Process for producing lycopene and intermediate thereof

Details Process for producing lycopene and intermediate thereof Process for producing lycopene and intermediate thereof

2000-07-24

2001-12-18

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Phosphorus containing

C568S011000, C568S032000, C585S015000, C585S600000

Reexamination Certificate

active

06331652

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the production of lycopene, a carotenoid that is important in the fields of medicines, feed additives and food additives and also to an intermediate of lycopene.
2. Description of Related Art
For the synthesis of lycopene, which is a symmetric C40 compound, there have been known following methods such as a method of coupling two C15 compounds and a C10 compound, a method of coupling two C10 compounds and a C20 compound (e.g., Pure & Appl. Chem., Vol. 69, 2039 (1997) or Helv. Chim. Acta, Vol. 39, 463 (1956)) and a method of coupling two C8 compounds and a C24 compound (e.g., DE 2554924 A1). However, these methods were not always satisfactory in that they required to synthesize two different compounds of different carbon numbers and molecular structures. There have also been known methods of coupling two C20 compounds as reported in Proc. Chem. Soc., 261 (1961) and Liebigs Ann. Chem., 1146 (1977), however, these methods are not always practical from an industrial point of view because they required multistep Wittig reactions and oxidation-reduction reactions to obtain C20 compounds.
SUMMARY OF THE INVENTION
An object of the invention is to provide a method for producing lycopene using a novel intermediate compound.
Further objects of the invention are to provide industrially advantageous two C20 compounds for producing the intermediate compound and methods for producing the two C20 compounds from an inexpensive C10 compound linalool or geraniol in an industrially advantageous manner.
The present invention provides:
1. a process for producing a sulfonaldehyde derivative of formula (2):
wherein Ar represents an aryl group which may be substituted, R
1
represents a lower alkyl group or a protective group of a hydroxyl group and the wavy line depicted by “
” indicates a single bond and stereochemistry relating to a double bond bound therewith is E or Z or a mixture thereof,
 which comprises oxidizing a sulfone alcohol derivative of formula (1):
wherein Ar, R
1
and the wavy line respectively have the same meanings as defined above;
2. a sulfonaldehyde derivative of formula (2) as defined above;
3. a process for producing a phosphonium salt of formula (3):
wherein Ar, R
1
and the wavy line respectively have the same meanings as defined above, Y represents a lower alkyl group or an optionally substituted aryl group, and X represents a halogen atom or HSO
4
,
 which comprises reacting a sulfone alcohol derivative of formula (1) with a salt of a tertiary phosphine compound of formula: PY
3
, and a protonic acid, or with a tertiary phosphine compound of formula: PY
3
, in the presence of a protonic acid, wherein Y represents the same as defined above;
4. a phosphonium salt of formula (3) as defined above;
5. a process for producing a sulfone derivative of formula (4):
wherein Ar and R
1
are the same or different and independently represent the same as defined above and the wavy line has the same meanings as defined above,
 which comprises reacting a phosphonium salt of formula (3) as defined above with a sulfonaldehyde derivative of formula (2) as defined above in the presence of a base or an epoxide;
6. a sulfone derivative of formula (4) as defined above; and
7. a process for producing lycopene of formula (5):
wherein the wavy line has the same meaning as defined above,
 which comprises reacting a sulfone derivative of formula (4) as defined above with a basic compound.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be hereinafter explained in detail.
The protective group of a hydroxyl group in the substituent R
1
of the sulfone alcohol derivative (1), sulfonaldehyde derivative (2), phosphonium salt (3) and sulfone derivative (4) in the present invention include an acyl group, a silyl group, an alkoxyalkyl group, an aralkyl group, a hydrocarbyloxycarbonyl group and the like.
Examples of the acyl group include a group of formula: Q-C═O, wherein Q is a hydrogen atom, a (C1-C6)alkyl group or
a phenyl group which may be substituted with a (C1-C3)alkyl group, a (C1-C3)alkoxy group, a halogen atom or a nitro group.
Specific examples thereof include an acetyl, pivaloyl, benzoyl, p-nitrobenzoyl group, p-methylbenzoyl group, p-methoxybenzoyl group and the like.
Examples of the silyl group include a silyl group substituted with three groups selected from a (C1-C4)alkyl group and a phenyl group. Specific examples thereof include trimethylsilyl, t-butvldimethylsilyl, t-butyldiphenylsilyl group and the like.
Examples of the alkoxyalkyl group include a (C2-C5)alkoxyalkyl group such as tetrahydropyranyl, methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl and the like.
Examples of the aralkyl group include a methyl group substituted with at least one phenyl group, which phenyl group may be substituted with a (C1-C3)alkyl group(e.g. methyl, ethyl, n-propyl, i-propyl), a (C1-C3)alkoxy group(methoxy, ethoxy, n-propoxy, i-propoxy), a halogen atom, a nitro group and the like. Specific examples thereof include a benzyl group, p-methoxybenzyl group, p-nitrobenzyl group, tributyl group, a benzhydryl group and the like.
Examples of the hydrocarbyloxycarbonyl group include a (C1-C7) alkyl- or aralkyl-oxycarbonyl group such as a benzyloxycarbonyl group, a t-butoxycarbonyl group, a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group or the like.
Examples of the lower alkyl group in the substituent R
1
include a (C1-C4) straight or branched chain alkyl group such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl group.
Preferred are the lower alkyl group and acyl groups for R
1
.
Examples of the aryl group which may be substituted represented by “Ar” include
a phenyl group and a naphthyl group, both of which may be substituted with at least one group selected from
a C1 to C6 alkyl group(e.g. a methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, t-amyl, or n-hexyl group),
a C1 to C6 alkoxy group(e.g. a methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, t-butoxy, n-pentyloxy, t-amyloxy, or n-hexyloxy group),
a halogen atom and a nitro group.
Specific examples thereof include a phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-iodophenyl, m-iodophenyl, p-iodophenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-nitrophenyl, m-nitrophenyl and p-nitrophenyl group.
The substituent X of the phosphonium salt (3) represents a halogen atom (e.g. a chlorine atom, bromine atom and iodine atom) or HSO
4
.
The sulfonaldehyde derivative (2)can be obtained by a process which comprises oxidizing, the sulfone alcohol derivative (1).
The oxidizing of the sulfone alcohol derivative (1) is usually conducted by one of the following methods and the like.
The oxidizing of the sulfone alcohol derivative (1) can be conducted by (a) subjecting the sulfone alcohol derivative (1) to contact with a metal oxidant.
Alternatively, the oxidizing may be conducted by
(b) subjecting the sulfone alcohol derivative (1) to contact with a sulfoxide compound, a sulfoxide-activating compound and optionally a base, or
(c) subjecting the sulfone alcohol derivative (1) to contact with a sulfide compound, a halogenating agent and a base, or
(d) subjecting the sulfone alcohol derivative (1) to contact with an aldehyde in the presence of a catalyst selected from an aluminum alkoxide or aryloxide, and a boron compound, or
(e) subjecting the sulfone alcohol derivative (1) to contact with an oxygen in the presence of a catalyst.
A description will be made to the oxidizing reaction (a).
Examples of the metal oxidant include a salt or oxide of chromium or manganese, an oxide of nickel or selenium, or a salt of silver. Specific examples thereof include pyridinium chlorochromate, pyridinium dichromate, manganese dioxide, nickel peroxide, selenium dioxide and silver carbonate. The amount of

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