DE1668276C - - Google Patents

Description

R ₃ R ₁

used, in the A a nitrogen or phosphorus ao ⁴ . *

atom R ₁ , R ₂ and R _{3 represent} lower alkyl radicals

that are connected with each other and with A a ³

can form a heterocyclic ring, R ₄ a

Alkyl or cyclohexyl radical and X ~ an anion where A represents a nitrogen or phosphorus atom,

indicates. as X ~ represents an anion and R ₁ , R ₂ , R ₃ and R ₄ unsub-

2. The method according to claim 1, characterized in that substituted or substituted hydrocarbon radicals are characterized in that the catalyst used is tetraethylammo-, at least two of which are used by R ₁ , R ₂ and nium chloride. R ₃ represented radicals optionally combined or

3. The method according to any one of the preceding can be condensed, so that with A a heterocyclic claims, characterized in that it is formed as a 30 shear ring.

Carboxylic acid a «, / ^ - unsaturated carboxylic acid If R ₁ , R ₂ , R ₃ and R _{4 represent} four separate radicals

used. len, then they can be the same or different, where-

4. The method according to claim 3, characterized in that at least three of the said radicals are characterized in that the carboxylic acid used is acrylic acid and alkyl radicals with preferably not more than 4 carbons. There are 35 atoms in each alkyl radical. When R ₁ , R ₂ , and

5. The method according to one of the preceding R _{3 represent} alkyl radicals, then R _{4 can represent} a sub-claims, characterized in that the substituted or unsubstituted alkyl, cycloalkyl catalyst is represented in an amount of 0.5 to 10 Ge or aralkyl radicals. As examples of weight percent, based on the weight of the carquaternary ammonium and phosphonium salts in bonsäure used. 40 of these categories should be mentioned: Tetra-

methylammonium salts.Tetraäthvlammoniumalze.Do-

decyltrimethylammonium salts, cetyltrimethylammonium salts, cyclohexyltrimethylammonium salts, ben-

zyltrimethylammonium salts, carboxymethyltrimethyl-45 ammonium salts, tetraethylphosphonium salts and

Tributylmethylphosphonium salts.

It is known that carboxylic acid chlorides by Um- As examples of heterocyclic rings made by

Settlement of carboxylic acids with phosgene produced union of two of the can be represented by R ₁ , R ₁ and R ₃ . It is advantageous to use a catalytic radical with the radilyser represented by A, so that the reaction can be formed smoothly. It should be mentioned that the pyrrolidine, pyrroline, the piperidine, who will. Morpholine, the piperazine and the pyrrole ring.

From French patent specification 1 226 245 it is known as examples of heterocyclic rings, carboxylic acid chlorides by reacting unification or condensation of R ₁ , R ₁ and R, carboxylic acid with phosgene, whereby dimethyl 55 represented radicals with the A represented formamide or other carboxylic acid N-alkylamides are formed as an atom, should be mentioned: Quinucli catalysts are used. Surprisingly, din, 1,4-diazabicyclo (2,2,2) octane, pyridine and quinine have now been found that purer reaction profiles. Quaternary salts of these types which are obtained with the products of the invention if certain quaternary processes according to the invention can be used , are ammonium or phosphonium salts instead of di- 60 z. B. methylpyridinium, cetylpyridinium, cyclomethylformamide can be used. The enthexylpyridinium, benzylpyridinium, and pyridylpyridinium products are less discolored and essentially free from tarry impurities. lium- and N, N'-ethylene-2,2'-bipyridiliumsaize.

The invention thus relates to a method for producing the anion X- of the quaternary salts can be an anion

position of carboxylic acid chlorides by conversion 65, which is different from an inorganic or an organic Carboxylic acid derived with phosgene in the presence of a niche acid. Examples of suitable quater catalysts at elevated temperature, where the new secondary salts are the chlorides, bromides, iodides, metho-invention consists in using a sulfate, ethosulfate, acetate, acrylate, methacrylate,

and benzoates. If necessary, the anion can be kept at 90 ° C. After the reaction has ended

quaternary salt of the same acid that is used with the increases the temperature to 125 to 130 ⁰ C and

Phosgene is converted, derive. Acryloyl chloride is loaded with balls over a short

Any carboxylic acid can be collected through the packed column with phosgene. A yield from processes according to the invention will be implemented. Thus, 5,346 parts of acryloyl chloride with a content of 3% of aliphatic, cycloaliphatic, arylaliphatic / S-chloropropionyl chloride can be obtained,
or aromatic mono- or polycarboxylic acids. Without tetraethylammonium chloride, this can be used. Examples of carboxylic acids that can be used in an attempt to implement a reaction are: acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, docecanic acid, io bis ρ ie 1 2
Acrylic acid, methacrylic acid, crotonic acid, oleic acid,

Chloroacetic acid, oxalic acid, succinic acid, adipin- In a mixture of 432 parts of acrylic acid, 1 part

acid. Sebacic acid, benzoic acid, phenylacetic acid, copper (II) acetate and 12 parts of tributylmethylphosphate

Cinnamic acid and terephthalic acid. phonium iodide of 85 ⁰ C are 720 parts of phosgene

The inventive method is particularly conducted for 15, with the aid of reflux condensation

the production of acid chlorides from ft, /? - unsaturated - the temperature is kept between 78 and 85 ° C.

th carboxylic acids, such as. B. acrylic acid, can be used. The distillation of the mixture under atmospheric

because the acryloyl chloride obtained thereby has an important pressure via a short column packed with spheres

Intermediate product especially for the production gives 355 parts of acryloyl chloride with a content of

of dyes with acrylamido groups. At 20 3 ^U / _O / J-chloropropionyl chloride. Without tributylmethyl

Reaction of acrylic acid with phosgene takes place a phosphonium iodide can lower the reaction temperature

small addition of hydrogen chloride to the double not maintained and no conversion

binding instead, so that the reaction product must therefore be observed
usually a mixture of acryloyl chloride and

/ S-chloropropionyl chloride. If a Λ, / 9-unge- as B is ρ ie 1 3
saturated carboxylic acid is used, it is advantageous to

a Kiipfer salt, such as copper (I) chloride or In a mixture of 116 parts of n-caproic acid and

Copper (II) acetate, to be used in order to polymerize 2 parts of tetraethylammonium chloride to be 105 parts

inhibit tion. Phosgene introduced at 86 to 108 ⁰ C; the mixture becomes

The process according to the invention can either be distilled under reduced pressure, 95 parts being obtained continuously or batchwise with n-caproyl chloride. Without tetraethyldene. A suitable method is that ammonium chloride cannot maintain the reaction temperature of phosgene in a mixture of the carboxylic acid and the phosgene and a reaction is not initiated. The catalysts, that is to say, are observed
the quaternary ammonium, quaternary phosphorous 35

nium salts vary somewhat in their activity from Example 4
bond to bond, but it was found that

usually 0.5 to 10 percent by weight, based on In a mixture of 270 parts of stearic acid and 1.5

the weight of the carboxylic acid, these onium salts from parts of tetraethylammonium chloride are 130 parts

pass. The phosgene is preferably introduced in a gentle 40 phosgene, the temperature between 88

th excess, for example 2 to 20 ° / ₀₎ over the and 106 ⁰ C is kept. That under diminished

mixture distilled stoichiometrically for reaction with the carboxylic acid pressure gives 268 parts of stearoyl

required amount is used. Optionally, chloride.

an inert solvent, such as. B. a hydrocarbon. Without tetraethylammonium chloride, the reagent or a chlorinated hydrocarbon for the reaction temperature cannot be maintained and a circulation can be used. The reaction is exothermic, settlement cannot be observed
and the temperature can largely be adjusted by adjusting the rate of addition of the phosgene
be controlled. Reaction temperatures in the range of

70 to 100 ⁰ C are usually in the case of Λ, / J-un- 50 In a mixture of 122 parts of benzoic acid and

applied saturated acids; higher temperatures 2 parts of tetramethylammonium chloride are 130 parts

can be used with other carboxylic acids. Ie phosgene introduced, with a temperature of 95

The carboxylic acid chloride can be maintained from the reaction to 118 ° C. The under-

mixture are separated in the usual way. So tem pressure can be over a short one packed with bullets

after removal of the dissolved hydrogen chloride, the 55 column distilled mixture gives 129 parts of benzoyl

Carboxylic acid chloride can be obtained by distillation. chloride.

The invention is illustrated by the following examples. Without tetramethylammonium chloride, the reaction can

explained in more detail. The examples are not maintained in the restriction temperature and a change

understandable sense. All parts are set in weight cannot be observed

expressed. 60

Example 6
example 1

In a mixture of 36 parts of acrylic acid, 0.1 part

In a mixture of 432 parts of acrylic acid, 1 part of copper chloride and 1 part of trimethylcyclohexyl

fer (II) acetate and 12 parts of tetraäthylammoniumchlo- 65 ammonium iodide are 60 parts of phosgene during 680 parts of phosgene are passed in at 85 ° C. over a period of 10 hours. The mixture results

initiated for 14 hours, the reaction temperature being 56.5 parts of crude product, equivalent to 38.5 parts temperature with the help of reflux condensation to 80 to acryloyl chloride.

Example 7

In a mixture of 36 parts acrylic acid, 0.1 part Copper (I) chloride and 3.5 parts of methylchinounium iodide are passed in 67 parts of phosgene over the course of 7 hours, the temperature being kept at 85 to 97.degree. The mixture gives 60 parts of raw product, equivalent to 37.4 parts of acryloyl chloride.

Example 8

Into a melt of 50 parts of 1,3-cyclohexanedicarboxylic acid (mixed cis / trans-isomers), and 1 part of tetraethylammonium chloride were introduced at 132 to 137 ° C 4Vj hours 75TeOe phosgene After degassing at 136 ° C, I ^s / «hours , the mixture was distilled under reduced pressure to give 51.6 parts of 1.3 bis (chlorocarbon!) cyclohexane (content 97.2%).

Example 9

93 parts of oleic acid and 0.75 parts of tetraethylammonium chloride were heated to 75 ° C. and 55 parts of phosgene were passed in at 75 to 84 ° C. for 5 hours. After degassing bej 79-80 ⁰ C, I ¹ / * hours, the mixture gives 93 parts of oleyl chloride (content 98.6%).

Example 10

In a mixture of 86 parts of cis-l ^ cyclohexanedicarboxylic acid, 1 part of tetraethylammonium chloride and 51 parts of o-DichlorbenzoI phosgene was 9 ¹ / * hours were introduced long to 120 parts of phosgene is added at 135 to 145 ° C. After degassing at 137 ° to 145 ° C, I ¹ / * hours, the mixture under reduced pressure was distilled to give 90 parts of cis-l, 4-bis- (chlorocarbonyl) cyclohexane (content 98.3%).

Claims (1)

1 2 Compound of the general formula Claims: R1 1. Process for the preparation of carboxylic acid- 5 ^ 4 - A ⁺ R ₂ X
Chlorides by reacting a carboxylic acid with I. Phosgene in the presence of a catalyst at er R ₃ elevated temperature, characterized in that the catalyst used is a Ver in which A is a nitrogen or phosphorus atom, bond of the general formula 10 R ₁ , R ₂ and R _{3 represent} lower alkyl radicals can form a heterocyclic ring connected to one another and to A, R _{4 is} an alkyl or cyclo-Ri hexyl radical and X ~ is an anion ί Suitable quaternary ammonium and phosphorous R ₄ - A ⁺ - R ₂ X- is nium salts are compounds of the formula: