HU184738B - Plant growth regulating compositions containing alfa-amino-acet anilide derivatives and process for the preparation of alfa-amino-acetanilide derivatives - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to plant growth regulators comprising the aminoacetanilide derivatives of formula (I) and to the preparation of O-aminoacetanilides of formula (I). Wherein R1 is hydrogen or halogen, nitro, alkyl or alkoxy, R2 is hydrogen or halogen, or alkyl, R3 is hydrogen or halogen or alkyl, R5 is alkyl, alkenyl or phenylalkyl; the alkylene group attached to the aromatic ring, - R5 alkyl, alkenyl, or alkynyl, R6 and R7 alkyl, or - (CHnL1 - optionally substituted Tenet, - X halogen ion. The agents of the present invention are a narrower group of compounds of formula I) contains active substance, in amounts of 0.1 to 95%.

Description

The present invention relates to plant growth regulators containing quaternary ammonium salts of a-aminoacetanil derivatives derived from secondary anilines, and to a process for the preparation of a-aminoacetanilide derivatives.

Agents containing the quaternary ammonium salts of a-aminoacetanilide derivatives of the general formula (III) derived from primary anilines are known to influence plant development (German Patent Publication No. 2627728).

It is also known that in the aryl ureas, anilides and N-aryl carbamates which inhibit photosynthesis, the ArNHCOR group plays an important role. The substitution of the primary aniline derivatives with alkyl (Ar-N; structure) for biological biological activity. reduces or abolishes (A. Barth and H.J. Michel, Pharmazie 24, 11-23 (1969), ND Camper and DE Moreland, Biochim. Biophys. Acta 94, 383 (9965), N.E. Good, Plant Physiology 36,788 / 1961). /).

Contrary to the known data, it has been found that agents containing the quaternary ammonium salts of the GLaminoacetanilide derivatives of the general formula (I) derived from secondary anilines have an effect on plant growth and their action on plant growth is described in German Patent Publication No. 26,572,728. It is superior to agents containing the primary aniline derivatives of formula III.

In the general formula (I)

- R ^{1 is} hydrogen, halogen, nitro,

C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

- R ^{2 is} hydrogen, halogen or C 1 -C 4 alkyl,

- R ^{3 is} hydrogen or halogen,

- R ^{4 is a C} 14 alkyl group, a C 24 alkenyl group, a phenyl C 14 alkyl group or a C 24 alkylene group ortho to the aromatic ring,

- R ^{5 is C} 1-6 alkyl. C 24 alkenyl or C 24 alkynyl,

- R ⁴ and R ⁷ are independently C 14 alkyl, or

- R ^S and R ⁷ together are - _{(CH2) n} - group with n = 4, 5 or 6, - optionally substituted by C1-4 alkyl or hydroxy substituted, and may contain one double bond, and which may be interrupted by oxygen,

- X represents a halide ion.

The plant growth regulators of the present invention contain from 0.1 to 95% by weight of a compound of formula (I)

R ^{1 is} halogen or C 14 alkyl,

- R ^{2 is} hydrogen, halogen or C 14 alkyl,

- R ^{3 is} hydrogen or halogen,

- R ^{4 is C} 14 alkyl, C 24 alkenyl or phenyl (C 1 -C 2 alkyl),

- R ^{s is C} 14 alkyl or C 24 alkenyl,

- R * and R ⁷ are independently C 14 alkyl, or

- R * and R ⁷ together are - _(CH?) - forms a group - n is 4, 5 or 6, and /

- X represents a halide ion.

Halogen in the various symbols is, for example, bromine, chlorine or fluorine, alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl or isobutyl, alkoxy is, for example, methoxy, ethoxy, propoxy, such as isopropoxyl or butyloxy, phenylalkyl may be benzyl, alkenyl may be vinyl, allyl or propenyl.

When R @ ⁷ and R @ ⁷ form together - (C 1-6 -), together with the nitrogen atom to which they are attached, a heterocyclic ring forms, for example, a pyrrolidine, piperidine, hexamethyleneimine ring and a double bond, and may contain an oxygen atom such as 1,2,5,6-tetrahydropyridyl or morpholyl, said heterocyclic groups being optionally substituted with C14 alkyl or hydroxyl.

X is preferably chloride or bromide.

The α-aminoacetanilide derivatives of formula I can be used as active ingredients of plant growth regulators.

Plant growth regulators can exert a variety of effects on plants. The effect of the agents essentially depends on the time of application and the amount of active ingredient applied to the plants and the mode of application. In all cases, plant growth regulators should favorably influence the development of crop plants.

For example, plant growth regulators may inhibit vegetative growth of plants. The inhibitory effect of this type of growth is of economic importance for, among other things, grasses, because by reducing the growth of grass, for example in ornamental gardens, parks, sports grounds and roadside benches, the number of lawn mowers required can be reduced. It has a role in inhibiting the growth of dry and woody plants on roadside edges and near power lines or, more generally, in areas where dense vegetation is undesirable.

An important area of application of plant growth regulators is to inhibit the growth of cereals, since the reduction of stem length prevents, or at least reduces, the incline of the plants before harvest. Growth regulators may also cause the stalk of the grain to become stronger.

Inhibition of vegetative development results in denser growth than many crop plants, thus increasing the amount of crop per unit area.

Crop growth induced by plant growth regulators is based on the fact that nutrients are more conducive to flower and fruit development while vegetative development is reduced.

Vegetable growth regulators can often stimulate vegetative development. This is useful when vegetative parts of plants are harvested. Increasing vegetative development can simultaneously stimulate generative development, such as producing more or more fruit.

The amount of the crop can often be increased by interfering with the metabolism of the plant without appreciably altering vegetative development. Growth regulators can also change the composition of plants, resulting in better quality of the harvested crop. For example, it is possible to increase the sugar content of sugar beet, cane, pineapple and citrus fruits or to increase the protein content of soy or grain.

Plant growth regulators can produce seedless fruits and affect the sex of the flowers.

Growth regulators may favorably influence the formation or recovery of secondary plant products, for example by increasing latex formation on rubber trees.

As plants grow, growth regulators can promote branching shoots by chemically affecting buds. This may be important, for example, when folding with cuttings. The development of side shoots can also be inhibited, for example in tobacco plants, the formation of side shoots can be suppressed, thereby increasing leaf development.

Under the influence of plant growth regulators, the foliage of plants can be influenced by leaving the leaves of the plants at the desired time. This type of decontamination can be significant to facilitate mechanical harvesting, for example in grapes or cotton or to reduce evaporation when planting plants.

The use of plant growth regulators can prevent early fruit loss, but it is also possible to increase fruit loss, for example in orchards, to some extent. Growth regulators can also be used to reduce the power needed to harvest the crop at the time of harvest by weakening the stem, thereby enabling mechanized harvesting of plants and facilitating manual harvesting.

Growth regulators can accelerate or delay the ripening of the crop and place the ripening time before or after the harvest. This is particularly important as the harvest can be regulated according to the needs of the market. Growth regulators can often improve the color of the fruit and ripen at a given time. This creates the condition that, for example, tobacco, tomato or coffee can be fully mechanized or manually harvested at the same time.

The use of plant growth regulators can influence the dormant period of plant seeds and buds, i.e. the endogenous rhythm of the year, so that plants, such as pineapple or horticultural ornamental plants, germinate, shoot or bloom at a time when they are not otherwise prone.

Plant growth regulators also help to delay bud sprouting or seed germination, such as reducing frost damage in spring in frost-prone areas.

Growth regulators can also increase the salt tolerance of crop plants, thus creating the possibility that crops can be cultivated on saline soils.

Growth regulators can increase the frost resistance and drought tolerance of plants.

The preparation of the amino-acetanilide derivatives of formula (I) is illustrated in Scheme (A).

The secondary aniline derivative of formula (V) is reacted with an o-halogenocarboxylic acid halide of formula (VI) - X halogen - to produce an alpha-halocarboxylic acid anilide of formula (VII) (Houben-Weyl, Vol. 11/2) Page 35). The anhaloCarboxylic anilide of Formula VII is converted to the a-aminoacetanflide derivative of Formula IIA with a substituted secondary amine of Formula VIII and quaternized with an alkylating agent of Formula IX to form a compound of Formula I. The ammonium salts of formula (I) may also be prepared directly by reaction of the α-halogenocarboxylic anilide of formula (VII) with the tertiary amine of formula (X).

The aniline of formula (V) is, for example, N-methylaniline, N-methylaniline, N-propylaniline, 4-chloro-N-methylaniline, 2,4-dichloro-N-methylaniline, 4-chloro- 2,6-dimethylaniline, N-allyl-4-chloro-2-methylaniline, 4-chloro-N-ethyl-2-methylaniline, 4-chloro-2-methyl-N-propylaniline, 4-chloro-2-methyl-N-propargyl aniline, 3-chloro-4-fluoro-N-methylaniline, 3,4-difluoro-N-methylaniline, 3-methoxy-N-methylaniline, N-methyl-3-nitroaniline, 3-ethyl-5,8-dimethylaniline,

3-isopropyl-N-methylaniline, 4-fluoro-3,5,8-dimethylaniline,

2.4-djfluoro-N-methylaniline, 4-fluoro-3N-dimethylaniline,

3-Chloro-N-methylaniline can be used.

The halogen carboxylic acid halide of formula (VI) may be, for example, o-chloroacetyl chloride or α-bromoacetyl bromide.

Examples of secondary amines of formula (VIII) are ptrrolidine, piperidine, hexamethylene amine, morpholine,

3,5-dimethylmorpholine, diethylamine, dipropylamine, 1,2,3,6-tetrahydropyrimidine, 3-hydroxypiperidine, 3,5-dimethylpiperidine, 3-methylpiperidine, 4-methylpiperidine,

4-hydroxypiperidine, 2,6-dimethylmorpholine.

Suitable quaternizing agents of formula IX include methyl bromide, bromoethane, bromopropane, bromobutane, 3-methyl bromobutane, allyl bromide, crotyl bromide, propargyl bromide.

Examples of tertiary amines of formula (X) include N-methylpyrrolidine, N-ethylpyrrolidine, N-propylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-propylpiperidine, N-methylmorpholine. .

The reaction of the compound of formula IX can be carried out, for example, at a temperature of from 10 to 150 ° C, optionally in the presence of a solvent such as ethanol, methanol, chloroform, methylene chloride, acetonitrile, dimethylformamide or ethyl acetate at atmospheric pressure or above atmospheric pressure. .

The compound of formula (IX) is used in an excess of from 10 to 100% by weight, based on the stoichiometric amount of the compound of formula (IIA).

The reaction of a compound of formula VII with a compound of formula X is carried out, for example, at a temperature of from 10 to 150 ° C, optionally in the presence of a solvent.

e.g. ethanol, methanol, chloroform, methylene chloride, acetonitrile, dimethylformamide or ethyl acetate -31

184,738, at atmospheric pressure or higher.

The compound of formula (X) is reacted in an excess of 10 to 100% by weight relative to the stoichiometric amount of compound of formula (VII).

In the following Examples A and B, the starting compounds, Examples 1-4. Examples 1 to 6 describe in detail the preparation of compounds of formula (I).

Example A)

Preparation of the halocarboxylic acid anilides of formula VII

To a solution of N-chloroacetyl-N-methyl-4-chloro-2-methylaniline (Compound AO) in g of N-methyl4-chloro-2-methylaniline in 150 ml of acetone was added 44 g of sodium acetate in 200 ml of water, followed by 56 g of chloroacetyl chloride are added dropwise over 3 hours. Below 35 ^o C during the reaction temperature. After stirring at room temperature for 2 hours, the reaction mixture was cooled to 5-1 ° C by the addition of 200 ml of ice-water, the product was filtered off with suction, washed with water and dried at 60 ° C under vacuum. Yield 85 g. M.p. 85-87 ° C.

Example B)

Preparation of α-aminoacetanilides of formula II

N-acetyl-N-pyrrolidino-methyl-4-chloro-2-methylaniline

(Compound Al)

To a solution of 46.4 g of N-chloroacetyl-N-methyl-4-chloro-2-methylaniline in 300 ml of ethanol was added 42.6 g of pyrrolidine. After stirring for 3 hours at room temperature, the ethanol was evaporated, the residue obtained was dissolved in ether / water, the aqueous phase was extracted several times with ether, the combined organic phases were washed with water and dried over sodium sulfate. the ether is evaporated. The product crystallizes upon trituration with n-pentane. The product crystallizes upon trituration with n-pentane. Yield 46 g. Melting point: 59 ° C.

In a similar manner, compounds of formula (IIB) and II (Table II) may be prepared. o-aminoacetanilides of formula XI as shown in Table II.

Table H. Compounds of formula XI

A38 H <CHj) - <ch ₂ ) ₂ - A39 H <CH ₂ ) - <CH2) ₂ - A4O H <CH ₂ ) ₄ - • <CH ₂ ) 3- A41 H <CH ₂ ) ₅ - ( ^CH 2 ^ 3 ' A42 Cl <CH ₂ ) ₄ - ÍCHjk- A43 Cl <CH ₂ ) ₄ - ^ ^CH 2b ' A44 Br <CH ₂ ) ₄ - - (CH ₂ ) ₂ - A45 Br <CH ₂ ) ₄ - ^4CH 2? 3 ·

(IB)

Table I

Row- song R ¹ R ² R ³ R ⁴ R ⁷ R ⁶ al 2-CH q 4-C1 H ch ₃ • CCH ₂ ) 4 · THE 2 2-CH ₃ 4-a ¹ H ch ₃ "( ^CH 2 ^ 5 ' THE 3 3-Cro H H ch ₃ A4 4-F 3-C1 H ch ₃ <ch ₂ ) ₄ - A5 3-CH ₃ H H ch ₃ <ch ₂ ) ₅ - A6 2-F 4-F H ch ₃ <ch ₂ ) ₄ - A7 3-OCH ₃ H H ch ₃ - (CH ₇ ) ₄ - A8 2-NO ₂ H H ch ₃ <ch ₂ ) ₄ - A9 3-C ₂ H _s 5-CH H ch ₃ A10 3-isopropyl H H ch ₃ - <ch ₂ ) ₄ . All 3-CH ₃ 3-F H ch ₃ <ch _? ) ₄ - A12 4-C1 H H ch ₃ < ^CH 2> 4- A13 3- ^C 2 ^H 5 5-CH H ch ₃ «Γ AL4 3- ^C 2 ^H s 5-CH ₃ H ch ₃ Al 5 ^3C 2 ^H 5 5 € H ₃ H CHG <ch ₂ ) ₅ - A16 2-F 4-F H ch ₃ <ch ₂ ) ₅ - A17 4-C1 H H ch ₃ ( ^CH 2 ^ 5 '

M.p.

59 ^Ü C oil

184,738

A15 3-OCH H H CH A16 2-F 4-F H ch ₃ A17 4-C1 H rf CH A18 3-NO ₂ H H ch ₃ A19 3-CH ₃ 4-F H ch ₃ A20 3-isopropyl H H ch ₃ A21 ^2CH 3 4-C1 H ch ₃ A22 2- ^ch 3 4-C1 H CH A23 2-CH 4-C1 H ch ₃ A24 4-F ^J 3-CH ₃ H ch ₃ A25 2-CH ₃ 4-C1 H allyl A26 2-CH ₃ 4-C1 H ch ₃ A27 2- ^ch 3 4-C1 H ch. A28 2-CH 4-C1 H ch ₃ A29 4-Br H H ch. A30 H H H ch ₃ A31 2-C1 4-C1 6-a ch ₃ A32 2-C1 3-a 4-a ch. A33 2-CH ₃ 4-a 5-a ch ₃ A34 2-CH ₃ 4-a H C, H A35 2-CH ₃ 4-a H n-Pr <5pil A36 2-CH ₃ 4-a H propargyl A37 2-CH ₃ 4-Cl H isopropyl

< _CH2 ) _r <ch ₂ ) ₅ <ch ₂ ) ₅ < ^ch 2) ₅ <ch ₂ ) _s <CH ₂ ) 5-ch ₂ Uch ₃ (ch ₂ ) ₃ propyl propyl (ch ₂ ) ₆ (ch ₂ ). ₄ ethyl ethyl ./(ch _{2) 2/2,} p <CH C'HCH,), O _{<CH2) 4} <W 4 · <V _{CH2 <CH2) 4 <CH2) 4 <CH2) 4} <ch ₂ ) ₄ <ch ₂ ) ₄ .

Example 1

N- (2- (4-Chloro-2-methyl-N-methylanflino-2-oxo) -ethyl-N-allylpyrrolidinium bromide g N-pyrrolidinoacetyl-N-methyl-4-chloro- A solution of 2-methylaniline and 42 g of 1-bromopropene-2 in 200 ml of ethyl acetate was refluxed for 4 hours, after cooling, the precipitated product was filtered off with suction, washed with ethyl acetate and dried. 173-175 ° C.

Example 2

N- (2- / 4-Chloro-2-methyl-N-methylanilino) -2-oxo) ethyl-N-ethylpyrrolidinium lumium bromide g N-pyrrolidinoacetyl-N-methyl-4-chloro- A solution of 2-methylaniline and 15.9 g of ethyl bromide in 200 ml of acetonitrile was stirred at room temperature for 14 hours and then concentrated. The crystalline residue was triturated with ether, filtered off with suction and dried. Yield 25. g. 179-181 ° C.

Example 3

N- (2- (4-Chloro-2-methyl-N-methylanilino) -2-oxo) ethyl-N-methylpiperidinium chloride

To a solution of 46.4 g of N-chloroacetyl-N-methyl-4-chloro-2-methylaniline in 150 ml of acetonitrile was added dropwise 40 g of N-methyl plperidine. Meanwhile, the temperature of the reaction mixture was maintained below 25 ° C. After 14 hours, the precipitated product was washed with ether and dried. Yield 52 g. Melting point above 230 ° C.

4Q Example 4

N- (2- (4-Chloro-2-methyl-N-methylanilino / -2-oxo) ethyl-N-methylpyrrolidipium bromide g bromomethyl and 30 g N-pyrrolidinoacetyl N- A solution of methyl 4-chloro-2-methylaniline in acetone (300 ml) was stirred at room temperature for 14 hours. The precipitated product is filtered off with suction, washed with ether and dried. Yield: 37 g. M.p. 157 ° C.

It may be prepared analogously to the preceding example. III. Compounds of formula (I) shown in Table II and Table IV. Compounds of formula (XII) in Table I below and compounds of formula (I) in Table V.

_ © (I)

III. t ABLE Row- song R ¹ R ² R ³ R ⁴ R ³ R ^R R ^Z X 1 2-CH ₃ Τ <3 H CH? ΑΐΙΠ ~ W ₂ ) ₄ - Br 2 2-CH 4-d H CH? allyl <ch ₂ ) ₅ - Br 33-CFj H H ch ₃ allyl Br 4 4-F 3-C1 H CH? Allyl <ch ₂ ) ₄ - Br 5 3-CF ₃ H H ch ₃ · allyl Br 6 2-F 4-F H CH? AUU - (0¾) - Br 7 3-OCH ₃ H H ch ₃ allyl <ch ₂ ) ₄ . Br 8 3-NO ₂ H H ch ₃ allyl <ch ₂ ) ₄ - Br 9 CJH-3 ,. 5-CH ₃ H ch ₃ allyl <ch ₂ ) ₄ - Br 10 3-isopropyl H H ch ₃ allyl w ₄ - Br 11 3-CH ₃ 4-F H ch ₃ allyl <ch ₂ ) ₄ - Br 12 4-C1 H H CH? allyl {ch ₂ ) ₅ - Br 13 3-C ₂ ^h s 5-CH ₃ H ch ₃ allyl Br. 14 3-C ₉ H, 5-CH Η, CH? allyl <ch ₂ ) ₆ Br 15 3-OCH H ³ H CH? allyl <ch ₂ ) ₅ - Br 16 2-F * 4-F H CH? allyl <ch ₂ ) ₅ Br 17 4-d H H CH? allyl - (ch ₂ ) ₅ - Br 18 3-NO ₂ H H ch ₃ Allyl <ch ₂ ) - Br 19 3- ^CH 3 4-F H CH? allyl ÍC ^h 2) ₅ - Br 20 3-iso-propyl H H CH? AUU <ch ₂ ) ₅ . Br 21 2-CH 4-d H CH? Allyl -ích ₂ ) ₆ - Br 22 2-CH ₃ 4-d H CH? crotyl <CHX Br 23 2-CH ₃ 4-d H ch ₃ Allyl -CH.CHCH. · -ÍCH λ - Br 24 2-CH ₃ 4-d H CH? AUU Propu PropÜ Br 25 2-CH ₃ 4-d H ch ₃ propargyl w ₄ bt 26 27 2-CH 4-F 4-C1 3-CH H H CHj ch ₃ CH Allyl <ch ₂ ) ₄ - <ch ₂ V Br Br 28 2-CH ₃ 4-σ H allyl AUU '(CH ₂ ? ₄ . Br 29 2-CH 4-d H CH? ETU <ch ₂ Í- Br 30 2-CH ₃ 4-d H ch ₃ propyl <αζ) ₄ . Br 31 2-CH ₃ 4-d H CH? butyl <ch ₂ ) ₄ . Br 32 2-CH ₃ 4-d H CH? ETU EtU EtU d 33 2-CH 4-d H ch ₃ CH3 - / _{(CH2) 2/2} O d 34 35 2-CH ₃ 2-CH ₃ 4-d 4-d H H CHj ch ₃ allyl AUU - / _{(CH2) 2/2} ^o - Br <CH ₂ CH ₃₎ -, Br 36 2-CH ₃ 4-d H ch ₃ AUU -H ₂ CHOH- Br 37 2-CH ₃ 4-C1 H ch ₃ AUU - (CH ₂ ) ₃ - -ch ₂ ch = ch- Br 38 ^2CH 3 4-d H ch ₃ allyl -ch ₂ chch ₂ - Br -OH (CH ₉ ) j- 39 2- ^ch 3 4-d H c ₂ h ₅ AUU • < ^CH 2) 4- Br 40 2-CH 4-d H n CjHj AUU <ch ₂ ) ₄ - Br 41 2-CH 4-d H i-CjHj AUU <ch ₂ ) ₄ - Br 42 2-ch ₃ 4-d H propargyl AUU - (CH ₂ ) ₄ . Br 43 2-CH ₃ 4-d H ch ₃ (CHjkCH- - (CH ₂ ) ₄ - Br 44 2-CH 4-d H CH? CH <ch ₂ ) _s - cl 45 2-CH ₃ 4-C1 H ch ₃ allyl <ch ₂ ) ₄ - ch ₃ oxo. 46 2-CH 4-d H ch ₃ ch ₃ <ch ₂ ) ₄ - cf ₃ so ₃ 47 2-Cl 4-d 6-d ch ₃ Allyl <ch ₂ ) ₄ - Br

Melting point, ° C falls to Z-b)

173-175Z Resin Resin

124-126 Resin

172

145-147 Z

128-130

135–136 resin resin

100-103

123-125

90- 92 109-110 182

144-146

170- 172Z 96-101 Resin

91-98

171- 175Z 84-85

134Z 175-178Z 157 Z 180 Z Resin 179-181 208-210 170-172

210-211 Z 166-168 Z 168-169Z

81-83

148-149Z

86-88 Resin 168-169Z 230

184,738

48 2-Cl 3-C1 4-Cl CH allyl <ch ₂ ) ₄ - Br 188 Z 49 2-CH ₃ 4-C1 5-C1 ch ₃ allyl <ch ₂ ) ₄ · Br 50 2-CH ₃ 4-C1 H ^C 2 ^H 5 ch ₃ < ^ch 2) ₄ - Br 60 51 2-CH ₃ 4-C1 H ^{c 2h} - CH <CH) - Br 88-89 52 2-CH ₃ 4-C1 H ^C 2 ^H 5 Alii! <CH ₂ ) ₅ - Br 88-90 53 2-CH 4-C1 H Cft2C ₆ H ₅ allyl Br 168-170Z 54 H H H CH allyl Br 136 Z 55 3-C1 H H 1 CH allyl <ch ₂ ) ₄ - Br 134 Z 56 3-C1 H H CH CH <ch ₂ ) ₄ - Br 123 Z 57 H H H CH CH <ch ₂ ) ₄ - Br 130 Z 58 H H H CH c ₂ ph Br 57 -59 3-C1 H H ch ₃ ^C 2 ^H 5 -rCH2) ₄ - Br 129 Z

Table V.

Serial number R ¹ R ¹

68 2-methyl 4-chloro 69th 2-methyl 4-chloro 70th 2-methyl 4-chloro 71st 2-chloro 4-chloro 72nd 2-chloro 4-chloro 73rd H H 74th 2-methyl 4-chloro 75th 3-chloro H 76th H H

Compounds of formula (I)

R ³ R ⁴ R ⁵ 5-chloro methyl ethyl 5-chloro methyl allyl 5-chloro methyl ethyl H methyl allyl H methyl allyl H methyl izoproenil H benzyl methyl H methyl allyl H methyl ethyl

R ⁶ R ⁷ X M.p.

<ch ₂ ) ₅ - Br 171 Z <ch ₂ ) ₅ - Br 203 Z <ch ₂ ) ₄ - Br 209 z <ch ₂ ) ₄ - Br 160 <ch ₂ ) ₅ Br 160 -162 - (CH ₂ ) ₄ - 192-194 <ch ₂ ) ₄ . Br 210 Br 165 Z <ch ₂ ) ₄ - Br 57

ARC. spreadsheet Compound of Formula XII Row- R ¹ R ⁶ R ⁷ R ⁵ R ⁴ X Mp ° C song 60th H <ch ₂ ) ₄ allyl <ch ₂ ). Br 178 (decomposes) 61st H <ch ₂ ) ₄ - allyl <ch ₂ ) ₃ - Br 160 (decomposes) 62nd H -ích ₂ ) ₅ - allyl <ch ₂ ), - Br resin 63rd H <ch ₂ ) ₅ - alli, -ích ₂ ) ₂ - Br 64th cl <ch ₂ ) ₄ - allyl <CH ₂ ) 2 · Br 65th cl <ch ₂ ) ₄ - allyl -ích ₂ ) ₃ - Br 66th Br <ch ₂ ) ₄ - allyl <ch ₂ ) ₂ - Br 67th Br <ch ₂ ) ₄ . allyl <ch ₂ ) ₃ - Br

The plant growth controlling agents of the present invention contain from 0.1 to 95%, preferably from 0.5 to 90%, by weight of the active ingredient. The application rate of the agent according to the invention is 0.001 to 3 kg / ha or more, preferably 0.01 to 1 kg / ha, depending on the desired effect. 55

The agents of the present invention may be in the form of solutions for direct spraying as well as powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, dispersants, granules. These forms of application are fully adapted to the intended use and must, in each case, enable the homogeneous distribution of the active ingredient to be as uniform as possible.

For the preparation of sprayable solutions and emulsions, pastes of the present invention, oil dispersions of water, medium and high-spin mineral oils such as kerosene or gas oil, coal tar oil and vegetable and animal oils, aliphatic, cyclic and aromatic hydrocarbons, benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohe-71

184,738 xanol, cyclohexanone, chlorobenzene, isoforone, a highly polar solvent such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone can be used.

Direct use agents can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), or by adding water to an oil dispersion. For the preparation of emulsions, pastes or oil dispersions, the active ingredient is dissolved in a solvent or an oil, homogenized in water in the presence of a surfactant. Concentrates of the active ingredient, surfactant additive and optionally solvent or oil can be prepared which can be diluted with water. According to their role in the agents according to the invention, surfactants are primarily wetting agents, tackifiers, dispersants or emulsifiers.

The surfactant additives of the present invention include the alkali metal, alkaline earth metal ammonium salts, naphthalenesulfonic acid, phenolsulfonic acid, alkyl aryl sulfonate, alkyl sulfonate, dibutylnaphthalenesulfonic acid, sulfuric acid, and alkaline earth metal salts, salts of sulphated hexadecanols, heptadecanols and octadecanols, salts of sulphated fatty alcohol glycol ethers, condensation products of sulphonated naphthalene and naphthalene derivatives with polydaldehyde, ether, ethoxylated isooctylphenol, octylphenol and nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkyl aryl pollether alcohol, isotridecyl alcohol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin, sulphite impurity and methyl cellulose.

Powders, dusts and dusts may be prepared by mixing and / or grinding the active ingredient with a solid carrier.

Granules, such as coated, impregnated and homogeneous granules, may be prepared by binding the active ingredient to a solid carrier. Examples of solid carriers include minerals such as silicic acid, silicate, talc, kaolin, clay, limestone, loess, dolomite, diatomaceous earth, calcium and magnesium sulfate, ground plastics, fertilizers such as ammonium sulfate, ammonium nitrate, bark, wood and bones, cellulose powder can be used.

It is to be understood that the agents according to the invention always contain the active ingredient and the excipients in a mixture, the term being to be interpreted in its broadest sense, including coating and impregnation.

The agents of the present invention are used to treat plants, seeds or soil, for example, by spraying, watering, dusting, dressing or impregnating, optionally after dilution.

Other pesticides or active ingredients, such as herbicides, insecticides, growth regulators, and fungicides or their active ingredients, as well as fertilizers, may be added to the agents or active ingredients of the present invention. Many mixtures may also produce a synergistic effect, i.e., the efficacy of the combination product is greater than the sum of the effects of the individual components.

The following examples illustrate the plant growth regulating effects of the agents of the present invention, without excluding their further use as plant growth regulators.

Example 5

Effect on sunflower

Sunflowers were planted in plastic pots filled with peat soil and 11.5 cm in diameter, filled with peat soil in a greenhouse. The agent of the invention (prepared as in Example 12) was sprayed on the leaves in varying amounts of active ingredient.

The treatment was carried out on 12 cm plants. During the 23-day experimental period, the treated plants were significantly lower in growth compared to untreated plants, as determined by length measurement. Each assay was carried out on 14-14 plants using known 2-chloroethyl trimethyl & ammonium chloride (CCC) for comparison. The results are shown in Table VI. Table 1.

VI. spreadsheet

Effect on length of sunflower __ (treatment of leaves) ___

agent number Used quantity kg / ha Growth height cm % untreated control CCC (known) - 26.8 1.5 0.5 1.0 1.5 100 23.0 17.5 17.0 17.0 85.8 653 63.4 63.4 Example 6 Effect on soybeans

In a greenhouse, similar to the sunflower assays, the effect of the agents of the invention (prepared as in Example 12) on soybean grown in te45 pot was investigated. The results obtained after 36 days are shown in Table VIL.

VII. spreadsheet

Effect on soybean length increase_

Active Substance Used Growth Height Serial Number Quantity cm% __kg / ha Untreated “-——— Control CCC (Known) 1.

- 28.0 100 13 27.0 96.4 6.0 26.5 94.6 1.5 103 373 63 103 373

Example 7

Effect on soybeans

To observe the effect of the agents of the invention on the development of soybean over a longer period of time, soybeans grown in larger pots filled with clayey sand were used. The soil was fertilized with 0.5 g of nitrogen in the form of ammonium nitrate and 0.5 g of phosphorus pentoxide in the form of potassium phosphate. The plants were grown in a fully air-conditioned greenhouse under optimal conditions of development. Plants of 20 cm were sprayed with the test substance (prepared according to Example 12). During the two-month trial period, untreated control plants grew to a height of about 60 cm, while untreated plants showed a reduction in growth height of up to 56%, and the plants were dense and distinctly dark green in color.

The comparative agent used was the compound containing ammonium salt of formula XIII known from German Patent Publication No. 26,572,728. The results are shown in Table VIII. Table 1.

VIII. spreadsheet

Effect on soybean length increase_

Active ingredient Used Growth height serial number, cm% _kg / ha_ untreated

control - 58.6 100 CCC (known) 0.5 60.0 102.4 1.0 59.0 100.7 XIII 1.5 58.0 99.0 compound 0.5 41.0 70.0 1.0 30.0 51.2 1.5 29.0 49.5

Example 8

Effect on sunflower and soybean

The experimental plants were grown in 12.5 cm diameter pots filled with soil and sufficient nutrients in a greenhouse. After emergence, the plants are sprayed with an aqueous spray containing the active compounds to be tested (prepared according to Example 12). ammonium chloride (CCC).

Along with the decrease in length of plants, the color of their leaves became more vivid. Based on the increased chlorophyll content, we can expect an increase in photosynthesis and, as a result, an increase in yield.

The results are shown in Table IX. and Table X.

IX. spreadsheet

Effect on the growth of sunflower ('Weise 1 variety')

Serial number of the active substance Used quantity (Kg / ha) Relative growth height (%) untreated control _ 100 CCC (known) 1.5 89.5 6.0 81.7 12th 1.5 73.9 6.0 66.2 13th 1.5 72.1 6.0 53.3 22nd 1.5 84.6 6.0 84.6 24th 1.5 87.7 6.0 78.4 28th 1.5 75.1 6.0 73.1 39th 1.5 72.6 6.0 56.1 70th 1.5 80.2 6.0 63.4 71st 1.5 74.6 6.0 63.4 72nd 1.5 72.8 6.0 67.2

Effect on growth of soybeans (variety SRF 400) Serial number of the active substance Used for Relative Growth quantity (Kg / ha) height t%) untreated control 100 CCC (known) 1.5 90.4 6.0 83.0 28th 1.5 71.0 6.0 48.4 39th 1.5 74.2 6.0 64.5 42nd 1.5 70.1 6.0 55.4 53rd 1.5 50.3 6.0 47.0

The following examples illustrate the composition and preparation of some representative agents of the invention. The active compounds are designated by the serial number of the preparation example.

EXAMPLE 9 The active ingredient # 1 sr was mixed with 0 <RTI ID = 0.0> sr </RTI> of water to give a droplet mixture.

Example 10 sr. The active ingredient 12 is dissolved in 80 parts by weight of xylene from 10 parts by weight of 8-10 moles of ethylene oxide and 1 mole of N-monoethanolamide oleic acid, 5 parts by weight of dodecylbenzenesulfonic acid salt 91

184,738 and a mixture of 40 mol of ethylene oxide and 1 mol of castor oil in 5 parts by weight. The solution was poured into 100,000 liters of water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 11 sr. The active ingredient (71) is dissolved in a mixture of 25 parts of cyclohexanol, 65 parts of a boiling point oil of 210-280 ° C and 10 parts by weight of 40 parts of ethylene oxide and 1 mole of castor oil. The solution was poured into 100,000 liters of water and uniformly distributed to give an aqueous dispersion containing 0.2% active ingredient.

Example 12 sr. Active ingredient No. 1 is thoroughly mixed with 3 parts of diisobutyl-naphthalene-α-sulfonic acid sodium salt, 17 parts of lignin sulphonic acid sodium salt from a sulphite slurry and 60 parts of powdered silica gel and then ground in a hammer mill. The mixture was uniformly distributed in 20,000 liters of water to give a spray solution containing 0.1% active ingredient.

Example 13 sr. Active ingredient No. 13 is thoroughly mixed with 97 parts by weight of powdered kaolin. A powder containing 3% by weight of active ingredient is thus obtained.

Example 14 sr 24 is mixed thoroughly with 92 g of powdered silica gel and 8 g of paraffin oil sprayed on the surface of the silica gel. We get a good adhesive,

EXAMPLE 15 The active ingredient number 1 sr was thoroughly mixed with 10 grams of sodium salt of phenolsulfonic acid urea formaldehyde condensate, 2 grams of silica gel and 48 grams of water. A stable aqueous dispersion is obtained which can be diluted with 100,000 liters of water to an aqueous dispersion containing 0.04% by weight of the active ingredient.

Example 16 The active ingredient number 22 of sr sr was thoroughly mixed with 2 grams of calcium salt of dodecylbenzenesulfonic acid, 8 grams of fatty alcohol polyglycol ether, 2 grams of sodium salt of phenolsulfonic acid urea-formaldehyde condensate and 68 grams of paraffinic mineral oil. A stable, oily dispersion is obtained.

Claims (2)

PATENT CLAIMS 1. Plant growth regulators which contain 0.1-95% by weight of the active ingredient o0 2 drawings containing a-amoacetanilide derivative of formula (I) - R ^{1 is} halogen or C 1 -C 4 alkyl, - R ^{2 is} hydrogen, halogen or C 14 alkyl, - R ^{3 is} hydrogen or halogen, - R ^{4 is C} 14 alkyl, C 24 alkenyl or phenyl (C 1 -C 2 alkyl), - R ^{s is C} 14 alkyl or C 24 alkenyl, - R ⁶ and R ⁷ are independently C 14 alkyl, or - R ⁶ and R ⁷ together form a group and n is 4.5 or 6, X is a halide ion solid or liquid carrier or diluent preferably natural or artificial mineral powders, aliphatic, aromatic or cyclic hydrocarbons, petroleum fraction, and a surfactant additive, preferably an anionic or nonionic dispersing, emulsifying or wetting agent. A process for the preparation of a-aminoacetanilide derivatives of the formula (I): wherein: - R ^{1 is} hydrogen, halogen, nitro, C 14 alkyl or C 14 alkoxy, R ^{2 is} hydrogen, halogen, or C 14 alkyl, - R ^{3 is} hydrogen or halogen, - R ^{4 is a C} 14 alkyl group, a C 24 alkenyl group, a phenyl C 14 alkyl group or a C 24 alkylene group ortho to the aromatic ring, - R ^{s is C} 1-6 alkyl, C 24 alkenyl or C 24 alkynyl, - R ⁶ and R ⁷ are independently C 14 alkyl, or - R ⁶ and R ⁷ together - (CH 3 is n is 4, 5 or 6) which is optionally substituted with C 14 alkyl or hydroxy and may have a double bond and may be interrupted by oxygen, -X represents a halide ion - with the addition of 11 (a) reacting an alpha-aminoacetanilide derivative of formula (HA) with an alkylating agent of formula (IX) - X halogen; or b) reacting the q-halo carboxylic acid anilide of formula VII with an amine of formula X.