DE1445733C - Process for the production of imide chlorides. Elimination from: 1179214 - Google Patents

Description

Cl NR ²

C C

I Il

C C

R ² X Cl

(Ia)

(Ib)

wherein R ^{1 is} a 1,1,2,2-tetrachlorethylene, a 2-oxa or 2-thia-1,1,3,3-tetrachloropropylene group, R ^{2 is} a hydrogen or chlorine atom and X is a methine or chloromethine group or denotes a nitrogen atom, characterized in that a carbarnic acid chloride of the general formula II

CO-Cl

CH,

R ⁵

R ³

R ⁴

(H)

wherein R ³ and R ^{4 are} hydrogen or chlorine atoms and R ^{5 is} ethylene, propylene or 2-oxa, 2-thia or. N-chlorocarbonyl-2-aza-propylene group means in a first stage at temperatures between -20 and about + 140 ° C with replacement of all easily exchangeable hydrogen atoms by chlorine and in a second stage when the temperature is increased by 10 ° C per hour chlorinated to 250 ⁰ C to the end.

2. The method according to claim 1, characterized in that the chlorination in the presence of a inert solvent and optionally carried out under irradiation with ultraviolet light will.

According to an older proposal of our own (now German Patent 1,141,278), chlorine-substituted methyl isocyanide ^{dichlorides are obtained by chlorinating dimethylcarbamic acid chloride at temperatures above 160 ° C.}

It has now been found that this reaction is capable of substantial expansion.

The invention therefore relates to a process for the preparation of imide chlorides in general Formula Ia and Ib

Cl
\ N
y ^x
\ \ /
C.
/ \ Cl
/ \ /
R ¹ \
Cl Cl
\ .N R ²
/ \ /
C. C. \
C. \
C. C.

(Ia)

(Ib)

Cl

wherein R ^{1 is} a 1,1,2,2-tetrachlorethylene, a 2-oxa or 2-thia-l, l, 3,3-tetrachloropropylene group, R ^{2 is} a hydrogen or chlorine atom and X is a methine or chloromethine group or a nitrogen atom means which is characterized in that a carbamic acid chloride of the general formula II

CO-Cl

I.

NR ³

CH ₂

R ⁴

wprin_R ³ and R ^{4 are} hydrogen or chlorine atoms and R ^{5 is} an ethylene, propylene or a 2-oxa, 2-thia or N-chlorocarbonyl-2-aza-propylene group, in a first stage at temperatures between '- 20 and about + 14O ⁰ C, with the replacement of all easily replaceable hydrogen atoms chlorinated by chlorine, and in a second stage in raising the temperature to 10 ⁰ C per hour up to 250 ⁰ C at the end.

As starting compounds for the invention

contemporary chlorination processes come e.g. B. in question:

COCl

/ \
CH ₂ CH ₂

CH ₂ CH ₂

55 N.
COCl

60

65

CH ₂ CH ₂ CH ₂ CH ₂ \ N ' COCl

CH ₂
CH,

CH ₂

N
COCl

CH ₂ CH ₂
CH ₂ CH ₂

COCl

CH ₂
CH,

CH ₂
CH,

directed. The increase in the chlorination temperature after the exothermic reaction has ended is 10 ° C./hour. At 210 to 220 ⁰ C for 3 hours is post-chlorinated.

It is then fractionally distilled. 438 parts by weight of dichloropyrazine are obtained. Bp.i ₂ 71 to 74 ° C, n ^! S = 1.5651.

Analysis: C ₄ H ₂ Cl ₂ N ₂ .

Calculated:

C 32.2, H 1.34, N 18.8, Cl 47.7%;
found:

C 32.22, H 1.45, N 18.8, Cl 48.1%.

The dichloropyrazine can be converted into trichloropyrazine by continued chlorination under reflux and under UV irradiation. Bp. ₁₂ 88 to 90 ° C.

Analysis: C ₄ HCl ₃ N ₂ .

Calculated:

C 26.08, H 0.55, N 15.2, Cl 58.1%;
found:

C 26.04, H 0.67, N 14.98, Cl 58.25%.
25th

Example 2

N
COCl

30th

45

The abovementioned temperature control is of essential importance for the reaction according to the invention. In the majority of cases, completely resinified, black reaction products are obtained from which practically nothing can be isolated if the temperature is increased too quickly during the chlorination. This is due to the condensation reactions of the very reactive chlorine atoms in the α position to the nitrogen atom with Η atoms not yet substituted by chlorine with elimination of HCl. This reaction occurs even from about 130 to 14O ⁰ C.

The chlorination can also be carried out under irradiation with ultraviolet light and / or in the presence of inert solvents. For substances whose melting point is above 140 ⁰ C, z. B. chlorination in solvents such as trichlorobenzene, pentachloroethane, hexachloroethane or tetrachloroethane, appropriate. In the chlorination of Ν, Ν'-bis-chlorocarbonylpiperazine, the initial reaction temperature is chosen to be higher for the same reason (cf. Example 1).

Those which can be produced by the process according to the invention, some of which are not accessible in other ways Products are valuable intermediate products in the manufacture of pesticides, Dyes, pharmaceuticals and plastics, or they themselves have an effect in these areas. Some of the new compounds prepared according to the invention have herbicidal properties.

B β i s ρ i e 1 1

598 parts by weight of Ν, Ν'-bis-chlorocarbonyl-piperazine are ^{melted at 150 to 16O 0} C and under irradiation with UV light chlorine in the melt 492 parts by weight of N-chlorocarbonyl-morpholine are first under irradiation with UV light at 20 ⁰ C chlorinated. Initially, the reaction is highly exothermic and care must be taken by cooling that the temperature does not exceed 12O ⁰ C. When the exothermic reaction has subsided, is weiterchloriert with a temperature increase of 10 ° C / hour until it reaches a temperature of 210 ⁰ C. Chlorination is continued for a further 4 hours at this temperature.

The compound obtained in this way has the constitution according to analysis and spectrum

CCl,

CCl
CCl ₂ CCl ₂
O

Bp. ₁₂ 125 to 128 ° C, nl ° = 1.5388.
Analysis: C ₄ Cl ₇ NO.

Calculated:

C 14.71, N 4.91, Cl 76.1, O 4.91%;
found:

C 14.87, N 4.82, Cl 76.25, O 4.71%.

Example 3

221 g (1.5 mol) of N-chlorocarbonyl-piperidine were chlorinated with stirring and UV exposure. The temperature was held at the beginning of the chlorination few hours at 100 ⁰ C and then gradually increased to 200 ° C.

The reaction mixture, a clear, light brown liquid, was then blown out with nitrogen and

then fractionated in vacuo. 196 g of a mixture of isomeric tetrachloropyridines with a boiling point of ₁₂ 110 to 125 ° C. were obtained. A fraction of boiling point _J2 125-140 ⁰ C., from 42 g = 11% of theory pentachloropyridine on cooling -. 125-126 ° C from ethanol colorless polyhedron mp -. Crystallized further 45 gave g tetrachloro-pyridine. The total yield of tetrachloropyridines was thus 24Ig = 74% of theory. The isomer mixture could be split up into individual components by distillation through a column.

Analysis: C ₅ Cl ₅ N (251.4).

Calculated ... C 23.89, N 5.57%;

found C 24.08, N 5.74%;

24.27, 6.04%.

Analysis: C ₅ HCl ₄ N (216.9). Calculated:

C 27.69, H 0.47, Cl 65.39, N 6.46%; found:

C 27.67, H 0.65, Cl 65.4, N 6.51% 27.97, 0.82, 65.6, 6.6%.

Claims (1)

Patent claims: 1. Process for the preparation of imide chlorides of the general formulas Ia and Ib, Cl N Cl C C R ¹ Cl