DE2405510A1 - HETEROCYCLIC ANILIDES - Google Patents

Description

VELSICOL CHEMICAL CORPORATION

341 East Ohio Street

Chicago, Illinois 60611 /V.St.A.

Our reference: V

Heterocyclic anilides

The invention relates to new compounds of the formula

wherein Y is hydrogen, a lower alkyl group or

Is halogen; R means hydrogen, a lower Al-

p
kyl or lower alkoxy group; R is a lower one

3
Alkyl group; R is hydrogen or a lower alkyl

group; X is halogen; η is an integer from 1 to 2;

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Dr. Ha / Gl

and Q consists of
R ⁴

-CH

- C - R- ^(CH 2> _m

or

- C - R " ^N o

i '

1 2
wherein Z and Z are independently oxygen or sulfur; R, R, R, R and R independently of one another represent hydrogen or a lower alkyl group and m is an integer from 0 to 2.

The term "lower" means a straight or branched carbon chain of up to 4 carbon atoms.

The compounds according to the invention are surprisingly suitable as herbicides and particularly useful for control grassy weeds.

In a preferred embodiment of the invention, X is hydrogen, X is chlorine or bromine and at least two of R, R

R and R are hydrogen.

The compounds according to the invention can be prepared by reacting a compound of the formula

, 2

N - (CH ₂ ) _n - Q

(II)

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1 2
wherein Y, R, R, η and Q have the meaning described above, with an α-haloalkanyl chloride of the formula

Cl-C-CHX

R ³ "(HD

wherein X and R have the meaning described above, are prepared. This reaction is through Combination of a compound of the formula II with a compound of the formula III in an inert organic Reaction medium, e.g. dioxane, in the presence of an acid acceptor, e.g. an alkali metal carbonate or bicarbonate at a temperature of about -10 to about 25 ° C and stirring the mixture formed during causes about 15 to about 120 minutes. The reaction mixture can then be mixed with water to remove inorganic Salts washed and solvent can be distilled off to obtain the desired product. This product can be used as such or by recrystallization or other conventional means getting cleaned.

The compounds of the formula II in which Q

R ⁴

-CH

No. ¹ I.
- C
ι 2> ■ R ⁵ I.
(CH
I. m Z ² I.
* - C ¹ 7th ■ R ⁶ I.
R.

is, can by reaction of a substituted AniliP-s the formula

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R ²

(IV)

1 2
wherein X, R and R have the meaning described above

with a compound of the formula

R ⁴

Hai - (CH ₂ ) _n - CH (CH ₂ ) _m

^ Z ² - C - R ⁶

in which Hal is halogen, e.g., chlorine or bromine

12 4 5 6 7

and Z, Z, R _1, R, R, R, η and m have the meanings described above. This reaction takes place by combining a compound of the formula IV
with a compound of the formula V in an inert organic reaction mixture, for example dimethylformamide, in the presence of an acid acceptor, for example an alkali metal carbonate or bicarbonate, with refluxing the mixture obtained for about 4 to about 48 hours. The reaction mixture can then be filtered and distilled to obtain the desired product.

The compounds of the formula V are obtained by reacting an acetal of the formula

OCH ₃ Cl - (CH ₂ ) _n - CH

^0CH 3 (VI)

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where η has the meaning "described above", with a diol or dithiol of the formula

R -

C -

< ^CH 2> m -

R ⁶ CR ^

(TU)

wherein R, R, R, R, Z, Z and m have the meanings given above. This reaction takes place through Coordination of the compound of the formula VI with the compound of the formula VII in approximately equimolar amounts and in Presence of an acid catalyst, e.g. sulfuric acid or toluenesulfonic acid, under anhydrous conditions. The mixture can be refluxed for about 1 to 4 hours. Then the reaction mixture can take distilled under reduced pressure to give the desired product.

The compounds of the formula II in which Q

-R ¹

is can be done by hydrogenating the nitrogen-carbon double bond of a compound of the formula

N = CH.

-R

(VIII)

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12 8
wherein R, R and R are as defined above, obtained with lithium aluminum hydride. This reaction is effected by adding the lithium aluminum hydride to a solution of the compound of Formula VIII in an organic solvent such as ether and heating the resulting reaction medium to temperatures up to the reflux temperature of the mixture for about 15 to about 120 minutes. Then you can add methanol and water to the reaction mixture and filter it to remove inorganic salts. The reaction mixture can then be washed with water and dried, and solvent is distilled off to give the desired product.

The above hydrogenation can also be carried out with hydrogen gas in the presence of a suitable catalyst such as platinum or palladium. This reaction will therein at room temperature and at pressures between atmospheres

2 2

spherical pressure and about 7 kg / cm (100 pounds / inch).

If the compounds of formula VIII are not available stand, they can react in approximately equimolar amounts a compound of the formula

NILE

(IX)

1 2
wherein R, R and Y have the meanings given above

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and a "compound of the formula

OCH

(X)

wherein R has the meaning given above, can be obtained.

This reaction takes place by combining the compounds of the formula IX and X in an inert organic Solvent, e.g., benzene, and heating the mixture to a temperature up to the reflux temperature of the mixture for about 4 to about 96 hours. Then the desired product can be used after evaporation of the Solvent can be obtained.

For example, compounds of the formula X which are suitable for the preparation of the compounds according to the invention, are 2-furfural, 4-methyl-2-furfural, 4-ethyl-2-furfural, 4-propyl-2-furfural, 4-butyl-2-furfural, 4-isopropyl-2-furfural, a-fur-2-ylacetaldehyde, α- (4-methylfur-2-yl) acetaldehyde and the same.

Examples of substituted anilines of the formulas IV and IX are 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-isopropylaniline, 2-butylaniline, 2,6-dimethylaniline, 2,6-diaethylaniline, 2,6-dipropylaniline, 2, G-dibutylaniline, 2-methoxy-6-methylaniline, 2-methoxy-6-ethylaniline, 2-ethoxy-6-methylaniline, 2-ethoxy-6-ethylaniline, 2-propoxy-6-methylaniline, 2-butoxy-6-ethylaniline, 2,4,6-trimethylaniline, 2,4,5-iriaethylaniline, 2,4,6-tripropylaniline, 2,6-Mmethyl-4-butylaniline, 2,4-dimethylaniline, 2,4-diaethylaniline, 2-methyl-4-chloroaniline,

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2-ethyl-3-bromaniline, 2,6-dimethyl-4-iodoaniline, 2,6-diaethyl-4-chloroaniline and the same.

Examples of α-haloalkanyl chlorides of the formula III are Chloroacetyl chloride, bromoacetyl chloride, iodaoetyl chloride, a-chloropropionyl chloride, a-brorapropionyl chloride, a-chloro-butyryl chloride, α-chlorovaleryl chloride, α-chlorocapronyl chloride and the same.

Examples of diols and dithiols of the formula VII which are suitable for the preparation of the compounds of formula V are 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1-butanediol , 4, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methylpentanediol-2,4, 2-methylpropanediol 1,2, 2-methylbutanediol-2,3, 3-methylbutanediol-1,3, hexanediol-1,2, hexanediol-1,3, hexanediol-1,4j hexanediol-2,3} hexanediol-2,4 > 2,5-hexanediol, 3,4-hexanediol, 3-methylhexanediol-3,4, 3-ethylhexanediol-3,4, ethanedithiol-1,2, propanedithiol-1,2, propanedithiol-1,3, butanedithiol-1 , 2, But and it hi ο 1-1,3, butanedithiol-1 , 4-, butanedithiol-2,3, pentanedithiol-1,2 and the like.

The preparation of the compounds according to the invention is explained in detail in the following examples.

example 1 Production of 2-chloromethyl-1,3-dioxolane

The dirnethylacetal of 2-chloroacetaldehyde (125 g; 1.0 mol) and 1,2-ethanediol (62 g; 1.0 mol) are poured into one with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. Add 0.3 g of toluenesulfonic acid to the flask and hold

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the reaction mixture. about 2 hours at reflux. Then, the Reaktionsmisohung is distilled under Saugpartialdruck to remove methanol, giving the desired product, namely 2-chloromethyl-1,3-dioxolane,

Example 2

Preparation of N- (1,3-dioxolan-2- ylmethyl) -2,6-dimethylaniline

2,6-diraethylaniline (75 g), 2-chloromethy1-1,3-dioxolane (25 g) potassium carbonate (34 g) and dimethylformamide (50 ecm) were placed in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser given. The reaction mixture was refluxed for about 18 hours. Then one filtered and distilled, the desired product, namely H- (1,3-dioxolan-2-ylmethyl) -2,6-dimethylaniline, received.

Example 3

Production of IT-α-chloro ac e ty 1-1T- (1,3- dioxolan-2-ylmethyl) -2,6-dimethylaniline

N- (1,3-Dioxolan-2-ylmethyl) -2,6-dimethylaniline (7.8 g), sodium bicarbonate (7.0 g), dioxane (20 ecm) and water (4 ecm) were in a with a mechanical stirrer and a thermometer equipped glass reaction flask. The mixture was cooled to about ⁰ ° C. and then 5.0 g of chloroacetyl chloride were added with stirring over about 15 minutes. After the addition had ended, stirring was continued for about 1 hour. Then 100 ecm of ether were added and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and solvents were evaporated leaving a solid residue

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stopped. This residue was recrystallized from an ether-pentane mixture, giving the desired product, namely. ΙΤ-α-Ο hloracethyl-N-t1,3-dioxolan-2-ylmethyl) -2,6-dimethylaniline with a melting point of 58 to 60 ⁰ C received.

Example 4

Preparation of F- (1,3-Dioχolan-2- ylmethyl) -2, 6-diaethylaniline

2,6-diaethylaniline (75 g; 0.5 mol), 2-chloromethyl-1,3-dioxolane (25 g; 0.2 mol), potassium carbonate (22 g; 0.2 mol) and dimethylformamide (50 ecm) were added placed in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel was heated with stirring for about 18 hours. It was then filtered and distilled to give the desired product, namely F- (1,3-dioxolan-2-ylmethyl) -2,6-diaethylaniline.

Example 5

Production of Fa-chloroacetyl-IT- ( 1,3-aioxolan-2-ylmethyl) -2,6-diaethylaniline

H- (1,3-Dioxolan-2 ~ ylmethyl) -2,6-diaethylaniline (7.7 g), sodium bicarbonate (6.0 g), dioxane (20 ecm) and water (4 ecm) were in a with a mechanical stirrer and thermometer equipped glass reaction flask. This mixture was e.-r "about cooled ⁰ ° C and with stirring was added during e;.. = 15 minutes 4.0 g of chloroacetyl chloride Upon complete addition, stirring was continued for about 1 hour, the mixture was then admixed with 100.. ecm ether and washed the resulting solution with water. The washed solution was then dried over anhydrous magnesium sulfate and solvents were left behind

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a solid residue distilled off. This residue was recrystallized from an ether-pentane mixture, giving the desired product, namely ΪΓ-.α-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2,6-diaethylaniline with a melting point of 86 Ms 87 ⁰ O received.

Example 6

Preparation of N- (1,3-Dioxolan-2- ylmethyl) -2-methyl-5-chloroaniline

2-methyl-5-chloroaniline (75 g), 2-chloromethyl-1,3-dioxolane (25 g), potassium carbonate (22 g) and dimethylformamide (50 ecm) were placed in a reaction basket equipped with a mechanical stirrer, thermometer and reflux condenser given. The mixture was heated with stirring for about 26 hours. Then it was filtered and distilled to give the desired product H (1,3-dioxolan-2-ylmethyl) -2-methyl-5-chloroaniline having a boiling point from 116 to 118 ⁰ C at a pressure of 0.1 mm Hg received.

Example 7

Production of Na-chloroacetyl-N- (1,3-dioxolan-2-ylraethyl) -2- <methyl- 5-chloroaniline

IT- (1,3-Dioxolan-2-ylraethyl) -2-methyl-5-chloroaniline (8 g), sodium bicarbonate (7 g), dioxane (50 ecm) and water (5 ecm) were poured into one with a mechanical stirrer and thermometer equipped glass reaction flask. The mixture was ^{cooled to about 0} ° C., and 4.3 g of chloroacetyl chloride were added with stirring for about 15 minutes. After the addition had ended, stirring was continued for about 1 hour. Then 100 ecm of ether were added to the mixture and the resulting solution was washed with water. The washed solution was then poured over anhydrous magnesium

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sulfate dried and solvent was distilled off leaving a solid residue. This residue was recrystallized from hexane and the desired product was obtained, namely IT-α-chloroacetyl-U- (1,3- · dioxolan-2-ylmethy3) -2-methyl-5-chloroaniline with a melting point of 88 ms 89 ⁰ C

Example 8 Preparation of 2-chloromethyl-1,3-dithiepane

The dimethyl acetal of 2-chloroacetaldehyde (125 g; 1 * 0 mol) and 1,4-butanedithiol (122 g; 1.0 mol) are in one with placed in a glass reaction flask equipped with a mechanical stirrer, thermometer, and reflux condenser. Man add 0.3 g of toluenesulfonic acid to the reaction mixture and keep the mixture under reflux for about 2 hours. Then it will be the reaction mixture is distilled under suction pressure and the desired 2-chloromethyl-1,3-dithiepan is obtained,

Example 9

Preparation of H- (1,3-dithiepan-2- ylmethyl) -2,6-diaethylaniline

2,6-diaethylaniline (75 g), 2-chloromethyl-1,3-dithiepan (36.5 g), potassium carbonate (34 g) and dimethylformamide (75 ecm) are poured into a with a mechanical stirrer, Glass flask equipped with a thermometer and a reflux condenser. The reaction mixture is about 18 hours heated to reflux. Then the mixture is filtered and the desired product is distilled, viz IT- (1,3-dithiepan-2-ylmethyl) -2,6-diaethylaniline.

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Example 10

Preparation of Ua-Ghloraoetyl-IT- ( 1,3-dithiepaji-2-ylmethyl) -2,6-diaethylaniline

LKif3-dithiepan-2-ylmethyl) -2 _t 6-diaethylaniline (15 g), sodium bicarbonate (10 g), dioxane (30 ecm) and water (5 ecm) are placed in a glass reaction flask equipped with a mechanical stirrer and thermometer. The mixture is cooled to about 0 ° C. and, with stirring, 7 g of chloroacetyl chloride are added over the course of about 15 minutes. When the addition is complete, the mixture is stirred for about 1 hour The washed solution is then dried over anhydrous magnesium sulfate and solvents are distilled off to leave a solid residue, which is recrystallized to give the desired product, namely N-α-chloroacetyl-N- (1,3-ditblepan-2-ylmethyl) -2 , 6-diaethy! Aniline.

Example 11 Preparation of 2-chloromethyl-1,3-dioxane

The dimethyl acetal of 2-chloroacetaldehyde (125 g; 1 »0 mol) and 1,3-propanediol (76 g; 1.0 mole) are in one with placed in a glass reaction flask equipped with a mechanical stirrer, thermometer, and reflux condenser. Man the reaction mixture is mixed with 0.3 g of toluenesulfonic acid and then refluxed for about 3 hours. Thereon it is distilled under suction pressure and the desired product, namely 2-chloromethyl-1,3-dioxane, is obtained.

Example 12

Preparation of H- (1,3-Dioxan-2-ylmethyl) -2,6-diaethylaniline

2,6-Diaethylaniline (75 g)? 2-chloromethyl-1,3-dioxane (H g) s potassium carbonate (34 g) and dimethylformamide

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(60 ecm) are poured into one with a mechanical stirrer, Glass reaction flask equipped with a thermometer and a reflux condenser. The reaction mixture is refluxed for about 18 hours. Then filtered one and distilled where "with one the desired product, namely ϊΓ- (1,3-dioxan-2-ylraethyl) -2,6-diaethylaniline receives.

Example 13

Production of IT-a-chloroacetyl-IT-Ci, 3- dioxan-2-ylmethyl) -2,6-diaethylaniline

N- ( _r 1,3-dioxan-2-ylmethyl> -2,6-diaethylaniline (25 g), sodium bicarbonate (10 g), dioxane (30 ecm) and water (4 ecm) v / ground in a with a mechanical The mixture is cooled to about ⁰ ° C. and mixed with 15 g of chloroacetyl chloride for about 15 minutes with a stirrer. When the addition is complete, the mixture is stirred for about 1 hour The solution obtained is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and solvents are distilled off to leave a solid residue. The residue is recrystallized and the desired product is obtained, namely Na-chloroacetyl-F-Ci, 3-dioxane 2-ylmethyl) -2,6-diaethylaniline.

Example 14 Preparation of 2-chloromethyl-1,3-dioxepane

The dimethyl acetal of 2-chloroacetaldehyde (125 g; 1.0 mol) and 1,4- butanediol (90 g; 1.0 mol) are in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser

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given. 0.3 g is added to the reaction mixture (Doluenesulfonic acid and the mixture is then refluxed for about 3 hours. It is then distilled under suction pressure and receives the desired product, namely 2-chloromethyl-1,3-dioxepane.

Example 15

Preparation of 1? - (1,3-Dioxepan-2- ylmethyl) -2,6-diaethylaniline

2,6-Diaethylaniline (75 g), 2-chloromethyl-1,3-dioxepane (15 g), potassium carbonate (34 g) and dimethylformamide (60 ecm) are placed in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is refluxed for about 18 hours. Daaan is filtered and distilled, giving the desired product, namely Ή- (1,3-dioxepan-2-ylmethyl) -2,6-diaethylaniline.

Example 16

Production of IT-a-chloroacetyl-N-ti, 3- Dioxepan-2 ~ ylmethyl) -2, 6-diaethylaniline

H- (1,3-Dioxepan-2-ylmethyl) -2,6-diaethylaniline (26.3 g), Sodium bicarbonate (15 g) »dioxane (30 ecm) and water (4 ecm) are placed in a glass reaction flask equipped with a mechanical stirrer and thermometer. The mixture is cooled to about 0 C and mixed with it while stirring for about 15 minutes 15 g of chloroacetyl chloride. After the addition has ended, the mixture is stirred for a further 1 hour. Then add to the mixture 100 ecm of ether and wash the resulting solution with water. The washed solution is then poured over anhydrous magnesium sulfate dried and the solvent is

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a solid residue remains distilled off. The residue is recrystallized, giving the desired product, viz. I-α-chloroacetyl-F- (1,3-dioxepan-2-ylmethyl) -2,6-diaethylaniline is obtained.

Example 17 Production of IT-furfurylidene-2,6-diaethylaniline

2,6-diaethylaniline (0.3 mol), 2-furfural (0.3 mol) and Benzene (100 ecm) was placed in an equipped with a mechanical stirrer, thermometer and reflux condenser Glass reaction flask given. The reaction mixture was then refluxed with stirring for about 76 hours heated. It was then distilled and the desired product was obtained, namely N-furfurylidene-2,6-diaethylaniline a boiling point of 105 to 107 ° C at 0.4 mm Hg.

Example 18 Production of! -! Furfuryl-2,6-diaethylaniline

If-eurfurylidene-2,6-diaethylaniline (22.7 g; 0.1 mol), dissolved in 100 ecm of ether, were placed in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser. 2 g of lithium aluminum hydride was added to the flask and the resulting mixture was stirred at room temperature for about 1 hour. The reaction mixture was then refluxed with stirring for a further hour. 10 ecm of methanol and 10 ecm of water were then added, and the mixture obtained was filtered. The filtrate was washed out with 7 / water and dried over anhydrous magnesium sulfate. From the dried solution the solvent was distilled off to obtain the desired product N-furfuryl-2,6-diethylaniline with a boiling point of 103-105 ⁰ C at 0.1 mm Hg.

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Example 19

Production of IT-furfuryl-2,6-diaethyl ~ a chloroacetanilide

N-furfuryl-2,6-diaethylaniline (8 g), sodium bicarbonate (7 g), dioxane (20 ecm) and water (4 com) were placed in a glass reaction flask equipped with a thermometer and mechanical stirrer. The mixture was ^{cooled to about 0} ° G and a-chloroacetyl chloride (4.3 g) was added in part. After the addition was complete, the mixture was stirred for about 1 hour and allowed to warm to room temperature. Then 100 ecm of ether were added while stirring. The resulting mixture was then washed with water and dried over anhydrous magnesium sulfate. The dried solution was freed from solvent and the residue was dissolved in hexane. The hexane solution was used to precipitate the desired product, namely H-furfuryl-2,6-diaethyl-achloracetaniHid in the form of a krii
the melting solid is cooled,

ehloracetairüid in the form of a crystalline at 36 to 38

Example 20

Production of Ή- ( 4-methylfurfurylidene) - 2,6-dimethylaniline

2,6-dimethylaniline (0.3 mol), 4-methyl-2-furfural (0.3 mol) and benzene were added to a glass reaction flask equipped with a mechanical stirrer, thermometer, and reflux condenser given. The reaction mixture was then heated to reflux with stirring for about 48 hours. The reaction mixture was then distilled to give the desired product, namely 1- (4-methylfurfurylidene) -2,6-dimethylaniline received.

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Example 21

Production of N- (4-methylfurfuryl) -

2,6-dimethylaniline

U- (4-methylfurfurylidene) -2,6-diraethylaniline (21.5 g; ' 0.1 mol), dissolved in 100 ecm of ether, are poured into a with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. Add 2 grams of lithium aluminum hydride to the flask and stir the mixture obtained at room temperature for about half an hour. Then the reaction measurement is carried out heated to reflux with stirring for a further hour. Then they are mixed with 10 ecm of methanol and 10 ecm Water and filtered. The piltrate is washed with water and dried over anhydrous magnesium sulfate. The dry solution is freed from solvent and the desired product is obtained, namely F- (4-methylfurfuryl) -2,6-dimethylaniline.

Example 22

Production of H- (4-methylfurfuryl) - 2,6-dimethyl-a-chloroacetanilide

H- (4-methylfurfuryl) -2,6-diraethylaniline (11.7 g; 0.05 mol), sodium bicarbonate (10 g), dioxane (20 ecm) and water (5 ecm) are put into a thermometer and mechanical Glass reaction flask equipped with a stirrer. The mixture is ^{cooled to about 0} ° C. and a portion of 5.7 g (0.05 mol) of chloroacetyl chloride is added. When the addition is complete, the reaction mixture is stirred for about 1 hour and allowed to warm to room temperature. 100 ecm of ether are then added to the mixture while stirring. The obtained mixture is washed with water and dried over anhydrous magnesium sulfate. The dry solution is freed from solvent, giving the desired product, namely IT- ( _> 4-methylfurfuryl) -2,6-diraethyl-a-chloroacetanilide.

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Example 25

Production of K-Eurfuryliden-2- methyl-5-chloroaniline

2-methyl-5-chloroaniline (42.5 g; 0.3 mol, 2-furfural (29 g; 0.3 mol) and benzene (100 ecm) are poured into one with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. The reaction mixture is then refluxed with stirring for about 72 hours. Then you distill taking the desired product, namely N-furfurylidene-2-methyl-5-chloroaniline receives.

Example 24

Production of N-furfuryl-2- methyl-5-chloroaniline .

H-furfurylidene-2-methyl-5-chloroaniline (22 g; 0.1 mol), dissolved in 100 ecm of ether are poured into one with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. Man add 2 g of lithium aluminum hydride to the flask and stir the resulting mixture for about 1 hour at room temperature. The reaction mixture is then refluxed for a further hour with stirring, whereupon 10 ecm of methanol is added and 10 ecm of water is added and the mixture formed is filtered. The filtrate is then washed with water and dried over anhydrous magnesium sulfate. The dry solution is freed from solvent, whereby the desired product, namely iT-furfuryl-2-methy1-5-chloroaniline receives.

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Example 25

Production of IT-furfuryl-2- methyl-5-a-dichloroacetanilide

IJ-Methylfurfuiyl ^ -methyl ^ -chloraniline (11 g; 0.05 mol), sodium bicarbonate (10 g), dioxane (25 ecm) and water (6 ecm) are placed in a glass reaction flask equipped with a thermometer and mechanical stirrer. The mixture is ^{cooled to about 0} ° C. and a portion of 5.7 g (0.05 mol) of chloroacetyl chloride is added. When the addition is complete, the reaction mixture is stirred for about 1 hour and allowed to warm to room temperature. 100 ecm of ether are then added to the mixture while stirring. The resulting mixture is washed with water and dried over anhydrous magnesium sulfate. The dry solution is freed from solvent, giving the desired product, namely IT-purfuryl-2-methyl-5-a-dichloroacetanilide.

Example 26

Production of F-furfurylidene- 2-methylaniline

2-methylaniline (31.8 g; 0.3 mol), 2-furfural (29 g; 0.3 mol) and benzene (100 ecm) are poured into one with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. The reaction mixture is then stirred for about 36 hours held at reflux. The mixture is then distilled and the desired product is obtained, namely U-purylidene-2-methylaniline.

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Example 27

Production of IT-i ¹ urfuryl-2- methylaniline

N -]? Urfuryliden-2-methylaniline (18.4 g; 0.1 mol), dissolved in 100 ecm of ether, were placed in a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser . 2 g of lithium aluminum hydride are added to the flask and the resulting mixture is stirred for about 1 hour at room temperature, after which it is refluxed for a further hour with stirring. Then 10 ecm of methanol and 10 ecm 'of water are added and the mixture obtained is filtered. The filtrate is washed with water and dried over anhydrous magnesium sulfate. The dry solution is freed from solvent and the desired product is obtained, namely K-purfuryl-2-methylaniline.

Example 28

Production of ΪΓ-furfuryl-Na phlorpropionyl-2-methylaniline

N-furfuryl-2-methylaniline (9.2 g; 0.05 mol), sodium bicarbonate (10 g), dioxane (30 ecm) and water (5 ecm) are in one with a thermometer and a mechanical Glass reaction flask equipped with a stirrer. The mixture is then cooled to about 0 C and partially with 6.4 g (0.05 mol) of α-chloropropionyl chloride offset. When the addition is complete, the mixture is stirred for a further 1 hour and allowed to warm to room temperature heat. Then 100 ecm of ether are added with stirring. The obtained mixture is washed with water and dried over anhydrous magnesium sulfate. Solvent is distilled from the dry solution starting with the desired product, namely IT-PurfuryllT-Q-chloropropionyl-2-methylaniline receives.

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Example 29

Preparation of N-furylaethylidene- 2,6-diaethylaniline

2,6-Diaethylaniline (45 g; 0.3 mol), aI ¹ ur-2-ylacetalde- hyd (33 g; 0.3 mol) and benzene (120 ecm) are in a with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. The reaction mixture is then refluxed with stirring for about 72 hours. It is then distilled and the desired product is obtained, namely F-furylaethylidene-2,6-diaethylaniline.

Example 30

Production of ΪΓ-furylaethyl- 2,6-diaethylaniline

ff-furylaethylidene-2,6-diaethylaniline (14.1 g; 0.1 mol), dissolved in 100 ecm of ether are poured into one with a mechanical stirrer, thermometer and reflux condenser equipped glass reaction flask. 2 g of lithium aluminum hydride are added to the flask and the resulting mixture is stirred Mixture for about 1 hour at room temperature, whereupon the mixture is refluxed with stirring for a further hour. Then 10 ecm of methanol and 10 ecm of water are added and the mixture obtained is filtered. The Piltrat is washed with water and dried over anhydrous magnesium sulfate. The dry solution is removed from Freed solvent, giving the desired product, namely E-furylaethyl-2,6-diaethylaniline.

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Example 51

Production of N-furylaethyl- 2 ₁ 6-diae thyl- a-broraao etanilide

ir-Parylaetbyl-2 _f 6-diaethylaniline (12 g; 0.1 mol), sodium bicarbonate (10 g), dioxane (25 ecm) and water (6 ecm) are placed in a glass reaction flask equipped with a thermometer and mechanical stirrer. The mixture is ^{cooled to about 0} ° C. and 7.9 g (0.05 mol) of bromoacetyl chloride are added to it. After the addition has ended, the reaction mixture is stirred for about 1 hour and allowed to warm to room temperature. Then 100 ecm of ether are added to the mixture with stirring, washed with water and dried over anhydrous magnesium sulfate. Solvent is distilled off from the dry solution, giving the desired product, namely N-furylaethyl-2,6-diaethyl-a-bromoacetanilide.

Further compounds falling within the scope of the invention can be detailed according to the examples above described method can be obtained. In the following examples the main starting materials are mentioned, which are required for the preparation of the specified compounds by the methods described above.

Example 52

The dimethyl acetal of 2-chloroacetaldehyde + 1,2-ethanediol + Methylaniline + chloroacethyl chloride = N-α-chloroacethyl-ir- (1,5-dioxolan-2-ylmethyl) -2-methylaniline.

409833/1083

Example 55

The dimethyl acetal of 2-chloroacetaldehyde + 1,2-ethanediol + 2-ethylaniline + chloroetyl chloride = Ιί-α-chloroacetyl-lf- ( 1,3-dioxolan-2-ylmethyl) -2-ethylaniline.

Example 54

The dimethyl acetal of 5-chloropropionaldehyde + ethanediol + 2,6-diaethylaniline + chloroacetyl chloride = H-α-chloroacelyl-N- (1,3-dioxolan-2-ylaethyl) -2,6-diaethylaniline.

Example 55

The dimethyl acetal of 2-chloroacetaldehyde + propanediol-1,2 + 2,4-diraethylaniline + bromoacetyl chloride = IT-a-bromoacetyl-1-C4 ~ methyl-1,5-dioxolan-2-ylmethyl) -2,4-dimethylaniline.

Example 36

The dimethyl acetal of 2-chloroacetaldehyde + 1,2-butanediol + 2-propyl-4-brotnaniline + α-chloropropionyl chloride = ΪΓ-α-chloropropionyl-K "- (4-ethyl-1,3-dioxolan-2-ylraethyl) -2-propyl-4-" bromaniline.

Example 57

The dimethyl acetal of 2-chloroacetaldehyde + pentanediol-1,2 + 2,4,6-tributylaniline + chloroacetyl chloride = Fa-chloroacetyl-IT- (4-propyl-1,3-dioxolan-2-ylmethyl) -2,4,6 -tribaty! aniline.

409833/1083

Example 38

The dimethyl acetal of 2-chloroetaldehyde + 1,2-hexanediol + 2-methyl-6-methoxyaniline + α-chloroacetyl chloride - N-.a - chloroacetyl-N- (4-'butyl-1,3-dioxolan-2-ylmethyl) -2-methyl-β-methoxyaniline.

Example 39

The dimethyl acetal of 2-chloroacetaldehyde + hexanediol-3,4 + 2,3-Diaethyl-6-aethoxyaniline + α-chlorobutyryl chloride = li-α-chlorobiityryl-Ii- (4 »5-diaethyl-1,3-dioxolan-2-ylmethyl) -2,3-diaethyl-6-ethoxyaniline.

Example 40

The dimethyl acetal of 2-chloroacetaldehyde + 1,3-propanediol + 2-methyl-4-iodoaniline + iodoacetyl chloride = U-α-iodoacetyl-F- (1,3-dioxan-2-ylethyl) -2-methyl-4-iodoaniline.

Example 41

The dimethylacetal of 2-chloroacetaldehyde + 1,3-butanediol + 2-methyl-6-butoxyaniline + chloroacetyl chloride = rr-Q-chloroacetyl-L ^T - (4-methyl-1,3-dioxan-2-ylmethyl) -2- methyl-6-butoxyaniline.

Example 42

The dimethyl acetal of 2-chloroacetaldehyde + 1,4-butanediol + 2-propyl-4-ethylaniline + α-chlorocapronyl chloride U-α-Chlorcapronyl-N- (1,3-dioxepan-2-ylmethyl) -2-propyl-4-ae t hylani1in.

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Example 43

The diraethylacetal of 2-chloroacetaldehyde + ethanedithiol-1,2 + 2,6-dimethylaniline + chloroacetylohloride = ff-a-chloroacetyl-H-C1,3-dithiolan-2-ylmethyl) -2,6-dimethylaniline.

Example 44

The dirnethylacetal of 2-chloroacetaldehyde + 1,3-propanedithiol + 2,6-diaethylaniline + chloroetyl chloride = li-a-chloroacetyl-ir-C 1,3-dithian-2-ylmethyl) -2,6-diaethylaniline.

Further compounds falling within the scope of the invention which can be obtained by the methods described in the preceding examples are N-Eurfuryl-2-propyl-a-chloroacetanilide, N-furfuryl-2-bu.tyl-a- chloroacetanilide, N-Purfury1-2, ö-dipropyl-a-chloroacetanilide, EI ¹ Ur furyl-2,6-di "butyl-α-chloroacetanilide, N-I'urfuryl-2-methyl-6-methoxy- a-chloroacetanilide, li-I ^l urfuryl-2-methyl-6-aethoxy-a-chloroacetanilide, l ί-ϊ ¹ urfuryl-2-methyl-6-propoxy-a-chloroacetanilide, IT-purfuryl-2-methyl- 6-butoxya-chloroacetanilide, N-purfuryl-2,4,6-trimethyl-a-chloroacetanilide, 1 ^ '- purfuryl-2-methyl-4-bromo-α-chloroacetanilide, IT-purfuryl-2-ethyl-5 -fluoro-a-chloroacetanilide, Ή- purfuryl-2-ethyl-4-iodo-a-chloroacetanilide, lf -]? urfurylir-Q-chlorobutyryl-2,6-diaethylaniline, K'-i'urfuryl-li-abromliutyryl- 2,6-diaethylaniline, If-iurfuryl-Ua-chlorvaleryl-2,6-diaethy! Aniline, IT-Purfuryl-Ua-chlorocapronyl-2,6-diaethylaniline, IT- (4-ethylfurfuryl) -2,6-diraethyl- α-chloroacetanilide, E- (4-propylfurfuryl) -2,6-dimet hyl-q-chloroacetanilide, IT- (4-butylfurfuryl) -2,6-dimethyl-a-chloroacetanilide, F-furfuryl-2,6-dimethyl-4-ethy1-a-chloraoetanilide, N-furfuryl-2,6- dimethyl-4-propyl-a-chloroacetanilide, H-purfuryl-2,6-diemthyl-4-butyl-a-chloroetanilide and the like 409333/1083

Purely for practical use as herbicides, the Compounds according to the invention usually incorporated herbicidal compositions, which consist of an inert ! rager and a herbicidally toxic amount of such a compound exist. Such herbicidal compositions allow easy application of the active compound to the weed areas in any desired Lot. These compositions can be solids, e.g., dusty powders, granules, or wettable Powder; they can also be liquid and in the form of solutions, Aerosols or as emulsifiable concentrates.

Dust-like products are obtained, for example, by grinding and mixing the active compound with one solid inert carriers such as talc, clay, silica, pyrophyllite and the like. Granules are obtained by granular carriers, e.g. attapulgites or vermiculites, which usually have a particle size of about 0.3 to 1.5 mm, with the compound usually dissolved in a suitable solvent impregnated. Wettable powders that can be dissolved in water or oil up to any concentration of the active compound can be dispersed, is obtained by incorporating wetting agents into concentrated dust-fine particles Compositions.

In some cases the active compounds are in common organic solvents, e.g. kerosene or xylene soluble to the extent that they can be used directly as solutions in these solvents. Often can Solutions of herbicides are sprayed under overpressure as aerosols. Preferred liquid herbicidal compositions are, however, emulsifiable concentrates, which are composed of an active compound according to the invention and a Solvent and an emulsifier exist as an inert carrier. Such digestible concentrates can 409833/1083

with water and / or oil to any concentration of the active compound and applied to the site of the Weed infestation can be sprayed on. The emulsifiers most commonly used in these concentrates are non-ionic or mixtures of non-ionic with anionic see surfactants. When using some emulsifier systems, a reverse emulsion (water in oil) for direct application to weed areas.

A typical herbicidal composition according to the invention is illustrated in the following example, in which the amounts given are parts by weight.

Example 45 Production of a fine composition

Product of Example 2 10 lime powder 90

The above ingredients are mixed in a mechanical abrasive mixer and formed into a homogeneous, grind free flowing dust with the desired particle size. This dust is suitable for direct application to the point of weed infestation.

The compounds according to the invention can be applied as herbicides in any manner known to Pachraann. One method of controlling weed growth is to locate the weed with a herbicide Contact the composition consisting of an inert carrier and an amount herbieidally toxic to that species of weed an active ingredient, namely a compound of the invention. The concentration of the

409833/1083

The compounds of the present invention in the herbioid compositions vary widely with the nature of the composition and the intended use; as a rule, however, the herbicidal compositions contain about 0.05 to about 95 wt .- ^ of the active according to the invention Links. In a preferred embodiment of the invention, the herbicidal compositions contain about 5 'to about 75 weight percent of the active compound. the Compositions can also contain other substances, for example other pesticides such as insecticides, nematoids, fungicides and the like, stabilizers, spreading agents, deactivators, adhesives, tackifiers Contain substances, fertilizers, activators, synergistic substances and the like.

Such herbicides can also be used in the compositions according to the invention in the form of their salts, esters, amides and other derivatives can be used.

Weeds are undesirable plants that grow unintentionally, have no economic value and which Disrupt the production of plaster plants or ornamental plants or impair the well-being of livestock. The invention Compounds are particularly useful for weed control as they are useful for many types and varieties of weeds toxic, but are relatively non-toxic to many crops. The exact amount of Compound depends on several factors, including the hardiness of the particular weed variety, the weather, the type of soil, the type of application, the type of crops on the same area and like. from. While so applying only about 1 or 2 ounces of active compound per acre for good Control of a slight weed infestation that is awake under unfavorable conditions may be sufficient, the

409833/1083

Applying 10 pounds or more of active compound per acre provides good control of a dense weed of a stubborn, perennial, under
favorable conditions for growing weeds may be required.

The herbicidal toxicity of the compounds according to the invention has been demonstrated by tests in which several types of weeds are checked before the seeds emerge became. In these experiments, small plastic flower pots filled with dry soil were used with the weed seeds sown. 24 hours or less after sowing, the pots were soaked with water until the Soil sprayed and the test compounds were in the form of aqueous emulsions containing emulsifiers Acetone solutions in the specified concentrations sprayed the soil surface.

After spraying, the pots were brought into the greenhouse and, if necessary, additionally heated and daily or watered more often. The plants were kept under these conditions for 25 to 35 days, at which point then the condition of the plants and the degree of their deterioration on a scale from 0 to 10 as follows was measured: O = no impairment, 1.2 = slight Impairment, 3,4 = moderate impairment, 5,6 = moderately severe impairment, 7,8,9 = severe impairment and 10 = dead. The following data show the herbicidal effectiveness.

409833/1083

Degree of impairment

Weed species

Test connection concentration
Pounds / acre Carex Sorghum
halepense Cheno-
_i podium Setaria
lutescens Echinochloa
crus-galli Oigitaria
sanquinalis Avena
sativa Leersia
oryzoides Product of
Example 3 10
4th 10
10 cn cn 10
10 10
9 10
10 10
10 2 10 10 10 9 9 10. 1 10 8th 10 8th 9 9 Product of
Example 5 10
4th 10
10 cn cn 10
9 10
9 10
10 10
9 co 2 10 8th 9 9 9 9 co
co 1 10 8th 3 9 8th 9 y
f—; Product of
Example 19. 10
4th 10 *
10 * VO OO 8th
10 10
10 10
10 9
10 OO VO VO VO OO 2 9 * 9 9 9 10 10 8th 9 to 1 10 * 5 9 9 10 9 5 4th Product of
Example 33 10
4th 9
10 2
1 10
10 10
9 10
9 5 ·
7th 2 10 O 9 9 8th VJl 1 10 O 3 8th 4th 4th

* grown from tubers instead of seeds

cn

CT CD

Claims (1)

Claims where T is hydrogen, a lower alkyl group or \
Halogen means, R is hydrogen, a lower alkyl 2 group or a lower alkoxy group, R a lower one ■ 5 Alkyl group, R is hydrogen or a lower alkyl group, X is halogen, η is an integer from 1 to 2 and Q "Ι _
/, H or Λ 4th -CH ( CH ₂ ) _m ο / ^Χ ζ ² - (LR ⁶ Ι7 -R 1 2
denotes in which Z and Z independently of one another Oxygen or sulfur, R ^, R ⁵ , R, R 'and R are independently hydrogen or a lower alkyl group and m is an integer from 0 to 2. 2. Compound according to claim 1, namely IT-α-chloroacetyl-F- (1,3-dioxolan-2-ylraethyl) -2,6-dimethylaniline. 409833/1083 3. Compound according to claim 1, namely H-α-chloroacetyl-ΪΓ- (1,3-dioxolan-2-ylmethyl) -2,6-diaethylaniline. 4. Compound according to claim 1, namely IT-α-chloro ac etyl-l ·! - ' (1,3-dioxolan-2-ylmethyl) -2-methyl-5-chloroaniline. 5. A compound according to claim 1, namely U-a-chloroacetyl-N- (1,3-dioxolan-2-ylmethyl) -2,6-diaethylaniline. 6. A compound according to claim 1, namely U-a-chloroacetyl-N- (1,3-dioxepan-2-ylmethyl) -2,6-diaethylaniline. 7. A compound according to claim 1, namely F-furfuryl-2,6-diaethyl-α-chloroacetanilide. 8. A compound according to claim 1, namely IT- (4-methylfurfuryl) -2,6-dime thyl ~ a-chlorac etanilide. 9. Compound according to claim. 1, namely. U-Purfuryl-2-methyl-5-α-dichloroacetanilide. 10. A compound according to claim 1, namely H-pururfuryl-U-achlorpropionyl-2-methylaniline. 11. Connection to. Claim 1, namely N-furylaethyl-2,6-diaethyl-a-bromoacetanilide. 12. Compound according to claim. 1, namely IK-furfurylaethyl-2, G-dimethyl-α-chloroacetanilide. 13. Herbicidal composition consisting of an inert carrier and a weed toxic amount of an active Compound according to claim 1. 409833/1083 14. A method for controlling weed growth, characterized in that the weeds with a herbicidal Composition which brings together an inert carrier and an amount toxic to weeds an active compound according to claim 1 consists ■ / ' 409833/1083