DE1542956C3 - N-carbyloxymethyl-substituted 2-alkyl] 6-tert-buly] -anilide and herbicidal preparations - Google Patents

Description

in which X = Cl, Br or I; A is a primary or secondary alkyl radical and R is a hydrogen atom, a hydrocarbon radical optionally substituted by OH groups or an oxaalkyl radical denotes, where the radicals A and R each contain 1 to 8 carbon atoms.

2. Herbicidal preparation, characterized by a content of a compound according to claim 1 as an active ingredient.

The invention relates to N-carbyloxymethyl-substituted ones 2-Alkyl-6-tert-butyl-anilides of the general formula

CO-CH ₂ -X

CH ₂ -OR

C (CH ₃ ) ₃

umhydroxid or potassium hydroxide. The product is insoluble in water, but in hydrocarbon solvents, Soluble such as benzene, toluene, xylene or hexane and can be obtained by customary crystallization or vacuum distillation getting cleaned.

The compounds of the invention are useful as herbicides, especially as pre-emergence herbicides and at low application ratios as grass-specific pre-emergence herbicides.

The invention is explained in more detail below with the aid of examples and experiments.

example 1

2'-tert-butyl-2-chloro-6'-ethyl-N-hydroxy-

methylacetanilide

1 g of hexadecyltrimethylammonium bromide is then dissolved in 100 ml of water to which 200 g of ice have been added by adding a further 200 ml of water. 50 g of 2'-tert-butyl-2-chloro-N-chloromethyl are added to this ice-water mixture -6'-äthylacetanilid added and the mixture stirred. The initial temperature of the mixture is 0 ⁰ C; 2 1/2 hours after mixing, however, the temperature has risen ^{to 18 ° C.} Stirring is continued slowly for 17 more hours. The sticky product is dissolved in 200 ml of benzene. The lower water layer is separated off and discarded. The benzene layer is washed twice with 500 ml of water. The benzene is evaporated and the product is dissolved in hexane. The hexane solution is frozen and filtered. The hexane filtrate is then evaporated again and receive a sandy solid (mp. 67 to 70 ⁰ C). This sandy solid was washed with a 3: 1 mixture of heptane and benzene. Product yield: 8.0 g.

Elemental analysis (C15H22CINO2):

40 found

Calculated

in which X = Cl, Br or I; A is a primary or secondary alkyl radical and R is a hydrogen atom, a denotes a hydrocarbon radical optionally substituted by OH groups or an oxaalkyl radical where the radicals A and R each contain 1 to 8 carbon atoms, as well as herbicidal preparations made by a content of a compound of the above formula are characterized.

The compounds according to the invention are prepared by reacting the appropriate one N-halomethyl-a-haloacetanilides with water or an alcohol or phenol of the desired carbon number.

To achieve maximum yields, the alcohol or similar reactants should be at least Equimolar amount to the other reactant and preferably be present in excess. the The reaction is conveniently carried out at room temperature; H. carried out at about 20 to 25 ° C; but it can also higher or lower temperatures can be used as the temperature is not critical. A Acid-binding reagent is preferably used in at least an equimolar amount to the amount to be expected Hydrogen halide used. This can be a tertiary amine, for example trimethylamine, triethylamine, pyridine, it can also quaternary ammonium hydroxides, metal alcoholates or inorganic bases, such as sodium

C. 63.4 H 7.9 Cl 12.7

63.5

7.8

12.5

IR analysis of the product showed the presence a hydroxymethyl group.

Example 2

2'-tert-Butyl-2-chloro-6'-methyl-N-methoxymethyl-acetanilide

20 g of 2'-tert-butyl-2-chloro-6'-methyl-N-chloromethylacetanilide are placed in a beaker and 100 ml of trimethylamine in methanol (25% solution) admitted. An exothermic reaction takes place immediately and the product that separates out is insoluble in water and therefore no quaternary salt. Methanol and the excess trimethylamine are evaporated, water is added to the residue and the oil layer is extracted with hexane The desired product is placed in a cooling apparatus and a crystalline product is separated off. the Filter off solid, wash with cold hexane and air dry. The white solid melts at 77 up to 78 ° C and weighs 12.5 g.

Elemental analysis (C15H22CINO2):

Found

Calculated

C. 63.3 H 7.9 Cl 12.5

63.5

7.8

12.5

Example 3

10

2-Bromo-2'-tert-butyl-6'-methyl-N-niethoxymethyl-acetanilide

130 g (0.74 mol) of 2-tert-butyl-6-methyl-N-methyleneaniline and 300 g of toluene are placed in a 1 liter four-necked flask. 160 g (0.79 mol) of bromoacetyl bromide are then added over the course of 45 minutes with stirring, the temperature rising from room temperature to about 85.degree. The mixture obtained is transferred to a feed funnel and added to 240 g (1 mol) of 25% strength trimethylamine in methanol over the course of 1 hour with stirring, the temperature being kept between 10 and 15 ° C. by cooling in an ice bath. The reaction mixture is stirred for a further half an hour. The toluene layer is then washed twice with water and the toluene evaporated in a stream of air. The syrupy residue is dissolved in 300 ml of a heptane / toluene mixture (4: 1). A small amount of insoluble material is removed from the solution by filtration and the mixture is placed in a freezer; no crystallization occurs. The solvents are evaporated in vacuo, the remaining amounts of solvent being removed at 0.25 torr at a bath temperature of up to 95 ° C. The residue is a brown oil (refractive index n " = 1.5516). The brown oil, which was colorless in a thin layer, weighs 155 g.

Elemental analysis (CiSH ₂₂ BrNO ₂ ):

40

Found

Calculated

25.1

24.3

45

Example 4

2'-tert -Butyl-2-iodo-6'-methyl-N-methoxymethyl-acetanilide

105 g of iodoacetyl chloride and 100 g of dry toluene are placed in a 1 liter four-necked flask. The flask is flushed with dry nitrogen and, with stirring and external cooling, 87.5 g are obtained (0.5 mol) 2-tert-butyl-6-methyl-N-methyleneaniline in increasing amounts within 20 minutes, with the temperature was kept below 20 ° C was added.

The reaction mixture is heated to 50 ° C. then cooled to 15 ° C. and 53 g of triethylamine in 100 ml of dry methanol are added, the temperature being kept below 15 ° C. Methanol and triethylamine are added within ^x hours . Little heat is generated during the addition. The flask and contents are heated to about 50 ° C over 45 minutes. It is then cooled and the product washed 3 times with 500 ml of water each time. The oil layer is separated from the water and that

55 solvent at 30 torr and a bath temperature of 60 ° C evaporated. It is a further half hour at 6O ⁰ C and 0.5 to 0.15 Torr heated From the residue, a small sample is taken, dissolved in a toluene / heptane mixture and the solution in dry ice, there is obtained no precipitation. The remainder of the residue in the flask is dissolved in 300 ml of benzene and 250 ml of hexane are added. The solution is filtered to remove a small amount of insoluble material. The filtrate is evaporated again in vacuo. 168 g of a viscous brown oil are obtained.

60 elemental analysis:
carbon
hydrogen
iodine

49.5

6.2

33.8

Example 5

N-ButoxymethyW-tert-butyl ^ -chloro-6'-methyl-acetanilide

60 g of chloroacetyl chloride and 100 g of n-heptane are placed in a 1 liter four-necked flask 87.5 g (0.5 mol) of 2-tert-butyl-6-methyl-N-methyleneaniline are added over a period of 10 minutes with stirring. the The temperature rises from 20 to 75 ° C. The flask contents briefly rise to a bath temperature of 103 ° C heated and heated to 30 ° C using a reflux condenser to exclude moisture chilled. Then 296 g (4 mol) of n-butanol containing 60 g of triethylamine are poured in and the Mixture stirred for 15 minutes. The temperature rises to 35 ° C. The reaction mixture is in 750 ml of cold water poured, mixed by shaking and an oily layer separated The Solvent is distilled off from the oil layer. After about half of the solvent is removed is, there is a voluminous precipitation of triethylamine hydrochloride in the form of fine needles, which are removed by filtration. The filtrate is with a Distilled bath temperature of 75 ° C at 25 Torr. The residue weighs 175 g. For this purpose, 200 ml of toluene given and frozen overnight. The next morning, the precipitate that has occurred in the flask becomes filtered off from the toluene solution and washed the precipitate with n-heptane. Adhering solvent will removed from the precipitation by evaporation at 10 torr and a bath temperature of 105 ° C

The weight of the still impure product obtained is 156 g. 200 ml of heptane and 5 g of activated charcoal are added to the product. The carbon is removed by filtration and the solvent evaporated in vacuo. The evaporation is stopped at 0.07 Torr and 130 ° C bath temperature. The product, which weighs 141 g, is a dark, amber-colored oil π ^! o ⁵ = 1.5252).

Elemental analysis (Ci ₈ H _{2 SClNO 2} ):

Found

Calculated

carbon 65.7 66.4 hydrogen 8.4 8.7 chlorine 12.0 10.9

The following compounds are prepared analogously to Examples 1 to 5:

2'-tert-butyl-2-chloro-6'-methyl-N-hexoxy-

methyl acetanilide

2'-tert-butyl-2-chloro-6'-methyl-

N- (2-propynoxymethyl) acetanilide

2-bromo-2'-tert-butyl-6'-methyl-

N- (propynoxymethyl) acetanilide

2'-tert-butyl-2-chloro-6'-methyl-

N- (2-methoxyethoxymethyl) acetanilide

2-bromo-2'-tert-butyI-6'-methyl-N- (2,3-di-

hydroxy-propoxymethyl) acetanilide. ι ο

In order to explain the advantages of the compounds according to the invention, the pre-emergence herbicide Effect determined in greenhouse studies, in which a certain number of seeds of different Plants were planted in greenhouse areas.

For this purpose, surface soil was placed in aluminum dishes and to a depth of 9.52 to 12.7 mm pressed against the surface of the shell. A predetermined number of seeds was placed on the surface given to different plants. In the surface tests, the seeds were filled in by the Dish covered with soil and scraping off the supernatant. The measured amount of the material to be examined Substance in a solvent or as a wettable powder was applied to this surface upset.

The soil incorporation method was the amount of soil required to post the pods To replenish the sowing, in a bowl pre-weighed a certain amount of the herbicide in a solvent or applied as a wettable powder, mixed thoroughly with the soil and as a covering layer for the sown shells used. After the treatment, the dishes were taken to a greenhouse where they - if necessary - were watered from below to give them germination and growth to supply the necessary moisture.

About 14 days after sowing and treatment was on the plants found the herbicidal effect. The evaluation was carried out using a scale that corresponds to the Average percent germination was obtained.

The ratings are as follows:

0 no phytotoxicity

1 slight phytotoxicity

2 low phytotoxicity

3 severe phytotoxicity

The pre-emergent herbicidal activity of the compounds according to the invention was shown in Table I for the various application conditions. In Table I the different seeds are through Letters

It means general grass A. generally broad-leaved B. Funnel winch C. Wild oats D. Bromgrass E. Reygrass F. radish G sugar beet H cotton I. Corn J Foxtail K Chicken millet L. Crabgrass (fingergrass or blood millet) M. Pigweed (goosefoot) N Soybean O wild buckwheat P. tomato Q Sorghum R. rice S.

The individual ratings for each plant were determined. The overall rating for all grass plants and the overall rating for broad-leaved plants were also determined. In the "Comments" column is under (1) the surface application of the herbicide and under (2) its incorporation into the Ground specified. The data given in Table I show the extraordinary general and selective herbicides Effectiveness of the compounds according to the invention.

Table I.

Pre-emergence herbicidal effectiveness

connection

Amount of plant

(kg each
8914 m ² ) ABCDEFGHIJKLMNOPQRS

Overall rating grass broad leaf

Remarks

2'-tert-butyl-2-chloro-6'-ethyl-1/2

N-hydroxymethyl-acetanilide 1/8

2'-tert-butyl-2-chloro-6'-1

methyl-N-methoxymethyl-0.05
acetanilide

2-bromo-2'-tert-butyl-6'-1

methyl-N-methoxymethyl-0.05
acetanilide

2'-tert-butyl-2-iodo-6'-methyl-1

N-methoxymethyl-acetanilide 1/4

N-butoxymethyl-2'-tert-1

butyl-2-chloro-6'-methyl-1/4
acetanilide

2'-tert-butyl-2-chloro-5

6'-methyl-N-hexoxymethyl-1
acetanilide

3003230001333310031 22 4 (2)

2002110000333210010 14 3 (2)

3333332323333322333 27 20 (2)

2212131301333202310 17 12 (2)

323 333 321 333 311 233 27 16 (2)

300 233 0000 233 110 033 22 2 (2)

3113330203333301233 27 9 (2)

3103330102333310233 26 7 (2)

203332203333302233 27 11 (2)

3113331101333100333 25 7 (2)

2 2 3 3 3 12 3 3 3 1113 18 11 (1)

1000000000323000020 10 0 (2)

The contact herbicidal effectiveness of the invention Compounds were determined in greenhouse studies. The compound under investigation was established on plants of certain ages of the same grasses and broad-leaved plants that are in the above The pre-emergence studies described were used, sprayed the same number of seeds of the same plants were planted in aluminum trays

After the plants had reached the desired age, each aluminum dish was sprayed with a certain volume of a 0.5% solution of the compound. The spraying corresponded to an amount of 1 kg per 891.4 m ² . The herbicidal solution was out

Table Il

Contact herbicidal effectiveness

IO an aliquot of a 2% solution of the compound in question in acetone, a certain amount of cyclohexanone emulsifying agent mixture and sufficient water to maintain the volume. The emulsifying agent was a mixture consisting of 35% by weight Butylamine dodecylbenzenesulfonate and 65% by weight of a tall oil-ethylene oxide condensate containing about 6 moles of ethylene oxide per mole of tall oil existed.

The plant damage was observed about 14 days later. They are compiled in Table II. The herbicidal ratings are the same as above.

connection

2'-tert-Butyl-2-chloro-6'-methyl-N-methoxymethyl-acetanide 2-bromo-2'-tert-butyl-6'-methyl-N-methoxymethyl-acetanilide 2'-tert-butyl-2-iodo-6'-methyl-N-methoxymethyl-acetanilide 2'-tert-butyl-2-chloro-6'-methyl-N- (2-propynoxymethyl) acetanilide 2-bromo-2'-tert-butyl-6'-methyl-N- (2-propynoxymethyl) -acetanilide

AHg. grass AIIg. wide leafy plant 3 2 1 2 1 O 2 2 1 3

The above data show the beneficial properties of the compounds according to the invention.

To demonstrate the technical progress of the compounds according to the invention, further Experiments carried out in which two compounds according to the invention (VI and VII, see below) with the from H. Kurth, "Chemical Weed Control", 1963, page 105 ff. Known compound CTAA (V) and with four known from Belgian patent specification 6 22 131

Pre-emergent herbicidal activity

Compounds (I to IV) were compared. The individual connections were made in the following Amounts given in the table according to the test method already described above, the seeds of the various Plants added.

The experiments show that the compounds according to the invention have a significantly greater herbicidal action than the known herbicides used for comparison.

connection Granted Funnel- Wild bromgrass ryegrass 0 0 Radish. Wilder Sugar tree wool Corn Fox rice crowd wir.de oats 0 0 beets tail kg / 8914 m2 0 2 I. 0.07 0 0 0 0 0 0 - 3 II 0.01 0 0 0 0 0 0 - - 0 III 0.05 0 0 1 2 0 0 - - 3 IV 0.01 0 0 3 3 0 0 - - 1 V 0.07 0 0 0 0 1 - 0 VI 0.01 0 1 Pigweed Soybean 0 0 0 0 2 VII 0.05 0 2 (Goosefoot) 0 0 0 3 (Continuation) tomato connection Chicken millet Crab grass Sorghum (Finger resp. Buckwheat Blood millet)

2 0 3 1 0 3 3

0
0
3
0
0
1
2

0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 1

0 0 2 3 0 1 3

2'-t-Butyl-2-chloro-N- (2-methoxyethyl) -6'-methylacetanilide. ■■ 2'-t-Butyl-2-chloro-N- (2-ethoxyethyl) -6'-ethylacetanilide.
■ 2'-t-amyl-2-bromo-6'-methylacetanilide.
■■ 2'-t-butyl-2-bromo-6'-ethylacetanilide.

N ', N'-diallyl-2-chloroacetanilide (CDAA).

2'-t-ButyI-2-chloro-N-i2-methoxyethoxymethyl) -6'-methyIacetanilide.

2'-t-Butyl-2-chloro-N- (2-propynyloxymethyl) -6'-methylacetanilide.

709 642/16

Next was 2'-tert-butyl-2-iodo-6'-methyl-N-methoxymethyl-acetanilide (1) and the compound 2'-tert-butyl-2-iodo-6'-methyl-acetanilide mentioned in Belgian patent specification 6 22 131 (2) tested for effectiveness as a pre-emergence herbicide. The experiments show that the compound (1) according to the invention is a less damage to the broad-leaved crops a to e and greater damage to the Weed grasses f to j.

Amount expended 1.0 a b C. d ... e Tested I plant G H i j total (kg / 8914 m *) 0.25 • Total f damaging 1.0 damage supply 0.25 0 2 0 0 2 3 3 3 3 15th (Ο radish 0 1 0 1 2 4th 3 3 3 3 3 15th sugar beet 3 3 - 3 3 4th 3 3 3 - 3 12th (2) cotton 3 3 - 3 3 12th 3 0 3 - 3 6th Soybean 9 0 a = tomato b = Wild oats c = Trespe d = Foxtail e = Chicken millet f = Blood millet g = h = i = j =

The herbicidal preparations according to the invention are either solids or liquids that contain the Active ingredient and either a finely divided solid or a liquid herbicidal adjuvant containing the Aid is a preparation aid or conditioning agent that allows the preparation to be carried out quickly can be mixed with a suitable solid or liquid carrier.

As mentioned, quite different effects can be achieved by modifying the application of the herbicidal Preparation can be obtained.

In general, the compounds according to the invention are in water and in many organic solvents insoluble. The active ingredient therefore does not need to be dissolved in the diluent. Rather, he can be dispersed or suspended in it. Suitable organic media for use as a diluent are for example hexane, benzene, toluene, acetone, cyclohexanone, methyl ethyl ketone, ispropanol, Butanediol, methanol, diacetone alcohol, xylene, dioxane, isopropyl ether or tetrachloroethane are real Solutions are desired, so mixtures of organic solvents are suitable, for example mixtures of Xylene and cyclohexanone in a ratio of 1: 1 and 1: 2.

Solid particulate diluents are also suitable for producing the preparations according to the invention.

The active ingredient is either absorbed or dispersed on or in the finely divided solid material. Such diluents are natural clays such as porcelain earths, bentonites and attapulgites, other minerals in their natural state such as talc, quartz, diatomaceous earth, Fuller's earth, chalk, kaolin or diatomaceous earth.
The powdery solid preparations are applied to the soil in a mixture with a particulate carrier material or as a wettable powder using a liquid carrier material. In the latter case, a wetting agent is added to render the particulate solid diluent wettable with water, thereby obtaining a stable aqueous dispersion or suspension suitable for use as a spray.

The liquid preparations preferably contain 5 to 95% by weight of active ingredient. The rest is an aid which can be the liquid diluent or wetting agent alone.

The preparations according to the invention can also contain other substances, such as artificial fertilizers and pesticides, contain.

The dose to be applied to the plants depends not only on the active ingredient, but also on the plant to be treated, its stage of growth, as well as on the part of the plant which is to be brought into contact with the toxic agent. In the case of non-selective foliar treatments, the herbicidal preparations are generally used in a ratio of 1 to 10 kg per 1790 m ² (or 5 to 50 kg per 8914 m ² ).

With non-selective pre-emergence treatments. The herbicidal preparations are generally used in an amount of 1 to 25 kg per 8914 m ² .

Claims (1)

Patent claims: 1. N-carbyloxymethyl-substituted 2-alkyl-6-tert-butyl-anilide the general formula CO-CH ₂ -X CH ₂ -OR C (CH ₃ J ₃