Alpha-substituted α,β-unsaturated E- or Z-aldehydes, use thereof, and processes for their preparation α,β
View Patent ↗This invention relates to novel alpha-substituted α,β-unsaturated E- or Z-aldehydes, or isomer mixture thereof, of the formula (I) in which R 1 and R 2 may be identical or different and are each H or a hydrocarbon, in which the hydrocarbon may have one or more heteroatoms and R 3 and R 4 may be identical or different and are each a hydrocarbon, in which the hydrocarbon may have one or more heteroatoms, and R 5 may be identical or different and is H or a hydrocarbon, in which the hydrocarbon may have one or more heteroatoms, to the use thereof, and to processes for their preparation. The invention further relates to the preparation of further intermediates for pharmaceuticals and to the preparation of the pharmaceuticals.
1. An alpha-substituted α,β-unsaturated E- or Z-aldehyde or isomeric mixture thereof of the formula (I), or the corresponding salt,
in which
R 1 and R 2 may be identical or different and are each H or an optionally substituted hydrocarbon which optionally has one or more heteroatoms, in which the hydrocarbon may especially be an oxygen protecting group, and in which R 1 and R 2 may optionally be bonded to one another to form a ring structure; and
R 3 and R 4 may be identical or different and are each an optionally substituted hydrocarbon with 1-6 C atoms, which optionally has one or more heteroatoms, and in which R 3 and R 4 may be bonded to form a ring structure.
2. An alpha-substituted aldehyde according to claim 1 or the corresponding salt, in which R 1 is H, 3-methoxypropyl or an oxygen protecting group and in which R 2 is H, methyl or an oxygen protecting group and in which R 3 and R 4 are each methyl.
3. An alpha-substituted aldehyde according to claim 1 , selected from the group of: 2-[1-[4-methoxy-3-(3-methoxypropoxy)phenyl]meth-(E)-ylidene]-3-methylbutyraldehyde or 2-[1 -[4-methoxy-3-(3-methoxypropoxy)phenyl]meth-(Z) -ylidene]-3-methylbutyraldehyde or an isomer mixture thereof,
2-[1 -[3-hydroxy-4-methoxyphenyl]meth-(E)-ylidene]-3-methylbutyraldehyde or 2-[1-[3-hydroxy-4-methoxyphenyl]meth-(Z)-ylidene]-3-methylbutyraldehyde or an isomer mixture thereof,
methanesulfonic acid 5-((E)-2-formyl-3-methylbut-1 -enyl)-2-methoxyphenyl ester or methanesulfonic acid 5-((Z)-2-formyl-3-methylbut-1-enyl)-2-methoxyphenyl ester or an isomer mixture thereof,
toluene-4-sulfonic acid 5-((E)-2-formyl-3-methylbut-1-enyl)-2-methoxyphenyl ester or toluene-4-sulfonic acid 5-((Z)-2-formyl-3-methylbut -1-enyl)-2-methoxyphenyl ester or an isomer mixture thereof, benzoic acid 5((E)-2-formyl-3-methylbut-1-enyl)-2-methoxyphenyl ester or benzoic acid 5-((Z)-2-formyl-3-methylbut-l-enyl)-2-methoxyphenyl ester or an isomer mixture thereof,
2-[1-(3,4-dihydroxyphenyl)meth-(E)-ylidene]-3-methylbutyraldehyde or 2-[1-(3,4-dihydroxyphenyl)meth-(Z)-ylidene]-3-methylbutyraldehyde or an isomer mixture thereof,
2-[1-(4-methoxy-3-trimethylsilanyloxyphenyl)meth-(E)-ylidene]-3-methylbutyraldehyde or 2-[1-(4-methoxy-3-trimethylsilanyloxyphenyl)meth -(Z)-ylidene]-3-methylbutyraldehyde or an isomer mixture thereof.
4. A process for preparing an aldehyde of the formula (I) which comprises reacting an aldehyde of the formula (IV)
in which R 1 and R 2 may be identical or different and are each H or an optionally substituted hydrocarbon which optionally has one or more heteroatoms, and in which R 1 and R 2 may optionally be joined to one another to form a ring structure
with an aldehyde of the formula (V) or the enamine thereof,
in which R 3 and R 4 are each as defined in claim 1 .
5. A process according to claim 4 , in which formula (IV) is a benzaldehyde with R 1 being 3-methoxypropyl or an oxygen protecting group and R 2 may be a hydrocarbon, preferably methyl or H, which gives an aldehyde of the formula (VII)
in which R 3 and R 4 may be identical or different and are each an optionally substituted hydrocarbon with 1-6 C atoms, which optionally has one or more heteroatoms, and in which R 3 and R 4 may be bonded to form a ring structure and then converting the compound of the formula (VII) to an aldehyde of the formula (I) by acidic elimination.