Preparation of styryl compounds

Details Preparation of styryl compounds Preparation of styryl compounds

2003-01-15

2004-12-07

Richter, Johann (Department: 1626)

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

Organic compounds

Nitriles

C558S361000

Reexamination Certificate

active

06828455

ABSTRACT:

The invention relates to a novel process for preparing styryl compounds and to the use of styryl compounds thus prepared for mass coloration of plastics and for dyeing and printing of hydrophobic fibre materials.
CH-A-56 9055 has already described styryl dyes for dyeing polyester fibres and also for mass coloration of specific plastics.
The preparation of these dyes by the process of CH-A-56 9055, however, is costly and inconvenient.
First of all, the aldehyde of the aniline derivative is prepared by Vilsmeier reaction with dimethylformamide/phosphorous oxychloride and subsequent neutralization and then is condensed with a suitable methylene-active compound, in a solvent, to give the styryl dye.
The apparatus required for preparing this class of dye is technically complex, the synthesis time over all the stages is very long, and the effluents have a high salt load.
It is an object of the present invention, therefore, to provide a simple process for preparing styryl dyes which no longer has the disadvantages of the prior art.
It has been found that this object is achieved by a process for preparing styryl compounds of the formula (I)
in particular of the formula (Ia),
with very particular preference of the formula (Ib)
in which
R
1
and R
2
independently of one another stand for C
1
-C
12
alkyl, which may be substituted by halogen such as F, Cl, Br, by hydroxyl, cyano, —OR
5
, SR
5
,
or for optionally substituted alkoxylates, preferably those of the formula
in which
R stands for H or optionally substituted phenyl, in particular phenyl substituted by halogen, preferably Cl or F, by C
1
-C
8
alkyl and/or by C
1
-C
8
alkoxy, and
n stands for a number from 1 to 50, in particular from 1 to 20,
especially those of ethylene oxides having an average degree of alkoxylation of from 1 to 50, preferably from 1 to 20, or
R
1
stands for the radical of the formula (III)
in which R
1
′, R
3
′, R
4
′ and Z′ are as defined for the radicals R
1
, R
3
, R
4
and Z above or below, or
R
1
and R
2
together form a C
4
-C
6
alkylene radical,
R
5
stands for C
1
-C
12
alkyl or C
6
-C
10
aryl, especially phenyl and naphthyl, it being possible for the aryl to be substituted, for example, by halogen such as Br, Cl, F, or by alkyl, carbonyl or carboxylic esters,
R
6
and R
7
stand independently of one another for optionally substituted aryl or alkyl,
R
3
and R
4
stand independently of one another for hydrogen, C
1
-C
6
alkyl, trifluoromethyl, C
1
-C
4
alkoxy, phenoxy and halogen such as F, Cl, Br,
Z stands for
 in which X, X
1
, X
2
, Y
1
and Y
2
independently of one another stand for C
1
-C
6
alkyl, C
5
-C
7
cycloalkyl, C
1
to C
3
alkylphenyl or for optionally substituted phenyl or naphthyl,
 it being additionally possible for
 Y
1
and Y
2
together with the nitrogen atom to which they are attached to form a 5-7-membered saturated heterocycle,
characterized in that a mixture of a trialkyl orthoformate of the formula (V) and a methylene-active compound of the formula (VI)
or of an acrylic compound of the formula VII
prepared preferably from (V) and (VI), is reacted with an amine of the formula
where R
1
, R
2
, R
3
and R
4
are as defined above.
All abovementioned C
1
-C
12
alkyl radicals may be substituted, for example, by OH, CN, halogen or C
1
-C
6
alkoxy.
For the purposes of this specification alkyl means preferably C
1
-C
12
alkyl, especially methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-dodecyl, n-octyl and n-nonyl, and also the corresponding branched alkyls.
Abovementioned aryl radicals may be substituted, for example, by halogen, especially F, Cl or Br, by C
1
-C
12
alkyl, C
4
-C
7
cycloalkyl, especially cyclopentyl, cyclohexyl, or by C
1
-C
4
alkoxy or benzyl.
Preferred styryl compounds are those of the formula (II)
in which
R
1
, R
3
, R
4
and Z are as defined above,
Alk is a C
2
-C
4
alkylene group,
Ar is phenyl, naphthyl or a phenyl or naphthyl radical which contains at least one C
1
-C
16
alkyl such as propyl, isopropyl, butyl, isobutyl, tert-butyl, isooctyl, isononyl, lauryl, C
5
-C
7
cycloalkyl such as cyclopentyl, cyclohexyl, C
1
-C
12
alkylmercapto, C
5
-C
7
cycloalkylmercapto, phenyl-C
1
-C
3
-alkylmercapto, phenylmercapto or hetarylmercapto substituent, and
is optionally substituted by further substituents such as, for example, C
1
-C
6
alkyl, C
5
-C
7
cycloalkyl, C
1
to C
3
alkylphenyl or halogen radicals such as F, Cl or Br.
Preference is also given to styryl compounds of the formula (VIII)
where B stands for optionally substituted C
2
-C
6
alkylene which may optionally be interrupted by one or more heteroatoms from the group consisting of O and CO or for one of the radicals of the formulae
—(C
2
-C
4
-alkylene)-O—(C
2
-C
6
-alkylene)-O—(C
2
-C
4
-alkylene)-,
—(C
2
-C
4
-alkylene)-O—(C
6
-C
10
-arylene)-O—(C
2
-C
4
-alkylene)-,
in which the alkylene and arylene groups may be substituted.
Particularly preferred styryl compounds are those of the formula (II) in which
Ar is a phenyl or naphthyl radical which contains at least one C
1
-C
16
alkyl such as propyl, isopropyl, butyl, isobutyl, tert-butyl, isooctyl, isononyl, lauryl, C
5
-C
7
cycloalkyl such as cyclopentyl or cyclohexyl, C
1
-C
12
alkylmercapto, C
5
-C
7
cycloalkylmercapto, phenyl-C
1
-C
3
-alkylmercapto, phenylmercapto or hetarylmercapto substituent.
Preferred compounds of the formula (I) are those of the formula (IIa)
in which R
1
and R
2
are as defined above.
In one preferred embodiment of the process of the invention the acrylic compound of the formula (VII)
is formed by reacting the compounds of the formulae
The compounds of the formulae (V) and (VI) may be used directly in a mixture with the amine (IV) or in a step beforehand may be separately precondensed and, if desired, isolated, to form the acrylic compound of the formula (VII), which is reacted with the amine in a second step.
In one preferred embodiment of the process of the invention the molar ratio of compounds IV to VII is from 1:1.0 to 1:1.4, from 1:1.0 to 1:1.2, in particular from 1:1.0 to 1:1.1.
Preferred compounds of the formula (V) are trimethyl orthoformate and triethyl orthoformate.
The process of the invention is preferably conducted in an organic solvent or in excess orthoformate, solvents being compounds which do not undergo reaction with the reactants or products under the reaction conditions.
Preferred solvents used are dioxane, chlorinated hydrocarbons, benzene, chlorobenzene, dichlorobenzene, toluene, xylene, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulphoxide and alcohols such as methanol, ethanol, propanols, butanols, pentanols, hexanols, heptanols, octanols, glycols such as ethylene glycol, diethylene glycol and the corresponding monoalkyl and dialkyl ethers of the glycols; very particular preference is given to using n-butanol, n-octanol, DMF and NMP or mixtures of these solvents.
The process of the invention preferably takes place at a temperature of from 70 to 180° C., in particular at from 90 to 140° C. It is operated, for example, under reflux, with some or all of the alcohol formed being distilled off optionally. It is also possible to operate under pressure in a closed system above the boiling point of the solvent used or of at least one reaction component, or else in the alcohol HOR which is released.
In one preferred embodiment of the process of the invention the reaction mixture is evaporated to dryness and the dry residue is then recrystallized from an appropriate solvent. With particular preference, the reaction mixture is cooled and filtered and the filter cake is washed with alcohol and water and then dried.
In the context of this invention, therefore, a condensation reaction is understood to be a reaction in the course of which alcohol is released.
The condensation of the invention proceeds readily even without further additions. As catalysts it is possible to add zinc compounds such as zinc dust or zinc halides, e.g. ZnCl, ZnBr
2
or ZnJ
2
, or copper compounds such as CuCl, for example.
In one preferre

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