FR2540489A1 - 2-TRIFLUOROMETHYL-4,6-DINITRO-PHENOL AND ITS DERIVATIVES, PROCESS FOR THEIR PREPARATION AND HERBICIDAL, ACARICIDAL AND CROP-REGULATING COMPOSITIONS CONTAINING THEM - Google Patents

Abstract

THE PRESENT INVENTION CONCERNS NEW COMPOUNDS AND THEIR PREPARATION. THIS IS 2-TRIFLUOROMETHYL-4,6-DINITRO-PHENOL AND ITS DERIVATIVES OF THE GENERAL FORMULA: (CF DRAWING IN BOPI) OR X REPRESENTS A HYDROGEN, AN ALKALINE METAL, AN ALKALINO-EARTH METAL, AN ALCOHOL IN CAC, AN ALCENYL-CARBONYL, A PHENYLCARBONYL, OR A PHENYLCARBONYL HALOGENO-SUBSTITUTE OR A GROUP OF THE GENERAL FORMULA: (CF DRAWING IN BOPI) OR R, R AND R ARE SIMILAR OR DIFFERENT AND MAY REPRESENT ALDROYLE, AN ALCOYLE, AN ALCOYLE, AN ALCOYLE ALCECYL, A HYDROXYALCOYL, A CYCLOALCOYL, A SUBSTITUTE PHENYL PHENYL. APPLICATION TO HERBICIDE, ACARICIDE AND CROP REGULATION COMPOSITIONS.

Description

The present invention relates to the novel 2-trifluoromethyl-4,6-dinitro-

  phenol and its derivatives, the herbicidal, acaricidal and crop-regulating compositions which contain them as active ingredients and a process for the preparation of the compounds. The novel 2-trifluoromethyl-4,6-dinitro-phenol and its derivatives may be characterized by the general formula I -X 02 N F 3 / I / o

X

  represents a hydrogen, an alkali metal, an alkaline earth metal, a C 1 to C 10 alkyl, or a

  alkenylcarbonyl, a phenylcarbonyl, a phenyl

  halo-substituted carbonyl, or a group of formula (a)

H N R 1 R 2 R 3

(a) o

  R 1, R 2 and R 3 are the same or different and represent

  hydrogen, alkyl, alkoxyalkyl, alkenyl

  nyl, hydroxyalkyl, cycloalkyl, phenyl or

substituted phenyl.

  NO 2 The compounds of general formula I exhibit herbicidal, acaricidal and crop-regulating activity. The compounds can be formulated into herbicidal, acaricidal or crop-regulating compositions, which preferably contain from 0.1 to 80% by weight of active ingredient and the usual carriers and excipients. The compositions can be prepared in the form of emulsifiable concentrates, aqueous suspensions, sprays in the form of a powder, an oily paste, granules, etc.

  The invention further provides a method of preparing

  tion of the compounds of general formula I by alkaline hydrolysis of 2chloro-3,5-dinitro-benzotrifluoride in aqueous medium without catalyst, and then if desired by conversion of the phenolate obtained into the final product

by a known method.

  It is known that 2-methyl-4,6-dinitrophenol

  similar, that is to say, the so-called dinitro-

  ortho-cresol (DNOC) and its alkali metal salts

  have herbicidal and acaricidal activity.

  Known compositions containing these ingredients

  assets are Novenda and Krezonit Similarly 2-sec-butyl-

  4,6-dinitro-phenol (DNBP) of similar chemical structure is a known herbicide, used at a lower dose as a biostimulator in corn crops (Ohlrogge, A: The Development of DNBP (Dinoseb) as a

  Biostimulant for Corn in Plant Growth Regulators, eds.

  publ: Stutte, C A pp 79-87 Advances Series in Chemis-

  try, 159 American Cnemical Society, Washington, 1977).

  No technical reference could be found to the preparation or biological activity of the compounds of general formula I according to the invention, only for analogous compounds. British Patent No. 1,378,994

  describes the preparation of 2,4-bis (trifluoromethyl) -6-

  nitro-phenol and its derivatives

  No. 3,813,446 discloses the preparation of 2,6-dinitro-4-

  trifluoromethylphenol and its derivatives

  known are conducted in an organic solvent, possibly

  in the presence of phase transfer catalysts In said processes unwanted side reactions, such as the formation of a derivative, occur.

  ether in methanol or the hydrolysis of the tri-

  fluoromethyl in the carboxylic group According to the invention

  There is no such side reaction.

  The process of the invention is suitable for the preparation

  of the compounds of the general formula I on the

  industrially and in a pure state.

  It has also been found that the new compounds

  present a surprisingly good biological activity.

  After having tested the various compositions of the invention,

  containing the new compounds as an ingredient

  active, it has been found that new composi-

  herbicide, miticide and crop regulation

  tures. When preparing the compounds of the general formula X represents hydrogen, an alkali metal, an alkaline earth metal, a C 1 -C 10 alkyl, or an alkenylcarbonyl, a phenylcarbonyl, a halo-substituted phenylcarbonyl, or a group of general formula (a),

  o R 1, R 2 and R 3 are similar or different and represent

  Feel hydrogen, alkyl, alkoxyalkyl, alkenyl, hydroxyalkyl, cycloalkyl, phenyl

or a substituted phenyl -

  We can proceed by starting by preparing a

  alkali metal or alkaline earth metal late by reacting 2chloro-3,5-dinitro-benzotrifluoride

  with an alkali metal or alkali metal hydroxide

  The reaction is carried out in an aqueous medium without catalyst at 20-1000 C, preferably at 60-80 ° C at an alkaline concentration of 5 to 20% by weight, preferably 10 to 15% by weight, if desired. , we

  transform the phenolate formed during alkaline hydrolysis

  phenol with an acid by a known method.

  If desired, the phenol is converted to a phenolate derivative using a base corresponding to the substituents of general formula I, the latter being used as an active ingredient as a pesticide after

isolation from the mixture.

  The pesticide composition is prepared using conventionally used carriers and excipients. The active ingredient content may vary within a range of from 0.1 to 80% by weight depending on the type of formulation and the method of application. The composition is used as a herbicidal, acaricidal or regulatory agent

cultures.

  The process of the invention is simple, economical and

  reproducible, and is suitable for the preparation of new

  calves compounds of the invention that expand the choice

  of pesticide agents by their bioactivity -

  The details of the invention are specified by the following examples which serve merely as a guide

and not limitation.

  Preparation of compounds of general formula I

Example 1

  To a 1000 cm flask equipped with a stirrer, a dropping funnel, a reflux and a thermometer is added 300 g (0.75 mol) of a solution of Na OH at% by weight on 81.3 g (0.3 mol) of 2-chloro-3,5-dinitro-benzotrifluoride with a purity of 95% are added while stirring. The temperature is raised to 60 ° C. and the reaction mixture is stirred at 60.degree.-65.degree. C for 4 h, while the aqueous suspension forms an emulsion.

  the reaction mixture at room temperature (20-

   C) while stirring and in 1 hour we add in several

  equal fractions while shaking vigorously

  37% hydrochloric acid solution corresponding to 0.82 mol of HCl is filtered off. The precipitated product is filtered off.

  wash with water and dry to constant weight at room temperature

  room temperature 2-trifluoromethyl-4,6-

  dinitrophenol (68.1 g, purity: 94%) The identification is conducted with a mass spectrometer connected to a

gas chromatograph.

Yield: 90%.

Example 2

  In a 250 liter enamelled reactor equipped with a mixer and a reflux, 60 kg of water are added and all

  with stirring, 32.5 kg of 2-chloro-3,5-dinitro-

  benzotrifluoride through a powder funnel The reaction mixture is heated to 75 ° C. and 65 kg of a 20% NaOH solution are introduced with a pump at an equal speed while maintaining the temperature at 75-800 ° C. The reaction mixture is stirred at 75-80 ° C. for 3 hours. The reaction mixture is cooled to room temperature and in 1 hour 9.5 cc of HCl are added at equal speed. The precipitated product is centrifuged, washed with water and dried to constant weight at room temperature.

  The product obtained is 2-trifluoromethyl-

4,6-dinitro-phenol (28 kg).

Purity: 94.3%, yield: 92.4%.

Preparation of the composition

Example 3

  Emulsifiable concentrate (CE) at 60% by weight.

  433 g of 2-trifluoromethyl-4,6-dinitro-

  97% phenol at 40 ° C. in a mixture of 200 g of isophorone

  and 25 g of xylene. The solution is cooled to room temperature.

  ambient temperature and cooled through a GAF filter of 0.1 micrometer to the filtrate is added while stirring

  36 g of Tensiofix B 7425 emulsifier and 6 g of Tensiofix LS.

Example 4

  Emulsifiable concentrate (CE) at 60% by weight.

  The procedure is as described in Example 3, but the isophorone is replaced by cyclohexanone and the xylene is replaced by an aromatol solvent and the following emulsifying agents are used:

A B C

  Tensiofix AS g 18 10 Tensiofix LS g 24 Emulsogen EL g 12 25

Sapoegenat T 180 g _ 10 -

Sapoegenat T 500 g 20 7

Example 5

  % by weight of water-soluble concentrate (CSE).

  To 300 g of an aqueous solution of 2-trifluoromethyl

  4,6-dinitro-phenol-Na at 30% by weight is added 50 g of ethylene glycol and 4 g of Tensiofix CG-21 emulsifiers. The solution is added to 450 g with water

  having undergone ion exchange while stirring.

Example 6

% by weight of oily dough.

  620 g of 2-trifluoromethyl-4,6-dinitro-

  97% phenol in 500 g of cyclohexanone and in this

  solution is poured 120 g of Vaseline oil cosmetic.

  The solution obtained is emulsified with a solution of

  % of Tensiofix PO-132 emulsifier by means of a mixture of

  After cooling to 15 ° C., 50 g of a Kelsan S ethylene glycol solution are dispersed in the mixture.

  0.2% by weight for 1 hour with slow stirring.

Example 7

  Test of herbicide activity in the greenhouse.

  In cropping boxes, oregano, amaranth, white anserine, ryegrass, and maize are sown in grains. When the seeds have grown, a 10% EC is prepared. 10% CSE from the compounds to be tested, and after dilution with water a 0.2% spraying product is prepared. This liquid is sprayed onto the 2- to 4-leafed plants so as to use for each compound a dose corresponding to 2.5-5-10 kg of active ingredient / ha At 14 days after treatment the importance of the damage to the plants is evaluated and expressed as a percentage The results

are shown in Table 1.

Table i

  compound Dose oregano amaran ansed rye wheat but

kg / ha te rined I Ita-t

kg / ha te white and tomato

2-trifluoran 6 ethy 1-

-4,6-dinitro phenol

2-trifluoromethyl 11-

4,6-dinitr-o-phenol

diethanolamine

2-trifiluoroffethyl 1-

4, 6-d initro-ph-e-ol-

diioethy 1-amine

2-trifluocroekthy 11-

4, 6-dlinitro-ph Mnol-

  1.25 2.55, 0 1.25 2.5, 0 1.25 2.5 1.25, 0

50 75 O O O

85 90 10 5 5

100 100 30 10 15

50 70 O O o

60 75

'85 80 10 10 10

50 70 O O O

65 75 O O O

80 85 20 10 10

g

O O O

O 10

15 15

J 2-trifluorcoe "thy 1-

4, 6-dlinitro-phenol

-K 1.25 2.5> O

45

85

100

o o o

O 10

15 15

Example 8

Determination of inhibition

of Hili's reaction.

  By the method of Arnon et al., Chlorine

  Spinach plastid With leaves removed from the nerves

  6 ml of a 0.35 molar solution of NaCl and 0.6 ml of 0.2 molar Tris buffer are added, the mixture is milled, and the homogenate is filtered through a multi-layered wire cloth and centrifuged for 5 minutes at a speed of 2000 rpm. The chloroplast precipitate is suspended in 0.035 molar NaCl, homogenized in a Potter tube and the thus obtained chloroplast suspension is maintained at

  use is made of a reaction mixture of the

  chloroplast pension, K 3 Fe (CN), K 2 HPO 4, Tris HCl buffer, Mg C 12 of appropriate concentration and ratios and a solution of compounds of formula (I) as

  inhibitors, N- (3,4-dichlorophenyl) -N ', N'-dimethyl-

  urea (DCMU) and dinitro-ortho-cresol (DNOC) as

  standards of a molar concentration of 1 x 10 10 -

  1 x 10-3 at an exposure of a luminous intensity of

  5000 lux for 20 minutes after which the reaction

  The precipitate is removed by centrifugation and the extinction of the solution at 420 nm is measured with a Spektromom 204 photometer. The series of experiments is also carried out with reaction mixtures maintained in the dark.

  Hill's reaction on the basis of the differences of extinc-

  measured in the dark and light reactions and converted to g / ml of potassium ferricyanide concentration on the basis of the calibration curve. The percentage values of the inhibition as a function of the concentration are reported. and we

  read from this curve the concentrations

  50% inhibition (I 50).

  The results are shown in Table 2.

Table 2

  compound 15 micromole / dm 3 2-trifluoromethyl 11 0.21 4,6-dinitro-phenol 2-trifluoromethyl 0.57

4,6-dinitro-phenol

  ditethanol-amine 2-trifluoromethyl 0.52

4,6-dinitro-phé'nol-

  d imethyl 11-amine 2-trifluoromethyl 0.25

-

  4,6-dinitro-phenol-NH 4 2-trifluoromethyl 11 0.20 4,6-dinitro-phenol-Na 2-trifluoromethyl 3,5-dinitro-phenol-K dinitro-ortho cresol-Na standard 0.86 N- / 3,4-dichloro-phenyl / -N ', N' 0,071 d imethyourea It is seen that 2-trifluoromethyl-4,6-dinitro-phenol

  and its salts are the same as N- (3,4-dichlorophenyl)

  N, N'-Dimethylurea inhibitors of the second photochemical system and that their effectiveness is between that of N- (3,4-dichloro-phenyl) -N ', N'dimethyl-urea and that of dinitro-ortho -cresol Among the compounds of 2trifluoromethyl-4,6-dinitro-phenol the amine salts

  are less effective than alkaline and ammonium salts.

Example 9

  Herbicide test in a corn field.

  The test is conducted with 2-trifluoromethyl-4,6-

  dinitro-phenol-Na 20 CSE formulated according to Example 5 and with 2-trifluoromethyl-4,6-dinitro-phenol 60 EC formulated according to Example 3 The experiment is conducted on

  a brown forest floor containing 1.8% organic substance.

  The soil is sown on 25 and 26 April with 3950 maize with a seed count of 73000 / ha at a depth of 8-10 cm.

  May 30 at 1.5 atm by means of a spraying machine.

  parcel equipped with a sprinkler system

  type Tee-Jet 11002 with water at a rate of 300 liters / ha at this time maize has 3 to 4 leaves, the main part of the weeds has 2 to 4 leaves The tests are repeated 4 times Au At the time of spraying the field is 87.5% weedy, 58% with amaranth, 27% with anserin

  white and the residue is covered with barnyardgrass.

  Activity is assessed on June 15 EWRC is assessed for weed control activity and

  phytotoxic symptoms observed in corn.

  The EWRC scale required for the evaluation is contained in Table 3 and the results are summarized in Table 4 The data in Table 4 are values

  averages obtained from 4 repetitions.

Table 3

  Scale of evaluation EWRC Scale Effect of Destruction Effect on the plants of evaluation of the% domesticated bad tion Reach Destruction% grass 1 excellent 100 null O 2 excellent 99 very 1 light 3 good 98 light 2 4 satisfactory -95 light 5 moderate sufficient 90 moderate 10 6 insufficient 75 average 25 7 bad 50 strong 50 8 very bad 25 very strong 75 9 not appropriate O complete destruction 100

Table 4

  EWRC values Composition Amaranth amaranth dose panic may 1 / ha white stalk 2-trifluoromethyl 5 3 2 5 1,5 4,6-dinitro-phenol 10 1,5 1 2 1, 5 Na 20 CSE 2-trifluoromethyl 1,6 4 3,5 7 1 4,6-dinitro-phenol 3,2 2 1 3, 5 1 EC

Example 10

Regulation of maize crops.

  Experimental compound: 2-trifluoromethyl-4,6-dinitro-

phenol NA 20% CSE.

  On April 10, MVSC 3780 corn is sown with

  a number of sprouts of 55,000 / ha.

  by helicopter on 22 July at the beginning of the

  flowering of the maize at a beard length of 4-5 cm.

  Application at the rate of 0.25 liter / ha (0.05 kg of

  Active groyant per ha) Plots of land are 4 ha and the test is repeated twice.

  Once 50 liters of water are harvested on November 3rd.

  The results are summarized in Table 5.

Table 5

  Length of head of weight of maize ear corn ear ear of corn covered with grains dkg cm 1 repetition 16.07 + 2.19 14.52 + 2, 80 22.96 + 6 62 % of 90.35% of ears are defecated with killer spike but are covered by kernels 2 rehearsal 17.06 + 2.71 15.35 + 3.93 20.84 + 5 66% of ears 93.34% are defunct ears is killer covered by grains 9 control 17,33 + 1,8715,33 + 2,48 19,16 + 4 84% of the ears 89,97% of the corn are ears is defective covered by grains Medium Crop: 1st repeat: 4.25 to / ha = 119.7% 2nd repeat: 4.08 to / ha = 114.9% 0 control: 3.55 to / ha = 100% According to test 2 -trifluoromethyl-4,6-dinitro-phenol-Na 20 CSE can induce a significant increase in harvests because of its effect to increase grain size and to improve

grain density.

Example 11

Test of acaricide activity.

  We set the test on Golden apples

  in a field of 7.5 x 4.5 m in particular.

  those of 5 trees arranged in rows Spraying is carried out on March 16 before budding at a pressure of 20 bar with a manual spray gun

  high pressure of a Haflinger spray.

  Experimental compounds: 2-trifluoromethyl-4,6-dinitro-

  phenol-Na 20% CSE and 2-trifluoromethyl-4,6-dinitro-

  phenol 60% EC Protective activity against red spider eggs surviving winter by collecting 5 x 10 pieces of fruit buds in treated and untreated plots 48 h after

  treatment The observations are continued in the laboratory.

  until the hatching of the spiders

  mine (12 days) The percentage mortality is determined based on the number of hatched spiders and is expressed as a percentage of the control. The results are presented

in Table 6.

Table 6

  Composition Concentration Number Mortality Infection of the compo of arai of% sition in dams eggs of the hatched liquid% control of pulveri in sation 5 x 10% pieces

of bour-

  fruit trees 2-trifluoromethyl 2,5 19 96,35 3,65

4,6-dinitro-phenol

  Na 20 CSE 2-trifluoromethyl 0.8 23 95.59 4.41

4,6-dinitro-phenol

  CE Dinitro-ortho 2.0 '27 94.82 5.18 cresol MDNOC-25) (paste) Untreated control 521 O 100 Compounds activity of the general formula I present Novenda-25 paste containing dinitro-ortho cresol.

Claims (3)

  1 2-trifluoromethyl-4,6-dinitro-phenol and its derivatives of general formula I O-X 02 N F 3   N 02 o X represents a hydrogen, an alkali metal, a metal   alkaline earth metal, a C 1 to C 10 alkyl, an alkenyl   nylcarbonyl, a phenylcarbonyl, or a phenyl   halogen-substituted carbonyl or a group of the general formula (a) OHNR 1 R 2 R 3 (a) R 1, R 2 and R 3 are the same or different and can represent a hydrogen, an alkyl, an alkoxyalkyl, an alkenyl, a hydroxyalkyl, a cycloalkyl,   phenyl or substituted phenyl.   2 A herbicidal, acaricidal or crop-regulating composition comprising as active ingredient a compound according to claim 1.   3 Process for the preparation of 2-trifluoromethyl-4,6-dinitro   phenol and its derivatives of the general formula I X is as given in claim 1, wherein the 2-chloro-3,5-dinitrobenzotrifluoride is hydrolyzed with an alkaline hydroxide or an alkaline earth metal hydroxide in an aqueous medium. without catalyst and, if desired, converting the obtained phenolate to phenol and, if desired, converting the phenol obtained to phenolate of the general formula I by a known method. Process according to claim 3, wherein the hydrolysis is conducted at an alkaline concentration of 5 to 20%   by weight, preferably 10 to 15% by weight.   Process according to any one of the claims   3 or 4, wherein the hydrolysis is carried out at 20-100 ° C, preferably at 60-80 ° C.