Method of producing alkyl chloride, alkenyl chloride and...

Details Method of producing alkyl chloride, alkenyl chloride and... Method of producing alkyl chloride, alkenyl chloride and...

2000-11-20

2001-06-12

Siegel, Alan (Department: 1621)

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

Organic compounds

Halogen containing

C570S217000

Reexamination Certificate

active

06245954

ABSTRACT:

The present invention relates to a novel process for preparing alkyl, alkenyl and alkynyl chlorides by reacting alcohols with chlorinating agents in the presence of urea compounds. Alkyl, alkenyl and alkynyl chlorides are known and are suitable as valuable intermediates for organic syntheses. They are obtained in known processes by reacting alcohols with phosgene in the presence of catalysts.
Thus, GB-A 2 182 039 discloses a process for preparing alkyl chlorides from alcohols by reaction with phosgene in the presence of triarylphosphine oxides or triarylphosphine sulfides as catalysts. EP-A 514 683 proposes aliphatic phosphorus compounds as catalysts.
EP-A-200403 discloses the halogenation of alkoxy compounds in the presence of unsubstituted urea.
The disadvantage of these processes is that they result in phosphorus-containing distillation residues which are difficult to dispose of owing to the formation of phosphoric acids.
It is an object of the present invention to remedy the abovementioned disadvantage and, in particular, to provide a process for preparing alkyl, alkenyl and alkynyl chlorides which makes do with small amounts of catalyst and substantially avoids the formation of byproducts.
We have found that this object is achieved by a process for preparing alkyl, alkenyl and alkynyl chlorides from alcohols by reaction with a chlorinating agent in the presence of a catalyst, wherein the catalyst is a urea compound of the formula (I)
R
1
R
2
N—CX—NR
3
R
4
  (I),
in which the radicals R
1
, R
2
, R
3
and R
4
can be identical or different, are, independently of one another, optionally mono- to tri-C
1
-C
4
-alkoxy-, C
2
-C
4
-acyl-, C
2
-C
4
-acyloxy-, phenoxy-, C
2
-C
8
-dialkylamino-, halo-, nitro- and/or cyano-substituted C
1
-C
20
-alkyl, C
2
-C
12
-alkenyl, C
2
-C
12
-alkynyl or optionally mono- to tri-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-, halo-, nitro- and/or cyano-substituted C
3
-C
12
-cycloalkyl, C
4
-C
12
-alkylcycloalkyl, C
4
-C
12
-cycloalkylalkyl, heterocycloalkyl, C
5
-C
20
-heterocycloalkylalkyl, C
6
-C
14
-aryl, C
7
-C
20
-arylalkyl or C
7
-C
20
-alkylaryl, or in which one of the radicals R
1
or R
2
can be, together with one of the radicals R
3
or R
4
, an optionally mono- to tri-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-, halo-, nitro- and cyano-substituted C
2
-C
12
-alkylene chain which may be interrupted by an ether, thioether, tertiary amino, keto, lactone, N-alkyl-substituted lactam or sulfone moiety, and in which X is an oxygen or sulfur atom, and/or a urea compound of the general formula II
in which X has the stated meaning, and R
5
, R
6
, R
7
and R
8
can be identical or different and, independently of one another, have the meaning given for R
1
to R
4
and/or
a compound of the general formula (III),
in which X, R
5
to R
8
have the abovementioned meanings and Z
l
, Z
2
, which may be identical or different, are an optionally mono- to tri-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-, halo-, nitro- and/or cyano-substituted methylene, ethylene or vinylene group.
The organic substituents R
1
to R
8
in the compounds I, II and III have the following meanings independently of one another:
C
1
-C
20
-alkyl, preferably C
1
-C
12
-alkyl, particularly preferably C
1
-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, especially C
1
-C
4
-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
C
2
-C
12
-alkenyl, preferably C
2
-C
8
-alkenyl, such as vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-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
2
-C
12
-alkynyl, preferably C
2
-C
8
-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, particularly preferably ethynyl, 1-propynyl and 1-butynyl.
Said groups may be substituted by 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. Substituted alkyl radicals are preferred, and alkyl radicals substituted by halogen or cyano, such as cyanomethyl, chloromethyl, are particularly preferred.
R
1
to R
8
are also:
C
3
-C
12
-cycloalkyl, preferably C
5
-C
8
-cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, particularly preferably cyclopentyl and cyclohexyl,
C
4
-C
12
-alkylcycloalkyl, preferably C
5
-C
10
-alkylcycloalkyl, particularly preferably C
5
-C
8
-alkylcycloalkyl,
C
4
-C
12
-cycloalkylalkyl, preferably C
5
-C
10
-cycloalkylalkyl, particularly preferably C
5
-C
8
-cycloalkylalkyl,
C
5
-C
20
-alkylcycloalkylalkyl, preferably C
6
-C
16
-alkyl-cycloalkylalkyl, particularly preferably C
7
-C
12
-alkylcycloalkylalkyl,
heterocycloalkyl such as a 5- or 6-membered ring with one or two O, N and/or S atoms in the ring, which may be aromatic or nonaromatic, such as 2- or 3-furyl, 2- or 3-thienyl, 2- or 3-pyrrolyl, 2- or 4-imidazolyl, 2- or 4-oxazolyl, 2- or 4-thiazolyl, pyridinyl, morpholyl, thiomorpholyl and pyrazolyl,
C
6
-C
14
-aryl such as phenyl, 1-naphthyl and 2-naphthyl, preferably phenyl,
C
7
-C
20
-alkylaryl, preferably C
7
-C
16
-alkylaryl, particularly preferably C
7
-C
12
-alkylphenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl and 4-ethylphenyl,
C
7
-C
20
-arylalkyl, preferably C
7
-C
16
-aralkyl, particularly preferably C
7
-C
12
-phenylalkyl such as benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, particularly preferably benzyl, 1-phenylethyl and 2-phenylethyl.
Said groups can be substituted 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.
Urea compounds of the formulae I, II or III which are preferably used are those which are liquid under the reaction conditions, particularly preferably N,N′-dimethylethyleneurea, N,N′-dimethylpropyleneurea, N,N,N′,N′-tetrabutylurea and N,N,N′,N′-tetramethylthiourea, N-chloromethyl-N′-cyanomethylpropyleneurea, N-methyl-N′-ethylpropyleneurea, 1,3-dimethyl-1,3-dihydrobenzimidazol-2-one, 1-methyl-3-phenylimidazolidine-2,4,5-trione, 1,3,4,6-tetramethyl-1,3,4,6-tetrahydroimidazo[4,5-d]imidazole-2,5-dione and 4-methoxy-1-methyl-3-phenylimidazolidine-2-thione.
Said urea compounds can be employed as such, in the form of their salts with hydrohalic acids, for example as hydrochlorides, or in the form of their salts obtainable by reaction with phosgene (Vilsmeier salts).
Alcohols suitable for use according to the invention are mainly those of the formula
in which
R
9
and R
10
can be identical or different and are hydrogen, alkyl, alkenyl, alkynyl, alkoxy, aryloxy, hydroxyalkyl, hydroxyalkenyl or hydroxyalkynyl groups.
Among the alcohols complying with the definition, those preferred in relation to the required products of the process are those in which the R
9
and R
10
radicals have the following meaning:
hydrogen,
C
1
-C
22
-alkyl, preferably C
4
-C
18
-alkyl, among these preferably C
6
-C
10
-alkyl such as, in particular n-hexy

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