DE1668026A1 - Process for the preparation of an N-trifluoromethylated sulfenic acid amide - Google Patents

Description

PAINT FACTORY ^{BAYERAG 1668026} LEVE RKU SEN Beyeiwerk

Patent Department September 27, 1967 Fy / Bl

Process for the preparation of an N-trifluoromethylated one Sulfenic acid amides

(Addition to patent patent application P 49

The main patent relates to a process for the preparation of N-trifluoromethylated sulfenic acid amides, which thereby is characterized in that fluorocarbonyl-N-trifluoromethylarylamine is used in a manner known per se the general formula

COP

/ r

^R 1 in which

R _{1 represents} hydrogen, fluorine, chlorine, bromine, nitro, alkyl or the trifluoromethyl group,

with a sulfenic acid halide of the general formula

R ₂ - SX

in which
Rp is an alkyl substituted by fluorine and / or chlorine

means rest and X stands for chlorine or bromine,

reacts in the presence of a tertiary organic base.

Ie A 10 050-1 - 1 -

109831/2165

In pursuit of the inventive idea on which the main patent is based, it has now been found that novel N-trifluoromethylated sulfenamides are obtained if the fluorocarbonyl-N-trifluoromethylarylamine is used the formula

COP
^ in a known manner with a sulfenic acid halide of the formula

R-SX

in which

R denotes an alkyl radical substituted by fluorine and / or chlorine and

X stands for chlorine or bromine,

in the presence of a tert. organic base as an acid acceptor.

The alkyl radical R substituted by fluorine and / or chlorine generally has 1-4 carbon atoms.

The fluorocarbonyl-N-trifluoromethylarylamine used as the starting compound can be obtained, for example, according to the method of German patent specification 1,170,414.

The sulfenic acid halides used for the process are known. The following compounds are mentioned as examples: Methyl sulfene acid chloride, chloromethanesulfene acid chloride,

Le A 10 050-1 - 2 -

109831/2165

Perchlonnethylmercaptan, Fluorodichloromethansulfeneäurechlorid,

The method according to the invention is explained as follows: COP COP

+ ClS-CCl ₂ P 7 ^ ^ -SGPCl ₂

In general, about the equimolar amount of sulfenic acid halide is used per mole of arylamine. Analogously, the Λ is used as an acid acceptor using place tertiary organic amine in at least equimolar amount, so that per mol freiwerdendem during the reaction hydrogen halide is at least 1 mole are available.

The acid acceptor can optionally also be used in an excess of up to about 30 % .

Examples of tertiary organic amines are: triethylamine, pyridine or those substituted by lower alkyl radicals Pyridines, quinoline or dimethylbenzylamine.

The method is in the temperature range of about 0 - 50 ⁰ C, preferably 20 - 40 ⁰ C is performed, is being carried out advantageously in the presence of an inert organic solvent such as methylene chloride, chloroform, benzene, chlorobenzene or dioxane. The batches are worked up in the customary manner.

Le A 10 050-1 - 3 -

109831/2165

It is surprising that the new compounds are thermal are extremely stable and are therefore undecomposed and without side reactions despite the presence of the fluorocarbonyl group let distill. The new sulfenic acid amides can be used as pesticides with insecticidal and fungicidal Find effect and as intermediates for further reactions use.

Le A 10 050-1 - 4 -

109831/2165 originally inspected

example Mycelial Growth Test Medium used:

20 Oewlchtstelle agar-agar, powdered 30 parts by weight of malt extract 950 parts by weight dist. water

Ratio of solvent to culture medium:

2 parts by weight acetone 100 parts by weight agar culture medium

One mixes the one for the desired concentration of active substance Im ' Nutrient medium required amount of active ingredient with the specified amount of solvent. The concentrate is mixed thoroughly with the liquid nutrient medium, cooled to 42 ° C, in the specified proportions mixed and poured into petri dishes with a diameter of 9 cm. In addition, control plates are used without the addition of a preparation set up.

If the nutrient medium has cooled down and is solid, the plates are inoculated with the types of fungi indicated in the table and incubated ^{at about 21 ° C.}

The evaluation is carried out depending on the growth rate of the Mushrooms after 4-10 days. In the evaluation, the radial · mycelium growth on the treated nutrient media increases with the growth compared to the control medium. The credit rating of the PiIz growth is done with the following key figures:

0 no fungal growth

1 very strong inhibition of growth

2 moderate growth inhibition. 5 weak growth inhibition

4 growth equal to the untreated control

Active ingredients, active ingredient concentrates and results go to the following TaDe ^ e ₉ Jejvo ^

Mycelial growth test table

GQ of

mushrooms

Active ingredients

Active ingredient concentration ppm

ο λ js φ

Ή Φ Ή Φ

H ^ M ti

O β Ph ο

O Ή

■ Η 4 »

Uh ο ο

O Λ ΦΉ • HJrf Ή TO Φ

4 »O

ΦΗ Ε »« Ι

Φ O O O

O Φ

O Φ

H g ι

cd φ

«Η d

O O

ο η

Φ. O Φ

ο g

φ φ φ 3 ο ρ «ο β

φ

4 »ti

00
^ω ι known UJT,
3 = 50565 50569 from MS 1 161 262 1 161 262 O) I. -HS-CCl
CJP 3 known from MS

N:

PCO

compound according to the invention

10 5

10 5

10 5

444444441 34 4444444 4444

44444444313 44444444444

4 4

4 4

10111220000 0 4143244000 0 2

example

To a solution of 131 g of 3-Pluorcarbonyl-6-methoxy-ff-trifluoromethylaniline and 94 g Fluordichlormethansulfenchlorid in 250 ml of benzene is added dropwise at room temperature 80 ml of triethylamine added and allowed the reaction temperature to 40 ⁰ C increase. After the exothermic reaction has subsided, the mixture is stirred for about 20 minutes, the triethylamine hydrochloride is filtered off with suction and the benzene solution is concentrated in vacuo. Subsequent distillation gives 183 g of the N-trifluoromethylated sulfenamide of the formula

COP

H - SCPCl ₂ CJP,

B.p .: 160-167 ° C / 13 torr .; P .: 60 - 65 ° C.

Le A 10 050-1 - 7 -

109831/2165

Claims (2)

Pat ent claims 1. Process for the preparation of N-trifluoromethylated sulfenic acid amides by reacting fluorocarbonyl-N-trlfluoromethylamines with sulfenic acid halides in the presence of a tertiary organic base according to the main patent. ... (German patent application F 49 313 IVb / 12o), characterized in that that in a known manner 3-fluorocarbonyl-6-methoxy-N-trifluoromethylaniline with a sulfenic acid halide the formula R-SX
in which R denotes an alkyl radical substituted by fluorine and / or chlorine and X stands for chlorine or bromine, in the presence of a tertiary organic base as an acid acceptor. 2. N-trifluoromethylated sulfenic acid amides of the general formula COF
wherein
R has the meaning given in claim 1 . Ie A 10 050-1 - 8 - 109831/2165