Method for producing chlorocarboxylic acid chlorides

Details Method for producing chlorocarboxylic acid chlorides Method for producing chlorocarboxylic acid chlorides

2000-04-20

2001-07-17

Geist, Gary (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic halides

C562S856000, C562S854000, C562S828000

Reexamination Certificate

active

06262300

ABSTRACT:

The present invention relates to a novel process for preparing chlorocarbonyl chlorides by reacting lactones with chlorinating agents in the presence of urea compounds.
Chlorocarbonyl chlorides are known useful intermediates for organic syntheses, in particular of crop protection agents and drugs.
DE-A 36 24 258 discloses the preparation of chlorocarbonyl chlorides by reacting the corresponding lactones with phosgene in the presence of quaternary ammonium salts as catalysts. Although good yields are obtained by using this process, it leaves something to be desired from an industrial point of view, since the quaternary ammonium salts are insoluble both in the lactones and in the chlorocarbonyl chlorides, which makes work-up of the reaction mixture and in particular a continuous operation of the process difficult.
EP-A 413 264 and EP-A 435 714 describe a process for preparing chlorocarbonyl chlorides by chlorination of lactones using phosgene in the presence of phosphine oxides where phosphorus-containing distillation residues are obtained whose disposal is complicated by the formation of phosphoric acid during the incineration of the residues. Furthermore, U.S. Pat. No. 341 8 365 discloses a process for preparing chlorocarbonyl chlorides from lactones using thionyl chloride, however, this process gives only unsatisfactory yields.
It is an object of the present invention to provide a process for preparing chlorocarbonyl chlorides by reacting lactones with chlorinating agents; which avoids the disadvantages of the prior art processes.
We have found that this object is achieved according to the invention by a process for preparing of chlorocarbonyl chlorides of the formula I
R
1
—CHCl—Y—COCl  (I),
where
R
1
is hydrogen, or is C
1
- to C
20
-alkyl, C
2
- to C
12
-alkenyl, C
2
- to C
12
-alkynyl, each of which is unsubstituted or mono- to trisubstituted by C
1
- to C
4
-alkoxy, C
2
- to C
4
-acyl, C
2
- to C
4
-acyloxy, C
2
- to C
8
-dialkylamino, halogen, nitro and/or cyano, or is C
3
- to C
12
-cycloalkyl, C
4
- to C
12
-alkylcycloalkyl, C
4
- to C
12
-cycloalkylalkyl, heterocycloalkyl, C
5
- to C
20
-heterocycloalkylalkyl, C
6
- to C
14
-aryl, C
7
- to C
20
-arylalkyl or C
7
- to C
20
-alkylaryl, each of which is unsubstituted or mono- to trisubstituted by C
1
- to C
4
-alkyl, C
1
- to C
4
-alkoxy, C
2
- to C
4
-acyl, C
2
- to C
4
-acyloxy, C
2
- to C
8
-dialkylamino, halogen, nitro and/or cyano, and
Y is a saturated or mono- or polyolefinically unsaturated C
2
-C
8
-alkylene chain which may be interrupted by an ether, thioether, tertiary amino, keto, lactone, N-alkylsubstituted lactam or sulfone group and is unsubstituted or mono- to trisubstituted by C
1
- to C
12
-alkyl, C
1
- to C
8
-alkoxy, C
2
-C
4
-acyl, C
2
-C
4
-acyloxy, C
2
-C
8
-dialkylamino, halogen, nitro and cyano,
by reacting the lactone of the formula II
where R
1
and Y are each as defined above, with a chlorinating agent in the presence of a urea compound of the formula III
R
2
R
3
N—CX—NR
4
R
5
  (III),
where the radicals R
2
, R
3
, R
4
and R
5
may be identical or different and, independently of the others, each has the meanings given for R
1
with the exception of hydrogen, or where one of the radicals R
2
or R
3
together with one of the radicals R
4
or R
5
are a hydrocarbon chain having 2 to 8 carbon atoms which may contain an ether, thioether, tertiary amino, keto, lactone, alkyl-substituted lactam, sulfone or diketo group and which is saturated or mono-or polyolefinically unsaturated and is unsubstituted or mono- to trisubstituted by C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
2
-C
4
-acyl, C
2
-C
4
-acyloxy, phenoxy, C
2
-C
8
-dialkylamino, halogen, nitro and cyano, or are a cycloalkylene group having 5 to 12 carbon atoms, a heterocycloalkylene group having 4 to 11 carbon atoms, an arylene group having 6 to 12 carbon atoms or a heteroarylene group having 3 to 11 carbon atoms, each of which is unsubstituted or mono- to trisubstituted by C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, phenoxy, C
2
-C
4
-acyl, C
2
-C
4
-acyloxy, C
2
-C
8
-dialkylamino, halogen, nitro and/or cyano, and where X is an oxygen or sulfur atom, and/or a urea compound of the formula IV
where X is as defined above, R
6
, R
7
, R
8
and R
9
may be identical or different and, independently of the others, each has the meanings given for R
1
, with the exception of hydrogen, and/or
a compound of the formula (V),
 where X, R
6
to R
9
are each as defined above and Z
1
, Z
2
, which may be identical or different, are a methylene, ethylene or vinylene group which is unsubstituted or mono- to trisubstituted by C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
2
-C
4
-acyl, C
2
-C
4
-acyloxy, phenoxy, C
2
-C
8
-dialkylamino, halogen, nitro and/or cyano.
Y is a C
2
-C
8
-alkylene chain which may be interrupted by hetero atoms such as oxygen or sulfur or by groups which are inert to the chlorinating agent under the reaction conditions, for example a tertiary amino, keto, lactone, N-alkyl-substituted lactam or sulfone group. Y may furthermore be mono- to trisubstituted by groups which are inert to the chlorinating agent under the reaction conditions, for example by C
l
-C
4
-alkyl, C
1
-C
4
-alkoxy, C
2
-C
4
-acyl, C
2
-C
4
-acoxy, C
2
-C
8
-dialkylamino, halogen, nitro and cyano. Preferably, Y contains only carbon atoms as building blocks of the chain,, and no further substituents. Y is particularly preferably C
2
-C
4
-alkylene such as ethylene, propylene and butylene, in particular ethylene and propylene.
Independently of one another, the organic substituents RI to R
9
in the compounds I, II, III, IV and V have the following meanings:
C
1
- to C
20
-alkyl, preferably C
1
- to C
12
-alkyl, particularly preferably C
1
- to C
8
-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl and isooctyl, in particular C
1
- to C
4
-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
C
1
-Cl
2
-alkenyl, preferably C
2
-C
8
-alkenyl, such as vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethylpropenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, particularly preferably vinyl, 2-propenyl and 1-butenyl,
C
1
- to C
12
-alkynyl, preferably C
2
-C
8
-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-methyl-2-propynyl, l-pentynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dirmethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, particularly preferably ethynyl, 1-propynyl and 1-butynyl.
The abovementioned groups may be substituted by C
1
-C
4
-alkoxy, C
2
-C
4
-acyl, C
2
-C
4
-acyloxy, C
2
-C
8
-dialkylamino, halogen, nitro and/or cyano. Preference is given to substituted alkyl radicals, particularly preferably halogen- or cyano-substituted alkyl radicals such as cyanomethyl, chloromethyl.
Furthermore, R
1
to R
9
are:
C
3
- to C
12
-cycloalkyl, preferably C
5
- to C
8
-cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, particularly preferably cyclopentyl and cyclohexyl,
C
4
- to C
12
-alkylcycloalkyl, preferably C
5
- to C
10
-alkylcycloalkyl, particularly preferably C
5
- to C
8
-alkylcycloalkyl,
C
4
- to C
12
-cycloalkylalkyl, preferably C
5
- to C
10
-cycloalkylalkyl, particularly preferably C
5
- to C
8
-cycloalkylalkyl,
C
5
- to C
20
-alkylcycloalkylalkyl, preferably C
6
- to C
16
-alkylcycloalkylalkyl, particularly preferably C
7
- to C
12
-alkylcycloalkylalkyl,
heterocycloalkyl, such as a 5- or 6-membered ring having one or two O, N

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