DE2155494A1 - ALPHA-CHLORO-N- (ALKEN-1-YL) ACETAMIDE, METHOD FOR THEIR PRODUCTION AND USE AS HERBICIDES - Google Patents

Description

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8 NOV. 1971

α-Chlor-N- (alken-i-yl) acetamides, process for their manufacture and their use as herbicides

The present invention relates to new a-chloro-N- (alken-1-yl) -acetamides, which have herbicidal properties and a method for their preparation.

It is already known that the α-chloro-NjN-diallylacetamide possesses herbicidal properties (see US Pat. No. 2,864,683).

It has now been found that the new α-chloro-N- (alken-1-yl) acetamides the general formula

Cl-CHp-CO-N-CH = CCl ¹ (I)

R ^R 2 in which
R for hydrogen, alkyl with 1 to 4 carbon atoms

or alkenyl with 2 to 4 carbon atoms and R ₁ and R ₂ each represent alkyl with 1 to 4 carbon atoms

stand,

have strong herbicidal properties.

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received mMdOtl * ^215549A

Furthermore, it was found that the new erhült oc-chloro-N- (ulkori-1_yl) -acetamide of the formula (I) are obtained when .alpha.-Ohloraoot - amides of the formula

Cl-CH ₂ -CO-NH-R (II) in which R has the meaning given above,

with aldehydes of the formula

O R

in which R ₁ and R _{2 have} the meaning given above,

optionally reacted in the presence of a diluent and optionally in the presence of a catalyst.

The active compounds according to the invention surprisingly show of the formula (I) a better herbicidal effect than the tt-chloro ~ N, N-diallyl-acetamide (A) known from the prior art, which is the chemically closest active ingredient with the same type of action is. So the active ingredients according to the invention are against grass weeds, z. B. Wild oats (Avena fatua), bluegrass (Poa) and Foxtail grass (Alopecurus) ", but also against dicots Weeds, e.g. B. French herb (Galinsoga) and chamomile (Matricaria), sometimes more effective than the oc-chloro-Ν, Ν-diallyl-acetamide (A). Above all, however, the active ingredients according to the invention are considerably better tolerated towards crops, e.g. B. rapeseed, soybeans, corn and cotton, as the previously known active ingredient (A).

It is particularly surprising that the invention Active ingredients against cereals, e.g. B.

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Barley, rye and wheat, in some cases, are considerably more tolerable than the previously known active ingredient (A).

The active compounds according to the invention can therefore, in contrast to the previously known active compound (A), for the selective control of Weeds and grass weeds are used in cereals.

The active ingredients according to the invention thus represent a significant enrichment in weed control technology.

If a-chloroacetamide and isobutyraldehyde are used as starting materials, the course of the reaction can be represented by the following equation:

Gl-CH ₀ -CO-NH ₀ + ^ CH-CHO tr-n-> Cl-CH _o -C0-NH-CH = cC

^{ά ά} CH " ^H 2Y ^ά

The compounds to be used as starting materials are clearly defined by the formulas (II) and (III). In formula (II) R preferably represents methyl and allyl. In formula (III), R- preferably represents methyl and ethyl; R2 is preferably for methyl and n-butyl.

The 06-chloroacetamides of the formula used as starting materials (II) and aldehydes of the formula (III) are known.

Suitable diluents are inert organic solvents which form azeotropic mixtures with water, such as Benzene, toluene, xylene, chlorobenzene, tetralin, dialkyl ethers; benzene, toluene and xylene are preferred.

Inorganic and / or organic acids such as sulfuric acid, phosphoric acid, oxalic acid, Sulfonic acids; p-toluenesulfonic acid is preferably used.

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The reaction temperatures can be varied over a wide range. In general, the reaction is preferably carried out from 50 to 220 ⁰ C, between 100 ° and 18O ⁰ C.

When carrying out the process, it is preferred to start from a mixture of 1 mole of oz-chloroacetamide and 2 moles of aldehyde, adds solvent and catalyst and removes the water formed in the reaction by azeotropic distillation.

The reaction mixtures are worked up by crystallization or fractional distillation in vacuo.

The active compounds according to the invention have strong herbicidal properties Properties and can therefore be used to control weeds. Under weeds in the broadest sense all plants are to be understood which grow in places where they are not wanted. As the active ingredients plant growth affect in different ways, they can be used in particular as selective herbicides. In higher Concentrations (> 25 kg / ha), the active compounds according to the invention are also suitable for total weed control.

The substances according to the invention can, for. B. in the following k Plants used: dicots, such as mustard (Sinapis), cress (Lepidium), burdock (Galium), chickweed (Stellaria), chamomile (Matricaria), French herb (Galinsoga), goose foot (Chenopodium), nettle (Urtica), ragwort (Senecio), cotton (Gossypium), beets (Beta), carrots (Daucus), beans (Phaseolus), potatoes (Solanum), coffee (Coffea); Monocots, such as timothy (phleum), bluegrass (Poa), fescue (pestuca), eleusine (eleusine), pennich (setaria), ryegrass (lolium), bromus (bromus), chicken millet (Echinochloa), maize (Zea), rice (Oryza), oats (Avena), barley (Hordeum), wheat (Triticum), millet (Panicum), sugar cane (Saccharum).

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The active ingredients are particularly suitable for selective weed control in cereals such as wheat, rye and barley, and also in rapeseed, soy, maize, cotton and others Crops.

The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solids Carriers, optionally with the use of surface-active agents, that is to say emulsifiers and / or dispersants. In the case of the use of water as an extender, z. B. also organic solvents as auxiliary solvents be used. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, Benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, Chlorethylene or methylene chlorides, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl = isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with Liquefied gaseous extenders or carriers are liquids which are meant, which at normal temperature and are gaseous under normal pressure, e.g. B. aerosol propellants such as halogenated hydrocarbons, e.g. B. Freon; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic minerals such as finely divided silica, aluminum oxide and silicates; as an emulsifier: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,

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ζ. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates j as dispersants: e.g. B. Lignin, sulfite = leach and methyl cellulose.

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

The formulations generally contain between 0.1 "and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as Ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates can be used. The application happens in the usual way, e.g. B. by pouring, spraying, atomizing, scattering, dusting.

The active compounds according to the invention can be used both before emergence and after emergence of the plants will. The active ingredients are preferably used in the pre-emergence process.

The amount of active ingredient used can be within larger ranges vary. It essentially depends on the type of effect desired. In general, the application rates are low between 0.1 and 50 kg of active ingredient per ha, preferably between 0.5 and 25 kg / ha.

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Example A:

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier 1 χ part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. Included the amount of water per unit area is expediently kept constant. The concentration of active ingredients in the preparation plays a role Doesn't matter, only the amount of active ingredient used is decisive per unit area. After three weeks, the damaging Determination of the degree of the test plants and denoted by the code numbers 0-5, which have the following meaning:

0 no effect

1 slight damage or growth retardation

2 significant damage or stunted growth

3 severe damage and only lack of development or only. 50 i » accrued

4 plants partially destroyed after germination or only 25 Ί » emerged

5 plants completely dead or not emerged

Active ingredients, application rates and results are based on the following Table out »

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Active ingredient expenditure in

Active ingredient

jESZha.

Table pre-emergence test

co

CD

N) • Η CO

co

co
U
(D
CU

pi

CQ • Η

CD

cd ο

I CQ

CQ 3

.Ej U

O pi

PS NO

CD

O «H £ Q) fi
(D Sh ^ Cd ft Cd

Cd CQ CQ Ή OJ JC O

ia Ph fs, EJfW ₁ EjHCd

o cd -H ο ο ο «j ο
co pci W fxj <i} ων-, pn

co

CD

Ph

CD
ttf)
ο

CQ

•H
H
CD

CD

cd ο

Ci-CH ₂ -CO-N (CH ₂ -CH = CH ₂ ) ₂
(known) "Randox"

"J Cl-CHp-CO-N-CH = C;

J3H,
"CH,

Cl-CH ₀ -CO-N-CH = C
!

CHp-GH = CHp

, H ₆

Cl-CHp-CO-N-CH = C,
CH,

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2.5

1.25

2.5

1.25

2.5

1.25

2.5

1.25

2 2 1

2 2 1

1-2 O O

O O

3 4-5 2 2 2-3 1

2 2 1

4 4 2

3 2-3 1 2 2 1

1-2 4 1

1 2-3 O

0 2 0

1-2 1 O

2 2 1 - 1 O 1

2-3 2

1-2 1

1

2-3 1

1-2 O

O

1
O
O

5
5
5

5
5
5

5
5

O 5

σ 5

O 5

5
5
5

5
5
5

5
4-5
4th

5
4th
2

5 5
5 5
4-5 4

4th
4th
3

4 4 3

5 5 4 5 4 4

5 5 5 4-5 4-5 5 5 4-5 4 4 4-5 4-5 3 4 3

5 5
4-5 5
4 4

4-5 4th NJ 4-5 4th cn 3 3 cn J? - CD

Example 1t

Cl-CH ₂ -CO-NH-CH = C:

JO,

CH

150 g (1.59 mol) of a-chloroacetamide, 230 g (3.2 mol) of isobutyraldehyde and 3 g of p-toluenesulfonic acid are refluxed in 1.2 liters of xylene for 40 hours, the water of reaction formed using a water separator is separated. The reaction mixture is then neutralized with triethylamine, evaporated in a water jet vacuum, and. the residue is recrystallized from a lot of water; Yield 180 g (77 1 * of theory), melting point 91 C ⁰

The compounds listed in the table can also be prepared in an analogous manner. The cleaning takes place at the compounds according to Examples 2-9 by high vacuum distillation.

Tabel

Cl-CH R. .R, R ₂ (D boiling point Torr CH ₅ -CO-N-CH = CC ' R ₂ 75 ° / 0.9 Torr C ₂ H ₅ c- \
R. CH 83 ^O / 1.2 Torr Example-
No. *1 CH ₅ 73- 94 ^O /1.3 Torr 2 nC ₄ H _g CH ₅ CH ₅ 81- 84 ° / 0.2 Torr 3 sec.-CJEq CH ₅ CH ₅ 92- 72 ° / 0.1 Torr 4th CH ₂ -CH = CH ₂ CH ₅ CH ₅ 82- 70 ° / 0.1 Torr VJl H CH ₅ CH ₅ 70- 05 ° / 0.3 Torr 6th CH ₅ CH ₅ nC ₄ H _g 67- 10 ° / 0.7 7th CH ₅ KC ₄ H ₉ 103-1 8th C ₂ H ₅ 108-1 9 C ₂ H ₅ Le A 14 066 - 9 -

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Claims (6)

40 Pfitontuntiprünho: 1) a-chloro-N- (alken-i-yl) -acetamides of the general formula * -. ι R in which R for hydrogen, alkyl with 1 to 4 C atoms or alkenyl with 2 to 4 C atoms and R ₁ and R ₂ each represent 'alkyl with Ί to 4 Carbon atoms. 2) Process for the production of ct-chloro-N- (alken-i-yl) -acetamides, characterized in that one CC-chloroacet = » amide of the formula Cl-CH ₂ -CO-NH-R (II) in which
R has the meaning given in claim 1, with aldehydes of the formula C-C <"(III) in which R ₁ and R _{2 have} the meaning given in claim 1, optionally reacted in the presence of a diluent and optionally in the presence of a catalyst. Le A 14 066 - 10 - ' 309821/117? 3) Herbicidal agents, characterized by a content of α-chloro-N- (alken-1-yl) acetamides according to claim 1. 4) methods of controlling unwanted plant growth, characterized in that Q £ -chloro-N- (alken-1-yl) acetamides according to claim 1 can act on the unwanted plants or their habitat. 5) Use of oc-Ohlor-N-Calken-i-ylJ-acetamides according to Claim 1 for combating unwanted plant growth. 6) Process for the preparation of herbicidal agents, characterized in that one CC-chloro-N- (alken-1-yl) acetamides according to claim 1 mixed with extenders and / or surface-active agents. Le AU 066 - 11 - 309821/1172