DE2025818A1 - Thioxime carbamates and processes for their preparation - Google Patents

Description

"Thioxime arbamates and process for their preparation "

The present invention relates to new thioxime carbamates and Process for their production via the corresponding thionocarbamates. .

A number of reactions are known in which a thionocarbamate ester is isomerized to the corresponding thiolocarbamate ester. Thus, the work of Newman and Karnes (J. Org. Chem. 1966 31 "3980) have shown that substituted Phenolthionocarbamate can be converted by pyrolysis at 130 to 400 ⁰ C in the isomeric Thiolocarbamate. It has now surprisingly been found that certain oxime thionocarbamates can be converted into the isomeric, hitherto inaccessible thioxime carbamates under considerably milder conditions than previously used for the rearrangement of thiono / thiolocarbamate.

-2 -

009849/2 0 60

The present invention therefore relates to a process for the preparation of thioxime carbamates of the general formula ι ·

■ ·

C = N - S - C - n '(I)

which is characterized in that one is a thionocarbamate of the general formula II:

IL S

C = N-O-C- N ^ (II)

produces and this isomerized at a temperature in the range from 0 to 100 ⁰ C, where R ,. and R, -, each an optionally substituted hydrocarbon »or hydrocarbon _{thio radical or a heterocyclic ring system or R- and R 0} together with the carbon atom of the adjacent imino group (C = N) mean a carbocyclic or heterocyclic ring system and R, and R ^ each represent a hydrocarbon radical or, together with the nitrogen atom of the adjacent carbamate radical, denote a ring system, optionally containing further heteroatoms, provided that at least one of the groups R. and Rp or, when R ^, Rp and the carbon atom of the imino group form a ring system, this ring system is a 7Γ- Contains electron system that come into conjugation with the TT bond of the imino group

The 'it electron system can be either a localized or delocalized / T-system. However, it is preferably a

009849/2060

delocalized system, as is the case when R _x . and Rp is an aromatic ring system, for example an optionally substituted phenyl, pyridyl, furyl or thienyl ring. Such a ring system can be bound to this imono group either directly or via a group which enables conjugation between the ring system and the imino group. Examples of such groups are ethylenic or acetylenic groups or individual atoms which have suitable 'Tt' orbitals, such as a sulfur atom. A suitable delocalized β * -electron system is also present when R _x ., Rp and the carbon atom of the adjacent imino group represent a fused carbocyclic or hiterocyclic ring system, such as a benzodithiol or fluorene ring.

The oxime thionocarbamate formed as an intermediate can by any of the standard methods for making thionocarbamates. A particularly convenient one One way, however, is to use a salt, conveniently an alkali salt, such as a sodium salt of an oxime of the general Formula III;

C = NOH (IH)

R ₂ .

either with a thionocarbamoyl halide of the general Formula IV:

N-C-HaI (IV)

0098 49/2060

1A-37848

or with thiophosgene and an amine of the general formula V:

HH

brings to reaction, where R ^, Rp, R ^ and R ^, the above Have meaning and Hal is a halogen atom, preferably a chlorine atom. The reaction is preferably carried out in an organic solvent and for reaction with the thionocarbamoyl halide is dimethylformamide a suitable solvent, while it is beneficial for reaction with thiophosgene and an amine, diethyl ether to be used as a solvent. s

The isomerization of the thionocarbamate (II) to the thioxime carbamate (I) can in some cases proceed slowly at room temperature, either in the presence or in the absence a solvent. However, the conversion from one isomer to the other is advantageously carried out in such a way that da.i one is a solution of the thionocarbamate in an organic Solvent heated to reflux for 15 minutes to 1 1/2 hours. The most favorable solvents for this reaction are certain chlorinated hydrocarbons, such as carbon tetrachloride or chloroform. But other solvents, such as diethyl ether, can also be used well. The best yields of the thioxime arbamate are obtained when the isomerization carried out under anhydrous conditions. The solvent should therefore be dried and distilled before use and the reaction is conveniently carried out in the presence of an inorganic drying agent. The inorganic desiccant should preferably be chosen so that there is no chemical reaction in any of the isomers (Concerns. Certain oxides and anhydrous »salts of alkaline earths such as calcium oxide or magnesium sulfate in particular

BAD ORIQWAL

1A-37848.

into the thioxirrcarbaniate The degree of conversion of the thionocarbamate and its purity the starting material and the product are most conveniently determined by spectroscopic methods. The infrared spectra of thionocarbamates are characterized by the presence

—1 be a strong band in the range of 960 to 1000 cm, the to the valence oscillation of the> C = S group. These , Band is not present in the spectra of the thioxime carbamate isomers, it is replaced by a band in the range from 1670 to 1690 cm, that of the stretching vibration of the ^ C = O-G group is attributable. For compounds of the formulas I or II which contain the N-GEL group in the carbamoyl group, provides The nuclear magnetic resonance absorption of the methyl protons is another suitable method for differentiating the two Isomers represent. Thus, the thionocarbainates show a characteristic Absorption usually occurs in the form of a doublet approx. »3.2 to 3.5 ppm from TMS downwards (downfield relative to tetramethylsilanes) (T = 6.5 to 6.8), while the thioxime carbamates a singlet at approx. 2.9 to 3.1 ppm (? = 6.9 to 7 »Ό for the absorption of these protons.

The invention also relates to new thioxime carbamates of the formula I, where R. is a phenyl-substituted alkenyl or alkynyl group or an optionally substituted phenyl group or a heterocyclic ring and Rp is an optionally substituted phenyl, phenylthio or alkyl group or R. and Ro together with the carbon atom of adjacent imino group denote a carbocyclic or heterocyclic ring and R, and R. each denote an alkyl or phenyl group or R ₅ , and R. together with the nitrogen atom of the adjacent carbamate group denote a heteroyclic ring system.

Preferred compounds are those in which R ,, a StyryL- or Phenylabhinylgruppe, a Ph-mylgruppe, which optionally by a halogen atom, especially a chlorine atom, or a

■ '- 6 ~ 009849/2060

Is substituted nitro or alkoxy, suitably methoxy group, _e i ^ne thienyl group which is optionally substituted by a halogen atom, suitably a bromine atom, .or a pyridyl or furyl group, R ₂ is an alkyl group having 1 to 6 carbon atoms, particularly a methyl group , or a phenyl group which is optionally substituted by a halogen atom, favorably a chlorine atom, or a nitro or alkoxy, favorably methoxy group, _f or a phenylthio group or R ^ and R ^ together with the carbon atom of the adjacent imino group a fluorene or benzodithiol ring and R and R each represent an alkyl group having 1 to 6 carbon atoms, for example a methyl or ethyl group, or a phenyl group or, together with the nitrogen atom of the adjacent carbamate group, a six-membered heterocyclic ring, conveniently a morpholine ring, =

It is known that oximes form in two stereoisomers, known as the syn and anti forms, and the same kind of stereoisomerism is with the thioxime carbamates of the present invention possible »The invention relates to the two isomeric forms as well as mixtures of these forms.

* The compounds according to the invention have biocidal properties and particularly show a herbicidal effect. The invention therefore also relates to herbicides which have a Carrier and / or "a surfactant together with contain a compound according to the invention »

The term "carrier" as used herein _{ means a substance, which can be inorganic or organic and synthetic or natural, with which the active compound is mixed for its application to plants, seeds ₉ soil or other materials to be treated or to facilitate their storage, transport or handling, Der! 'rager can be a

2 0 8.0 '

Be solid or a liquid. Any normally substance used in the manufacture of pesticides can be used as a carrier. Examples of suitable solid supports are: silicates, clays, e.g. kaolinite clay, synthetic hydrated silicone oxides, synthetic calcium sulfates, Elements such as carbon and sulfur, natural and synthetic resins, e.g. cximaron resins, rosin, copal resin, Shellac, iJannar resin, polyvinyl chloride and styrene polymers, and Copolymers, solid polychlorophenols, bitumen, asphaltite, waxes, e.g. beeswax, paraffin wax, montan wax and chlorinated Mineral waxes and solid fertilizers, e.g. superphosphates.

Examples of suitable liquid carriers are water, alcohols, such as isopropanol, ketones, e.g. acetone, methyl ethyl ketone, Methyl isobutyl ketone and cyclohexanone, ethers, aromatic Hydrocarbons, e.g. benzene and toluene, petroleum fractions, e.g. kerosene, chlorinated hydrocarbons, e.g. carbon tetrachloride, including liquefied, 'normally gaseous Links. Mixtures of different liquids are often suitable.

The surfactant can be a wetting agent, an emulsifier or a dispersing agent. He can not be ionic or ionic. Any of the surfactants normally used in the manufacture of Herbieiden or Insecticides used can also be used. Examples of suitable surface-active substances are the sodium or calcium salts of polyacrylic acids, the Condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the Contain molecule with ethylene oxide and / or propylene oxide; Partial esters of the above fatty acids with glycerol, sorbitol, sucrose or pentaerythritol. Condensation products of alkylphenols, e.g. p-octylphenol or p-octyl cresol with ethylene oxide and / or Pr opy Ie r; ox id; Sulphates or sulphonates of these

CHSS 4 9 , ■ '2 ■ "6 0 ^ ⁰ ORlGINAt.

1A-57 8 « ^202581δ

densification products; Alkali salts, preferably sodium salts,

of sulfuric acid or sulfonic acid esters, which are at least

Contains 10 carbon atoms in the molecule, e.g. sodium lauryl sulfate, Sodium secondary alkyl sulfates, sodium salts of sulfonated

tem castor oil and sodium alkylarylsulfonates, such as sodium

dbdecylbenzenesulfonate.

The agents according to the invention can be prepared as wettable powders, dusts, granulates, solutions, emulsifiable concentrates, emulsions and pastes. Wettable powders are generally prepared to contain 25, 50 or 75% of the poison and usually, in addition to the solid carrier, 3 to 10 % of a dispersant and, if necessary, 0 to 10% stabilizer (s) and / or other additives such as agents that facilitate penetration or contain tackifiers. Dusts are usually prepared as dust concentrates which are similar in composition to the wettable powders but without the dispersant and which are diluted with additional solid carrier when used to produce a composition which normally contains 1/2 to 10 % of the poison . Granules are generally made to have a grain size between 0.148 and 2.0 mm (10 to 100 BS mesh) and can be made by agglomeration or impregnation processes. In general, the granules contain 1/2 to 25 % poison and 0 to 25% additives such as stabilizers, slow release modifiers, binders, etc. Emulsifiable concentrates generally contain 10 to 50% by weight in addition to the solvent and, if necessary, additional solvent ./Vol. Poison, 2 to 20% w / v emulsifiers and 0 to 20 % suitable additives such as stabilizers, agents that facilitate penetration and corrosion inhibitors. Pastes are prepared as generally that a stable flowable product is formed, which is normally 10 to 60 - / o poison, 2 to 20% of suitable additives, and contains, as carrier, water or an organic liquid in which the poison is substantially insoluble.

009 8 * 4 9/2060 "

1A-37848

The inventive compositions may * contain other herbicides or Pesticide and tackifiers, for example, non-volatile 0Ie ₁ other ingredients, for example protective colloids such as gelatin, glue, casein, vegetable gums and polyvinyl alcohol ·, Natrimpolyphosphate ·, cellulose ethers, stabilizers such as ethylene diamine tetraacetic acid. ·

The invention also relates to aqueous dispersions and emulsions, such as, for example, by diluting a wettable powder or emulsifiable concentrate according to the invention with water can be obtained. The emulsions can be used as water-in-oil or in the form of oil-in-water emulsions and can have a thick "mayonnaise" -like consistency.

The two stages of the process of the invention and the compounds produced thereby are carried out by the following Examples explained in more detail.

Example _1 Acetophenone oxime NjN-dimebhylthionocarbamate

C = N - 0 - S. - H CH, —C Il - C - Gllf ^ CII ₃

7.85 g of nafcriuniacefcophenone oxime were made into one with stirring Solution of 9.5 g of dimethylbhiocarbamoyl chloride in 100 ml of dimethylformamide admitted. The temperature of the reaction mixture was kept below 15 ° O during the addition. The mixture was stirred for a further 1 h at 22 ° and then poured into 600 ml of ice water

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1A-37848

- 10 -

pour. The precipitated solid was filtered off, washed with ice-cold water and ^{dried at 0} ° C. in vacuo. Acetophenone oxime thionocarbamate was obtained. Fp. 91 to 92 ⁰ C.

analysis

For C ₁₁ H ₁₄ N ₂ SO: C, 59.5; H 6.4; S 14.4%

Found: C, 58.6; H 6.2; S 14.7%

IR spectrum 985 cm "(C = S stretching vibration)

NMR spectrum 3.37, 3.20, ppm (N.

Example 2 Benzophenone oxime-N-methyl, -N-phenylthionocarbamate

It

H-O-C-N

34.85 g Nabriumbenzophenonoxim were added with stirring at 0 to 5 C in a solution of 17.25 6 thiophosgene in 300 ml of dry Diäbhylu "bher. After complete addition the entsbehende pale yellow suspension was stirred at 0 ⁰ C a solution of 33.7 MIB The reaction mixture was ^{stirred for 30 min at 0} ° C. Into this 200 ml of water were added and the mixture was stirred for 5 min. The ether layer was removed, dried with MgSO. and the solvent in vacuo The remaining oil was filtered, washed with petroleum ether (pebroleum) and precipitated again with

- 11 O. _S O 9 8 4 9/2060. BATH ORIGINAL

1-37-11-

Petrolather (light petroleum) purified from benzene. Kan received the thionocarbamate as colorless needles. M.p. 97 to 98 ° C

Analysis ■

Calculated - for G ₂₁ H ₁₈ N ₂ SO: N 8.1%

Found: N 7.9%

—I
IR spectrum 972 cm "" (C = S-valence oscillation)

NMK spectrum 5.3 ^ ppm (N-GH ₃ ) Example 3

Corresponding to Examples 1 and ?. more Thionocarbaraate were hcrc ^ i-tellt, the physical and spectroscopic properties and analyzes are given in Table I.

TABLE 1:

- 12 C 098 / .9 / 2G 60

BATH ORIGINAL TABEL

Connection melting point

No./ ( ⁰ C)

analysis

IE (C = S Valenzschwin-_ _/. Cm supply ")

NMR (N-CH, ppm)

-C-ίθ

ro ο cn cn

73-83 Ber. for (decomp.)

Found

: C 44.5; H 3.7; S 35.5%: C 44.6; H 3.7; S 35.3%

3.42, 3.25

106.5-W Ber. for Gef.

C 67.6; H 5.7; S 11.3% C 67, S; H 5.7; S 11.4%

980

3.33, 2.78 ι

-ι

102-103 Ber. for Gef.

C 68.1; H 5.0; N 9.9% C 67.9; H 5.0; N 9.9%

3.45

116.5

Ber. for Gef.

: C 49.4; H 4.9: S 12.0%: C 49.4; H 5.0; S 11.9 %

995

3.42, 3.23

-Λ

VM CO

OD OO

OD

.94.5-95 Ber. for C ₁₁ H ₁₃ N ₂ SOCl: C 51.5; H 5.1; S 12.5; C1 13.8% found: C 51.5; H 5.1; S 12.8; C1 14, 2%

993

3.46, 3.29

Continued, to TABLE

V'er Melt Analysis IR NMR

bin point. (C = S (N-CH,

manure ·. Valence ppm) ^

No * ( ⁰ C) 'sohwin-_ ₁

gung cm)

6 91-92 Ber. for C ₉ H ₁₂ N ₂ S ₂ O: C, 47.5; H 5.5; N 12.5% o Found: C 47.4; H 5.5; N 12.0% · "° ⁵ ' ⁵ °» ⁵ > ⁵⁵

no> - "'"■' ■ "' '" - ■ - '■ ■' - ^ -— ■ '■ ■ ■'"■ ^ll ■. ι ι ι ι - ^ * -« ■ «- ■ -«

^ 7 · 110 Ber. for C _Q H " _o N _o S0 _o : C 50.9; H 5.7; N 15.2 %

T ¹ "- 5 42 5 25

^ Found: C, 50.8; H 5.9; N 15.2% ■ '■' ',

⁰ 8 100-101 Ber.
Found . for C ₁₃ H ₁₆ N ₂ SO : C
: C 62.9;
62.5; H
H 6.5;
6.4; CQ CQ 12.9%
15.0% 982 • - S. 105-106 Ber.
Found for C ₁₁ H ₁₅ N ₅ SO ₅ : C
: C 4-9.5;
49.9; H
H 4.9;
5.1; B. 15.7%
15.5% - 5.44, 5.28 10 92-95 Ber.
Found for C ₁₈ H ₁₈ N ₂ SO ₂ : N
: 'N 8.6;
8.4; S.
S. 9.8 9
10.0 Ό
% - - ι ■ 198
(Decomp.) Ber.
Found for O ₁₆ H ₁ ASO ₅ : C
: C 51.5;
51.5; H
H 5.8;
5.8; N 15.0%
14.6 % 995 5.40, 2.86

CO OO

Ports, to TABLE

Yer fusion bond

Mr. * ( ⁰ C)

analysis

IR

VaIence rate ₁
gung cm ")

NMR -CH ₅

ppm)

12th 115-116 Ber.
Found for ^C 16 ^H 14 ^N 2 SOCl ₂ : C
: C 54.4;
54.6; H
H 4.0;
4.3; Cl
Cl 20.1%
20.1% 990 2 , 94, 2, 20th 13th 141-142 Ber.
Found for ^C 18 ^H 20 ^N : , SO ₅ : C
: C 62.8;
62.4; H
H 5.9;
5.9; N
N 8.1% ".
7.8% 980 3 , 0, 2, 36

14th 90 Ber.
Found for C ₁₀ H ₁₅ N ₅ SO C.
: C 53.8;
53.0; H
H 5.9; N
5.8; N 18.8
18.8 ι 13th
12th , 0
, 7 -% ■
% 992 3 .48, 3, 30th 15th 124-126 Ber.
Found for C ₉ H ₁₁ N ₂ S ₂ OBr C.
. σ 35.2;
34.4; H
H 3.6; N
3.6; N 9.1
8.8 qJ "995 3 .45, 3, 27 16 93 Ber.
Found for C ₁₅ H ₁₄ N ₂ SO : C
: C 63.4;
63.3; H
H 5.7; N
5.7; N 11.4;
11.2; S.
S. 983 3 .46, 3, 24

17 58-59 Ber. for C ₁₅ H ₁₆ N ₂ S ₂ O

Found

: C, 60.8; H 5.1; N 8.9 %: C 60.6; H 5.2; N 9.0%

967

3.50, 3.31 "

00

1A-57 848

- 15 - -

* The compounds listed in Table I are the following:

1 = 1, P-Benzodithiol-3-one-oxime-N, N-dimethylthionocarbamate;

2 - benzophenone oxime N, N-dimethylthionocarbamate; 5 ^β fluorene-9-one oxime-N, N-dimethylthionocarbamate;

- M ' = 4 • -nitroacetophenone-oxira-N, N-dimethyl thionocarbamate;

5 = 4'-chloroacetophenone oxime-H, N-dimethylthionocarbamate;

6 = thien-2-yl-methylketoxime-1, N-dimethyl thionocarbamate;

7 = Fur - ^ - yl-methylketoxime-NjN-dimethylthionocarbamate;

8 = styryl methyl ketoxime-NjN-dimethylthionocarbamate;

9 «2'-nitroacetophenone oxime N, N-dimethylthionocarbamate;

10 = benzophenone morpholinylthiocarbonyloxime;

11 = ^, ^ '- urinitrobenzophenone oxime-N ^ -dimethylthionocarbamate;

12 = 4.4 ^l -dichlorobenzophenone oxime-1, N-dimethylthionocarbamate; 13 = 4,4'-dimethoxybenzophenone-oxime-li ^ N-dimethylthionocarbamate;

14 = Pyrid-J-yl-methylketoxime-HjH-dimethylthionocarbamate;

15 = 4-bromide-2-yl-methylketoxime-N, N-dimethyl thionocarbamate;

16 = phenylethinyl methyl ketoxime N ^ N -dimethylthionocarbamate;

17 ^ «Fhenylthio-benzoaldoxime-IVN-dimethylthionocarbamate.

- 16 -

S c t. ir ^y «... b

1A-37848

- 16 -

example 1.2-

- thioxime-NiN-dimethylcarbamate

Il

.__ N-S-C-N

CH,

1.0 g 1,2-BCnZOdItIUoI-J-On-OXiIn-N, N-dimethylthionocarbamate, which had been prepared according to Example 1, in 50 ml dry ether. Heated under reflux for 25 min. The solvent was evaporated in vacuo and the residue was purified by chromatography over aluminum y ^, with 10% ether in Benzene was used to elute. The desired product was obtained. Mp 122-123 ° C

analysis
Calculated for

Found ' :

IR spectrum 1675 cm ~ (C = O stretching vibration)

Nuclear Magnetic Resonance Spectrum 3.02 ppm (N-CH ₅ )

C 44.5; H 5.7; N 10.4; s 35.5% C 44.3; H 3.6; N 10.2; S 35.0%

Example 5 Benzophenone thioxime NJJ dimethyl carbamate

C = N-S-

Lh

CH,

CH,

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1A-37 848 - 17 -

5.0 e benzophenone oxime N, N-dimethylthionocarbamate, which had been prepared according to Example 1, in 250 ml of dry carbon tetrachloride, was refluxed for 30 minutes in the presence of 5.0 g of anhydrous magnesium sulfate. The mixture was then cooled and the insoluble residue was filtered off. From the filtrate, the solvent was evaporated in vacuo to give an oil which was the (80 G ⁰ Kp. 60) gave on trituration with petroleum ether the desired product as a solid. Ep. 145 to 146 ⁰ C.

analysis

Calculated for C ₁₆ H ₁₆ N ₂ SO: C 6 ?.6; H 5.7; N 9.9%

Found: C, 67.2; H 5.6; N 9.4%

" ¹

IR spectrum 1675 cm "(C = O stretching vibration) NMR spectrum 2.91 cm

Example 6 Acetophenone-thioxime- ^ N-dimethylcarbamate

0 GH ₃ C = NSG- N <^

' ^CH 3

5.0 g of acetophenone oxime-NjN-dimethylthionocarbamate, which had been prepared according to Example 1, in 150 ml of dry chloroform, were refluxed for 11/2 hours. The solution was then cooled and concentrated to give an oil which was the (60 to 8O ⁰ C Kp.) Yielded the desired product on trituration with petroleum ether. Mp. 84 to 86 ⁰ C.

- 18 00 984 9/206 0 '

Analysis Calculated for

1A-37848

C 59.5; H 6.4; S 14.4 % C 59.0; H 6.4; S 14.9 %

Found

IR spectrum 1690 cm (C = O stretching vibration) NMR spectrum 2.97 ppm (N-CH ₅ )

Example 7

4 ^L chloroacetophenone thioxime N, N-dimethylcarbamate

CH,

/ ³

c = n-s-c-n:

CH _x 3

CH,

5.0 g of 4'-chloroacetophenone oxime-N, N-dimethylthionocarbamate, which had been prepared according to Example 1, in dry, freshly distilled carbon tetrachloride, was 15 min under reflux in the presence of 5.0 g of anhydrous magnesium sulfate and refluxed 2.5 g of dry calcium oxide for 15 minutes. The mixture was cooled, filtered and the filtrate Concentrated to dryness, a residue remaining which, when recrystallized from a benzene / petroleum ether mixture, the desired product. Mp. 138 to 140 °.

analysis

Calculated for C ₁₁ H ₁₅ N ₂ SOCl: C 51.5, H 5.1, N 10.9, S 12.5;

Cl 13.8%;

Found: C 51.5, H 5.1, N 11.1, S 12.7;

Cl 13.9%.

IR spectrum 1682 cm (C = O stretching vibration) NMR spectrum 3.02 ppm (N-CH,)

- 19 -

009849/2060 '

1A-37 848 - 19 Example 8

According to Examples 4 to 7, further thioxime carbamates were used whose physical and spectroscopic properties and analyzes are given in Table II.

TABLE II:

- 20 - ■ 009649 / 2G6G '

Pi d-H

H O Φ St bo

ΙΙΗΛ d

O rt ο ρ

ω bo

O)

co

iH

rl
O) -P

O
O

O 3 N ^

co ft ι ι ω

h CJ C
Φ · Η 3 (η

κν.

IN vO

CJN VD CJn O CVJ LA IA W. W. V CJN vD co '
VD

O O

O CO CVi

U «Μ Φ O) FP ti)

VO

- 20 -

8th O co VO
O OJ I. v- KN LA O OJ V " LA V " CJN it ω ON VO VD VO LA VO LA V V " W. V W. KN VO KS CVJ KN V "V OJ CN. KN O V "V * LA LA Cn. KN O CN. O VD VD IA LA W "W W. CJN 3 ω CN- KN CJn OJ KN LA LA CN. O VD VO ν- ν LA O O O O O O O CVJ co co CVJ O CVI co CO (25 £ 5 CVJ OJ VO ΚΛ {2; v- v OJ OJ <H KN χ- ' w ~ φ W. Φ V On CiJ CJN Ci) O O O O U U <H "H f * L · ι Φ Φ φ φ φ φ PQ CiJ pq O PP PQ CO OJ V- O (A. ^ ~ K- O v r I. I. vO I. O O KN CJN V V " ω V OJ ON O V " OJ OJ OJ

1-37

CVJ

ο κ \

VO

V "

O O-

OJ V-

V "νιο co

ON CO

KN KN ON Φ O O O
co
KN KN
V V
V
O U "H Φ
pq Found vO
V 114- '

849/206

OJ

- 21 -

CQ
• P
fH
O

N. ti O

« Ti Ti

η oQ> ^ ω

II H. 3 FIG

ο ctf ο 3

K ^ p- CQ tiD

ω ω

ri
CO

Φ -P

Il

FI ti
Φ-H

-60

ti l

CJ

KN OJ

ο ο

sr v

CQ CQ

te

CQ

OJ

W ω

ι t

ω φ pq c!>

KN

OJ V

OJ

OJ

VD

V "

VD ro,

co ω

OJ

CQ OJ

CO ν O

Φ Φ

pq ο

D VD

21 - O Cl 20.1 % t 1A- ■ 37 84 ^ 8 O
v- CM OJ v- ~ OJ O KN (M ¹ 1680 ό
νο
V- KN 1680 1683 O
OJ
O 1680 KN IA
. «*. «* ■
ν v
03 CQ C ^ OJ V OO CO O JN- OO OJ oT co
ν- V " IA <t "
ν v- CO te te te te O VD * ^: CJN GN OO O LA LA O IA IA ΚΛ e- * " O Vd " W W | * T * j | rj • ■ CO W. ω cr> KN tN OJ
VD CN- ν he » KN KN
LA LA VV
LA LA O O OJ
VD CO IN- O O O O 'cm
rH
O
O
CQ
OJ O te te V KN
O
CQ
OJ O
CQ
KN
te
KN
V " IA
O
CQ vD
V
ü Found O
OJ O
CQ
OJ O
V
O V Fh CO
o ~ CO
v ~ Fh VD 5h Fh V "
OJ
O <H U Ber. '<M fH Ber.
Found "<H VD
VD
VD Ber. Vh O
σ »
ω
co U «H
Φ Φ
pq cti ;>) ■ - ~ t
V "
V Found Ber.
Found 226
(Decomp.) ω
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849/2000 '

1A-37848

1A-37848

- 23 -

* The compounds listed in Table II are the following:

18 = fluoren-9-one-thioxime-N _> N-dimethylcarbamate;

19 = 4'-methroacetophenone thioxime N ₁ N dimethyl carbamate;

20 = thien-2-yl-methyl-ketone-thioxime-N, N -dimethylcarbamate;

21 = Pur-2-yl-methylketone-thioxime-N, N-dimethylcarbamate;

22 = styryl methyl ketone thioxime N ^ N dimethyl carbamate;

23 = 2 ^L -itroacetophenone thioxime N ₁ N dimethyl carbamate;

24 β benzophenone thioxime HjN diethyl carbamate;

25 = benzophenori morpholinyl carbonyl thioxime;

26 = 4 _t 4 ^r -Dinitroben2ophenon-thioxime-N, U-dimethylcarbamate;

27 = 4,4'-dichlorobenzophenone-thioxime-N 1 H -dimethyl carbamate;

28 = 4 _t 4'-dimethoxybenzophenone-thioxime-N, H-dimethylcarbamate;

29 = benzophenone thioxime N-methyl-N-phenyl-carbamate;

30 = pyrid-3-yl-methylketone-thioxime-N, N-dimethylcarbamate;

31 - 4-BΓomthien-2-yl-methylketon-thioxime-N, N-dimethyl-

carbamate;

32 = phenylethinyl methyl ketone thioxime-NjN-dimethylcarbamate;

33 * 4 -Phenylthiobenzaldehyde-thi oxime-K, N-dimethylcarbaraat.

- 24 - 0Ö9849 / 2G60

1A-37 848 - 24 -

example

To the herbicidal effect of the compounds according to the invention To demonstrate, they were tested against a representative set of plants, namely oats (H; Avena sativa), Raygrass (RG; Lolium perenne), Welschkorn (WK; Zea mays), peas (E; Pisum sativum), sugar beet (ZR; Beta vulgaris), Flaxseed (L; Linum usitatissimum) and mustard (S; Sinapis alba).

The preparations used for the investigations consisted of 50 parts by volume of acetone, 50 parts by volume of water, 0.5 parts by weight an alkylphenyl / ethylene oxide condensate (Triton X-155) and one of the compounds of the invention in various Amounts.

Young plants of the species listed above were used with the preparations sprayed using a dose that was 10 kg of active substance per ha in a volume of 606 l / ha corresponded.

Comparative tests were also carried out, whereby the plants were sprayed with equal volumes of an agent in which the active component had been omitted was.

The herbicidal activity of the compounds investigated was assessed visually 7 days after the foliage had been sprayed and rated according to a 0 to 9 scale, 0 being no activity and 9 indicating a very strong herbicidal activity. The value 2 corresponds approximately to a reduction in the fresh weight of stems and leaves of the treated plants of 25%. The value 5 corresponds approximately to a weight reduction of 55 % and the value 9 to a weight reduction of 95 osy /. The results obtained in the tests are given in Table III below.

- 25 -

GÜ98A9 / 20 60

. 1A-37848

- 25 TAB EL LE III

Compound herbicidal activity

WK H RG E L S ZR

Thien-2-yl methyl ketone

thioxime-N, N-dimethyl-

carbamate 0 4 4 0 3 5 Ί

StyryIm e thyIk et on-
thioxime-N, N-dimethyl- '
carbamate 0 2 0 O 2 8th 4th Phenylethinylmethyl
ketone-thioxime-Ν, Ν-
dimethyl carbamate 0 0 0 0 7th 6th 7th 1-phenylthiobenzaldehyde
thioxime-lf, N-dimethyl-
carbamate 0 0 0 0 5 3 2

Patent claims:

- 26 -

Claims (17)

PATENT CLAIMS in R. and R ~ are each _a} optionally substituted ^ hydrocarbyl or hydrocarbylthio group or a heterocyclic ring system, or R - and Rp together with the carbon atom of the adjacent imino (C = N) a carbocyclic or heterocyclic ring system, and R ₇ and R ^ each denotes a hydrocarbon radical or, together with the adjacent nitrogen atom, a heterocyclic ring which may optionally contain more heteroatoms, with the proviso that at least one of the groups R ^. or R or if. R., R ~ and the carbon atom of the imino group form a ring system, this ring system contains a Ti electron system which can conjugate with the TT bond of the imino group. 2) Thioximcarbamate according to claim 1, characterized in that R /, a phenylsubstxtuierten alkenyl or Alkj.nylrest or one, optionally substituted. Phenyl or heterocyclic ring, R2 an optionally substituted ^ phenyl, phenylthio or alkyl radical or Ry. and Rp together with the carbon atom of the adjacent imino group form a condensed carbocyclic or heterocyclic ring and R, and R ^ are each an alkyl or phenyl radical or R, and R. together with the nitrogen atom of the adjacent carbamate group a heterocyclic ring 009 8 49/2060 ~ ^2? ~ ORfQSMAL 'INSPECTED S ΊΑ-37 848 - 27 - Ring mean 3) thioxime arbamates according to claim 1 or 2, characterized in that R ^ is a styryl or phenylethinyl radical, a phenyl radical which is optionally substituted by a halogen atom or a nitro or alkoxy group, an optionally halogenated, thienyl radical or a pyridyl or furyl radical , R _{2 is} an alkyl group having 1 to 6 carbon atoms or a phenyl radical, optionally substituted by a halogen atom or a nitro or alkoxy group, or a phenylthio radical or R _x . and R ₂ together with the carbon atom of the adjacent imino group represent a fluorene or benzodithiol ring and R, and R ^ each represent an alkyl group having 1 to 6 carbon atoms or a phenyl group or together with the nitrogen atom of the adjacent carbamate group a six-membered heterocyclic ring. 4) thioxime carbamates according to claim Λ to 3 »characterized in that R. is a styryl or phenylethinyl radical, a phenyl radical which is optionally substituted by a chlorine atom or a nitro or methoxy group, an optionally brominated thienyl radical or a pyridyl or furyl radical, R "A methyl group, a phenyl radical which is optionally substituted by a chlorine atom or a nitro or methoxy group or a phenylthio radical or R ^. and R ₂ together with the carbon atom of the adjacent imino group represent a fluorene or benzodithiol ring and R, and R ^ each represent a methyl, ethyl or phenyl radical or together with the nitrogen atom of the adjacent carbamate group a morpholine ring. 5) Process for the preparation of the thioxime carbamates according to Claim 1 to 4, characterized in that that you first have a thionocarbamate of the general formula II: C09iU3 /: 060 · "" ■ 1Δ-37-848 - 28 - C = N-O-C- NQ (II) and this thionocarbamate isomerized at a temperature in the range from 0 to 100 ° C, where R. to R ^, the have the meaning given above. 6) Method according to claim 5, characterized in that the thionocarbamate by Reaction of the salt of an oxime of the general formula III; C = NOH (III) either with a thionocarbamoyl halide of the general formula IV: H-C-HaI (IV) Jt or thiophosgene and an amine of the general formula V: HH (V) produces, where R. to R ^ have the meaning given above and Hai represents a halogen atom. - 29 - Oü9849 / 2060 1A-37 848 - 29 - 7) Method according to claim 6, characterized in that the reaction takes place in an organic Solvent is carried out. 8) 'method according to claim 7 »characterized in that the organic solvent for the Reaction with the thionocarbamoyl halide dimethylformamide and for the reaction with thiophosgene and the amine diethyl ether is. 9) Method according to claim 6 to 8, characterized in that the halogen atom is a ChIoratorn. 10) Method according to claim 5 to 9 ₅ , characterized in that the isomerization is carried out by refluxing a solution of the thionocarbamate in an organic solvent for 15 min to 1 1/2 h. 11) Method according to claim 10, characterized in that the organic solvent is a is chlorinated hydrocarbon. 12) Method according to claim 11, characterized in that the chlorinated hydrocarbon Is carbon tetrachloride or chloroform. 13) Method according to claim 10, characterized in that the organic «solvent is diethyl ether. 14) Method according to claim 10 to 13, characterized in that g e k e η η draws that the isomerization under anhydrous Conditions is carried out. - 30 - 0.09849 / 2060 1A-37 348 - 30 - 15) Process according to claim 14, characterized in that the isomerization in the presence an inorganic drying agent is carried out. 16) Method according to claim 15 ■> characterized geke η η draw'η et that the inorganic desiccant is anhydrous magnesium sulfate or calcium oxide. 17) Use of the thioxime carbamates according to claim 1 to in herbicidal agents, 62IXIT 009849/2060