N-alkylbenzanilide as a by-product is avoided and 2-substituted benzanilides with high germicidal activity and with a wide spectrum of activity against pathogens of plant diseases are obtained in high yield. The inventors have now found that optimal conditions are present when a 2-substituted alkyl benzoate is reacted with an aniline in an organic solvent which is difficult to azeotropically distill with the alcohol formed as a by-product. Furthermore, the inventors found that the reactivity differs depending on the number of carbon atoms in the alkyl group of the alkoxycarbonyl group of the 2-substituted alkyl benzoate. In the course of further investigation, it was found that 2-substituted benzanilides can be obtained in high yield without the formation of N-alkylbenzanilide as a by-product when 2-substituted alkylbenzoate having an alkoxycarbonyl group having a certain number of carbon atoms with an aniline in the presence of a specific one Alcoholate in an organic solvent which is difficult to azeotropically distillate together with the alcohol formed as a by-product.

It is an object of the present invention to provide a process for the preparation of 2-substituted benzanilides in high yield without the formation of N-alkylbenzanilide as a by-product.

This object is achieved according to the invention in that 2-substituted benzanilides of the general formula

X

[III]

30th

35

40

55

60

65

means and wherein Y represents a hydrogen atom, an alkyl, alkoxy, alkenyloxy, alkynyloxy, benzyloxy or halo-genbenzyloxy group, by reacting a 2-substituted alkylbenzoate of the formula

/ - ^ o

20th

OR

[I]

where R represents a C2_t alkyl group, with an aniline of the formula

25th

H? N

<3

[n]

wherein X produces a halogen atom or a lower alkyl group in the presence of an alcoholate in an organic solvent which is difficult to azeotropically distill with the alcohol formed as a by-product.

The 2-substituted alkyl benzoates can be compounds of the formula (I), where X is a halogen atom, e.g. B. a chlorine, bromine or iodine atom or a nitro group or a lower alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, and where R is a C2-4 alkyl group, such as ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl and preferably a C2-4 alkyl group. If R is a methyl group, N-methylbenzanilide is formed as a by-product. If R is an alkyl group with more than 5 carbon atoms or a phenyl group, the yield of 2-substituted benzanilide is relatively low.

Anilines of the formula (II) can be used, where Y is a hydrogen atom or an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, iso-pentyl, sec- Pentyl, tert-pentyl or an alkoxy group such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, pentyloxy, iso-pentyloxy, hexyloxy, octyloxy or Dodecyloxy, or an alkenyloxy group such as vinyloxy, allyloxy or 1-methylallyloxy or an alkenyloxy group such as acetylenoxy, propargyloxy, 1-propylpropargyloxy, or a benzyloxy group or a halobenzyloxy group such as chlorobenzyloxy.

The alcoholates used in the process according to the invention are preferably alkali metal alcoholates and alkaline earth metal alcoholates, such as potassium methylate, sodium ethoxide, sodium n-propylate, sodium isopropylate, potassium ethylate, potassium n-propylate, potassium isopropylate and the like. the like

When methylate is used, N-methylbenzanilide is formed as a by-product.

When methylate is used in conjunction with a compound of formula (I) in which R is a methyl group, a large amount of N-methylbenzanilide is formed.

The solvent is quite important for the present process. It is preferably a compound of the formula

619 925

4th

wherein R] represents a lower alkyl group or a chlorine atom, and wherein R2 represents a hydrogen atom or a lower alkyl group or a chlorine atom, and wherein R3 represents a hydrogen atom, a lower alkyl group or a chlorine atom, or a compound of the formula

Rr-0-R5 [V]

where R4 and R5 are alkyl groups with more than 5 carbon atoms. Suitable solvents include compounds of the formula (IV), wherein

(1) Ri methyl; R2 is a C1-t-alkyl group or Cl and R3 is H or Cl, or

(2) Rj Cl; R2 is H or Cl and R3 is H, or

(3) Rj is a C2_5 alkyl group and R2 and R3 are H or compounds of the formula (V), where R4 and Rs are C5_6 alkyl groups. Typical solvents are o-, m- and p-xylene, o-, m- and p-ethyltoluene, o-, m- and p-propylto-luol, o-, m- and p-cymene, o-, m- and p-chlorotoluene, 2,4-, 2,5- and 2,6-dichlorotoluene, 3,4-dichlorotoluene, chlorobenzene, o -dichlorobenzene, m-dichlorobenzene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene , iso-butylbenzene, sec-butylbenzene, tert-butylbenzene, n-amylbenzene, iso-amylbenzene, tert.-amyl-benzene, mesitylene, diethylbenzene, n- or iso-dibutyl ether, n-amyl ether, iso-amyl ether and the like. the like

When o-, m-, p-xylene or chlorobenzene is used in the case that R in the compound [I] is an n-propyl group, or when o-, m-, m-xylene, ethylbenzene or chlorobenzene is used is used in the case that R in compound I is an n-butyl group, or when o-xylene, ethylbenzene or chlorobenzene is used in the case that R in compound [I] is an isobutyl group, it comes in to a certain extent to an azeotropic distillation with the alcohol formed as a by-product in the reaction.

Other solvents have the following disadvantage:

When benzene or toluene is used, there is considerable azeotropic distillation with the alcohol formed as a by-product in the reaction, so that it is difficult to obtain 2-substituted benzanilide in a high yield. If dimethylformamide is used, it reacts with the aniline and formamidines are formed as by-products. If alcohol and lower alkyl ether% are used, the reaction will not proceed smoothly or the yield will be unsatisfactory. If chlorinated hydrocarbons, e.g. As chloroform, are used, so there are side reactions.

The reaction according to the invention is usually carried out by reacting the 2-substituted alkyl benzoate (I) with the aniline (II) under atmospheric pressure in the presence of the special alcoholate in the special solvent with stirring and with heating. For example, the 2-substituted alkyl benzoate (I) is added to a mixture of the special alcoholate and the aniline (II) in the special solvent with stirring and with heating, or the special alcoholate is added to a mixture of the 2-substituted alkyl benzoate (I) and the aniline (II) in the special solvent. The amount of the 2-substituted alkyl benzoate (1) is usually in the range of 0.9 to 1.5 moles, and preferably 1 to 1.3 moles, per mole of aniline (Ii). The amount of the specific alcoholate is usually in the range of 0.9 to 2.0 moles, and preferably 1 to 1.5 moles, per mole of the aniline (II).

The reaction temperature is preferably in the range from 100 to 200 ° C. and in particular in the range from 120 to 150 ° C. The reaction time is in the range from 1 to 20 hours and preferably in the range from 2 to 6 hours.

After the reaction, the target 2-substituted benzanilide is usually in the form of the alkali metal salt or the alkaline earth metal salt. Mineral acids are therefore usually added for the hydrolysis of the metal salts of the benzanilides. In the process according to the invention, however, the metal salts of the 2-substituted benzanilides can be hydrolyzed by adding water to the reaction mixture, the 2-substituted benzanilides (III) being able to be removed in high yield.

The process according to the invention has the following characteristic features and advantages: 2-substituted benzanilides, which are suitable for controlling pathogens of various plant diseases and have not hitherto been obtainable in high yield, can now be obtained in high yield. Furthermore, the 2-substituted benzanilides can be formed as by-products while preventing the formation of N-alkylbenzanilides. Since the product does not contain N-alkylbenzanilide, the effectiveness of the desired 2-substituted benzanilide is very great and it is suitable as a stable and highly effective agent for controlling plant diseases.

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

Preparation of 3'-iso-propoxy-2-methylbenzaniIid

50 ml of p-xylene, 15.1 g (0.1 mol) of m-iso-propoxyaniline and 37.4 g are placed in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel a 20% solution of sodium ethyl alcoholate (0.11 mol as NaOC2H5) in ethyl alcohol. The mixture is then heated to 80 to 90 ° C to distill off the ethyl alcohol.

The mixture is then heated to 130 ° C. and 19.6 g (0.11 mol) of isopropyl 2-methylbenzoate is added dropwise at 130 ° C. over 30 minutes with stirring, and the reaction is then continued for a further 5 hours. The isopropyl alcohol formed as a by-product by adding isopropyl 2-methylbenzoate is distilled off during the reaction. After the reaction, the reaction mixture is cooled and 50 ml of water are added. 50 ml of n-hexane are also added, and the crystals which have separated out are filtered off. 25.6 g (yield 95.2 white crystals of 3'-isopropoxy-2-methyl-benzanilide (mp. 91 to 92 ° C.) are obtained. Gas chromatographic analysis confirmed that N-alkyl-3-isopropoxy-2- methylbenzanilide is not formed as a by-product. The product has a purity of 99.8%.

Example 2

According to the procedure of Example 1, various 2-methyl-alkylbenzoates are reacted with m-isopropoxyaniline, namely in p-xylene, in ethylbenzene and chlorobenzene. When using methyl 2-methylbenzoate, N-methyl-3'-isopropoxy-2-methylbenzanilide is obtained as a by-product in all solvents. The yields of the 3'-isopropoxy-2-methylbenzanilides are summarized below.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

ch3

P y-C - OR + H2N

NaOC2Hs

solvent

CHÌ

0-C3H7-iso

C - NH

-Ö

619 925

O-CjH ^ -iso

Trial No.

R

Organic solvent (% yield) p-xylene ethylbenzene

Chlorobenzene

2-1 2-2 2-3 2-4 2-5 2-6

-ch3 -ch2ch3

-ch2ch2ch3

-ch (ch3) 2 - (ch2) 3ch3

-chch2ch3

73.6 93.1

80.1

95.2 79.1 93.5

72.3 92.1 93.7 94.0 78.3 92.7

74.9

91.2 79.9

94.6

72.7

93.3

2-7 2-8 2-9 2-10

2-11

CH3 -CH2CH (CH3) 2 -C (CH3) 3 - (CH2) 4CH3 - (CH2) 2CH (CH3) 2

■ o

93.8 97.3 64.1 66.5

65.9

78.6 95.9 65.1 67.3

66.3

74.4 96.7 66.4

67.0

63.1

Example 2 shows that when p-xylene is used as the solvent, the yield is low if R is an n-propyl group or an n-butyl group. If ethylbenzene is used as the solvent, the yield is low,

when R represents an n-propyl group or an n-butyl group. Even when chlorobenzene is used as the solvent, the yield is low when R represents an n-propyl group, a 40 n-butyl group or an iso-butyl group. The reactions according to the procedure of Example 2 were therefore carried out using p-cymene, cumene or mesitylene as the solvent. The yield is not reduced and 3'-isopropoxy-45 2-methylbenzanilide is obtained in a yield of more than 90%. However, the exceptions are cases in which R is a methyl group or an n-amyl group or an isoamyl group.

Example 3 50

Preparation of 4'-methoxy-2-methylbenzanilide In the flask according to Example 1, 50 ml of cumene, 13.7 g

(0.1 mol) of p-ethoxyaniline and 37.4 g of a 20% solution of sodium ethylate in ethyl alcohol (0.11 mol of NaOC2H5). The mixture is heated to 80 to 90 ° C to distill off the ethyl alcohol and 18.1 g (0.11 mole) of ethyl 2-methylbenzoate are added dropwise to the mixture at 130 ° C for 30 minutes with stirring, followed by the reaction is continued for 5 hours. The ethyl alcohol formed as a by-product in the reaction of the ethyl 2-methylbenzoate is distilled off during the reaction. After the reaction, the reaction mixture is worked up according to Example 1. 25.0 g (yield 92.9%) of white needles of 4-methoxy-2-methylbenzaniIide (mp. 149 to 149.50 C) are obtained.

Example 4

According to the procedure of Example 3, various alkyl 2-methylbenzoates and m-isopropylaniline are reacted in the presence of various alcoholates and various solvents, the 3'-isopropyl-2-methylbenzanilide being obtained. The results are summarized in Table 2.

619 925

ch3

coor + nh2

7 - (i)

Alcoholate

Solvent aCH3 conh—

.c3hy-ìso

Trial No.

R

Alcoholate

solvent

Yield,%

4-1

c2h5

NaOC3H7-n n-propylbenzene

93.4

4-2

C3H7-n

NaOC2Hs p-cymene

95.2

4-3

C3H7-iso

NaOC2Hs

Ethyl toluene

97.4

4-4

C4H9-n

NaOC2H5

Mesitylene

96.3

4-5

C4H9-sec.

NaOC2H5

Di-n-butyl ether

95.0

4-6

C4H9-so

NaOC2Hs n-Cymol

93.2

4-7

C4H9 tert

NaOC2H5

Di-n-amyl ether

94.6

4-8

C4Hy-tert

KOC3H7-i

2,3-dichlorotoluene

97.0

4-101

ch3

NaOCH3

benzene

39.3

4-102

c2h5

NaOC2H5

benzene

April 31

4-103

c2h5

NaOC2Hs

toluene

38.6

4-104

c2hs

NaOC2Hs

DMF

10.2

4-105

c2h5

NaOC2Hs

DMSO

24.3

4-106

c2hs

NaOC2Hs

-

58.2

Remarks:

1. In experiment Nos. 4-101 and 102, the reaction was carried out by azeotropically distilling off the alcohol formed during the reaction together with the benzene used as solvent under reflux conditions.

2. In Experiment No. 4-101, N-methyl-3'-isopropyl-2-methylbenzanilide was formed as a by-product in an amount of about 30%.

3. No by-product was formed in Experiment No. 4-102.

4. In experiment No. 4-103, the ethyl alcohol formed during the reaction was azeotropically distilled off under reflux conditions together with the toluene used as solvent.

5. In Experiment Nos. 4-104 and 4-105, the reaction was carried out at 130 ° C and formamidine was formed as a by-product.

6. In experiment No. 4-106, the reaction was carried out at 170 ° C. without solvent. A small amount of a polymer is formed as a by-product.

Example 5

whose solvent is reacted, the corresponding according to the procedure of Example 1 being different

2-substituted benzanilides can be obtained. The results 2-substituted alkyl benzoates and various aniline compounds are shown in Table 3. 45 fertilize in the presence of various alcoholates and various

Table 3

(ih)

Reaction conditions:

Experiment benzoate aniline alcoholate solvent reaction

No. (1) (11) (quantity) temperature (c C)

x = ch2

y = h

NaOC2Hs p-xylene

130

R = C2Hs

(20%)

18.1g

9.3 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

X = c2hs y = h

NaOC2hs p-Cymol

150

r = C4H9- (iso)

(20%)

22.7 g

9.3 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

7 619 925

Table 3 (continued)

\ request

Benzoate

aniline

Alcoholate

solvent

Reaction

No.

(i)

(ii)

(Amount)

temperature ("C)

5-3

X = C3H7- (iso)

y = h

NaOC2H5

p-xylene

130

R = C4H9- (tert)

(20%)

24.2 g

9.3 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-4

x = ch3

y = och3

NaOC3H7

o-Cymol

150

R = n-C3H7

(meta)

(20%)

19.6 g

12.3 g

45.1 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-5

x = ch3

y = OC3h7

NaOC2Hs p-xylene

130

R = C4H9- (sec.)

(para)

(20%)

21.1 g

15.1g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-6

x = ch3

y = OC4h9- (sec.)

NaOi-C3H7

p-cymene

150

R = C3H7- (iso)

(meta)

(10%)

22.7 g

16.5 g

90.3 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-7

X = CH3

Y = OC4H9- (n)

NaOC2H5

Chlorobenzene

125

r = c, h5

(meta)

(20%)

18.1g

16.5 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-8

x = ch3

Y = OC5H11- (sec.)

NaOC2H5

Ethylbenzene

130

r = c2hs

(meta)

(20%) "

18.1g

17.9g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-9

x = ch3

Y = OCH2 • Ph

NaOC2Hs

Mesitylene

150

r = c2hs

(meta)

(20%)

18.1g

19.9 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-10

x = ch3

Y = OCH2PhCl- (o)

NaOC2H5

Chlorobenzene

125

r = c2h5

(meta)

(20%)

18.1g

23.3 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-11

X = C1

Y = C3H7- (iso)

NaOC2H5

p-xylene

130

r = c2h5

(meta)

(20% ■)

20.3 g

15.1g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

attempt

benzene

aniline

Alcoholate

solvent

Reaction

No.

(1)

(11)

(Amount)

temperature (G C)

5-12

X = Br y = oc2h5

NaOC2H5

p-xylene

130

R = n-C3H7

(meta)

(20%)

31.9g

13.7 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-13

X = 1

Y = C3H7- (iso)

NaOC2H5

p-xylene

130

R = C2Hs

(meta)

(20%)

30.4 g

13.5 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-14

X = 1

Y = OC4H9- (sec.)

NaOC2H5

p-xylene

130

R = c2h5

(meta)

(20%)

30.4 g

16.5 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-15

X = I

Y = H

NaOC2Hs

Cumene

140

R = C3H7- (n)

(20%)

31.9g

9.3 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-16

x = ch3

y = ch3

NaOC2H5

p-xylene

130

RC2Hs

(meta)

(20%)

18.1 g

10.7 g

37.4 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

5-17

x = ch3

Y = C3H7- (iso)

NaOC3H7- (iso)

Ethylbenzene

130

R = C3H7- (ìso)

(meta)

(10%)

19.6 g

13.5 g

90.3 g

(0.11 mol)

(0.1 mol)

(0.11 mol)

619 925

Table 3 (continued) Products (III)

attempt

product

amount

yield

Melting point

Crystals

No.

(G)

(%)

r c)

5-1

x = ch3

19.5

92.4

125-126

White dust

Y = h

5-2

x = C2Hs

20.4

90.7

141-142

White dust

Y = h

5-3

x = C3h7- (iso)

20.3

84.9

135-136

White dust

y = h

5-4

x = ch3

22.3

92.1

74-75

white prisms

-Q

y = och3

(meta) 5-5 X = CH3

Y = OC3H7 (para)

5-6 X = CH3

Y = C4H9- (sec.) (Meta)

5-7 X = CH3

Y = OC4H9- (n) (meta)

5-8 X = CH3

Y = OCsH "- (sec.) (Meta)

5-9 X = CH3

y = och2-

(meta)

5-10 X = CH3 Cy_v y = och2 - // _ m (meta) V »

5-11 X = C1

= OC3H7- (iso) (meta)

5-12 X = Br

Y = OC2Hs (meta)

5-13 X = I

Y = C3H7- (iso) (meta)

5_14 X = I

Y = OC4H9- (sec) (meta)

5-15 X = I

Y = H 5-16 X = CH3

Y = CH3 (meta) 5-17 X = CH,

Y = C3H7- (iso) (meta)

25.7

26.3

27.4 27.7 28.3

31.0 26.9 29.2 35.2

36.0

29.1 20.9 23.9

95.5 92.9 96.8 93.3 89.3

88.1

92.8 91.3 96.5 91.1

90.1

92.9 94.5

151-152

75-77

87

70-73

114-115

115-116

/b.p.

i 173-175 ° C / \ 0.007 mmHg. 114-115

112-113

86-87

144-145 138 70-71

white powder white needles gray needles pale brown white needles white needles pale yellow oil white needles pale brown solid white needles white needles white needles white needles

The following typical compounds were prepared according to the above procedures. The connection numbers are used in the text below.

\ Connection No. 1

2'-methoxy-2-methylbenzanilide white prisms F-p. 74-75 C.

Connection No. 2

3'-methoxy-2-methylbenzanilide fine white prisms mp 142-143 ° C

60

Compound No. 3

4'-methoxy-2-methylbenzanilide white needles mp 136-137 ° C

Compound No. 4

2'-ethoxy-2-methylbenzanilide clear reddish oil Boiling point 148 ° C / 0.04 mmHg

65 Compound No. 5

3'-ethoxy-2-methylbenzanilide white needles mp 115-116 "C.

Compound No. 6

4'-ethoxy-2-methylbenzanilide white needles mp 149-149.5 ° C

Compound No. 7

2'-iso-propoxy-2-methylbenzanilide clear reddish brown oil Boiling point 143-145 ° C / 0, Ol mmHg

Compound No. 8

3'-iso-propoxy-2-methylbenzanilide white prisms mp 92 ° C

Compound No. 9

4'-n-Propoxy-2-methylbenzanilide powdery white crystals mp 151-152 ° C

Compound No. 10

3'-n-pentyloxy-2-methylbenzanilide white needles mp 90 ° C

Compound No. 11

3 '-Octyloxy-2-methylbenzanilide white needles mp 95 ° C

Compound No. 12

3'-n-Dodecyloxy-2-methylbenzanilide powdery white crystals mp 65-66 ° C

Compound No. 13

2'-Allyloxy-2-methylbenzanilide pale reddish brown oil mp 151 ° C / 0.025 mmHg

Compound No. 14

3'-Allyloxy-2-methylbenzaniIid powdery white crystals mp 85-89 ° C

Compound No. 15

3'-propargyloxy-2-methylbenzanilide fine white powder, mp. 93-95 '° C

Compound No. 16

3'-benzyloxy-2-methylbenzanilide white needles mp 114-115 ° C

Compound No. 17

3'-2-chlorobenzyloxy-2-methylbenzanilide fine white needles mp 116 ° C

Compound No. 18

3'-n-propoxy-2-methylbenzanilide white prisms mp 92-93 ° C

Compound No. 19

2'-sec-butoxy-2-methylbenzanilide, white needles, mp. 75-77 ° C.

619 925

Compound No. 20

3'-n-butoxy-2-methylbenzanilide gray needles mp 87 ° C

Compound No. 21

3'-methyl-2-chlorobenzanilide, white needles, mp. 124 ° C.

Compound No. 22

3'-methoxy-2-chlorobenzanilide white needles mp 143-144 ° C

Compound No. 23

3'-ethoxy-2-chlorobenzanilide needles

Mp 105-106 ° C

Compound No. 24

3'-n-propoxy-2-chlorobenzanilide pale yellow oil

Boiling point 172-175 ° C / 0.02 mmHg

Compound No. 25

3'-Isopropoxy-2-chlorobenzanilide pale yellow oil

Boiling point 173-175 ° C / 0.007 mmHg

Compound No. 26

3'-methoxy-2-bromobenzaniide white needles, mp. 162-164 ° C

Compound No. 27

3'-ethoxy-2-bromobenzanilide white needles mp 114-115 ° C

Compound No. 28

3'-isopropoxy-2-bromobenzanilide white prisms, mp. 89-91 ° C.

Compound No. 29

3'-isopropyl-2-bromobenzaniide white needles mp 79-80 ° C

Compound No. 30

3'-methyl-2-iodobenzanilide, white needles, mp. 164-165.5 ° C

Compound No. 31

3'-ethyl-2-iodobenzanilide white crystals mp 153-155 ° C

Compound No. 32

3'-isopropyl-2-iodobenzanilide pale brown needles mp 112-113 ° C

Compound No. 33

3 'methoxy-2-iodobenzanilide white needles mp 154-155.5 ° C

9

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

619 925

10th

\ Connection No. 34

3'-ethoxy-2-iodobenzanilide, white needles, mp. 126-128 ° C

Compound No. 35

3'-n-propoxy-2-iodobenzanilide white needles mp 114-115 ° C

Compound No. 36

3'-Isopropoxy-2-iodobenzanilide white prisms, mp 94-96 ° C

Compound No. 37

3'-n-butoxy-2-iodobenzanilide white needles mp 102-105 ° C

Compound No. 38

3'-isobutoxy-2-iodobenzanilide white needles

Mp 139.5-141.5 ° C

Compound No. 39

3'-sec-butoxy-2-iodobenzanilide white needles mp 86-87 ° C

Compound No. 40

3'-n-pentyloxy-2-iodobenzanilide white crystals mp 115-118 ° C

Compound No. 41

3'-n-Hexyloxy-2-iodobenzanilide white crystals mp 112.5-113.5 ° C

Compound No. 42

3'-methyl-2-nitrobenzanilide pale brown prisms, mp. 145-147 ° C

Compound No. 43

3'-methoxy-2-nitrobenzanilide pale yellow needles mp 155-157 ° C

Compound No. 44

3'-methyl-2-methylbenzanilide, white needles, mp. 138 ° C.

25th

30th

35

40

Compound No. 45

3'-ethyl-2-methylbenzanilide white needles mp 114-117 ° C

Compound No. 46

3'-isopropyl-2-methylbenzanilide white needles mp 70-71 ° C

Compound No. 47

3'-tert-butyl-2-methylbenzanilide yellow oil

Boiling point 181-186 ° C / 0.04-0.06 mmHg

Compound No. 48

3'-tert-pentyl-2-methylbenzanilide white crystals mp 68-71 ° C.

Test trials

Efficacy against rice sheath disease

Porcelain pots with a diameter of 9 cm are filled with soil from a rice field. Then you add water to the pot to simulate the conditions of a rice field. In each pot, 9 plants are planted in groups of 3 plants (strong seedlings Oryza sativa L. var. Kinmaze) and cultivated. As soon as the seedlings have reached the required stage, a wettable powder * of predetermined concentration in a quantity of 15 ml per pot is sprayed on. Rice sheath pathogens (Pellicuralia Sasakii) are cultivated on potato-saccharo-se agar medium and inoculated into the leaf sheaths.

After vaccination, the rice plants are placed in a high humidity chamber (25-30 ° C) and the length of the injuries to the leaf sheath areas is measured after 10 days. The following table shows the results for 3 pots per test.

Protection value (%) = 1 -

45

Total length of injuries to the treated plants Total length of injuries to the untreated plants x 100

Comment:

50

Preparation of the wettable powder One of the compounds (50%), diatomaceous earth (45%), sodium dinaphthyl methanesulfonate (2%) and sodium lignosulfonate (3%) are mixed and ground uniformly to form a wettable powder.

Table 4

Active ingredient

Concentration (ppra)

Total length d. injured areas (cm)

Protection value

(%)

Phytotoxicity (former damage)

Compound No. 1

2nd

3rd

4th

5

6

500 500 500 500 500 500

14.2 4.5 32.5 4.3 0 42.5

95.5

98.6 89.6 98.6

100 86.4

none none none none none none

11

619 925

Table 4 (continued)

Active ingredient

concentration

overall length

Protection value

Phytotoxicity

(ppm)

d. injured areas (cm)

CO

(former damage)

7

500

1.4

99.6

no

8th

500

0

100

no

9

500

24.5

92.1

no

10th

500

4.5

98.6

no

11

500

14.3

95.5

no

12

500

42.5

86.4

no

13

500

3.2

99.0

no

14

500

0

100

no

15

500

0

100

no

16

500

0

100

no

17th

500

12.5

96.0

no

18th

500

0

100

no

19th

500

0

100

no

20th

500

4.3

98.6

no

21st

100

127.9

72.3

no

22

100

138.1

70.1

no

23

100

72.5

84.3

no

24th

100

17.5

96.2

no

25th

100

0

100

no

26

100

76.2

83.5

no

27th

100

45.7

90.1

no

28

100

0

100

no

29

100

0

100

no

30th

100

62.3

86.5

no

31

100

26.3

94.3

no

32

100

0

100

no

33

100

86.8

81.2

no

34

100

40.6

91.2

no

35

100

0

100

no

36

100

0

100

no

37

100

0

100

no

38

100

0

100

no

39

100

0

100

no

40

100

0

100

no

41

100

0

100

no

42

100

109.4

76.3

no

43

100

136.7

70.4

no

44

100

92.3

80.0

no

45

100

49.9

89.2

no

46

100

0

100

no

47

100

0

100

no

48

100

0

100

no

Neo-asocin solution *

32.5

38.8

91.6

none not dealt with

-

461.7

0

no

Comment:

* Neo-asocine (trademark): iron III ammonium salt of methanarsonic acids: effective concentration 6.5 <7c.

s

Claims (9)

619 925 2nd PATENT CLAIMS 1. Process for the preparation of 2-substituted benzanides of the formula // C - NH— [III] wherein X represents a halogen atom or a lower alkyl group, and wherein Y represents a hydrogen atom, an alkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a benzyloxy group or a halobenzyloxy group by reacting an alkyl-2-alkylbenzoate Formula characterized in that the reaction is carried out at 100 to 200 ° C. 6. The method according to claim 5, characterized in that one carries out the reaction at 120 to 150 ° C. 5 7. The method according to any one of claims 1 to 6, characterized in that one selects a molar ratio of the alkyl-2-aI-kylbenzoate (I) to aniline (II) in the range from 0.9 to 1.5. 8. The method according to any one of claims 1 to 7, characterized in that one selects a molar ratio of the alcoholate io to the aniline (II) in the range from 0.9 to 2.0. 9. The method according to any one of claims 1 to 8, characterized in that a 2-substituted benzanilide of the formula [I] where R represents an alkyl group with an aniline of the formula /} \\ ^ Y H2N 15 [II] in the presence of an alcoholate in an organic solvent, characterized in that one uses an alkyl 2-alkyl-benzoate, in which R represents a C2-4 alkyl group and carries out the reaction in an organic solvent which with the alcohol formed as a by-product is difficult to distill azeotropically. 2. The method according to claim 1, characterized in that an alkali metal alcoholate or alkaline earth metal alcoholate having 2 to 4 carbon atoms is used as the alcoholate, and that a compound of the formula or R4 - O - Rcj, where Rj represents a lower alkyl group or a halogen atom, and wherein R2 or R3 represents a hydrogen atom or a halogen atom or a lower alkyl group, and wherein R4 or Rs represent an alkyl group having more than 5 carbon atoms. 3. The method according to any one of claims 1 or 2, characterized in that a solvent is used which is not azeotropic with the alcohol formed in the reaction. 4. The method according to any one of claims 1 to 3, characterized in that an ethylate, n- or isopropylate, n-, iso-, sec- or tert-butoxide of sodium or potassium is used as the alcoholate, and that as solvent o-, m-, p-xylene, ethylbenzene, propylbenzene, isopropylbenzene, o-, m-, p-cymene, trimethylbenzene, n- or iso-butylbenzene, amylbenzene, o-, m- or p-chlorotoluene , 2,4-, 2,5-, 2,6- or 3,4-dichlorotoluene, chlorobenzene, o-, m-, p-dichlorobenzene, n- or iso-dibutyl ether or n- or iso-amyl ether . 5. The method according to any one of claims 1 to 4, characterized CONH 20, where x is iodine or methyl and where Y is an alkyl group or alkoxy group. 10. The method according to claim 9, characterized in that Y represents a branched alkyl group or alkoxy group. 11. The method according to claim 10, characterized in that Y is the isopropyl group, the sec-butyl group, the isoprop-oxy group, the isobutoxy group, the sec-butoxy group, the tert-butoxy group, the isopentyloxy group or the sec-pentyloxy group . 30th