DE1768628A1 - Substituted propionaldehyde-O-phenylcarbamoyloxime and herbicides containing them - Google Patents

Description

Substituted propionaldehyde-0-phenyloarbamoyloxime and herbicides containing them

The present invention: relates to substituted propionaldehyde-O-phenylcarbamic oximes and herbicides containing these active ingredients.

It is known to use the N-phenylcarbamic acid isobutinyl ester as herbicidal active ingredient to use. Its effect is satisfactory However not.

It has been found that substituted propionaldehyde-O-phenylcarbamoyloxime the formula

CH, ⁰ X

CH ₃

in the A an aliphatic (acetyl, propionyl, butyryl, i-butyryl ,. Valeryl, i-valeryl, pivaloyl, capronyl), cycloaliphatic (mono- or bicyclic [^ -CO-, Γ / - CO-,

co- i ^ Tvco-

) or aromatic (benzoyl-, <χ- or β-l! aphthoyl-) acyl radical, each of these radicals by fluorine, chlorine, bromine, methoxy or ethoxy, the alicyclic and aromatic residues also by methyl, KthyL, propyl, i-propyl or t-butyl and the aromatic radicals also by the nitro

10 9 8 A 9/19 1 8

BATH ORIGINAL

- 2 - O.Z. 25 6l6

or trifluoromethyl radical be mono- or polysubstituted can, and A also a methoxythiocarbonyl, £ tftoxyth "l-o-

carbonyl-, n-propoxythiocarbonyl-, CH-z0-CH _o -CH _o -0C-,

SS ^ . ^dd S

O ₀ H _n O-CH ₀ -CH ₀ -OC-, CH ₇ S-CH ₀ -CH ₀ -OC-, C ₀ H ^ S-CH ₀ -CH ₀ -OC-,

<HV-O-C-, Phenoxythiocarbonyl- and Phenylsulfonrest or one Rest of the structure

N-C-

denotes, where R and R ^{1 are} identical or different and denote hydrogen or the methyl, ethyl, propyl, allyl, methoxyethyl, cyanoethyl or phenyl radical and furthermore R and R 'together with the nitrogen atom whose substituents they are , a pyrrolidine, piperidine, morpholine or thiomorpholine radical, X fluorine, chlorine, bromine or the nitro, methyl, ethyl, methoxy, xthoxy, mesyl, carbalkoxy, dialkylamidosulfonyl or trifluoromethyl radical and η the Values 0, 1, 2 or 3 mean, have a good herbicidal effect.

The active ingredients can be used as solutions, emulsions, suspensions or Dusts are used. The forms of application are directed according to the purposes of use; they should ensure a fine distribution of the active substance in each case.

It can be hydrocarbons, such as tetrahydronaphthaiin, and alkylated naphthalenes can be used as spray liquids.

- 3 -

109849/1918

BATH

^: - 3 - - Ό.Ζ. 25 € i6

Aqueous application forms can be made from emulsion concentrates, Pastes or wettable powders (wettable powders) can be prepared by adding water / water. For the production of emulsions you can the substances as such or dissolved in a solvent, be homogenized by means of wetting or dispersing agents in water or organic solvents. But it can also look like active substance, emulsifying or dispersing agent and possibly solvent existing concentrates are produced, which for Dilution with water are suitable.

Knowing about dusts by mixing or jointly marrying the " active substances are produced with a solid carrier.

The production of the new active ingredients can be done in a simple manner take place. The dimeric chloronitroso compound produced from isobutylene and ijitrosyl chloride is, for example, treated with thioacetic acid in the presence of acid-binding agents or with the alkali or alkaline earth salts or the ammonium salt of this acid 2-Methyl-2- (acetylthio) -propionaldoxin implemented, from which with

substituted isocyanates get the corresponding carbamates ^ can be. The latter are partly colorless, partly crystalline poorly crystallizing tough CIe-.

example 1

2-Hethyl-2- (acetylthio) -propionaldoxim 45, 6 parts (parts by weight ") thioacetic acid is dissolved in 350 parts of ethanol, are under ice-cooling, the stoichiometric amount llatrium-

109849/1918

- 4 - 'O.Z. 25 6l6

methylate dissolved in methanol and contributes within 30 minutes at an internal temperature of 20 to 30 ⁰ C in portions 73 parts of the dimeric chloronitroso compound prepared from isobutylene and nitrosyl chloride. Mixture is then stirred at 60 to 70 ⁰ C for 3 hours, cooled, filtered off from the precipitated sodium chloride and concentrate the FiItrat in vacuo.

90 parts (93 % of theory) of a pale yellow oil are obtained.

njp = 1.5136. C 44.75 H 6.93 N 8th > 7 S. 19th , 87 calculated: C 44.8 H 6.9 N 8th , 2 S. 20th A. found: Example 2 2-methyl-2- (benzoylthio) propionaldoxime

According to Example 1, from 138 parts of thiobenzoic acid and 122 parts of dimeric Chlornitrosoverbindunp after recrystallization from carbon tetrachloride / petroleum ether, 202 parts of the above-mentioned compound (Pp. 87 to 89 ⁰ C).

Example 3

2-methyl-2- (benzoylthio) propionaldehyde-0- (3, 5-dichlorophenyl carbamoyl) * oxime

11.2 parts of 2-methyl-2- (benzoylthio) propionaldehyde oxime are dissolved in 50 parts of acetone, gives 9.49 parts of 3,4-dichlorophenyl isocyanate and heated under reflux for 3 hours. After recrystallization from ethanol, the residue yields 20 parts of pure product with a decomposition point at 117 ° C.

109849/1918

BATH ORIGINAL

C. 52 , 7 - 5 - M. 6th , 82 O. Z. 25th 1 616 C. 52 , 6 N 6th , 6 7th 768628 calculated: H- 3, 89 S. 7, 3 Cl -17.3 found: H 1 S. "7, Cl 17.3

According to example 3, for example, the following were produced _:

2-methyl-2- (acetylthio) propionaldehyde-0- (phenylcarbainoyl) oxiiii

n ^ ⁵ : 1.5581

2-methyl-2- (acetylthio) -propionaldehyde-0- (3-chlorophenylcarbamoyl) -

oxime n ^ ⁵ : 1.5513

2-methyl-2- (acetylthio) -propionaldehyde-0- (4-chlorophenylcarbamoyl) -

oxime njp: 1.5696

2-methyl-2- (acetylthio) -propionaldehyde-0- (3,4-dichlorophenyl-

carbamoyD-oxine ■ n ^: 1.5712

2-methyl-2- (acetylthio) -propionaldehyde-0- ( ⁱ f-bromophenylcarbaiiioyl) -

oxime njp: 1,5B3O

2-methyl-2- (acetylthio) -propionaldehyde-0- ( ^I } -inethylphenylcarbamoyl) -

oxime 2-methy 1-2- (acetyl thio) -propionaldehyde-D- (3-inethoxyphenylcarbamoy I) -

oxime 2-methyl-2- (benzoylthio) -propionaldehyde-0- (phenylcarbanioyl) -oxira

M.p .: 115 ° (Z) I.

2-Methy1-2- (benzoylthio) -propionaldehyde-D- (4-methylphenylcarbamoyl) -

oxime m.p .: 7 ^ ° 2-Methy1-2- (benzoylthio) -propionaldehyde-D- (3-chlorophenylcarbamoyI) -

oxime melting point: 117 ° (Z) 2-r! ethyl-2- (o'.thylxanthof; enyl) -propionaldehyde-0- (phenylcarbamo'yl) -

oxime mp: 96-98 ° 2-methyl-2- (cithylxanthogenyl) -propionaldehyde-0- (3-chlorophenyl-

carbamo.yD-oxime mp: 125 ° (Z)

1 O 9 8 A 9 7 1 9 1 8

ORIGINAL

- t> - O.Z. 25 6l6

2-Methyl-2- (Sthylxanthogeny1) -propionaldehyde-O- (3, 4-dichloro-

phenylcarbanoyD-oxime Fp: l ⁱ i2 ° (Z)

2-methyl-2- (phenylsulfonyl) -propionaldehyde-O- (3,4-dichloro-

phenylcarbamoyl) oxime Pp: 47-49 °

The following examples demonstrate the use of the active ingredients.

Example 4

Lehniger sandy soil was filled into test pots and the seeds of maize (Zea Mays), beets (Beta vulgaris), marrow stem cabbage W (Brassica oleracea var. Bulgaris), einj. Bluegrass (Poa annua), crook grass (Dactylis glomerata), field foxtail (Alopecurus myosuroides), wind stalk (Aper'a spica venti) and plughead oat (Avena fatua) and sown with 2-methyl-2- (acetylthio ) at h kg / ha each ) -propionaldehyde-0- (phenylcarbamoyl) -oxime I and, in comparison, with N-phenylcarbamic acid isobutinyl ester II, each dispersed in 500 liters of water per hectare.

After 3 - H weeks, the result shown in the table below was obtained.

Active ingredient

II

Hais beets marrow stem cabbage einj. Bluegrass

- 10 - 100

20 - 30th 30 - l \ Q 20 - 30th ^c ? 0 - IOC

1 0 ^: i 3 U / I 9 1 S.

ORIGlNAL BATHROOM

-V- Ö.Z. 25 6l6

Active ingredient

II

90 - 100 ■ 90 90 90 - 100 RO - 90 - 100 90 100 90

Knucklegrass Field fuchsschvjranz Windhalm Plughafer

From the result it can be seen that I a better tolerance to shark, turnips and marrow-stem cabbage with a little
shows stronger herbicidal activity compared to II. |

Example 5

An agricultural area with a stock of one year . Bluegrass (Poa annua), cockerel grass (Dactylis glomerata), wind grove (Apera spica venti), white goose foot (Chenopodium album), chickweed (Stellaria media), small nettle (Urtica urens) was 10 kg at a height of 2 - P cm / ha of the active ingredient
2-ethyl-2- (acetyIthio) -propioraldehyde-0- (phenylcarbamoyl) -oxime dispersed in 500 liters of water per hectare treated.

After 2-3 weeks all plants had died. Afterward became the usable area with the crops tomatoes and marrow cabbage planted that continued to grow without damage.

-8th-

9-849 / 1918 \

BATH ORIGINAL

Claims (2)

. - 8 - O.Z. 25,616 claims ". Fjj 1. Substituted propionaldehyde-O-phenylcarbamoyloxim der formula CH, Q _Y ASC-CHsN-OC-NH - ^ - ^ f ⁿ GH,. in which A denotes an aliphatic, cycloaliphatic or aromatic acyl radical, each of these radicals by fluorine, chlorine, bromine, methoxy or ethoxy, the alicyclic ones and aromatic radicals also by methyl, ethyl, propyl, i-propyl or t-butyl and the aromatic In addition, radicals can be mono- or polysubstituted by the nitro or trifluoromethyl radical, and A furthermore a methoxythiocarbonyl, ethoxythiocarbonyl, n-propoxy S S thiocarbonyl-, CH ^ O-CH ₀ -CH ₀ -OC-, C ₀ Hj-O-CH ₀ -CH _n -OC-, _s 3 2 2 _S 2 5 ^{2 2} _S CH ₃ S-CH ₂ -CH ₂ -OC-, C ₂ H ₅ S-CH ₂ -CH ₂ -OC-, / Py_ ₀ _c_, phenoxythiocarbonyl and phenylsulfonyl radical or a radical of the structure NC- R ^ denotes, where R and R ^{1 are} identical or different and denote hydrogen or the methyl, ethyl, propyl, allyl, methoxyethyl, cyanoethyl or phenyl radical and also R and R ¹ together with the nitrogen atom whose substituents they are , a pyrrolidine, piperidine, morpholine or 109849/1918 BATH . . - 9 - '. ■ O.Z. 25 6l6 Thiomorpholine residue, X fluorine, chlorine, bromine or the nitro, Methyl, ethyl, methoxy, ethoxy, mesyl, carbalkoxy, Dialkylamidosulfonyl or trifluoromethyl radical and η die Values 0, 1, 2 or 3 mean. 2. Herbicide containing a substituted propionaldehyde-O-phenylcarbamoyloxime, as characterized in claim 1. Badische Anilin- & Soda-Fabrik AOL. λ / 4 ■ 1098A9 / 1918 BAD ORlGlMM.