Perfume compositions – Perfume compositions – Ring containing active ingredient
Reexamination Certificate
2000-11-07
2003-09-09
Warden, Jill (Department: 1743)
Perfume compositions
Perfume compositions
Ring containing active ingredient
C512S025000, C512S026000, C549S263000, C549S266000, C549S267000, C549S268000
Reexamination Certificate
active
06617304
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for the production of macrocyclic lactones which are useful as various synthetic intermediates and particularly important as ingredients of high quality perfumes.
2. Description of the Related Art
Most of macrocyclic lactones are important as fregrance raw materials having musky scent, and a large number of their production methods which use hydroxycarboxylic acid esters as the starting material have been reported. In the case of cyclopentadecanolide for example, British Patent 490,044 discloses a method in which a macrocyclic lactone is produced by intramolecular esterification from an ester of an oxycarboxylic acid with a high boiling point alcohol. According to this method, though it is described that a monohydric or polyhydric alcohol can be used as the high boiling point alcohol, only a polyhydric alcohol, glycerol, is shown in Examples. This method has problems such as reduction of yield due to decomposition of glycerol during the production of monoglyceride of 15-hydroxypentadecanoic acid to be used and the lactonization thereof.
Also, JP-B-41-7770 (the term “JP-B” as used herein means an “examined Japanese patent publication”) discloses a method in which the macrocyclic lactone is obtained by distillation of hydroxycarboxylic acid ester, the alcohol moiety of which has a lower boiling point than that of macrocyclic lactone, the reaction being with adding glycerol or a liquid capable of co-distilling with lactone. In this method, the macrocyclic lactone cannot be obtained in high yield unless the reaction is carried out by continuously supplying a large amount of the liquid which is co-distilled with the macrocyclic lactone.
In addition, JP-A-64-52739 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) discloses a method in which cyclopentadecanolide is produced from methyl 15-hydroxypentadecanoate containing dimethyl 1,15-pentadecandioate. But, this method causes sharp reduction of the yield when dimethyl 1,15-pentadecandioate is present in a large amount due to formation of a copolymer by transesterification with methyl 15-hydroxypentadecanoate, which accompanies distillation of methanol. Thus, not only it is necessary to remove the greater part of dimethyl 1,15-pentadecandioate before the intramolecular esterification of methyl 15-hydroxypentadecanoate, but also there is another problem in that the reaction residue becomes a highly viscous or solid substance which cannot be handled easily, due to formation of copolymers of 1,15-pentadecandioic acid, 15-hydroxypentadecanoic acid and 1,15-pentadecanediol after the reaction. Also, since diester of 1,15-pentadecandioic acid contained in the reaction residue becomes substantially unrecoverable as the result, it poses still another problem in that only about 70% of the diester can be recovered before the reaction.
SUMMARY OF THE INVENTION
The invention is a method in which a macrocyclic lactone represented by a formula (2) is produced by carrying out intramolecular esterification of a hydroxycarboxylic acid ester represented by a formula (1), and the macrocyclic lactone can be produced with high yield and high productivity by using a specified long chain alkyl ester of hydroxycarboxylic acid as the starting material.
In the formulae (1) and (2), m is an integer of from 5 to 10, n is an integer wherein m+n becomes from 11 to 16, X represents —CH
2
—, —CH═CH—, —O—, —S— or —NH—, and R represents a hydrocarbon group having from (m+n+2) to 40 carbon atoms or a group represented by —(AO)
p
R
1
wherein AO represents an alkyleneoxy group having from 2 to 4 carbon atoms, p is average addition mole number of alkylene oxide and R
1
represents a hydrocarbon group having a specified number of carbon atoms so that the total number of carbon atoms of the —(AO)
p
R
1
group becomes from (m+n+2) to 40.
Also, the invention is a method for the production of the macrocyclic lactone of formula (2), which comprises intramolecular esterification of a hydroxycarboxylic acid or a lower alkyl (1 to 5 carbon atoms) ester thereof, obtained by partially reducing a dibasic acid represented by a formula (6) or a lower alkyl (1 to 5 carbon atoms) ester thereof, in the presence of an alcohol represented by a formula (5).
wherein X, m and n are as defined in the foregoing.
HO—R (5)
wherein R is as defined in the foregoing.
DETAILED DESCRIPTION OF THE INVENTION
According to the invention, R of the ester represented by the general formula (1) has carbon atoms of from 13 to 40 in total, and its examples include straight chain alkyl groups such as eicosyl group and octadecyl group, branched-chain alkyl groups including methyl-branched type branched-chain alkyl groups such as 3,7,11,15-tetramethyl-2-hexadecenyl group and 1-methylpentadecyl group and Guerbet alkyl type branched-chain alkyl groups such as 2-decyltetradecyl group, 2-octyldodecyl group and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group, and polyoxyalkylene alkyl groups having an oxyalkylene addition mole number of from 1 to 12, an oxyalkylene carbon number of from 2 to 4 and an alkyl carbon number of from 1 to 16, such as —(CH
2
CH
2
O)
6
C
12
H
25
and —(CH
2
CH
2
O)
5
{CH
2
CH(CH
3
)O}
5
C
12
H
25
.
Among these groups, a branched-chain alkyl group or a polyoxyalkylene alkyl group represented by —(AO)
p
R
1
(wherein AO, p and R
1
are as defined in the foregoing) is preferable from the viewpoint of good reaction yield and easy handling due to low melting point, more preferred is a Guerbet alkyl type branched-chain alkyl group or a polyoxyethylene alkyl group having an alkyl carbon number of from 1 to 16 and an ethylene oxide addition mole number of from 1 to 10, and particularly preferred is a Guerbet alkyl type branched-chain alkyl group.
Also, the invention can be carried out within the R carbon number of from (m+n+2) to 40, but since the alcohol formed at the time of intramolecular cyclization reaction has sufficiently higher boiling point than that of the macrocyclic lactone and can therefore be easily separated when the R carbon number is m+n+5 or more, the total carbon number of R is preferably from (m+n+5) to 40, more preferably from (m+n+5) to 36, most preferably from (m+n+5) to 32, from the viewpoint of productivity.
The ester of formula (1) to be used in the invention can be obtained for example by the following methods 1 to 3.
(Method 1) One mole of a hydroxycarboxylic acid represented by a general formula (4)
(wherein m, n and X are as defined in the foregoing) or a lower alkyl ester thereof and from 1 to 10 moles, preferably from 1 to 3 mole, of an alcohol represented by the formula (5)
HO—R (5)
(wherein R is as defined in the foregoing) are heated at a temperature of from 30 to 300° C., preferably from 50 to 250° C., under ambient pressure to 1 kPa in the presence or absence of a catalyst, while removing the by-produced water or lower alcohol.
(Method 2) A dibasic diester represented by a formula (3)
(wherein R, m, n and X are as defined in the foregoing) is partially reduced in the presence of a hydrogenation catalyst, preferably a copper-based hydrogenation catalyst, more preferably a Cu—Cr catalyst, in an amount of from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, based on the diester, under a hydrogen pressure of from 1 to 40 MPa, preferably from 5 to 30 MPa, and at a temperature of from 100 to 350° C., preferably from 150 to 300° C.
In this case, the partial reduction is carried out under the condition to suppress the formation of diol by the reduction of both ester groups of the diester as much as possible. It is an effective method to suppress the conversion to keep high selectivity, because selectivity to hydroxycarboxylic acid ester is generally reduced when conversion of diester is increased. This tendency can be found in any of known reactions such as hydrogenation and hydride reduction by a metal hydride or
Aoki Takashi
Koshino Junji
Kotachi Shinji
Cole Monique T.
Kao Corporation
Warden Jill
LandOfFree
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