DE3403437A1 - NEW DINITROPHENOLS, METHOD FOR THEIR PRODUCTION AND THE PLANT PROTECTION COMPOSITIONS CONTAINING THESE COMPOUNDS - Google Patents

Description

NEW DINITROPHENOLS, THE PROCESS FOR THEIR PRODUCTION AND THE PLANT PROTECTION COMPOSITIONS CONTAINING THESE COMPOUNDS

The invention relates to new dinitrophenols, a process for their preparation and the herbicidal, acaricidal and growth regulating agents containing these compounds as active ingredients Compositions. The new compounds correspond to the general formula (I)

- X

(D

wherein NO ₂

X for hydrogen, alkali metal or alkaline earth metal, for alkyl or alkenyloarbonyl group with 1-10 carbon atoms, for phenylcarbonyl group optionally substituted by halogen or a group of the general

Formula (a) stands

+
HNR ₁ R ₂ R ₃ (a)

in the R., Rg and R_ independently of each other Hydrogen, alkyl, alkoxyalkyl, alkenyl, hydroxyalkyl, cycloalkyl or optionally substituted phenyl group.

The plant care compositions according to the invention contain the compounds of the general formula (I) preferably in a concentration of 0.1-80 wt the usual carrier, streok and Auxiliary materials. The compositions of the invention can be used as emulsifiable concentrates, aqueous suspensions, dusty ones Wettable powder, oily paste, ale granules or in any other form.

In the process according to the invention for the preparation of the compounds of the general formula (I), first S-chloro-JtS-dinitro-benzotrifluoride in an aqueous medium without Catalyst hydrolyzed under alkaline conditions and, if desired, that obtained phenolate in a manner known per se to others

Compounds of general formula (I) implemented.

It is known that this corresponds to the connections of the general Formula (I) structurally related 2-methyl-4,6-dinitrophenol (dinitro-ortho-kreaol; DNOC) and its alkali salts have a herbicidal and acaricidal effect. Compositio Nones with this substance as an active ingredient are e.g. Novenda and cresonite. Another well-known herbicide is 2-sec-butyl-4,6-dinitrophenol (DHBP), a compound related to dinitroortho-kreaol, which is available in smaller doses Can also be used as a biostioulator in maize crops can (Ohlrogge, A.J .: The Development of DNBP / Dinoseb / as a Biostinjulant for C »-> rn in Plant Growth Regulators; Editor: Mare CA. 79-87 pp. Advances in chemistry series; 159. American Chemical Society, Washington, 1977).

Production processes have hitherto only become known for compounds which are structurally close to the compounds of the general formula (I) according to the invention. The literature gives no information whatsoever about the preparation of the compounds of general formula (I) and about their biological properties. From the British patent Wr. The preparation of 2 ₍ 4-bis (trifluoromethyl) 6-nitrophenol and its derivatives is known in 1,378,994. The preparation of 2,6-dinitro-4-trifluoromethylphenols and its derivatives is described in US Pat. No. 3,134,446 These known processes are carried out in organic solvents, in some cases in the presence of a phase transfer catalyst. Undesired nebane reactions also take place, for example the formation of ether derivatives in a methanol-containing medium, or the hydrolysis of the trifluoromethyl group to form the carboxyl group. These side reactions do not occur in the process according to the invention on.

In own research a chemical process for the preparation of the compounds of general Formula (I) worked out that also on an industrial scale is economical and leads to products of suitable purity. As further experiments showed, those with the Compounds of the general formula (I) obtained new processes have significant biological activity.

The compounds obtained with the process according to the invention of the general formula (I) have been shown in the form below Compositions examined in series of scientific tests for their biological effectiveness. the Experiments were successful and proved that with the compounds of the general formula (I) the selection of pesticidal agents through new herbicidal, acaricidal and growth regulating agents Funds can be provided.

The compounds of the general formula (I)

- X

wherein

I door hydrogen, alkali metal or alkaline earth metal alkyl or Alkenyloarbonylgruppe having 1-10 carbon atoms, optionally durob halogen substituted phenylcarbonyl, or a group of the general formula (a),

HiK ₁ R ₂ H ₃ (a)

in the IL, R ₂ and R. independently of one another hydrogen, alkyl, alkoxyalkyl, alkenyl-j hydroxyalkyl, cycloalkyl or optionally

mean substituted phenyl group,

«Earth prepared by in the first step from 2-chloro-3,5-dinitro-benzotrifluoride by reacting with an alkali. or alkaline earth hydroxide produces the corresponding alkali or alkaline earth phenolate. The reaction is carried out a lye concentration of 5-20 wt .-%, preferably 10-15 wt .- ^ ₁ without catalyst in aqueous medium at 20-100 ⁰ C, preferably at 60-80 ⁰ C, and. The phenolate obtained in the hydrolysis can be converted into the phenol derivative by means of an acid in a manner known per se;

The compounds of the general formula (I) are isolated from the reaction mixture and can then be used to form pesticides be formulated. The carriers, extenders and auxiliaries generally used in crop protection are used for this purpose used. The form of formulation is chosen according to the intended use. Depending on the application and the type of agent, the formulations preferably contain 0.1-80% by weight of active ingredient. The formulations are

or used to regulate plant growth.

The new compounds of the general formula (I) enrich the selection of compounds with a similar direction of action. They are therefore an enrichment for technology The chemical process according to the invention has the advantage of making these compounds more economical, simple and good To deliver in a reproducible manner · It is also advantageous that the reaction can be carried out in an aqueous medium without Catalyst, no harmful side reactions during hydrolysis expire.

The invention is explained in more detail with reference to the following examples, but is not restricted to these examples.

Preparation of the compounds of the general formula (I)

example 1

In a flask with a volume of 1000 mm, which is equipped with a stirrer, Equipped with a drip triohter, reflux condenser and thermometer iet, 300 g of 10% NaOH solution (0.75 mol of NaOH) are presented. 81.3 g of 2-chloro-3,5-dinltro-benzotrifluoride are added to the liquor with stirring 95% sweetness (0.3 mol) given. The mixture is heated to 60.degree. C. and 60-65.degree Stirred for 4 hours. In the process, an oauleion is formed from the aqueous suspension.

Since · Reaktionegeraieeh is cooled with stirring to room temperature door (20-25 ⁰ C) and within an hour corresponding to the, 0.82 mole amount of HCl 37% strength by weight hydrochloric acid. The mixture is stirred vigorously while the metering is to be carried out evenly. The precipitated Niederaohlag is filtered off, washed with water and dried to constant weight at room temperature. 68.1 g of 2-trifluoromethyl-4,6-dinitrophenol with a degree of purity of 94% are obtained (identified with a mass spectrometer connected to the Gaachromatograph). Yield: 90%.

Example 2

60 kg of water are poured into an enamelled reactor with a volume of 250 liters and a stirrer and reflux condenser. 32.5 kg of 2-chloro-3,5-dinitrobenzotrifluoride are stirred into the water while stirring using a powder funnel. The reaction mixture is heated to 75.degree. By a metering pump 65 kg 20% sodium hydroxide solution are pumped into the reactor at a uniform speed, the temperature is at 75-80 ⁰ C ge keep. The reaction mixture becomes fester for 3.5 hours stirred at the specified temperature and then cooled to room temperature. Ninety-five kg of concentrated hydrochloric acid are added at a steady rate over the course of an hour. The precipitate is centrifuged off, Washed with water and in the air until constant weight dried. 28 kg of 2-trifluoromethyl-4,6-dinitrophenol with a degree of purity of 94.3% are obtained. Yield 92.4%.

Making the compositions

Example 3 60% by weight emulsion concentrate (EC 60)

Ground 433 g of 2-trifluoromethyl-4,6-dinitrophenol (97%) « at 40 ° tJ in a mixture of 200 g of isophorone and 25 g of xylene solved. The solution is cooled to room temperature and filtered through a GAP filter with a pore size of 0.1 μm. The filtrate 36 g of Tensiofix B 7425 and 6 g of Tensiofix LS are used as emulsifiers

added while stirring

Example 4

60% emulsion concentrate (EC 60) The procedure described in Example 3 is followed, using Jedooh instead of isophorone, cyclohexanone, and instead of xylene the solvent Aromatol. The products mentioned in the table below are used as emulsifiers.

Emulsifier. in gi A B C Tenslofix AS 18-10 Tenaiofix LS 24 - -

fimileogen EL - 12 25

Sapogenate T 1Θ0 10 Sapogenat T 500 20 7 Example 5

20% by weight water-soluble concentrate (WSC 20) To 300 g of a 30% strength aqueous solution of 2-trifluoromethyl 1-4,6-dinitro-sodium phenolate, 50 g of all emulsifier are grounded Given ethylene glycol and 4 g of Tensiofix CG-21. The solution is made up to 450 g with deionized water while stirring.

Example 6

20% by weight oily paste

620 g of 2-trifluoromethyl-4,6-dinitrophenol are in 500 g Dissolved cyclohexanone and added 120 g of cosmetic vaeeline oil to the solution. With the help of an Ultra-turrax-l & aohera the solution obtained is emulsified with a 10 #lgen solution of the Bnulgatora Tensiofix PO-I32, the temperature increasing to 30 ⁰ C, is held. The mixture is cooled to 15 ° C. The 0.25 strength solution of Kelean S in ethylene glycol is distributed in an amount of 50 g in the mixture over the course of one hour, with slow stirring.

Effect studies Example 7

Investigation of the herbicidal effect in the greenhouse The seeds of white mustard, crooked amaranth, white goosefoot (melde), Italian fennich, winter wheat and quays are sown. After the emergence the plants were in the 2-4 leaf stage with 0.2 #iger Spray mixture (produced by diluting 10 # EC and WSC preparations made from the test compounds) sprayed, each compound being tested at application rates of 2.5, 5 and 10 kg / ha. On the 14th day after the

action, the damage to the plants was determined in percent. The results are shown in Table 1.

Tabel Ι mustard Ama
ranth Geese
foot Pennioh wheat Corn link dose
kg / ha 45
75
95 50
85
100 75
90
100 0
10
30th 0
5
10 0
5
15th 2-trifluoromethyl
4,6-dinitrophenol 1.25
2.55
5.0 40
60
80 50
60
85 70
75
80 0
10 0
10 0
mm
10 2-trifluoromethyl
4,6-dinitrophenol
diethanolamine 1.25
2.5
5.0 45
55
75 50
65
80 70
75
85 0
O
20th 0
0
10 0
0
10 2-trifluoromethyl
4.6-dinitropheny1-
dimethylamine 1.25
2.5
5.0 50
80
100 60
85
100 70
90
100 0
10
15th 0
0
15th 0
10
15th 2-trifluoromethyl
4,6-dinitrophenol-
sodium 1.25
2.5
5.0 65
75
90 45
85
100 70
90
100 0
10
15th 0
0
15th 0
10
15th 2-trifluoromethyl
4,6-dinitrophenol-
potassium 1.25
2.5
5.Ο Example 8

Determination of the inhibition of the Hill reaction

Using the method of Amon et al., Chloroplasts were isolated from spinach. To one gram of veined spinach leaves were added 6 ml of 0.35 molar saline solution and 0.6 ml of 0.2 molar TRIS buffer. The whole was ground, filtered through several pieces of cheesecloth, and then centrifuged at a speed of 2000 for 5 minutes. I> 6r low chloroplasts was suspended in 0.035 molar KooheaXelöaung, homogenized in the Potter tube and the chloroplast suspension obtained was ^{stored at 0 0} C until use.

From the chloroplast suspension and K ~ Fe (CN) g, K ₃ HPO ₄ , A Gemisoh is prepared with TRIS.HCl buffer and MgCl _0. to

-10 -3 this will be in the concentration range of 10 to 10 KoI Prepared solutions of the compounds of the general formula (I) (as inhibitors) or as standard substances

'—Ϊ2 - * - -

Entepreohende solutions of N- (3,4-diochlorophenyl) -N * _f N '~ diniethyloarbaniid (DCMU) and dinitro-ortho-kreeol (DNOC) are given. The resulting mixtures are exposed to an illuminance of 5000 lux for 20 minutes. Then the heating is terminated by adding 25% triochloroacetic acid (TCA). The precipitate is removed by centrifugation and the absorbance of the solution is measured at 420 ntn with an ^s P ^ectromoin 204 photometer. The series of measurements is repeated with samples kept in the dark. Inhibition of Hill-Heaktion was due to the difference in absorbance those determined in the light and those kept in the dark and converted into / Ug / ml potassium ferrooyanide by means of a Kioh curve net. (The percentages of inhibition were given as the puncture of the Concentration, and the curve became one Concentrations belonging to 50% inhibition were read (I ₅₀ ).) The results are shown in Table 2.

Compound I- (micromoles / dm)

2-trifluoromethyl-4,6-dinitrophenol 0.21

2-trifluoromethyl-4,6-dinitrophenol diethanolamine

2-trifluoromethyl-4 _i 6-dinitrophenoldlmethylamine

2-trifluoromethyl-4,6-dinitol; rophenol-Na

ο, 57 ο, 52 ο, 25th ο, 20th ° * 31 ο, 66 ο. 071

Comparison substances » Dinitro-ortho-cresol-Na N- (3,4-Dlohlophenyl) -N », N'-dimethyloarbamide

From these statements it is evident that 2-trifluoromethyl-4,6-dinitrophenol and its salts are similar to the N- (3,4-diochlorophenyl) -N *, N'-dimethyloarbamide inhibitors of the second photochemical systems and their effectiveness are roughly between that of N- (3,4-Diohlorphenyl) -N *, N'-dimethyloarbamids and des Dinitro-ortho-cresols lies. Of the compounds according to the invention, the amine salts show a lower value in this test Effectiveness of the alkali and ammonium salts.

Example 0

The investigations were carried out with the 2-trifluoromethyl-4,6-dinitrophenol-Na WSC 20 formulated according to Example 5 or with the 2-trifluoromethyl-4,6-dinitrophenol EC 60 formulated according to Example 3 . On 25/26 In April, maize grains of the Pioneer 3950 variety with a germ count of 73,000 / ha 8-10 om were sown in brown forest soil, which contained 1.8 % organic substances. On May 30, spraying was carried out with a plot spraying device (spray head Tee-Jet 11002, 1.5 atm Druok) and a water application rate of 300 liters / ha. At this point, most corn plants had 3-4 leaves, most weeds 2-4 leaves. Each composition was tested in four parallel experiments · At the time of treatment, the Pläohe was 87.5 X with weeds covered. Of that, 58 % was amaranth, 27 pounds goosefoot and the remainder was buttercup. The effect was evaluated on June 15th. The herbicidal effect on the weeds and the phytotoxic effect perceived on maize were determined using the EWRC scale.

Table 3 shows the rating scale, in Table 4 are the Results summarized. Each value is the mean of 4 parallel versions.

Table 3
EWRC value scale

Value Weed-killing destruction Damage to crops in percent action%

1 excellent 100 no 0 10 2 excellent 99 very weak 1 25th 3 Well 98 weak 2 50 4th satisfactory 95 eohwaoh to moderate 5 75 5 appropriate 90 moderate complete VerniohtunglOO 6th insufficient 75 mediocre 7th soles 50 strong 8th very bad 25th very strong 9 unusable .0

- 14 Table 4

EWRC values for different plants

Active ingredient and dose
Plant -— ^^^ 2-trifluoromethyl-4,6- 2-trifluoromethyl-
dinitrophenol-Na 4,6-dinitrophenol
20 WSC 60 EC
5 l / he 10 l / ha 1.6 l / ha 3.2 l / ha Amaranth
white goosefoot
Eohinoohloa
Corn 3 1.5 4 2
2 1 3.5 1
5.2 7 3.5
1.5 1.5 1 1

Example 10

Guard rotation and yield promotion in maize On April 20, maize of the MVSC 3780 variety was sown with a number of eggs of 55,000 / ha. At the beginning of the flowering period, on July 22nd, the Hubaohrauber was sprayed with 2-trifluoromethyl-4,6-ainitrophenol-Na (20 WSC). The application rate was 0.25 liters / ha (0.05 kg / ha). Each of the two parallel trials was carried out on a 4 hectare plot. 50 liters of water were used per hectare. The shark was _{harvested on #} 3 Movember. The results are compiled in Table 5 below.

parameter

Table 5 Versuoh I

Experiment II

control

Piston length, cm

Proportion of those not completely occupied with grains
Piston, %

16.07 + 2.19 17.06 + 2.71 17.33 + 1.87

62

66

with grains
of the piston busy
cm t / ha
in % of Part .
14, 52 + 2.80 15.35 + .3, 93 15.33 + 2.48 % 90, 35 93 , 34 89 97 Dedicated to a piston, G 229 , 6 + 6 208, 4 + . 5 191, 6 + 4 Crop yield, control 4,
119 25th
7th 4,
114 08
9 3,
100 55

The experiments showed that the 2-trifluoromethyl-4,6-dinitrophenol-Na exerts its yield-increasing effect through larger grains and a better occupation of the cob with grains.

Example 11

Investigation of the acaricidal effectiveness The tests were carried out on apple trees (Golden delicious) planted at intervals of 7.5 m by 4.5 m. On ^March _t before the expulsion of the shoots were sprayed from a Haflinger Sprühauto aua with a Hoohdruoksprühpistole (20 bar) · NaOH 46 hours of treatment were obtained from each plot, whether treated or untreated, 5 collected x 10 fruit shoots (on each plot grew 5 trees) and observed them in the laboratory until, in the case of the untreated control, all of the weaver mites had been popped out (12th position). The mortality was calculated from the number of mites hatched as a percentage of the control. The results are given in Table 6

Table 6 composition

Conc. Hatched dead £ mites (pcs.) Bene eggs from 5x10 shoots%

Infestation in % of the control

2-trifluoromethyl-4,6-dinitrophenol-Na

20 WSC 2 * 5

2-trifluoromethyl-4,6-dinitrophenol EC 60 0, B

Dinitro ortho-

kreaol

(DNOC-25) paste 2.0

untreated

Control -

19 23

27 521

96.35

95.59

94, Θ2

3.6

4.41

- 5.18

100

As the table shows, the compounds of the general formula (I) exceed the effect of the reference substance dinitroortho-cresol (paste Nov-enda 25)

Preferred compounds of the general formula (I) are those at where X is alkylcarbonyl, such as methyl, ethyl and propyl carbonyl.

The preferred alkenyl carbonyl compounds are based on vinyl., Isopropyl and allylcarbonyl.

When X stands for halogen-substituted phenylcarbonyl group 2-chloro-phenyl, 4-chloro-phenyl and 2,4-dichloro-phenyl are special preferred.

If X stands for a group of the general formula (a) , the preferred meanings of the substituents R ₁ , R and R are alkyl, such as methyl, ethyl; n-propyl, isopropyl, η-butyl, isobutyl, t-butyl and sec. To mention butyl; Of alkoxyalkyl, methyloxyethyl and ethyloxyethyl are preferred; of alkenyl allyl and 2-methyIaIIyI; in the case of hydroxyalkyl, 2-OH-ethyl; in the case of cycloalkyl, cyclopentyl and cyclohexyl; in the substituted phenyl group, 2-trifluoromethyl-phenyl, 3-trifluoromethyl-phenyl, 2-chloro-5-trifluoromethyl-phenyl and 3-trifluoromethyl-4-chloro-phenyl are preferred.

Claims (7)

DEAA-31642.7 February 1, 1984 NEW DINITROPHENOLS, PROCESS FOR THEIR PRODUCTION AND PLANT PROTECTION COMPOSITIONS CONTAINING THESE COMPOUNDS Patent claims 1 .. Dinitrophenols of the general formula (I) (D wherein X for hydrogen, alkali metal or alkaline earth metal, for alkyl or Alkenylcarbonyl group having 1 to 10 carbon atoms, for optionally phenylcarbonyl group substituted by halogen or a group of the general formula (a) stands in the R, R "and R independently of one another are hydrogen, alkyl-, alkoxyalkyl, Mean alkenyl, hydroxyalkyl, cycloalkyl or optionally substituted phenyl group. 2. Process for the preparation of new dinitrophenols of the general formula (I) (I) wherein X for hydrogen, alkali metal or alkaline earth metal, for alkyl or alkenylcarbonyl group having 1 to 10 carbon atoms, for phenylcarbonyl group optionally substituted by halogen or a group of the general formula (a) stands in the R., R "and R independently of one another are hydrogen, alkyl, alkoxyalkyl, Alkenyl, hydroxyalkyl, cycloalkyl or optionally substituted Pheny! Group mean characterized in that 2-chloro-3,5-dinitro-benzotrifluoride hydrolyzed with an alkali or alkaline earth metal hydroxide in an aqueous medium in the absence of catalysts and that if desired, the phenolate obtained is converted to the phenol or to other compounds of the general formula (I). 3. The method according to claim 2, characterized in that that the hydrolysis is carried out at an alkali concentration of 5 to 20% by weight, preferably 10 to 15% by weight. 4. The method according to claim 2 or 3, characterized in that the hydrolysis at temperatures of 20 to 100 ⁰ C, preferably 60 to 80 ⁰ C, is carried out. 5. Plant protection agents, characterized by 'a content of compounds of the general formula (I). 6. Plant protection agent according to claim 5, characterized in that it is 0.1 to 80 wt .-% as an active ingredient Contain compounds of the general formula (I) in addition to the customary carriers, extenders and auxiliaries. 7. Use of the compounds e'er general formula (I) as pesticides and as growth regulating substances.