DE1668089B2 - METHOD FOR PRODUCING CHLORINATED ISOCYANIDE DICHLORIDES AND CHLORINATED ISOCYANIDE DICHLORIDES AS SUCH - Google Patents

Description

R ³ R ²

have the meaning indicated above in which X, R ^1, R ² and R ^3, with at least the stoichiometric amount of chlorine and cyanogen chloride with addition of a Friedel-Crafts catalyst in the temperature range of about - 30 to about converts +70 ⁰ C

2. The method according to claim 1, characterized in that one is in the presence of an inert organic solvent works

3. The method according to claim 2, characterized in that cyanogen chloride is used as the solvent will.

4. Isocyanide dichlorides of the formula

R ^v X

I I

Cl-CC-NCCI ₂
R ² 'R "

in the

X 'fluorine, chlorine or bromine and
R ¹ , R ² , R ³ 'are hydrogen or a C _{1 to C 4} alkyl radical which is optionally substituted by chlorine

mean.

The production of chloroalkyl isocyanide dichlorides from chlorine, cyanogen chloride and olefinic compounds is Subject of German patent 16 18 401.

If one sets z. B. chlorine with vinyl chloride in liquid cyanogen chloride at temperatures around ^{0 0} C in the absence of catalysts, only trichloroethane is formed.

It has now been found that in the presence of Friedel-Crafts catalysts under otherwise identical conditions predominantly U-dichloroethyl isocyanide dichloride arises The course of the reaction as such is surprising. Although Friedel-Crafts catalysts are the Favor trimerization of cyanogen chloride is produced in the process according to the invention no or only in small amount of cyanochloride.

The invention therefore relates to a process for the production of chlorinated isocyanide dichlorides general formula

R ³ X

Cl-C-C-NCCl,
R ² R ¹

in the

X stands for halogen,

R 'R ² R ^{3 represent} hydrogen, an optionally substituted alkyl or cycloalkyl radical, or an optionally substituted aromatic radical, or R ¹ and R ^{2 can} also be part of a carbocyclic or aromatic ring system,

which is characterized in that a compound of the general formula

XR ¹

R ³

R ²

in which X, R ¹ , R ² and R ^{3 have} the meanings given above, with at least the stoichiometric

rule amount of chlorine and cyanogen chloride with the addition of a Friedel-Crafts catalyst in the temperature range of about -30 ° C to about + 70 ° C.

Optionally substituted aliphatic radicals are, for example, straight-chain or branched ones Alkyl radicals having 1-12, preferably 1-6 carbon atoms called

Cycloaliphatic radicals are those with 5-12, preferably named 5-6 carbon atoms in the ring system.

Examples of substituents on the aliphatic or cycloaliphatic radical are: NO2, halogens (preferably fluorine, chlorine, bromine), - N = CC1 ₂ , alkoxy (preferably 1-4 carbon atoms).

In general, the sum of the carbon atoms in the radicals R ¹ to R ^{3 is} not more than 15. Optionally substituted aromatic radicals are preferably those with up to 10 carbon atoms in the ring system (very particularly preferably phenyl), in general not more than 2 of the radicals R ¹ to R ^{3 represent} an aromatic radical. NO. <, Halogens (preferably fluorine, chlorine, bromine), -N = CCb or alkoxy (preferably 1-4 carbon atoms) may be mentioned as substituents on the aromatic radical.

Preference is given to using olefinic compounds in which X represents fluorine, chlorine or bromine.

As suitable olefinic compounds that are part of a C atoms of the double bond have bonded halogen, for example: vinyl chloride, vinyl fluoride, Vinyl bromide, 1-chloropropene-1-chlorostyrene, 1-chlorocyclohexene-1.

The inventive method is in the temperature range of about -30 ° C to +30 ⁰ C, preferably between about -10 ° and about + 20 ⁰ C, most preferably between -5 ° and +10 ⁰ C, optionally in the presence of inert organic solvents such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene

Chlorine, olefinic compounds and cyanogen chloride are generally used in stoichiometric amounts used.

Very particular preference is given to using cyanogen chloride as solvent in excess

Compounds such as those described in Friedel-Crafts and Related Reactions, Volume I ₁ 1963, p. 201, come into consideration as catalysts. Examples are:

AlCl ₃ , AlBr ₃ , BeCl ₂ , CdCl ₂ , ZnCl ₂ , BF ₃ , BCl ₃ , BBr ₃ ,
GaCl ₃ , GaBr ₃ , TiCl ₄ , TiBr ₄ , ZrCl ₄ , SnCl ₄ , SnBr ₄ ,
SbCl ₅ , SbCl ₃ , BiCl ₃ , FeCl ₃ , UCl ₄

AlCl ₃ , BF ₃ , FeCl ₃ , ZnCl ₂ are preferably used. In general, the catalysts are used in 0.05 to 10 percent by weight (preferably 0.1 to 0.5 percent by weight) based on cyanogen chloride

The reaction mixture obtained by the process according to the invention can be obtained by fractional distillation separated and so the desired reaction product can be isolated.

The compounds produced according to the invention are new. In particular, are connections of general formula

R ^J - ΧΙ I
Cl-C-C-NCCl,

R ² 'R "

in the

X fluorine, chlorine or bromine and

R ¹ ', R ² , R ³ ' are hydrogen or a C1 to Cs alkyl radical which is optionally substituted by chlorine

mean called.

The invention therefore also relates to these last-mentioned new isocyanide dichlorides.

They represent valuable intermediate products for the production of plastic auxiliaries and can also can be used directly as a pesticide.

example 1

In 300 ml of cyanogen chloride (= 6MoI) containing 10 g of aluminum chloride, 360 g of chlorine (5.2 mol) and 330 g of 15.2 mol) of vinyl chloride are passed in over 4 hours with stirring and cooling. The temperature rises during the reaction -5 ° to + 5 ° held. Excess cyanogen chloride is then distilled off under normal pressure. The reaction products are distilled off from the reaction vessel in a water pump vacuum and then fractionated. 540 g (= 55% of theory) of 1,2-dichloroethyl isocyanide dichloride with a boiling point of 71-72 ° / 13 Torr are obtained. Analysis C ₃ H ₃ Cl ₄ N (194.89):

Calc .: C 18.5, H 1.6, Cl 72.8, N 7.2; Found: C 18.7, H 1.4, Cl 73.2, N 7.0.

Example 2

In 500 ml of cyanogen chloride at -5 "C 20 g of anhydrous iron (i; i) dissolved chloride and introduced under stirring and cooling at -5 ⁰ C to 0 ⁰ C within 5 hours 420 g of chlorine to 450 g vinyl chloride excess cyanogen chloride is under normal pressure, the reaction products are distilled off from the reaction vessel at approx .

Example 3

2-chloro-1-fluorine-ethyl isocyanide dichloride

350 g (5 mol) of chlorine and 275 g (6 mol) of vinyl fluoride are introduced into 1000 g (16.3 mol) of cyanogen chloride at -5 to ^{0 ° C.} Subsequently, the excess cyanogen chloride at room temperature '.m vacuum is withdrawn. The residue is fractionally distilled. Yield: 297 g (33.4% of theory). Kp. ,, 53 to 56 ° C.

Example 4

Isocyanide dichlorides from cis- and trans-1 -chloro-propene

A solution of 0.25 mol of ice or trans-1-chloropropene and 10 mg of iron (III) chloride in 1 mol of cyanogen chloride is at -5 ° with 0.25 Mo! Chlorine implemented. The reaction mixture is distilled and the distillate is analyzed by gas chromatography and separated into its components. Three isomeric isocyanide dichlorides are obtained (see Table 1), the various NMR spectra of which correspond to the structures, but do not allow any assignment. The mass spectrum allows the positional isomers to be assigned due to the appearance of the fragments CHCINCCl _{2 and CH3CHNCCI2.}

CH,

CUCH CH -CH,

CKCH-CH-CH,

N CCl,

26.2 "

Cl

CI-CH-CM CH.,

N CCI ₂ 22.6 + 26.2 '

't

l
\

Cl ₂ CH-CH-CH,

Cl

CH ₃

45.9 "Cl ₂ CH-CH-CH, N = CCl ₂
Ι8.4 ^Λ

Kp.,;,: 84-87

Cl

Cl-CH-CH-CH ₁

N = CCl ₂
17.4 + 18.4 '"

"I mole percent isolated by distillation.

*) MoI- ¹ M in the reaction mixture, gaschromatographisc.i determined.

`` MoI-% Ihro- and eryfhro-Vcrbinduni !. Tiaschromatocrciphrsch determined).

Example 5 1 ^ 3-Trichloro-2-dichloromethyleneimino-propane

72 g of 2,3-dichloropropene (-1) and 65 g of Cl _{2 are} added ^{simultaneously at 0 °} C. to 150 ml of cyanogen chloride. The mixture is subsequently stirred at 0 ^° C. for 2.5 hours. The excess cyanogen chloride is stripped off in a water jet vacuum, and the residue is fractionated in a high vacuum

This gives 73 g (47% of theory) isocyanide, Kp ₁ W 54-56 ° C, and 29 g of 1,2,3-trichloropropene (-1) and 7 g of 1,2,2-trichloropropene.

Example 6 1,3,4-Trichloro-2-dichloromethyleneimino-butene (-1)

80 g of 2,3,4-trichlorobutene (-1) and 25 g of chlorine ^{are added simultaneously at 0 °} C. to 125 ml of cyanogen chloride and 2 g of iron (III) chloride. It is stirred for 1 hour at 0 ⁰ C, then the excess cyanogen chloride in

.15 Water jet vacuum removed. The residue is distilled in a high vacuum.

This gives 49 g of 2,3,4-trichlorobutene back, as well as 10 g of boiling point isocyanide Kp.oi 65 -68 ^C C (20% of theory), in addition to small amounts of the corresponding isocyanate.

Example 7
2,3,4-trichloro-2-dichloromethyleneimino-butane

624 g of 1,3-dichlorobutene (-2) and 35 g of chlorine are simultaneously added to 125 ml of cyanogen chloride at 0 ° C.

The excess cyanogen chloride is removed after a reaction time of 1 hour at 0 ^° C. in a water jet vacuum. The residue is distilled on a bridge in a high vacuum.

26 g (19% of theory) of the isocyanide dichloride with a boiling point of bp 0.5 85-90 ° C. are obtained.

Use of the isocyanide dichlorides according to the invention as crop protection agents

to combat fungi and dipteras

Comparative experiments

(Example I) Mycelial Growth Test

Medium used:

20 parts by weight of agar-agar

200 parts by weight of potato decoction

5 parts by weight of malt

15 parts by weight of dextrose

5 parts by weight of peptone

2 parts by weight Na2HPO ₄

0.3 parts by weight Ca (NOs) ₂

Ratio of solvent mixture to nutrient medium:

2 parts by weight of solvent mixture 100 parts by weight of agar culture medium

Composition of solvent mixture:

0.19 part by weight of DMF or acetone

0.01 part by weight of emulsifier alkylaryl polyglycol ether

1.80 parts by weight of water

2 parts by weight solvent _{mixture ft}

The amount of active ingredient necessary for the desired active ingredient concentration in the nutrient medium is mixed in the specified amount of the solvent mixture.

The concentrate is mixed with the liquid soil, cooled to 42 ° C, in the specified proportions thoroughly mixed and poured into petri dishes 9 cm in diameter. Furthermore will Control plates set up without admixture of the preparation.

When the culture medium has cooled down and is firm, turn the plates with the ones given in the table below Inoculated species of fungi and incubated at about 21 ° C.

The evaluation is carried out after 4–10 days, depending on the rate of growth of the fungi. In the Evaluation is the radial mycelial growth on the treated nutrient medium with the growth ituf dem Control medium compared. The rating of the mushroom growth is done with the following key figures:

1 no fungal growth

to 3 very strong inhibition of growth

up to 5 moderate growth inhibition

to 7 weak inhibition of growth

up to 9 growth same as the untreated control

Active ingredients, active ingredient concentrations and results are shown in the table below:

Tabel

Myzclwachsliims-Tcst mushrooms

Active ingredients

ε .2 ^ s ε

a 1.2 I μ Ii. * _ Il i _a is ti ti 11ε υ Ii ü it ^ -si -M ιέ H ^

5l & 5-s £ i ί-3 δε S-I £ € is fS = ί.

- ■ _ »ε-

H Cl

Cl-CCN = CCl ₂ 10

according to example 1 of
Registration P 16 68 089.0

Cl Cl _NC _ _C _ _C _ _CC , ₇ ίο 9 9 9 9 9 9 9 9 9 9

I I

Cl Cl

according to example 5
CA-PS 7 41 794

Cl Cl
C- (L (L _n = CCI, 10 9 9 9 9 9 9 9 9 9 9

Cl Cl

according to example 3
CA-PS 7 41 794

(Example II) ₄ o table

LT ₁₀₀ -Test for Diptera LT ₁₀₀ -Test for Diptera (Aedes aegypti) Test animals: Aedes aegypti.

Solvent: acetone. _ΛηηηΛ,, active ingredients% of animals

_{2 parts by} weight of active ingredient were in 1000 volume 45 ml

share solvent added. Knock down

2.5 ml of this 0.2% active ingredient solution were in effect

a petri dish is pipetted on the bottom of the

Petri dish was a filter paper (diameter CH ₂ C1 — CHC1 — N = CC1 ₂ 100

about 9.5 cm). The Petri dish remained open for so long ₅ o

stand until the solvent has completely evaporated according to the example »

was. After about 25 test animals in the Petri dish of application P 1668089.0

had been given, the bowl was marked with a _ _lsJ _ _rr - _n

Glass lid covered CO ₃ -CU ₂ N-CCi ₂

The condition of the test animals was continuously monitored _{55 according to} Example 3 of CA-PS 7 41749 After 120 minutes, the percentage of test animals exhibiting the knock-down effect was determined NC-Ca ₂ -CCl ₂ -N = CCl ₂ 0

"ASelÄÄSTÄ" ^ ^md "- BeMe. i * r CA-PS, 4,7,4

Claims (1)

Patent claims: 1. Process for the preparation of chlorinated isocyanide dichlorides of the general formula R ³ X I I Cl-C-C-NCCU R ² R ¹ in the X stands for halogen, R ¹ , R ² , R ^{3 represent} hydrogen, an optionally substituted alkyl or cycloalkyl radical or an optionally substituted aromatic radical or R ¹ and R ^{2 can} be part of a carbocyclic or aromatic ring system, characterized in that a compound of the general formula XR ¹