Claims
- 1. Process for the manufacture of an aldehyde of the formula ##EQU11## in which either R.sub.1 and R.sub.3 together represent alkylene with 2 or 3 chain carbon atoms, or R.sub.2 and R.sub.3 together represent alkylene with 3 or 4 chain carbon atoms and the remaining R.sub.2 or R.sub.1 is hydrogen or lower alkyl, which comprises condensing a compound of the formula ##EQU12## wherein R.sub.1, R.sub.2 and R.sub.3 have the above meanings, with the aminoaziridine of the formula ##EQU13## in which R.sub.4, R.sub.5, R.sub.6 and R.sub.7 each represents a member selected from hydrogen, lower alkyl, lower alkenyl, lower cycloalkyl, phenyl, tetrahydronaphthyl or phenyl substituted by at least one halogen, lower alkyl or phenyl, or R.sub.5 and R.sub.6 together are alkylene with 3 to 5 carbon atoms and R.sub.4 and R.sub.7 are hydrogen, at about room temperature and heating the condensation product to about 170.degree. until the evolution of molecular nitrogen ceases.
- 2. Process as claimed in claim 1, wherein at least one of the radicals R.sub.4, R.sub.5 R.sub.6 and R.sub.7 stands for said cycloalkyl or phenyl radical and the other for hydrogen.
- 3. Process as claimed in claim 1, wherein R.sub.4 stands for phenyl or phenyl substituted by at least one halogen, lower alkyl or phenyl and R.sub.5, R.sub.6 and R.sub.7 represent hydrogen.
- 4. Process as claimed in claim 1, wherein R.sub.4 represents phenyl, P-chlorophenyl, p-bromophenyl or biphenyl and R.sub.5, R.sub.6 and R.sub.7 represent hydrogen.
- 5. Process according to claim 1, wherein R.sub.4 stands for phenyl and R.sub.5, R.sub.6 and R.sub.7 stand for hydrogen.
- 6. Process according to claim 1, wherein R.sub.4 represents tetrahydronaphthyl and R.sub.5, R.sub.6 and R.sub.7 represent hydrogen.
- 7. Process according to claim 1, wherein R.sub.5 and R.sub.6 represent phenyl, p-chloro-phenyl or p-bromo-phenyl and R.sub.4 and R.sub.7 stand for hydrogen.
- 8. Process according to claim 1, wherein R.sub.5 together with R.sub.6 is alkylene having 3 to 5 carbon atoms and R.sub.4 and R.sub.7 represent hydrogen.
- 9. Process according to claim 1, wherein R.sub.5 together with R.sub.6 is 1,4-butylene and R.sub.4 and R.sub.7 represent hydrogen.
- 10. Process as claimed in claim 1, wherein 1,2-epoxy-1-formyl-cyclopentane is used as starting material.
- 11. Process as claimed in claim 1, wherein 1,2-epoxy-1-acetyl-cyclopentane is used as starting material.
- 12. Process as claimed in claim 1, wherein 2-methyl-2,3-epoxy-cyclohexan-1-one is used as starting material.
- 13. Process as claimed in claim 1, wherein 2,3-epoxy-cyclohexanone is used as starting material.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 14014/68 |
Sep 1968 |
CH |
|
CROSS REFERENCES TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 856,478, filed Sept. 9, 1969 (now abandoned). Application Ser. No. 679,200, filed Oct. 30, 1967 discloses a process for the manufacture of .alpha.-oxo-.alpha.,.beta. -seco-.beta.(.gamma.)-acetylene compounds of the general formula ##EQU3## in which R.sub.1-3 and R.sub.0 each represents hydrogen or an organic residue and at least two of these residues are linked together, characterized in that a compound of the general formula ##EQU4## in which R.sub.1-3 and R.sub.0 have the above meanings, X represents a diazonium residue or a residue which can be converted into a diazonium residue under the decomposition conditions, and Y represents a residue convertible into an oxo group under the reaction conditions and by a possibly following hydrolysis, is decomposed with fragmentation and elimination of molecular nitrogen, and the resulting product, if desired, is hydrolyzed. The said specification describes more especially the fragmentation, accompanied by development of nitrogen of .alpha.,.beta.-oxido-.gamma.-carbonyl compounds of the formula ##EQU5## in which X' represents a nitrogenous derivative of an oxo group, such as the oximido group or a derivative thereof esterified or etherified on the oxygen, or a hydrazino group or a derivative thereof substituted by a nucleofuge group, or an iminoaziridine group. This process is specially concerned with the manufacture of cycloaliphatic .alpha.-oxo-.alpha.,.beta.-seco-.beta.(.gamma.)-acetylene compounds and of .alpha.-oxo-.alpha.,.beta. -seco-steroid-.beta.(.gamma.)-ines.
The present invention is based on the observation that the fragmentation of compounds of the formula II, in which R.sub.0 represents a hydrogen atom, can be achieved especially easily and with particularly good yields via the iminoaziridine derivatives.
Accordingly, the present invention provides a process for the manufacture of aldehydes of the general formula ##EQU6## in which R.sub.1-3 have the above meanings, which is characterized in that an iminoaziridine compound of the general formula ##EQU7## in which R.sub.1-3 have the above meanings and R.sub.4-7 each represents hydrogen, an alkoxycarbonyl, cyano, nitro or sulphonyl group or an alkyl, alkenyl, cycloalkyl or aryl residue, and two or more of these residues may be linked together, is fragmented with development of nitrogen.
This fragmentation of the epoxy-iminoaziridine is accompanied by elimination of molecular nitrogen, splitting of the bond between carbon atoms .alpha. and .beta. and formation of a triple bond between carbon atoms .beta. and .gamma. and of an oxo group on carbon atom .alpha., according to the general scheme ##EQU8##
The starting materials to be used in the present process are derived from .alpha.,.beta.-epoxy-carbonyl compounds of the general formula ##EQU9## in which R.sub.1-3 each represents a hydrogen atom or an organic residue, preferably at least one of these symbols representing one of the following residues:
The organic residues mentioned above may contain additional functional groups.
Preferred starting materials are, for example, compounds derived from the following .alpha.,.beta.-epoxyketones:
1-(1-oxo-5-ethyl-hept-4-en-1-yl)-1,2-epoxy-cyclopentane,
1-propionyl-1,2-epoxy-cyclohex-4-ene,
1-formyl-1,2-epoxy-cyclooctane and epoxy-cedrenal.
2-ethyl-2,3-epoxy-cyclopentan-1-one,
2-buytl-2,3-epoxy-cyclopentan-1-one,
2-pentyl-2,3-epoxy-cyclopentan-1-one,
2-hexyl-2,3-epoxy-cyclopentan-1-one,
2-heptyl-2,3-epoxy-cyclopentan-1-one,
2-(4-methyl-pent-3-en-yl-[1])-2,3-epoxy-cyclopentan-1-one,
2-decyl-2,3-epoxy-cyclopentan-1-one,
2-methyl-2,3-epoxy-cyclohexan-1-one and
2-(dec-4-en-yl[1])-2,3-epoxy-cyclohexan-1-one.
Starting materials derived from the carbonyl compounds of groups (a), (b) and (c) furnish by the present process acetylene compounds which may be used in a variety of ways as intermediates in the manufacture of technically valuable known and new compounds. Those acetylene compounds which simultaneously contain a carbonyl group may be converted into known or new aromas or flavours, for example by catalytic partial or total hydrogenation.
As preferred starting materials there may be further enumerated those which are derived from .alpha.,.beta. -epoxy-.gamma.-oxosteroids whose epoxide group is attached to vicinal carbon atoms of the steroid ring skeleton and whose .alpha.-carbon atom does not at the same time belong to two rings.
They belong especially to the androstane, pregnane, cholane, cholestane, spirostane, furostane or cardanolide series or their A-nor, A-homo, B-nor and/or B-homo derivatives or their 19-nor derivatives, for example to the oestranes and they contain the oxo group in one of the positions 1,2,3,4, 15, 17 or 20. In the first place starting materials are used that are derived from 3-oxo-1,2-epoxy-steroids, 4-oxo-2,3-epoxy-steroids or from 20-oxo-16,17-epoxy-steroids of the series referred to above.
Preferred starting materials are more especially those in which the residues R.sub.1 and R.sub.2 (formula V) are linked together. It goes without saying that with starting materials that give rise to extremely highly tensioned cyclic systems, for example to a cyclobutine or cyclohexine ring, the fragmentation of this invention cannot or can only restrictedly be carried out.
The iminoaziridine derivatives to be used as starting materials are derived from aminoaziridines of the general formula ##EQU10## in which at least one of the residues R.sub.4-7 represents a cycloalkyl residue, preferably the cyclopentyl, cyclohexyl or tetrahydronaphthalene residue, an aryl residue, such as a phenyl residues which may be substituted 20 by halogen atoms, such as chlorine or bromine atoms, or by lower alkyl such as methyl or ethyl or phenyl residues, for example the phenyl, p-chlorophenyl or biphenyl residue, or in which R.sub.4 or R.sub.5 is linked with R.sub.6 or R.sub.7, for example through an alkylene residue with 3 to 5 carbon atoms, which may also carry a fused-on phenylene residue, and the others represent hydrogen atoms. Particularly suitable aminoaziridines are the 2-phenyl-aziridine, 2,3-diphenylaziridine or their p-chloro or p-bromo derivatives, the 2-tetrahydronaphthalene-, 2,3-butylene(1',4')- or 2,3-[2',3'-benzo-butylene(1',4')]-1-amino-aziridine.
The fragmentation according to this invention can be achieved thermally or photochemically, in certain cases even at room temperature. The reaction may be conducted in an organic solvent such as a hydrocarbon, mineral oil, ether, phenol, dimethylformamide or other dialkylformamide, or in dimethylsulphoxide.
In certain cases the decomposition and the fragmentation are extremely easy to achieve. Thus, it is possible for the starting materials often to decompose in the desired manner even under the conditions of their formation. Therefore, the present invention includes also those variants of the present process in which the starting materials are formed in situ.
Most of the compounds obtained by the process of this invention are known and have as such valuable industrial or physiological properties and may be used as they are for a variety of purposes or they may be used as starting materials or intermediates in the manufacture of known or new industrially valuable organic compounds.
The process of this invention may be applied in the most varied spheres of organo-chemical industry. For example, with the aid of this process it is possible to manufacture aldehyde-acetylene compounds which were in the past only accessible with difficulty.
Most of the starting materials used in the present process are new; they may be prepared by known methods. Thus, the aminoaziridines may be reacted with the epoxyketones in the usual manner to form the imino compounds. The aminoaziridines in turn are likewise accessible by known methods.
The following Examples illustrate the invention.
US Referenced Citations (2)
| Number |
Name |
Date |
Kind |
| 3210396 |
Horvitz |
Oct 1965 |
|
| 3835160 |
Tanabe |
Sep 1974 |
|
Non-Patent Literature Citations (1)
| Entry |
| Felix et al., Helvetica Chim. Acta, 51, 1461 (1968). |
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
856478 |
Sep 1969 |
|
Patent Grant
3939207
