DE2232263A1 - METHODS AND MEANS FOR INHIBITION OF PLANT BUD GROWTH - Google Patents

Description

American Cyanamid Company, Wayne, New Jersey, V.St.A.

Method and means for inhibiting plant bud growth

The invention relates to a method and an agent for inhibiting the growth of buds on plants and in particular relates to the inhibition of bud growth on plants by means of non-phytotoxic amounts certain substituted 2,6-dinitroanilines.

In horticulture, an agent for inhibiting the growth of plant buds is often desired. The growth of shoots from axial buds on crops decreases fruit yields and affects in the case of tobacco detrimental to the formation of marketable leaves. An uncontrolled development of terminal buds also affects plants and yield. Furthermore, there is uncontrolled development of the weave and terminal buds also on harvested tubers and onions, for example potatoes and onions advantageously avoided.

A common method of ensuring an adequate supply of crop leaves and fruits with nutrients is to physically remove the unwanted bud growth. The plant height will controlled by removing the stem tip. In the case of tobacco, the flowers and some end leaves are removed for this purpose, when the plant is about fully grown. This process is commonly known "as" Kanpening ". In the case of axillary buds or side shoots, the unwanted shoot growth is generally done by hand in a laborious and time-consuming process Operation removed.

The invention therefore aims to provide a convenient chemical Method of inhibiting the growth of buds on plants without adversely affecting crop leaves and fruits or other desired and useful parts thereof. The invention is also intended to provide chemical agents with which bud growth can be effectively controlled. Such means should not be toxic Residues get into the leaves and fruits of crops if the agents are applied in large quantities to plants, that inhibit bud growth.

It has now been found that bud growth on plants is effective with certain substituted 2,6-dinitroanilines can be controlled. These compounds have the following formula

where R. is hydrogen, a lower C.-Cg-alkyl radical, a substituted lower C.-C "-alkyI radical or a lower C ₂ -C ₄ alkenyl radical, R _{2 is} a lower C ₂ -C ₄ -alkenyl radical, a Cg-Cg -Cycloalkyl radical, a lower Cj-Cg-alkyl radical or substituted lower C.-Cg-alkyl radical, R, a hydrogen atom, a halogen atom, a lower C.-C ^ -alkyl radical, a lower C 1 -C . -Alkoxy group or the groups -CF ₃ , -CN, -SO ₂ NR ₅ R ₆ or -SO ₂ R ₇ , R ₄ a hydrogen atom, a halogen atom, an amino group, a lower mono- or di-Cj-Cg-alkylamino group, a ^C 2 ~ ^c e ~ alkoxyalkoxy group, a lower Cj-C ^ -alkylthio group or a lower C.-C.-alkyl radical, R ₅ and Rg each represent a hydrogen atom or a lower C.-C ^ -alkyl radical and R7 a lower C.sub.16 .-C.-alkyl radical.

The term "substituted lower alkyl" is understood to mean alkyl radicals with 1 to 8 carbon atoms which are halogen, C ₁ -C ₂ -AlkOXy, amino, nitro, cyano, C ₃ -Cg -cyclalkyl or lower C. ^ Have Cy-alkylthio substituents.

The preferred compounds include those in which R. and R ₂ together contain a total of 3 to 6 carbon atoms.

Exemplary lower alkyl radicals are methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, 3-pentyl, 2-pentyl, 3-hexyl, n-heptyl, n-octyl, and the like.

The lower alkenyl radicals include, for example, vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl and 3-butenyl and the same.

2 OB ö b ¹ 7. I 12 O 9

Exemplary cycloalkyl groups are cyclopropyl, cyclobutyl, Cyclopentyl and cyclohexyl.

The halogen substituents are fluorine, chlorine, bromine and iodine. Chlorine is preferred.

Examples of the compounds which are suitable for the purposes of the invention are given below.

N, N-di-n-propyl-4-trifluoromethyl-2,6-dinitroaniline, N, N-diallyl-4-trifluoromethyl-2,6-dinitroaniline, N-ethyl-N-n-butyl-4-trifluoromethyl-2,6-dinitroaniline, N, N-di-n-propyl-2,6-dinitroaniline, N, N-di-n-propyl-2,6-dinitrotoluidine, 3,4-Dimethy1-2,6-dinitro-N, N-di-n-propylaniline, 3-chloro-4-methyl-2,6-dinitro-N, N-di-n-propylaniline, 4-chloro-3-methyl-2,6-dinitro-N, N-di-n-propylariiline, 3,4-dimethyl-2,6-dinitro-N-n-propyl-N-cyclopropyl-aniline, 2,6-dinitro-4-trifluoromethyl-N-n-propyl-N-cyclopropylmethylaniline, 4-tert-butyl-2,6-dinitro-N-sec-butylaniline, 2,6-dinitro-4-trifluoromethyl-N- (cyclopropylmethyl) aniline, 4-tert-butyl-2,6-dinitro-N, N-di-n-propylaniline, 4- (Dimethylsulfamoyl) -3-methyl-2,6-dinitro-N, N-di-n-propylaniline, N-sec-butyl-2,6-dinitro-3-methyl-4- (methylsulfonyl) aniline, 3,4-dimethyl-2,6-dinitro-N- (3-pentyl) aniline, N-sec-Buty1-3,4-dimethyl-2,6-dinitroaniline.

Suitable methods for producing some of the active ingredients are known from the literature, for example from US Pat 3,257,190. Other methods will be discussed.

In practicing the invention, the aniline compounds are applied to the plants, at where control of bud growth is desired. The active ingredients generally have systemic activity on, which is why direct contact between the active ingredient and the bud can be useful, im in general, however, is not required. The order

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can therefore be on the foliage of the plant or when harvested Onions and tubers are done directly on this. The active ingredients are preferably used in combination used with auxiliaries, additives and preparation aids customary in horticulture. They can be used in combination Used with solid or liquid auxiliaries and as dusts, dust concentrates, wettable powders and liquids are prepared. Field application can be carried out according to the usual methods, for example with powder dusters, Boom and hand sprayers, spray dusters and the like.

The active ingredient can initially be prepared as a concentrated agent, which the active ingredient in a solid or contains liquid adjuvant that serves as a preparation aid or as a conditioning agent, whereby a further mixing of the concentrates with a suitable solid or liquid carrier in a form is made possible, which leads to rapid assimilation by the plant systems.

Suitable liquid excipients in which the active ingredient is dissolved, suspended or distributed include for example the following organic solvents and mixtures thereof: hexane, benzene, toluene, acetone, cyclohexanone, Methyl ethyl ketone, isopropanol, butanediol, methanol, xylene, dioxane, isopropyl ether, methylene dichloride, tetrachlorethylene, hydrogenated naphthalene, naphthalene solvents, and petroleum fractions such as kerosene.

Suitable solid excipients in which the active ingredient can be absorbed or dispersed include, for example natural clays such as china clay, bentonites and

S 0 ü I) [\> I \ 2 Q 9

Attapulgite, other natural substances such as talc, pyrophyllite, Quartz, diatomaceous earth, fuller's earth, chalk, phosphate rock, kaolin, diatomite, volcanic ash and sulfur, chemically modified substances such as acid-washed bentonite, precipitated calcium phosphate, precipitated potassium carbonate, calcined magnesium oxide and colloidal silicon dioxide and other substances such as cork powder, wood flour and powdered Pecan walnut shells. For maximum absorption and handling, these substances are in the form of fine particles Applied in the size range from 0.83 to 0.36 mm (20-40 mesh; Tyler). Before the field order, the fixed and liquid concentrates are generally diluted by adding a solid or liquid carrier. To suitable solid carriers with which the concentrates can be mixed, or on or in which they can be absorbed the aforementioned solid auxiliaries, fertilizers such as ammonium nitrate, urea, superphosphate, compost, manure and humus, pesticides, other herbicides, sand and the like. Suitable liquid carriers in which the Concentrates that can be dissolved, suspended or emulsified and dispersed are, for example, among others Water and the aforementioned liquid auxiliaries.

Dusts can be obtained by grinding from about 0.01 to about 25 percent by weight of the active compound with about 99.99 to about 75 percent by weight of a solid inert Diluents are produced.

Dust concentrates are made in a similar manner, but the weight fraction of the active ingredient is used increased to about 25 to about 75 percent by weight of the composition.

2 0 5) H f = \> I j 2 U Ü

Wettable materials suitable for the purposes of the invention Powders can be prepared by milling about 25 to 75 percent by weight of the active compound with about 15 to 65 percent by weight of a finely divided solid carrier such as attapulgite, kaolin, diatomaceous earth or talc, about 2 to 5 percent by weight of a dispersant, for example sodium lignosulfonate, and about 2 to 5 weight percent an anionic-nonionic emulsifier, for example one of the ones mentioned below in Table I, getting produced. Such wettable powders are intended for application in water or other non-phytotoxic Dispersed liquids.

Aqueous solutions and / or suspensions are preferred preparations. Concentrations of the active ingredient in the range from about 100 ppm to about 4000 ppm are generally effective in controlling axial bud growth. Agents with lower concentrations are generally suitable for controlling the sprouting of bulbs and onions. For example, compositions in which the active ingredient is present in concentrations of about 10 ppm to about 1000 ppm are generally suitable for controlling the formation of sprouts on white potatoes and onions. For this purpose, they can simply be immersed in a solution of the active ingredient for about 30 to 90 seconds and then left to dry.

Typical liquid preparations are described in Table I below. In any case, they relate indicated percentages by weight.

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Tabel

liquid preparation A 45% - a ^

5% - nonylphenoxypolyoxyethylene ethanol 50% - xylene

liquid preparation B

35% - N, N-di-n-propyl ~ 4-trifluoromethyl-2,6-dinitroaniline

5% - anionic-nonionic emulsifier calcium myristylbenzenesulfonic acid and oleate ester of a polyoxyethylene glycol (molecular weight = 350)

60% - xylene

liquid preparation C 40% - N, N-diallyl-4-tri £ luoromethyl-2,6-dinitroanilln

7% - anionic-nonionic emulsifier (as under B) 53% - xylene

Typical wettable powders for the purposes of the invention are described in Table II below.

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Table II

wettable powder A

40% - 3,4-dimethyl-2> 6-dinitro - N, N-di-n-propylaniline 50% - Attaclay

5% - sodium lignosulfonate 5% - nonylphenoxypolyoxyethylene ethanol

wettable powder B

% - N, N-di-n-propyl-2,6-dinitroaniline% - diatomaceous earth 3% - sodium lignosulfonate

2% - ionic-nonionic emulsifier calcium myristyl-

benzenesulfonic acid and oleate from polyethylene glycol (molecular weight = 350)

wettable powder C

50% - N _f N -diethyl-4-trifluoromethyl-2,6-dinitroaniline

% - kaolin

(R)

3% - dispersant (Marasperse ⁷ N, a neutral

Sodium Lignosulfonate from Marathon Corp. )

2% - anionic-nonionic mixed emulsifier

wettable powder D

40% - N _f N -di-n -propyl-4-sulfamoyl-2,6-dinitroaniline

% - Attaclay

(R)

3% - dispersing agent (Marasperse 'N)

3% - sodium dioctyl sulfosuccirate

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In tobacco plantations, bud growth is common controlled in two mechanical operations. As before, the plant height is determined by cutting off the terminal flower buds of the tobacco plant in one operation regulates known as "caps". This method promotes the formation of the large leaf that is marketable Yield forms. The formation of large leaves is enhanced by lateral development (axillary) buds lifted. The lateral growth (called "shoot growth") in turn reduces the nutrients feed for the development of large leaves. Therefore, a second mechanical operation is required, namely the manual removal of the shoots from each tobacco plant. According to the invention, the annoying and costly mechanical interventions can be avoided by two spray treatments. The terminal bud development can through Spraying the active ingredient can be combated. The development of the runners can be prevented by later spraying the Plant stems and leaves are combated.

Harvesting of the marketable leaves or main leaves of dried tobacco is usually started 1 to 2 weeks after treatment and harvesting can continue for 4 or 5 weeks. Usually three leaves at the bottom of the stem are cut at weekly intervals. During this time, inhibiting the growth of side buds is important as such treatment results in improved ^{H +} quality, better texture and better yield of the main or marketable leaves. The inhibition of axillary bud growth on capped Burley tobacco

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Is also important to improve tobacco quality and tobacco yield, although harvesting is something done differently. That is why the Burley tobacco is sprayed with a solution of the active ingredient after capping, to inhibit the development of side buttons, and then about 5 to 10 weeks after treatment as usual the whole trunk was harvested. .

Through the following examples, which include the manufacture describe active ingredients according to the invention, the invention is further explained. Parts and percentages are by weight unless otherwise is specified.

Examples 1 to 57 Control of axillary tobacco buds

Tobacco saplings are made in 15 cm (6 inch) plastic pots transplanted with a greenhouse soil mix (Loam earth: sand: manure, 1; 1: 1) included. The plants will Grown in the greenhouse for 8 to 10 weeks and then cut just above the eleventh knot. The active ingredients are applied to the entire plant as a foliar spray immediately after cutting. Any spray solution is made by dissolving the desired amount of active ingredient in an acetone-water mixture containing 0.5% Contains polyoxyethylene sorbitan monolaurate (Tween 20, Atlas Powder Company). The plant to be sprayed is placed on a turntable. Then 65 ml of the spray solution from 3 directed nozzles are applied to the plant upset. The concentration of the active substance in the spray solution ranges from 100 to 1600 ppm. After spraying

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the plants are randomly distributed on a greenhouse bench and watered normally for 2 weeks. At the end In each test, the shoots are removed from all nodes and weighed. The results are called inhibition given in percent in comparison to the fresh weight of shoots from untreated control plants. The results obtained are shown in Table III below. For comparison, maleic hydrazide is a commercially available bud growth regulator (Example 2) is given in the table.

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Table III

Example

structure

Inhibition,%

800 4OO 200 100

ppm ppm ppm ppm ppm

C ₃ H ₇ -n NO "

CF. 99 96 98 96 41

99 98 89 80 51

82 79 37 40

N (CH ₂ CH = CH ₂ ) ₂

CF, 98 97 98 82

79 99 98 86

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Table III (cont.)

example

Structure inhibition,%

1600

800 400 200 1OO

ρργι ppm ppm

90 95 98 95

96 99 99

98 95 96 57

88 90 52

ⁿ ~ ^C 3 ^H 7 O ₂ N-

70 62 70

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Table III (cont.)

Example

structure

Inhibition,

1600
ppm

SO-CALLED
pt> m

400
ppm

200

100 ppm

N (C.

CH. 98 95 96 94 38

NH-C ₃ H ₇ -Ii

98 96 99 72

97 90 62 56 -1

NO

2—

NO,

Ύ ⁿ ch.

CH.

100 95 49 63 62

N (CH ₂ CH = CH ₂ )

-5 37 25 27 4O

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Tab eile III (cont.)

example

Structure inhibition /%

800 400 200 100 ppm ppm ppm ppm ppm

H-CH-C ₂ H ₅ CH ₃

NO,

CH. 97 97 97 94 86

H-CH (CH ₃ )

I. CH-, ■ 99 99 93 91 51

97 96 99 93 95

NH-CH "CH _o CH_-0-CH_

I Δ JL Δ J

NO

CH. 84 74 15 -53 22

NH-CH

^N0

97 97 95 96? 8

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Table III (cont.)

example

structure

Inhibition,

800 400 200 ppm ppm ppm ppm ppm

NH-CH ₂ CH ₂ CH

NO

2- ~ ry 98 95 83 23 -2

NO,

C ₂ H ₅ C ₃ H ₇ NO ₀

CH-

CH. 88 97 90 46

NH-CH ₂ CH ₂ CH ₃

Cl

H. 20 -80 -30 13

9 * 3 NH-CHCH ₂ CH ₃

NO ^ - /> \ ^ N0 _o

Cl

CH. 11 -14 31 21

N (C ₃ H ₇ -n) ₂

65 41 36 35

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Table III (cont.)

example

structure

Inhibition _f %

800 400 2OO 100 pom ppm pnm ppm ppm

CH. 98 99 98 97 91

N- (C ₃ H ₇ -n) ₂

98 96 96 85 61

NH-CH ₂ CH (CH ₃ )

67 73 13. 54 -59

NO,

NH-CH-CH ₂ CH ₃

CH,

SO3CH 94 98 97 97 77

NH-CH

SO ₂ CH ₃ 12 12 15

30th

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T a be 1 1 e III (cont.)

example

structure

Inclusion,

800
ppm ppm

400

pt> m

200 ppm

ppm

NO,

^{N (C} 2 ^H 5> 2

- NO,

CH-) ₂ CH ₃ "59 80 64-65

NO,

N (C ₃ H ₇ -H) ₂

98 96 64 36

N (C ₂ H ₅ )

.NO,

CH. 81 73 57 26 -3

NH-CH ₂ CH = CH ₂

77 90 73 59 -45

NO,

Cl

NO ₂

CH. 93 80 32 -1

Table III (cont.)

example

structure

Inhibition,%

800 400 2OO 100 ppm ppm nnm pnm ppm

21 4 31 -37

NO,

NH-CH - CH (CH_) _O

9O 37 6-18

38 NO,

97 84 84 57

NO,

66 70 64 45

NO

NH-C (CH ₃ J ₃ NO "

CH. 39 79 52 63 49

2U9ÖÜ2 / 1.20 9

Table III (cont.)

example

structure

Inhibition f

800 400 200 10Q ppm ppm ppm pnm ppm

? ^H 3 NH-CH-CH (CH ₀ )

NO

Cl

99 93 94 76 73

NO,

CTHT, 2

p-CHCH ₂ CH ₃

Cl

96 96 96 95 94

<? ^H 3

NO,

CH.

Cl

93 97 96 91 87

r \

ί ^N ° ^cir *

CH ₁

3 6 2 6) 10 L /

5 1 14> 7 -58

CH

.. '0 ■) B H.' / ι '> 0 f)

Table III (cont.)

example

structure

Inhibition ,%

1600 800 4OO 2OO 100

pnm ppm onm ppm ppm

NO,

like controls

HCHC ₂ H ₅

⁶ 2 ^H 5

NO,

98 76 75 98 98

C ₀ H ₁ .

I ^{2 5}

NH-CH-C ₉ H ₁ .

NO

CH.

Cl

C, H ₅

NO

HH

• τ: r

he,

98 95 80 96 92

^tIO

(IH-CII (CH ₁ ).,

82 56 5 ^c i 44

CH

Table III (cont.)

example

structure

Inhibition,%

16OO 8OO 400 200 ppm ppm ppm ppm ppm

NH-CH

NO,

NO.

CH. like controls

0-C_H_-n

NO.

NO,

0-CH (CH ₃ J ₂

NO,

CH.

H. 86.7 39.9

36 -23

NO-

H-CH-C

H.

CH.

8O 47 31 0 0

CH.

NO,

-tr

95 98 97 89

1209

Table III (cont.)

For example

structure

Inhibition,%

1600 800
pnm ppm

400 200

ppm

100

pom

NO,

CH. NT NT NT 98 NT

57 NO

C (CH ₃ ) 84 91 94 54 -48

NT = no test

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Example 58

Following the general procedure of Examples 1 to 57, the results obtained with a solution of 100 ppm N, N-di-n-propyl-4-trifluoromethyl-2,6-dinitroaniline can be compared with the results obtained by a Solution with 800 ppm maleic acid hydrazide, a common one Bud inhibitor. The Burley tobacco plants will be capped, treated with the test solutions and placed in the greenhouse, where they are taken care of as usual. The plants are examined two weeks after treatment and the leaves removed and photographed. The test shows that the untreated control plants Shoots approximately 25 cm (10 inches) in length at multiple nodes on the stem of the tobacco plant have developed. Tobacco treated with the aqueous maleic acid hydrazide solution has shoots with a length about 10 cm (4 inches) at several knots. The plants that are substituted with the aqueous solution of the 2,6-Dinitroaniline treated are practically free from shoots.

Example 59

The procedure of Example 1 is repeated with uncapped tobacco plants. By applying Ν, Ν-dipropyl-4-trifluoromethyl-2,6-dinitroaniline In concentrations of about 100 ppm to about 1600 ppm, a drive control of over 90% is achieved.

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Example 60 Inhibition of Leaving Potatoes

Even tubers are picked from 1 year old potatoes that have been stored in the cold. the Tubers are placed in aqueous solutions of N, N-di-npropyl-4-trifluoromethyl-2,6-dinitroaniline immersed in different concentration obtained by diluting

(R) a '45.5 percent solution made by Treflan (Elanco-Products Co.). The treatment is carried out for 60 seconds, after which the tubers are allowed to dry and placed in plastic bags. They are then placed in a cold room at 1 ^° C (34 ^° F) for 2 days, after which they are placed in a dark room at 24 ^° C (75 ^° F) until the experiment is over (4 weeks after treatment ). The potatoes are examined and the shoots are removed and weighed.

This method of working is done with the commercially available bud inhibitor Isopropyl N- (3-chlorophenyl) carbamate repeated. The results and values obtained in each case for untreated controls are shown in Table IV below.

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Tabel

IV

link

HC ₃ H ₇

CF.

Isopropyl N- (3-chlorophene y1) carbamate

Guess pom Fresh weight /
Shoot (mg) 0.01 20th 0.1 20th 1.0 43 10.0 14th 100.0 14th 1000.0 5

0.01

0.1

1.0

10.0

100.0

1000.0

42 31 68 18 17 5

Untreated control 23 22

35 36

- 27 -

O O

Example 61 Preparation of N- (ethoxycarbonyl) -3, 4-diinethy! Aniline

To prepare the compound mentioned, first 51.5 g of 3,4-dimethylaniline are dissolved in 250 ml of benzene. The solution is then while being maintained at a temperature in the range 20 to 30 ⁰ C, is slowly added a benzene solution of 23.9 g of ethyl chloroformate. The mixture is left to stand at room temperature overnight and then filtered. The filtrate is evaporated in vacuo, leaving the desired product in the form of a dark purple liquid weighing 30 g.

Example 62 Production of N- (ethoxycarbonyl) -3,4-dimethyl-2,6-di-

nitroaniline

30 ml of concentrated sulfuric acid are added to 84 ml of cold concentrated nitric acid. The solution obtained is cooled to -5 to -10 ° C., whereupon the nitration mixture is slowly admixed with 30 g of N- (ethoxycarbonyl) -3,4-dimethylaniline with external cooling. Then the mixture is poured onto ice and extracted with ethyl ether. The extract is washed with water and with aqueous sodium bicarbonate solution. After evaporation of the ether, an oil remains behind which is recrystallized from absolute ethanol to 3 g of the desired product as a yellow solid having a melting point of 51-54 ⁰ C recrystallized.

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Example 63 Preparation of 3 _y 4-dimethyl-2 _r 6-dinitroaniline

2.85 g of N- (ethoxycarbonyl) -3,4-dimethyl-2,6-dinitroaniline are added to 30 ml of concentrated sulfuric acid. The mixture is heated to a temperature in the range from 110 to 120 ^° C. for 15 minutes and then poured onto ice. The deposited solid is separated off and recrystallized from absolute ethanol to give the desired product with a melting point of 141.5 to 142.5.degree.

Example 64 Preparation of 1-chloro-3,4-dimethyl-2,6-dinitrobenzene

A cuprous chloride solution is prepared by dissolving 3.24 g of CuSO ₄ .5H ₂ O in water and adding NaCl to the warm solution. While keeping the blue solution in an ice bath, a solution of 1.24 g sodium metabisulfite and 0.52 g NaOH in 12 ml water is added. A white precipitate forms, which is dissolved in 12 ml of concentrated hydrochloric acid.

2 g of 3,4-dimethyl-2,6-dinitroaniline are warm in 40 ml Dissolved glacial acetic acid. The solution is cooled to room temperature and very slowly with 0.9 g of sodium nitrite in 7 ml cold concentrated sulfuric acid is added, as a result of which a solid substance forms in the mixture. These Mixture is then added to the solution of cuprous chloride in concentrated hydrochloric acid to form a diazonium mixture to create.

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The diazonium mixture is then heated, whereby the desired product forms as a solid precipitate. The solid substance is filtered off and purified by recrystallization from cyclohexane. The desired product has a melting point of 109 to 111 ⁰ C.

The procedure described is repeated with 16 g of 3,4-diraethyl-2,6-dinitroaniline, as a result of which 11.0 g of the desired product with a melting point of 111 to 113 ^° C. are obtained.

Example 65 Preparation of 3,4-dimethyl-2, e-dinitro-NyN-di-n-propyl

5 g of 1-chloro-S ^ -dimethyl ^ ö-dinitrobenzene and 5.05 g of di-n-propylamine are dissolved in toluene and the mixture is then heated to reflux temperature. The mixture obtained is filtered and the filtrate is evaporated in vacuo. The residue is treated with hexane and the mixture is cooled in a dry ice-acetone bath. After filtration and drying, the desired product in the form of a solid substance is obtained with a melting point of 42 to 43.5 C ^0.

Examples 66 to 94

The general procedure of Example 65 is followed by several Repeated amines instead of di-n-propylamine. In either case, the desired aniline will be accordingly

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the following reaction diagram. In the following Table V gives the melting points of the products obtained.

Cl

+ R R NH

H.

H.

2 U Ü ü U y I 1 2 0 9

Table V

Ex. ^R l structure M.p.
° C solvent
to the recrystalline NO. H R ₂ lize 66 H H 141-142 Ethanol 67 C ₄ H ₉ C ₃ H ₇ 71-71.5 Cyclohexane 68 CH ₂ CH = CH ₂ ^C 2 ^H 5 oil 69 CH ₃ CH ₂ CH = CH ₂ 41-42 Benzene / hexane 70 0 CH ₃ 84-85 Methanol 71 * m. t 1 ... _ -1

72 C ₃ H ₇ 73 H 74 H

C ₃ H ₇

CH ₂ C (CH ₃ )

CHCH ₂ CH ₂ CH (CH ₃ )

CH-,

42-43.5 hexane 88-89 methanol

79-80

CH

CHC ₄ H ₉ -t

48-49

100-101

^C 2 ^H 5

^C 2 ^H 5

^C 6 ^H 13

oil oil

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Ex.

- 33 -

structure

Melting point solvent for recrystallization

68-70

Methanol

CH ₃ CHC ₂ H ₅ 43-44

30-31

Hexane

Methanol

82 H CH (CH ₃ ) 2 83 H CH ₂ CH (CH ₃ ) 2 84 H CH ₂ CH = CH ₂ 85 H CHCH ₀ CH (CH-) CH ₃ 86 ^C 2 ^H 5 CH ₂ CH ₂ CH ₃ 87 H CH (C ₂ H ₅ ) ₂ 88 H CHCH ₂ CH ₂ CH ₃

67-68 H ₂ O / methanol

CH.

H CH ₂ CH ₂ CH (CH ₃ ) ■ Ο - C- - H CH-CH (CH-) _o

46-47

81-82

81-82

oil

56-57

42-43

61-63

Methanol

Methanol

Methanol

Methanol

Methanol

48-50 methanol

106-108 cyclohexane 120-122 cyclohexane

Methanol

CH.

93 H C (CH ₃ ) ₃ 2 ^H 5 94 H CH ₀ CH-C 1209 CH
20 98 8 2 * /

66-67
44-45

Hexane

Examples

95 big 99

Preparation of N-sec-butyl-3-chloro-4-methyl-2,6-dinitroaniline

A mixture of 10.04 g (0.04 mol) of 2,4-di-chloro-3,5-dinitrotoluene, 5.85 g (0.08 mol) of sec-butylamine and 200 ml of cyclohexane is refluxed for 6 hours touched. The mixture is filtered and the filtrate is concentrated under reduced pressure. The residue is partitioned between ether and dilute hydrochloric acid. The organic phase is washed with water and brine, dried over magnesium sulfate and evaporated in vacuo. Recrystallization of the residue from ethanol gives 7.71 g of orange-colored crystals with a melting point of 40 to 46 ^° C. Two recrystallization from ethanol gives an analytically pure sample with a melting point of 45 to 47 C.

Analysis calculated for C ₁₁ H _{14 ClN 3} O ₄ : C 45.92; H 4.90; Cl 12.32; N 14.61. Found: C 45.96; H 4.97; Cl 12.36; N 14.78,

Using the same procedure, corresponding other amines instead of sec-butylamine products of the following structure with melting points like them given below in Table VI.

CH.

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Table VI

structure

Example R ₁ R ₂ m.p.

95 -H 'CHo

ι 3

45-47 83-85

67-70

41-44.5

HB TJ -CHCH ₂ CH ₃ 96 -H -CH ₂ CH ₂ CH ₃ 97 —CH «CH ^ CHο -CH (CH-), 98 -CH ₂ CH ₃ ■ "CH -j CH .ρ CH ο 99 _mlm / ~ t TT / ^ TT

Examples 100 to 102

Preparation of 4-methyl-2,6-dinitro-N-propyl-3- (propylamino) -

aniline

A mixture of 10.04 g (0.04 mol) of 2,4-dichloro-3,5-dinitrotoluene and 25 ml of n-propylamine is refluxed for 2 hours. After diluting with 5 ml of ethanol, the diluted mixture is refluxed for 21 hours. The solvent is evaporated and the residue is recrystallized as in Example 95 to give 11.5 g of an orange oil. Recrystallization of the oil from ethanol yields 8.80 g of a golden-colored solid of melting point 42 to 44 ⁰ C. By recrystallization from ethanol is obtained an analytically pure sample with a melting point of 43 ° -44 ⁰ C.

BAD ORIGlNAt 2 U 9 B ü 2 I 1 2 0 9

Analysis calculated for ^c ₁ 3 ^H ₂ o ^N 4 ^O 4 ^{: C 52} ' ⁶⁹ ' ^H 6>8Ο; N 18.91. Found: C, 52.75; H 6.64; N 18.35.

Links this. Type with two different amine functions can be achieved by implementing the corresponding Amines can be prepared with the compounds listed in Table VI.

Compounds prepared in this manner have the following structure and melting points given in Table VII below.

NR ₃ R ₄

Table VII

R. structure ^R 2 ^R 3 ^R 4 M.p. C. BeisDiel -H -CH ₂ CH ₂ CH ₃ -H -CH ₂ CH ₂ CH ₃ 43-44 100 CH ₃ CH-
1 y -H -CHCH ₂ CH ₃ -H -CHCH ₂ CH ₃ oil 101 -CH ₃ -CH ₃ -CH ₃ -CH ₃ 85-88 102

2U98U2 / 1209

BATH ORIGINAL

Examples 103 to 113 Preparation of N-isopropyl-4-methyl-3-methoxy-2,6-dinitroaniline

A solution of 5.47. 1.79 g (0.033 mol) of sodium methoxide are added to g (0.02 mol) of 3-chloro-N-isopropyl-4-methyl-2,6-dinitroaniline in 100 ml of methanol while stirring. The reaction mixture is stirred under reflux for 3 hours, cooled to room temperature and filtered. The filtrate is evaporated under reduced pressure and the residue is partitioned between ether and dilute hydrochloric acid. The organic phase is washed successively with water, saturated sodium bicarbonate solution and brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent in vacuo gives 5.0 g of the desired product with a melting point of 72 to 77 ^° C. Two recrystallization from methanol gives an analytically pure sample with a melting point of 77.5 to 79 ^° C.

Analysis calculated for C ₁₁ H ₁₅ N ₃ O ₅ : C, 49.07; H 5.62; N 15.61. Found: C 49.35; H 5.66; N 15.77.

According to this general procedure, the corresponding sodium alkoxides and chloroanilines are converted into compounds with the following Structure made. The melting points observed are given in Table VIII below.

BATH 209882/1209

Table VIII

at ^R l structure R ₂ ^R 5 M.p. game H ^CH 3
CHCH ₂ CH ₃ CH ₃ ⁰ C 104 ^C 2 ^H 5 ^C 2 ^H 5 CH ₃ oil 105 ⁿ " ^C 3 ^H 7 nC ₃ H _? CH ₃ 106 H CH ₃
CHCH ₂ CH ₃ ^C 2 ^H 5 31.5-33 107 H CH (CH ₃ ) ₂ ^C 2 ^H 5 50-51 108 ⁿ " ^C 3 ^H 7 ⁿ " ^C 3 ^H 7 C ₂ H ₅ 109 H CH (CH ,,)., CH (CH-,)., oil 110 H CH (CH ₃ ) 2 HC ₄ H ₉ 45-49 111 nC ₃ H ₇ nC ₃ H ₇ HC ₄ H ₉ 63-66 (raw) 112 H CH (CHo), 48-51 113 63-66

Example 114 Preparation of N- (3-hexyl) -4-allyl-3-methyl-2,6-dinitroaniline

One equivalent of 4-allyl-3-methyl-2,6-dinitrochlorobenzene is used Dissolved in three volumes of xylene containing two equivalents of 3-hexylamine. The mixture is taking 5 hours Held at reflux and then poured into water. The organic

2 09882/1209

Phase is washed with 5 percent hydrochloric acid and then with water, dried over calcium sulfate and evaporated in vacuo, whereby the above product is obtained as a residue.

Example 115 Preparation of 4-chloro-N-isopropyl-3-methyl-2 _f 6-dinitroaniline

9.0 g (0.15 mol) of isopropylamine are added to a mixture of 10.04 g '(0.04 mol) of 3,6-dichloro-2,4-dinitrotoluene and 50 ml of ethanol. The mixture is stirred at room temperature for 2 hours and then under reflux for 1 hour. The solution is allowed to cool to room temperature and the crystalline precipitate is filtered off and washed with a small amount of hexane, giving 10.2 g of the desired product as gold-colored crystals with a melting point of 69 to 73 ^° C. Recrystallization twice from methanol yields an analytically pure sample with a melting point of 69 to 70 ^° C.

Analysis calculated for C ₁₀ H _{12 ClN 3} O ₄ : C, 43.88; H 4.42, Cl 12.96; N 15.35. Found: C 44.09; H 4.43; Cl 13.02; N 15.42.

In an analogous manner, other primary amines with 3,6-dichloro-2,4-dinitrotoluene implemented. In cases where the product is difficult to crystallize, the solvent will evaporated and the product isolated by extraction.

BATH ORIGINAL

2 uy 8! - ■ / 11 2 ü a

-AO-

Examples

116 to 135

Production of 4-chloro-3-methyl-2, e-

A solution of 10.04 g (0.04 mol) of 3,6-dichloro-2,4-dinitrotoluene, 12.2 g (0.12 mol) of di-n-n-nronylamine and 60 ml of toluene is stirred under reflux for 9 hours . The mixture is cooled, diluted with ether and extracted twice with dilute hydrochloric acid. The organic phase is then washed successively with water, aqueous sodium bicarbonate solution and brine and dried over magnesium sulfate. Evaporation of the solvent under reduced pressure gives 12.5 q of the desired product in the form of an oil. By recrystallizing the product from hexane, 9.08 g of a yellow solid substance with a melting point of 36 ° to 38 ° C. are obtained. Recrystallization from 9 5 percent aqueous ethanol provides an analytically pure sample with a melting point of 41 to 42 ^° C.

Analysis calcd for: C ₁₃ H ₁₈ ClN ₃ O ₄ : C 49.45; H 5.75; Cl 11.23; N 13.31

found :

C 49.45; H 5.80; Cl 11.38; N 13.17,

Following the general procedure described above, appropriate amines are used instead of di-npropylamine Obtain compounds with the following structure. The melting points observed are in Table IX below specified.

Cl

BATH ORIGINAL

209882/1209

Table IX At- structure

play R. R “Schmn. C.

116 H H 123-125

117 H CH ₀ CH ₂ CH ₃ 83.5-85

118 H CH ₉ CH = CH ₂ '61-62.5

119 H CH (CH ₃ ) ₂ 69-70

120 H CH "CH (CH.J" 52-55

121 H CHCH ₂ CH ₃ oil

122 HC (CII ₃ ) ₃ 41-46

123 H CH (CH ₂ CH _{3) 2} 41.5 to 44.0

130 H 131 CH ₃ 132
133 ^C 2 ^H 5
CH ₂ CH = CH ₂ 134 CH ₂ CH ₃ CH ₃ 135

CH ₀ CH 2 ^CH ₃ ) ₂ 3 2 CH ₉ CH = CH (CH 2 CH (CH CH ₃ CH ₂ CH ) ₃ 3> 2 ?H
CHCH ₂ 2 ^CH 3 C (CII ₃ CH ₂ CH (CH 5 ^CH 3> 3> 2 CHCH ₂ CH ₂ OCH ₃ (CH ₂ ) 3 CH ₃
CHCH ₂ CH (CH CH ₂ CH
CH ₂ CH ₂ CH
₂ CN • Ο

124 H CHCH ₂ CH ₂ CH ₃ 31-32

125 H (CH ₂ ) ₅ CH ₃ 32.5-34

CH ₃

126 H C H _{CH 2} CH (CH ₃ ) ₂ - 62.5-65.5

127 H CH ₂ CH ₂ CH ₂ OCH ₃ 42.5-46.5

128 H CH ₂ CH ₃ CN 101-104

129 H -N \. 84-87

93-94

CH ₃ 67.5-70.0 C ₂ H ₅ oil

CH ₂ CH = CH ₂ oil

CH ₂ CH ₂ CH ₃ 41-43

- 117-120.5

209882/1209

Example 136 Preparation of 3'-methyl-p-toluenesulfone-p-anisidide

A solution of 8.2 g (0.06 mol) of 3-methyl-p-anisidine in 50 ml of pyridine is mixed with 7.2 g (0.063 mol) of p-toluenesulfonyl chloride added, while the temperature is kept at 25 to 30 C. After stirring for several hours at room temperature the reaction mixture is poured into excess dilute hydrochloric acid. The mixture is cooled down and the desired Product that separates out as a solid is filtered off and dried.

Example 137

Preparation of 3'-methyl-2 ', 6'-dinitro-p-toluenesulfone-p-

anisidid

11.0 g of 3'-methyl-p-toluenesulfone-p-anisidide are added to 80 ml of glacial acetic acid and the mixture obtained is heated to 45 to 50.degree. At this point 40 ml of concentrated nitric acid is carefully added. The temperature is kept at 45 to 50 ^{° C. with an ice bath.} After the addition has ended, the reaction mixture is ^{stirred for 30 minutes at 40 to 45 °} C. and then poured onto ice. The desired product, which separates out as a solid substance, is filtered off and dried.

BATH ORIGINAL

2098 «2/1209

Example 138

Preparation of 3-methyl-2,6-dinitro-p-anisidine

3 '-methyl-2, 6-dinitro-p-toluolsulf on-p-anisi <lin is hydrolyzed with concentrated sulfuric acid at 30 to 40 ⁰ C until thin layer chromatography indicates that the reaction has ended. The reaction mixture is then poured onto ice and the desired product, which separates out as a solid, is filtered off and dried.

Example 139 Preparation of 4-chloro-2-methyl-3,5-dinitroanisole

3-Methyl-2,6-dinitro-p-anisidine is prepared by means of the usual Sändmeyer reaction in 4-chloro-2-methyl-3,5-dinitroanisole convicted.

Example 140

Production of M-sec.-Butyl-4-methoxy-3-methyl ~ 2 »6-dinitro-

aniline

100 ml of toluene are mixed with 24.6 g of 4-chloro-2-methyl-3,5-dinitroanisole and then mixed with 14.6 g of sec-butylamine. The received The mixture is refluxed until it is determined by gas-liquid chromatography that the implementation is finished. The solvent is removed in vacuo and the desired solid product is made from a recrystallized suitable solvent.

B eisp ie 1 141 Manufacture of potassium 4-chloro-3 _f 5-dinitro - o-toluenesulphonate

A mixture of 1000 ml of concentrated sulfuric acid and 170 ml of 23 percent fuming nitric acid is added to 166.0 g (1.31 mol) of m-chlorotoluene and heated to 100 ⁰ C ". Then, the solution is cooled to 25 ⁰ C and carefully 400 g of potassium nitrate are added at 35 to 45 ^° C. After the addition has ended, the reaction mixture is ^{stirred for 1 hour at 40 to 45 °} C. and then slowly ^{heated to 100 °} C. and kept at 100 to 110 ^° C. for 1.5 hours the reaction mixture is cooled and poured onto 12,000 ml of ice. The desired product separates out as a solid substance and is filtered off, washed with water and then recrystallized from 5 liters of water. The crude yield of the potassium salt is 305.0 g.

Example 142 Preparation of 4-chloro-3,5-dinitro-o-toluenesulfonylchloride

A mixture of 60.0 g of potassium 4-chloro-3,5-dinitro-o-toluenesulfonate, 70 g of phosphorus pentachloride and 120 ml of phosphorus oxychloride is refluxed for 3 hours. The mixture is filtered to remove insoluble solids. The filtrate is carefully poured into water at 20 to 30 ° C. The solid precipitate is filtered off and dissolved in 500 ml of benzene. The benzene solution is washed with water and then dried _{over MgSO 4.} After the magnesium sulfate has been removed, the benzene is concentrated to 100 ml and 400 ml of hexane are added. The desired product separates out as a solid substance is filtered off and recrystallized from 300 ml of hexane and 1OO ml of benzene 50.0 g of solid substance having a melting point 105-107 ⁰ C.

20988 /! / 1 209 /

, B e i s ρ i e 1 143

I Preparation of 4-chloro-3,5-dinitro-o-toluenesulfonamide

y A solution of 10.0 g (0.0318 mol) of 4-chloro-3,5-dinitro-o-

_i} - toluenesulfonyl chloride in 150 ml of acetone at -15 ⁰ C.

ί chilled. 1.08 g (0.064 mol) of ammonia are condensed

] and then evaporated into the acetone solution. After finished

f adding is the reaction mixture in an equal volume

ί Poured water and deposited it as a solid precipitate

i dene ¹ desired product is filtered off. The raw

} yield of white solid matter with a melting point

! from 205 to 215 ^° C. is 6.8 g.

\ ■ ■. · "■ - ■

[Examples 144-152

I 4 4

Preparation of 2-methyl-3,5-dinitro-N, N -dipropylsulfanilamide

\ A mixture of 3.4 g of 4-chloro-3,5-dinitro-o-toluenesulfone

j amide, 3.4 g Ν, Ν-dipropylamine and 50 ml of toluene is on

Brought to reflux temperature, resulting in complete dissolution. After refluxing for 24 hours, the Mixture cooled and washed successively with water, dilute mineral acid and finally with water. the

^{Separate 1} organic layer and dry over MgSO. dried.

! ■ ■ ·

"After removing the MgSO. And solvent, the

Ϊ Got the product you want.

According to this general procedure, when using appropriate amines and dinitrosulfonamides instead of N, N-dipropylamine or 4-chloro-3,5-dinitro-o-toluene sulfonamide Compounds with the following structure and those in the table below X given melting points obtained.

209882/1209

CH.

^R l so ₂ ^R 2 NO. R _K
4 5 ^R 5 SchmO. ⁰ C. H T a b e 1 1 C ₄ H ₉ -SeC. e X H at H structure C ₃ H ₇ -n H 126-129.5 game H H ^R 4 H 108-109 144 ^C 3 ^H 7 ~ ⁿ C ₃ H ₇ -n H CH ₃ 226-228 145 C ₃ H ₇ -n ^C 3 ^H 7 " ⁿ H CH ₃ 140-142 146 C ₃ H -n ^C 3 ^H 7 ~ ⁿ H -CH-C-, Ης 124-127 147 H 132-134 148 ^CH 3 149 H

CH.

150 CH ₃ H H ^CH 3 206-208 151 H C ₄ H ₉ -SeC CH ₃ CH ₃ 120-122 152 H C ₄ H ₉ SeC. H C ₄ H ₉ -SeC. 112-114

Examples

153 to 158

Preparation of N-sec-butyl-3-methyl-2 _r 6-dlnitro-4- (trl-

fluoromethyl) aniline

A nitration mixture of 16.1 ml H ₃ SO ₄ (d = 1.84) and 1.9 ml HNO ₃ (d = 1.5) is ^{heated to 55 °} C. and slowly mixed with 3.5 q 5-chloro-2 - (trifluoromethyl) toluene added. The mix will

209882/1209

Heated to 55 ^° C. for 1 hour and then to 110 ^° C. for 1 hour. The reaction mixture is then cooled and poured onto ice, whereby 5-chloro-2- (trifluoromethyl) -4,6-dinitrotoluene is obtained as a cream-colored solid precipitate, which from cyclohexane gives 3.6 g of cream-colored crystals with a melting point of 81 to 82 ⁰ C is recrystallized.

A mixture of 1.8 g of 5-chloro-2- (trifluoromethyl) -4,6-dinitrotoluene with 3 ml of sec-butylamine and 30 ml of benzene is refluxed for 15 minutes. After the reaction mixture has cooled, the desired product is filtered off as a solid precipitate, washed with water until neutral, dried and vacuum-dried. It will be g N-sec-butyl-'3-methyl-2,6-dinitro-4- (trifluoromethyl) aniline obtained 1.5 as a yellow solid having a melting point 38 to 39 ⁰ C.

According to this general procedure, using appropriate amines instead of sec-butylamine, compounds with the following structure and the melting points given in Table XI.

NO.

CF.

209882 / 12Ö9

Tabel

example

structure

M.p. C.

-NH-CH (CH ₃ )

-N (CH ₃ )

32-35

yellow crystals, 75-76

yellow crystals, 107-108

-Ni

-NHCH (C.

orange-brown oil

44-45

example

159

Production of

10 g 3,5-dinitro-4-chloro-o-toluic acid are heated on a water bath with 9.2 g of phosphorus pentachloride and 3O ml of benzene _r whereby complete dissolution takes place. The benzene is then distilled and the phosphorus oxychloride is removed under reduced pressure. The desired product, which is obtained as an oily residue, solidifies on cooling.

Example 160 Preparation of 3,5-dinitro-4-chloro-o-toluamide

3,5-Dinitro-4-chloro-o-toluoylchloride is added with 2 equivalents Ammonia treated in cold acetone. The mixture is poured into water and that deposited as a solid Product is filtered off.

209882/1209

Example 161 Preparation of 3,5-dinitro-4-chloro-o-tolunitrile

15.5 g (0.051 mol) of finely powdered 3,5-dinitro-4-chloro-otoluamid are heated with 12 g (0.084 mol) of phosphorus pentoxide 15 minutes for 300 to 350 ⁰ C. The resulting nitrile is distilled off from the reaction flask. Recrystallization of the solidified product from methanol yields the desired product as an analytically pure material.

Example 162 Preparation of 4-cyano-3-methyl-2,6-dinitro-N, N-dipropy / aniline

A mixture of 4.82 g of 3,5-dinitro-4-chloro-o-tolunitrile and 3.0 g of di-n-propylamine in 25 ml of toluene is refluxed for 8 hours. The cooled mixture is then washed sequentially with water, dilute mineral acid and water. The organic layer is separated and dried _{over MgSO 4.} After filtering off the MgSO- and concentration of the filtrate in vacuo, the desired product is left behind as an oil which crystallized on cooling to form a solid substance having a melting point 97 to 99 ⁰ C.

Be i s ρ i e 1 163

Production of N-sec-butyl-3- (ethylthio) -4-methyl-2,6-

dinitroaniline

From 1.95 g (0.036 mol) of sodium methoxide and 4 ml of ethyl mercaptan A sodium ethyl mercaptide solution is prepared in 120 ml of cold methanol. This solution is under

2098 8 2/1209

Stirring with 8.63 g (0.03 mol) of N-sec-butyl-3-chloro-2,6-dinitro-p-tolu ± din, and the mixture is stirred for 2 hours at 5 to 10 ⁰ C. The reaction mixture is left to stand at room temperature for 3 days and then the solvent is evaporated off under reduced pressure, whereby 9.30 g of the desired product are obtained in the form of an oil. Chromatography on silica gel yields 2.7 g of purified product as an oil, which is identified by its infrared and nuclear magnetic resonance spectrum.

Example 164 Preparation of 3-chloro-6- (methy! Sulfonyl) -2,4-dinitrotoluene

A slurry of 4.9 g of 4- (methylsulfonyl) -2,6-dinitrom-cresol in 21 ml of phosphorus oxychloride is added to N, N-dimethylaniline at such a rate that the temperature does not exceed 34 ⁰ C. When the addition is complete and the initial exothermic reaction has subsided, the mixture is heated to 60 to 65 ° C. and held at this temperature for 10 minutes. The reaction mixture is then carefully decomposed by pouring it into a mixture of ice and water. The desired product separates out as a solid (4.49 g) is separated and recrystallized from benzene / petroleum ether to a solid substance having a melting point 174-175 ⁰ C.

Analysis calculated for CgH ₇ ClN ₂ OgS: C 32.59; H 2.37; N 9.50;

S 10.86; Cl 12.05.

Found: C 32.62; II 2.37; N 9.39;

S 10.65; Cl 12.25.

2Ü9ÜÜ2 / T20

Examples 165 to 172

Production of N- (I-methylhutyl) -4- (methylsulfonyl} -2,6-

dinitrp-m-toluidine

A mixture of 10.0 g (0.07 mol) of 3-chloro-6- (methylsulfonyl) l. 2,4-dinitrotoluene and 6.1 g (0.07 mol) of 2-amino-oentane in
75 ml of benzene is refluxed for 4 hours. After standing overnight, the mixture is washed successively with dilute hydrochloric acid, water, 5 percent strength aqueous potassium carbonate solution and water and then dried over magnesium sulfate. After removal of the magnesium sulfate
and the solvent remains the desired product
as a yellow oil, which crystallizes easily on cooling. The crude product becomes 9.5 g of substance from ethanol
with a melting point of 85 to 88 ⁰ C recrystallized. According to this general procedure, using appropriate amines instead of 2-aminopentane
Connections made with the following structure. Her
Melting points are given in Table XII below.

SO ₂ CH ₃

209882/1209

Table XII

at ^R l structure ^R 2 85-88 game H CH-C ₃ H ₇ -n 165 CH ₃ 150-152 C ₂ H ₅ ^C 2 ^H 5 166

167 C ₉ H ₁ - nC.H _Q 81-84

168 H ⁿ " ^C 3 ^H 7 167-169

169 H ISO-C ₃ H ₇ 156-158

170 H SeC-C ₄ H ₉ 66.5-69

171 ⁿ " ^C 3 ^H 7 ⁿ " ^C 3 ^H 7 112-115

172 H CH-C ₁ H ₁ , 135-136

Examples 173-190

Following the procedure of Examples 103 to 113., but with the appropriate sodium alkoxide and Chloraniün the compounds of the following Examples 173 to _{t t} 178 179, receive 182, 189 and 190th

209882/1209

¹ - ■ - 53 -

Likewise, after the procedure of Examples 100 to 102 the compounds of Examples 181 and 183 below were obtained using the appropriate amine.

When performing the procedure of Example 65
with the corresponding 3,4-substituted l-chloro-2,6-dinitrobenzene and the corresponding amine are the
Compounds of Examples 175, 176, 177, 180, 184, 185, 186, 187 and 188 are obtained.

209882/12 09

Table XIII example

173 O 174 CD CO OO N) 175 O CO 176

177

··. · ■ .. ■ 178

CH (C ₂ H ₅ ) ₂ Cl CH (C ₂ Hg) ₂ Cl CH-C ₃ H ₇ -Il -SO ₃ CH ₃ CH-C ₂ H ₅ -SO ₂ -NH-CH ₃ CH ₃
CHCH ₂ OCH ₃ -SO ₂ CH ₃ CH ₃
CH-C ₃ H ₅ -CF ₃

-OH.

-OH.

Schmo. C.

51-54 39-43

85-88 117-119

126-128

oil

- 54 -

OJ NJ NJ CO CO

label 1 e XIIl (cont.)

example

R, Schittp. ⁰ C

179

180

O 181 cc

"182

183

184

- ^C 2 ^H 5

-CH ₂ -CH = CH, HH

9 ^H 3

- ^C 2 ^H 5

-CH *

-CH-CH = CH,

-CH

-OCH ₂ CH ₂ OCH ₃

-NH,

-NH-CH (C ₂ Hg) ₂

-OH.

-NH ₂

oil

108-109 74-75

53-55

Oil 160-161

185

CH ₁ . CH-C ₂ H ₅

-NH,

155-156 ro - ro co hO - 55 - INJ CTJ co

Table XIII (cont.)

example

M.p. C

186

C ₃ H ₇ -Ii -C ₃ H ₇ -Ii

-CH.

-NH,

124-125

N. ' 187

bad 188

-CHCH ₂ OCH ₃

-CH (C ₂ H ₅ )

-CH.

-CH.

-CH.

46-47.5

189

190

-C ₃ H ₇ -Ii -C ₃ H ₇ -Ii

-CH (C ₂ H ₅ )

-CF.

-Cl

-OH.

-OCH ₂ CH ₂ OCH

34.5-38 oil

- 56 -

NJ 'GO

NJ NJ CO OJ

Example 191

Preparation of 3-chloro-2 _y 4-dinitro-6-methyl ~ carbanilshure

ethyl ester

Il

NHCOC ₂ H ₅

CH.

HCOC ₂ H ₅

CH.

A solution of 61.35 g (0.2871 mole) of S-chloro-ö-methyl-carbanilsäureäthylester in 600 ml of concentrated H ₂ SO ₄ is stirred and cooled with an ice bath at 5 ⁰ C. At a temperature of 5 to 10 ⁰ C, 40.22 g (0.5742 mol) of 90 percent HNO- are added dropwise. After the addition has ended, the solution is ^{stirred at 5 to 10 °} C. for 1/2 hour and then poured onto 8 l of ice. The solid is filtered off, washed well with water and dried. The product is a cream-colored solid (82.15 g, 94.2%) with a melting point 160-168 ⁰ C. Recrystallization from carbon tetrachloride provides a white solid of melting point 175-176 ⁰ C.

Analysis calculated for C ₁₀ H _{10 ClN 3} O ₆ : C 39.55; H 3.32; N 13.84; Cl 11.68. Found: C 39.80; H 3.19; N 13.79; Cl 11.78,

20 98 827 12 09

Example 192

Preparation of 5-chloro-4,6-dinitro-o-toluidine

NHCOC ₂ H ₅

70% H ₃ SO ₄

CH.

161.6 g (0.532 mol) of 3-chloro-2 ^ -dinitro-e-methyl-carbanilic acid ethyl ester are brought to 110 for 3 hours with 70 percent H ₃ SO ₄ (900 ml H ₂ O + 2100 ml concentrated H ₂ SO ₄ ) ⁰ C, then the solution is cooled and filtered through a coarse sintered funnel and the filtrate is poured onto 12 l of ice. The resulting yellow-brown solid is filtered off, washed well with water and dried, whereby 85.3 g (69.2%) of orange-yellow solid substance with a melting point of 185 to 190 ° C. are obtained. Recrystallization from toluene provides the yellow-brown solid of melting point 202-203 ⁰ C. From 95 nrozentigem ethanol are bronze-yellow needles. Melting point of 206 to 207 ⁰ C obtained.

Analysis calculated for C ₇ H _{6 ClN 3} O ₄ : C 36.30; H 2.61; N 18.15; Cl 15.31. Found: C 36.62; H 2.57; N 18.17; Cl 15.56.

2 098b2 / 1209

example

193

The test method of Examples 1 to 57 is with 4-chloro-N- (1-ethylpronyl) -2,6-dinitro-m-toluidine and 4-chloro-N- (1-ethylpropyl) -2,6-dinitro-m-anisidine repeated as test compounds and maleic hydrazide as comparative standard. 2 weeks after After the treatment, the shoots are removed from all nodes of the treated tobacco plants and weighed. The results are reported as percent inhibition compared to the fresh weight of shoots from untreated controls. The results obtained are shown in the table below. For comparison, the table contains maleic hydrazide, a commercially available bud growth regulator.

In similar tests, the compounds of Examples 173-188 are applied to tobacco plants at an application rate of 1,600 ppm applied, with which an inhibition of shoots of 50 to 99% is achieved.

Table XIV

1600 800 Inhibition,% 200 100 structure ppm ppm 400 tram ppm ppm NH-CH (C. 98 96.9 98.4 97.6 ² V ^ T ^N ° ² 96.5 X ^ OCH.
Cl W ₂ Ϊ

98

98

98.6

Maleic hydrazide

99.8 98.4

98

78.9

2Ü9882 / 1209

Example 194

The following tests are used to determine the inhibitory Effect of the compounds according to the invention on bud growth in wood plants, for example fruit and nut trees, carried out. When these compounds are used in amounts that inhibit bud growth, along with adjuvants Applied to fruit trees for horticultural purposes, for example before they develop buds, becomes a side branch effectively inhibited on the trees as shown below.

Red Delicious apple trees around 8 years of age are treated with aqueous solutions of before bud formation Test compounds sprayed. It becomes a trombone hand pump sprayer used with an adjustable conical nozzle that is used to generate droplets with moderately coarse Size is determined. 1.9 1 (1/2 gallon) aqueous solution containing test compound of 1200 ppm are added to each Tree upset. Untreated controls are used for comparison. The orders are carried out in early spring, and the trees are periodically placed on side branches on the inside during the growing season examined. Final examinations will be in late summer and early autumn about 3 to · 4 months after treatment carried out. The results are shown below.

209882/1209 j

Connection structure

-NO,

CF.

CH.

CH.

Table XV

Rate minor bud formation

ppm stems and internal branching

1200

1200

no

no

control

strong shoots trunk and branches

209882/1209

Claims (20)

Claims 1. A method for inhibiting bud growth on plants, characterized in that the plants with a the Bud growth inhibiting non-ohytotoxic amount a compound of the formula wherein R. is a hydrogen atom, a lower Cj-Cg-alkyl radical, a substituted lower C.-Cg-alkyl radical or a lower C - C - alkenyl radical, R2 is a lower C ₃ -C ₄ -alkenyl radical, a C ~ -Cg -Cycloalkyl radical, a lower C.-Cg-alkyl radical or substituted lower C.-Cg-alkyl radical, R _{3 is} a hydrogen atom, a halogen atom, a lower C.-C.-alkyl radical, a lower C 1 -C 4 alkoxy group or the group ~ CF_, —CN, —SO ₂ NR ₅ R— or —SOX, R _{4 is} a hydrogen atom, a halogen atom, an amino group, a lower mono-C.-Cg-alkylamino group, a lower di-C.-Cg-alkylamino group, a lower C ₁ -C ₄ -alkoxy groups, a lower C.-C - alkylthio group, a ^ -Cg -alkoxyalkoxy group or a lower Cj-C.-alkyl radical, R ₅ and Rg each a hydrogen atom or a lower C -C.- Alkylreet and R- mean a lower C ^ C ^ alkyl radical, brings into contact. 209882/1209 2. The method according to claim 1, characterized in that that a compound of the specified in claim 1 Formula used in which R ^ is a hydrogen atom. 3. The method according to claim 2, characterized in that a compound of the formula given in claim 1 is used, wherein R ₁ and R ₂ together contain a total of 3 to 6 carbon atoms. 4. The method according to claim 1, characterized in that a compound of the formula given in claim 1 is used used, where R. is the methyl radical. 5. The method according to claim 4, characterized in that a compound of the formula given in claim 1 is used, in which R 1 and R ₂ together contain a total of 3 to 6 carbon atoms. 6. A method for inhibiting the growth of axillary buds on tobacco plants, characterized in that tobacco plants with a bud growth inhibitor non-phytotoxic amount for the procedure treated according to claim 1 compound used. 7. The method according to claim 6, characterized in that that one applies the dinitroaniline to the tobacco plants as a solution in a liquid adjuvant which is about 10 ppm contains up to about 40OO ppm of the dinitroaniline. 209882/1209 8. The method according to claim 6, characterized in that the dinitroaniline is applied in an amount that about 0.11 to about 11.3 kg of the active compound per hectare of tobacco plantation to be treated (0.1 to 10 pounds per acre). 9. The method according to claim 8, characterized in that the solution about 1 to 8 weeks before harvesting the Tobacco leaves is applied to the foliage of the tobacco plants. 10. The method according to claim 8, characterized in that the dinitroaniline is N, N-dipropyl-2,6-dlnitro-4- (trifluoromethyl) aniline is used. 11. The method according to claim 8, characterized in that that as dinitroaniline 3,4-dimethyl-2,6-dinitro-N- (3-pentyl) aniline is used. 12. The method according to claim 8, characterized in that the dinitroaniline is 4-chloro-N- (1-ethylpropyl) -2,6-dinitrom-toluidine is used. 13. The method according to claim 8, characterized in that ' that as dinitroaniline N-sec-butyl-4-chloro-3-methyl-2,6-dinitroaniline is used. 14. The method according to claim 8, characterized in that the dinitroaniline is 3-methyl-N- (3-pentyl) -4- (trifluoromethyl) aniline is used. 209882/1209 15. The method according to claim 8, characterized in that that as dinitroaniline 4-chloro-N- (l-ethylpropyl) -2,6-dinitrom-anisidine is used. 16. The method according to claim 8, characterized in that that as dinitroaniline N-sec-butyl-3,4-dimethyl-2,6-dinitroaniline is used. 17. The method according to claim 16, characterized in that that the compound is applied as an aqueous solution to the tobacco plants in an amount of 0.57 to 3.83 kg per hectare (0.50 to 2.5 pounds per acre). 18. A method for inhibiting the growth of buds on plant bulbs and tubers, characterized in that that the bulbs or tubers with a bud growth inhibiting non-phytotoxic amount such as Treated in claim 1 defined compound. 19. Agent for inhibiting bud growth, characterized in that it is a bud growth inhibiting non-phytotoxic amount of a dinitroaniline as defined in claim 1 in combination with an excipient for Contains horticultural purposes. 20. A method for inhibiting secondary branches on fruit trees, characterized in that the trees are in front bud formation with a bud growth inhibiting non-phytotoxic amount of any as in claim 1 defined dinitroaniline in combination with an excipient for horticultural purposes. 209882/1209