DE1518025B - - Google Patents

Description

In the French patent 1,321,663 pesticides are described which as Active ingredient a compound of the general formula

O-CX-Y-R

NO,

(I)

0, N

NO,

(Π)

R ¹ -CH-R ²

in which R is an alkyl group having 1 to 12 carbon atoms and R ¹ and R ^{2 are} n-alkyl groups having 2 to 5 carbon atoms and together 6 to 10 carbon atoms.

The group R can contain 1 to 12 carbon atoms, but preferably contains only 1 to 4 carbon atoms, i.e. h., It is, for example, a methyl, ethyl, propyl, isopropyl, butyl or Isobutyl group. Those compounds in which R is a methyl or ethyl group are particularly preferred is. In particular, the methyl compounds have an excellent effect against powdery mildew, but the effect of the ethyl compounds is also very good.

The group R ¹ · (R ² ) CH is either an n-hexyl group, which is substituted in the α-position by an ethyl, n-propyl, η-butyl or n-pentyl group, or an n-butyl group, which is substituted in the α-position by an n-propyl group, or an n-pentyl group which is substituted in the α-position by an ethyl, n-propyl or n-butyl group.

There are already various methods of preparing dinitro derivatives of hydrocarbon-substituted ones Known phenols. However, the products of these processes were often mixtures of isomers. at the preparation of the phenols used as starting materials for the compounds according to the invention and their dinitro derivatives used compounds must therefore take special measures so that the desired compounds are obtained.

The compounds of the invention can be prepared by a compound of general formula

PQ

in which X and Y are identical or different and each represent an oxygen or sulfur atom, R is, inter alia, an alkyl group and one of the radicals R 'and R "is a nitro group and the other a branched aliphatic hydrocarbon group of 4 to 8 carbon atoms, a phenyl, substituted one Phenyl, cyclohexyl or substituted cyclohexyl group is included.

It has now been found that certain 2,6-dinitrophenyl carbonates, some of which fall under general formula I in that mentioned above Patent specification, however, are not listed by name, have a good fungicidal effect. · In particular some of the carbonates of the present invention have a stronger action against powdery mildew than those in FIG of the mentioned patent specification.

Another advantage of the compounds of the invention is their low phytotoxicity, which above all is lower is than that of the corresponding starting dinitroalkylphenols.

The carbonic acid alkyl (2,6-dinitro-4-alkylphenyl) esters according to the invention have the general principles formula

O — CO — OR

0, N

NO,

(III)

R ¹ -CH

wherein Q represents a hydrogen or alkali metal atom, preferably sodium or potassium, and R ¹ and R have the meaning given above diz- ^2, with an ester of the formula:

Z - CQ - OR

(IV)

in which Z is chlorine, bromine or iodine, preferably chlorine, and R is as defined above has, implemented, the reaction in the presence of an acid-binding agent, for example one Alkali carbonate, an alkali bicarbonate or a tertiary amine such as pyridine is carried out when Q is a hydrogen atom. This reaction is expediently carried out in solution of an inert solvent, for example a ketone such as acetone.

The phenolate of the formula III, in which Q is an alkali metal, can previously or preferably in situ in an inert organic solvent can be prepared before the haloformic acid ester is added is by the starting phenol V with a suitable alkali compound, for example a Alkali hydroxide, carbonate or bicarbonate, converts.

The preparation of the compounds according to the invention by reacting a phenolate of the general Formula III with a compound of the general formula IV is particularly advantageous because the_Verwen-. Generation of the phenolate in place of the starting phenol V and a tertiary base the process in general makes more economical.

Another advantageous process for the preparation of the compounds according to the invention consists in that the starting phenol V with a haloformic acid ester IV in an inert organic Solvent, for example a ketone such as acetone, in the presence of an alkali carbonate or alkali bicarbonate, preferably an alkali carbonate. This process, too, is generally more economical than the use of the starting phenol V and a tertiary base. The use of alkali carbonates or alkali bicarbonates is made preferred.

The starting dinitroalkylphenols of the formula

O, N

NO,

(V)

R ¹ -CH-R ²

in which R ¹ and R ^{2 have} the above meanings

can be obtained by dinitrating the corresponding alkylphenols. This dinitration can be done by any known method. Preferably, the 4-alkylphenol is in solution in an inert organic solvent, especially a hydrocarbon or a halogenated one Hydrocarbon, with stirring to aqueous nitric acid, the at least two equivalents of nitric acid contains, added, after the addition is complete, the temperature of the reaction mixture is increased, to complete the nitration, and after the reaction has ended, the reaction mixture cooled and the nitrophenol separated from the reaction mixture.

Alkylphenols similar to those used for the preparation of the carbonates according to the invention are analogous, are already by reacting phenol with an Aikyiierungsmittel, for example a Alkene or a mixture of an alkanol with a dehydrating agent. When applying this process produces a mixture of 2- and 4-alkylphenol and a mixture as the product obtained from alkyl side chain isomers. To practically pure 4-alkylphenol with the desired side chain structure To obtain, therefore, the mixture must be separated, for example by making it before or fractionally distilled after nitration.

The 4-alkylphenols can also be prepared by combining a p-hydroxyphenyl alkyl ketone with the corresponding alkyl magnesium halide, so that a tertiary carbinol is obtained. Subsequently the carbinol is dehydrated and then the olefin formed, for example using of palladium / activated carbon in ethanol, catalytically hydrogenated. The water can split off when heated take place spontaneously or with the aid of an acidic catalyst, for example potassium hydrogen sulfate, p-toluenesulfonic acid or sulfuric acid. When using such a procedure achieves that the 4-alkyl group has exactly the desired branching. In some cases it can be advantageous to use the methyl ether of p-hydroxyphenyl alkyl ketone to increase solubility to improve in the solvent used for the reaction and / or side reactions to avoid, the product of the reduction of the olefin then having to be demethylated.

The compounds can be used as pesticides of the invention can be used in conjunction with a carrier or diluent. You can if desired, in a mixture with other pesticidal active ingredients, for example other fungicidal active ingredients or acaricidal or insecticidal active ingredients are used. The carriers can be liquid or be solid and are intended to facilitate the application of the compound, either by making it easier to disperse Facilitate the point of use or together with the active substance produce a means that is of the Consumers can be converted into a dispersible preparation.

Liquid means thus contain the compound in the form of a solution or emulsion, which as such be used or with water or another diluent, for example to a spray, can be diluted. In these cases the carrier is a solvent or an emulsion base, the are not phytotoxic under the conditions of use. These agents generally also contain a Wetting, dispersing or emulsifying agents. Other liquid agents are, for example, aerosols, which the Compound together with a liquid carrier or propellant.

Solid preparations, such as dusts and wettable powders, granulates and pellets, and semi-solids, such as pastes, inert solids or liquid diluents, such as clays, can have a wetting effect by themselves have, and / or contain wetting, dispersing or emulsifying agents. Also binders and or or Adhesives can be included in such agents. The solid preparations also include smoke generators, which contain the compound together with a solid pyrotechnic component.

The production of the compounds according to the invention is explained in more detail below.

A. Preparation of the alkylphenols

The alkylphenols were prepared as described above using an alkylmagnesium halide and a hydroxyphenyl ketone or methoxyphenyl ketone, then followed. To derrn dehydration with potassium hydrogen sulfate - ^ corresponding olefin and hydrogenating the olefin in the "presence of palladium / charcoal in ethanol If the anisole derivatives had to be used, · the Methyliening of the hydroxy ketone in the usual f manner using dimethyl sulfate throughput \ been performed;. the final demethylation was then carried out by heating with hydrobromic acid in acetic acid to form the phenol.

An example of making an alkylphenol is: '

Production of 4- (l-n-propyl-n-butyl) -phenol

1. 4- (1-n-Propyl-n-butenyl) anisole

A solution of 42 g of n-propyl bromide in 50 ml of sodium-dried ether was added dropwise to 7.0 g of magnesium, which was covered piit 100 ml of sodium-dried ether, the rate of addition being adjusted so that the mixture was refluxed on The boil was kept. The mixture was then refluxed for a further IV2 hours, after which a solution of 45 g of p-methoxy-: n-butyrophenone in 40 ml of sodium-dried ether was added dropwise with stirring at such a rate that the mixture remained boiling. The reaction mixture was then refluxed for a further 3 hours, cooled, poured onto crushed ice and diluted with. Acidified sulfuric acid in excess. The ethereal layer was separated, washed with water and distilled on the steam bath at a pressure of 20 torr. 9 drops of concentrated sulfuric acid were added to the distillation residue, and this mixture was heated ^{to about 50 ° C. overnight.} Ether and dilute sodium hydroxide were added to the cooled mixture, and the ethereal solution was separated, washed with water and dried over sodium sulfate. The dried solution was filtered and distilled to give 41.9 g (yield 81%) of 4- (ln-propyl-n-butenyl) -anisole from Kp. _17145-150 ⁰ C, NF 1.5239.

Calculated ... C 82.35, H 9.80%;
found .... C 82.08, H 9.87%.

i O 1 O KJAO

2. 4- (In-propyl-n-butyl) anisole

A solution of 41 g of 4- (in-propyI-n-butenyl) anisole in 25 ml of absolute alcohol was added to a catalyst suspension of 2 g of activated carbon with 10% palladium in 25 ml of absolute alcohol, and the mixture was hydrogenated at about atmospheric pressure . After hydrogen uptake ceased, the catalyst was filtered off and the filtrate was distilled. This gave 37.1 g (yield 90%) of 4- (ln-propyl-n-butyl) -anisole from Kp. _15139-143 ° C, NF 1.4950.

C ₁₁₁ H ₂₂ O:

Calculated
found .

C 81.55, H 10.68%;
C 81.42, H 10.61%.

3. 4- (1-n-propyl-n-butyl) phenol

36 g of 4- (l-n-propyl-n-butyl) anisole were in a mixture of 250 ml of glacial acetic acid and 160.8 g of 47% strength dissolved aqueous hydrobromic acid. The mixture was refluxed for 11 hours, cooled and extracted once with 100 ml and then again with 50 ml of petroleum ether (boiling point 40 to 60 ° C.). the Solution was with water and then twice with 100 ml of a mixture of 50 ml of a 25%

- Washed sodium hydroxide solution and 50 ml of methanol. The combined alkaline extracts were then acidified with 100 ml of petroleum ether (bp. 40 to 60 ⁰ C) and washed with concentrated hydrochloric acid. The phenol formed was extracted once with 100 ml and then again with 50 ml of petroleum ether (boiling point 40 to 60 ° C.), and the solution in petroleum ether was washed with water, dried with sodium sulfate and distilled. This gave 31.35 g (yield 93.4%) of 4- (ln-propyl-n-butyl) -phenol, bp. _19156-160 ° C (mostly 158-159 ⁰ C) to needles F. 61 to 64 ° C (softening at 57 ⁰ C) solidified.

Q3H20O:

Calculated ... C 81.25, H 10.42%; found .... C 81.17, H 10.35%.

20 In Table I the properties of the obtained according to this process, 4-alkylphenols are together-detected.

Table I.

4-alkyl substituent on phenol

Gross formula

analysis

Found, %
CH

Calculated,% C H

1-n-propyl-n-butyl.
1-ethyl-n-pentyl ...
1 -n-propyl-n-pentyl
1-n-butyl-n-pentyl ..
1-ethyl-n-hexyl
1-n-propyl-n-hexyl.
1-n-butyl-n-hexyl ..
1-n-pentyl-n-hexyl ..

158 to 159

19 mm
154 to 155
15 mm
124 to 125
1.8 mm
180

20 mm

153 to 154

10 mm
167

12 mm
186-to 187

11 mm
131.5
to 132
0.45 mm

solid, m.p. up to 64 ° C 1.5105 (17)

solid, F. up to 37 ° C solid,

F. 55 ⁰ C 1.5070 (18)

1.5031 (21) 1.5008 (20) 1.5017 (20) C13H20O

Q3H20O
C ₁₄ H ₂₂ O

C ₁₅ H ₂₄ O
C ₁₄ H ₂₂ O
C ₁₅ H ₂₄ O
C ₁₆ H ₂₆ O

81.17
81.33
81.84
81.06
79.16
81.61
82.05
81.87

10.35 10.15 10.97

10.25 10.88 10.92 10.77

81.25 81.25 81.55 81.82 81.55 81.82 82.06 82.24

, 10.42 10.42 10.68 10.91 10.68

J0.91 11.11 11.29

B. Production of Dinitroalkylphenols

Production of
4- (1-n-propyl-n-hexyl) -2,6-dinitrophenol

_{A mixture of 22.5 ml of 69 to 72% HNO 3} 'and 22.5 ml of water was added to a solution of 19.2 g of 4- (in-propyl-n-hexyl) -phenol in 34.1 ml of ethylene dichloride . The mixture was _{refluxed IV for 2} hours. The ethylene dichloride layer was separated, washed with a saturated aqueous sodium sulfate solution, dried over anhydrous sodium sulfate and filtered. The ethylene dichloride was separated from the dried solution. The residue was dissolved in 125 ml of petroleum ether (bp. 40 to 6O ⁰ C). 15 ml of cyclohexylamine were added to the solution, and the mixture was cooled down, 24 g of orange crystals with a melting point of 162 to 164 ° C separating out, which after recrystallization from 33% strength aqueous isopropanol, 20.7 g of a salt with a melting point of 165 to 166 ° C ° C. This salt was dissolved in methanol and the solution was acidified with concentrated hydrochloric acid. The mixture was diluted with water, and the precipitating brown oil was extracted with petroleum ether (bp. 60 to 8O ⁰ C). The extract was washed with water, dried over anhydrous sodium sulfate and filtered, and the petroleum ether was separated from the filtrate. 14.9 g of 4- (in-propyl-n-hexyl) -2,6-dinitrophenol were obtained in the form of an oil.

In Table II are the physical properties of this compound and others, also about theirs Cyclohexylamine salts prepared Dinitroalkylphenole compiled.

1 Ölö UZÖ

Table II Refractive index des
Phenol
nf '· Gross formula Found,
N,% Calculated,
N,% 4-alkyl substituent
of 2,6-dinitrophenol F. of the cyclohexyl
amine salt *)
° c. 1.5528
1.5526
1.5482
1.5435
1.5464
rig 1.5424
1.5382
1.5345 Q ₃ H ₁₈ N ₂ O ₅
Q ₃ H ₁₈ N ₂ O ₅
Q ₄ H ₂₀ N ₂ O ₅
Q ₅ H ₂₂ N ₂ O ₅
Q ₄ H ₂₀ N ₂ O ₅
Q ₅ H ₂₂ N ₂ O ₅
Q ₆ H ₂₄ N ₂ O ₅
Q ₇ H ₁₆ N ₂ O ₅ 9.8
10.2
9.25
9.88
8.95
8.95.
8.22. 9.9
9.9
9.46
9.03
9.46
9.03
8.64
8.30 1-n-propyl-n-butyl
1-ethyl-n-pentyl
1-n-propyl-n-pentyl
1-n-butyl-n-pentyl:
1-ethyl-n-hexyl. ^:
1-n-propyl-n-hexyl
1-n-butyl-n-hexyl
1-n-pentyl-n-hexyl 197 to 199
171 to 172
179.5 to 181
184 to 185
164 to 166
165 to 166
180 to 182
183 to 184

*) Recrystallized from aqueous isopropanol.

C. Preparation of the carbonates

All carbonates were made from the corresponding 2,6-dinitro-4-alkylphenols. The physical properties of the carbonates are listed in Table III, the groups R, R ¹ and R ² having the meaning given at the beginning in connection with formula II. The radicals R are in each case n-alkyl groups, unless otherwise stated. All the carbonates listed were oil-like substances with a golden yellow to reddish brown color. The preparation of the compound of Example 26 is described below as an example of the preparation of a carbonate: 2.07 g of 2,6-dinitro-4- (1-ethylhexyl) phenol, 0.48 g of potassium carbonate and 10 ml of acetone were used

Heated under reflux for 30 minutes. The 'formed solution was added 0.84 g of ethyl chloroformate, and the mixture was refluxed for 2 hours and 45 minutes. The precipitated potassium--, chloride was filtered off. The acetone was evaporated from the filtrate and the residue was dissolved in Dissolved benzene and shaken with aqueous 2N sodium carbpnate. The benzene solution was made with water washed and dried over anhydrous sodium sulfate. The dried solution was filtered, and the benzene was evaporated from the filtrate under reduced pressure. 1.85 g of 2,6-dinitro- • 4- (l-ethylhexyl) phenylethyl carbonate were obtained in the form of my yellow oil. -

Table III

R. R ¹ R ² Refractive index
n'S Incision formula ^
ß analysis Calculated example Found, . N,% CH ₃ QH ₅ C ₄ H ₉ 1.5188 Q ₅ H ₂₀ N ₂ O ₇ N,% 8.24 1 QH ₅ QH ₅ C ₄ H ₉ 1.5148 Q ₆ H ₂₂ N ₂ O ₇ '8.1'5 _ 7.91 2 CH ₃ QH ₇ . QH ₇ 1.5179 Q ₅ H ₂₀ N ₂ O ₇ 8.16 8.24 yrs 3 QH ₅ : QH ₇ - C ₃ H ₇ 1.5127 Q ₆ H ₂₂ N ₂ O ₇ . 7.72 7.91 4th CH ₃ QH ₇ C ₅ H ₁₁ 1.5126 Q ₇ H ₂₄ N ₂ O ₇ 7.43 7.61 5 QH ₅ ^: QH ₇ C ₅ H ₁₁ 1.5085 Q ₈ H ₂₆ N ₂ O ₇ 7.85 ' • 7.33 6th CH ₃ QH ₇ C ₄ H ₉ 1.5131 - Q ₆ H ₂₂ N ₂ O ₇ 7.43 .7.91 . ' 7th QH ₅ QH ₇ C ₄ H ₉ 1.4995 Q ₇ H ₂₄ N ₂ O ₇ 7.90 7.61 8th CH ₃ C ₄ H ₉ C ₅ H ₁₁ 1.5102 Q ₈ H ₂₆ N ₂ O ₇ 7.81 7.33 9 QH ₅ C ₄ H ₉ QH ₁₁ 1.5063 Q ₉ H ₂₀ N ₂ O ₇ 7.31 7.07 10 sec-butyl QH ₇ C ₄ H ₉ 1.5033. Q ₉ H ₂₈ N ₂ O ₇ 7.03 7.07 11th CH ₃ C ₄ H ₉ C ₄ H ₉ 1.5132 *) Q ₇ H ₂₄ N ₂ O ₇ 7.01 7.61 12th QH ₅ C ₄ H ₉ C ₄ H ₉ 1.5085 Q ₈ H ₂₆ N ₂ O ₇ . 8.1 7.33 13th CH ₃ C ₅ H ₁₁ C ₅ H ₁₁ 1.5072 Q ₉ H ₂₈ N ₂ O ₇ 7.65 7.07 14th QH ₅ QH ₁₁ C ₅ H ₁₁ 1.5040 Q ₀ H ₃₀ N ₂ O ₇ 7.45 6.83 15th QH ₇ QH ₅ C ₅ H ₁₁ 1.5068 Q ₈ H ₂₆ N ₂ O ₇ . 7.52 7.3 ' 16 CH (CH ₃ ), QH ₅ C ₅ H ₁₁ n ¹ i 1.5062 Q ₈ H ₂₆ N ₂ O ₇ 7.3 7.3 17th C ₄ H ₉ QH ₅ C ₅ H ₁₁ 1.5049 Q ₉ H ₂₈ N ₂ O ₇ 7.4 7.1 18th sec-butyl QH ₅ C ₅ H ₁₁ 1.5030 Q ₉ H ₂₈ N ₂ O ₇ 7.1 7.1 19th Isobutyl QH ₅ C ₅ H ₁₁ 1.5035 Q ₉ H ₂₈ N ₂ O ₇ 7.0 7.1 20th QHi ₃ QH ₅ C ₅ H ₁₁ 1.5012 QiH ₃₂ N ₂ O ₇ 6.9 6.6 21 QHi ₇ QH ₅ QH ₁₁ 1.4930 Q ₃ H ₃₆ N ₂ O ₇ 6.9 6.2 22nd 6.2

*) Solidifies to brown crystals: F. 40 to 42 ° C.

009 544/443

continuation

R. R ¹ QH _n Refractive index
n'S Gross formula analysis Calculated, example ft 0 Found, N,% 1-methyl QH ₅ QHn 1.4927 Q ₃ H ₃₆ N ₂ O ₇ N,% "■ 6.2 23 n-heptyl QH _U 6.7 Q0H21 QH ₅ QHu 1.4926 C ₂₅ H ₄₀ N ₂ O ₇ 5.8 24 CH ₃ QH ₅ n * " ^d 1.5133 C ₁₆ H ₂₂ N ₂ O ₇ 5.8 7.91 25th QH ₅ Q ~ H ₅ η% 1.5084 C ₁₇ H ₂₄ N ₂ O ₇ 7.43 7.61 26th 7.85

Application attempts
with the compounds according to the invention

Pesticides were prepared by adding 25 g of the active ingredient of the invention, 4 g of calcium dodecylbenzenesulfonate and 4 g of ethoxylated nonylphenol were made up to 100 ml with heavy gasoline.

Testing of the agent against apple powdery mildew

Apple rhizomes were kept in a cool hothouse along with infected rhizomes for a long time held until they were infected with apple powdery mildew themselves.

Before the application of the drug solution, the amount of powdery mildew present on each rhizome became determined by determining the percentage of area on each leaf that is apparently infested by active powdery mildew was determined and rated the infection on the following scale:

0 = no powdery mildew present

1 = 0 to 3% of the leaf area with powdery mildew

infected

2 = 4 to 7% of the leaf area with powdery mildew

infected

3 = 8 to 17% of the leaf area with powdery mildew

infected

4 = 18 to. 41% of the leaf area with powdery mildew

infected

.5 · - 42 to 100% of the leaf area infected with powdery mildew

The powdery mildew on the leaves was rated up to a certain height of the apple root sticks, A little label was hung over the highest of the leaves evaluated, so that it was definitely after the Treatment the same leaves were assessed again.

After the evaluation, the plants were divided into four groups, each group with regard to the infection of the individual plants with powdery mildew was as homogeneous as possible. Within the groups one plant was used for each treatment, making a total of four Planting was carried out. Spraying was done with a large volume hand sprayer, see above that the Sorav was enough to make a hanging one Form film. The spray was made by adding the agent up to an active ingredient concentration diluted by 20 parts per million. To achieve a good wetting effect, sodium dioctyl sulfosuccinate was used introduced at a concentration of 100 parts per million. After the test hen the plants were closed in the cool greenhouse four blocks arranged in a random order.

The powdery mildew infection was reassessed 4 days later, with only that affected by active powdery mildew Area was taken into account. The mean score per leaf was calculated for the four test plants, and this score became used for statistical analysis. The sub

3P differentiated the averaged valuation numbers vdr der Treatments were not significant in 5%. Therefore, the percent eradication was calculated by the mean evaluation numbers per leaf (for the four test plants combined) for each treatment compared with the mean evaluation numbers per leaf for the untreated rhizomes.

Testing of the agent against barley powdery mildew

Pots with 10 barley seedlings each were kept in six groups, with each group having one pot for each treatment included. The seedlings were infected by getting spores from infected plants blew over it after removing all but the oldest leaves from each plant. ·

After the infection had developed sufficiently, the amount of powdery mildew present was determined, by rating the leaves on the scale given above.

The plants were then treated by immersing them in a solution with a concentration of active ingredient for 15 seconds of 20 parts per million and a concentration of sodium dioctyl sulfosuccinate of 300 parts per million dived.

After the treatment, the plants were kept in a cool greenhouse for 4 days, after which they were sheltered Using the rating scale above. Only active powdery mildew was assessed. For each test plant, the mean rating number per leaf was calculated, and these rating numbers were used for statistical analysis. Since the differences in the averaged evaluation numbers before treatment are not considerable at 5% the percent eradication was calculated by taking the mean score per leaf (of the six test plants combined) with the mean rating number per leaf of the untreated Seedlings compared.

Testing of the agent against cucumber powdery mildew

These tests were carried out as described in connection with apple powdery mildew, using the deviation that young cucumber plants with two leaves were used. The evaluation of powdery mildew of the cucumber plants before treatment was carried out according to the following scale:

0 = no powdery mildew present

1 = up to 0.5% of the leaf area affected by powdery mildew

2 = up to 1% leaf area affected by powdery mildew

3 = up to 2% of the leaf area affected by powdery mildew

4 = up to 4% of the leaf area affected by powdery mildew

5 = up to 8% of the leaf area affected by powdery mildew

6 = up to 16% leaf area affected by powdery mildew

7 = up to 32% of the leaf area affected by powdery mildew

8 = up to> 64% leaf area affected by powdery mildew

No wetting agent was added to the active ingredient solution to be sprayed.
The results were as follows:

Table IV

Percent eradication of powdery mildew 10 ppm barley
20 ppm cucumber
50 ppm concentration 99.8 96 97 example 20 ppm *) 99.5 98 1 100 99 2 98 99 3 94 92 4th 91 5 99.9 99 + 98 6th 99.4 99 + 7th 99.3 91 8th 99.2 90 9 100 99 10 99.6 98 12th 99.3 13th 98 14th 97 15th 99.8 16 96 25th 99.8 20th 26th

*) ppm = parts per million.

In the table below, the compounds according to the invention are shown in their action against Powdery mildew compared to known compounds. The compounds 1, 2, 21 and 22 are known from French patent 1,321,663 (corresponding to the unpublished USA patent 3 234 260 and German patent application P 16 93 200.6). The compounds 3 through 20 are Compounds according to the examples of the invention given in brackets.

All compounds 1 through 22 were tested for activity according to the procedure described above gsgsn .'viSHitS-u gepruii:

connection % Eradication barley of powdery mildew 38 1. 2,6-Dinitro-4-t-butylphenyl- at 20 ppm 5 methyl carbonate Apple (Comparison) 63 **) 22nd 2. 2,6-Dinitro-4-t-butylphenyl- ethyl carbonate IO (Comparison) 96 3. 2,6-Dinitro-4- (l -ethyl-n-pentyl) - phenyl methyl carbonate (Example 1) 100 98 4. 2,6-Dinitro-4- (l -ethyl-n-pentyl) - 15th phenyl ethyl carbonate (Example 2) 98 99.8 5. 2,6-Dinitro-4- (l -ethyl-n-hexyl) - phenvl methyl carbonate (Example 25) 98.5 99.8 20th 6. 2,6-Dinitro-4- (l -ethyl-n-hexyl) - phenyl ethyl carbonate (Example 26) 94 99 7. 2,6-Dinitro-4- (l -n-propyl-n-butyl) - phenyl methyl carbonate (Example 3) 90 *) 99 8. 2,6-Dinitro-4- (l -n-propyl-n-butyl) - phenyl ethyl carbonate (Example 4) 94 *) 94 3 °. 9. 2,6-Dinitro-4- (l -n-propyl-n-hexyl) - phenyl methyl carbonate (Example 5) 99.9 91 10. 2,6-Dinitro-4- (l -n-propyl-n-hexy I) - phenyl ethyl carbonate
/ TJ · · 1 £ \ ^ 99 + 35 (Example 6) y
11. 2,6-Dinitro-4- (l -n-propyl- 99.4 n-pentyl) phenyl methyl carbonate (Example 7) 99.3 99 + Δ0 12. 2,6-Dinitro-4- (l-n-propyl- n-pentyl) phenyl ethyl carbonate (Example 8) 99.2 91 13. 2,6-Dinitro-4- (l -n-butyl-n-hexyl) - phenyl methyl carbonate 45 (Example 9) 100 90 14. 2,6-Dinitro-4- (l -n-butyl-n-hexyl) - phenyl ethyl carbonate (Example 10) 99.6 99 15. 2,6-Dinitro-4- (l -n-butyl- 50 n-pentyl) phenyl methyl carbonate (Example 12) 99 *) 98 16. 2,6-Dinitro-4- (l -n-butyl- n-pentyl) phenyl ethyl carbonate (Example 13) 98 *) 17. 2,6-Dinitro-4- (l -n-pentyl-n-hexyl) - phenyl methy 1 carbonate (Example 14) 99.3 * 18. 2,6-Dinitro-4- (l-n-pentyl-n-hexyl) - 6o phenyl ethyl carbonate (Example 15) 98 *) 19. 2,6-Dinitro-4- (l-ethyl-n-hexyl) - phenyl hexyl carbonate (Example 21) 98 65

OK ppm. - *) 60 ppm.

continuation

% Eradication barley of powdery mildew connection at 20 ppm Apple 20. 2,6-Dinitro-4- (l -ethyl-n-hexyl) - 86 phenyl- (l -methyl-n-heptyl) - carbonate (Example 23) 21. 2,4-Dinitro-6- (l-methyl-n-heptyl) - 31 phenyl methyl carbonate (Comparison) 22. 2,4-Dinitro-6- (l -methyl-n-heptyl) - 24 phenyl ethyl carbonate (Comparison)

Claims (1)

Claim: Carbonic acid alkyl (2,6-dinitro-4-alkylphenyl) esters of the general formula COOR O ₂ N IO in which R is an alkyl group having 1 to 12 carbon atoms and R ¹ and R ^{2 are} n-alkyl groups each having 2 to 5 carbon atoms and together 6 to 10 carbon atoms.