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BACKGROUND OF THE INVENTION
(i) Field of the Invention
This invention relates to 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl
glycerine compounds (which may be hereinafter referred to simply as
position isomers of diglycerine dialkyl ethers) which are novel polyol
ether compounds, processes for the preparation of the same, and cosmetic
compositions comprising the compounds.
(ii) Description of the Prior Art
In the natural world, there are a number of polyhydric alcohol derivatives
having ether bonds therein, typical of which are monoalkyl ethers of
glycerine (hereinafter referred to as glyceryl ethers). For instance,
lipids of fishes contain palmityl glyceryl ether (referred to as chimyl
alcohol), stearyl glyceryl ether (batyl alcohol) and oleyl glyceryl ether
(selachyl alcohol).
These glyceryl ethers have wide utility as a substrate for cosmetics
because of their w/o type emulsifying characteristic (see Japanese
Laid-open Application Nos. 87612/1974, 92239/1974 and 12109/1977, and
Japanese Patent Publication No. 36260/1982). It is also known that the
ethers have pharmacological actions such as erythropoietic stimulating
effect to bone marrows, anti-inflammatory activity, and antitumor activity
(see Japanese Patent Publication Nos. 10724/1974 and 18171/1977).
In view of the fact that the glyceryl ethers serve as unique surfactants
which have a number of desirable characteristics, attempts have been made
to derive polyol ether compounds, which have molecular structures similar
to the glyceryl ethers (including ether bonds and hydrophilic OH groups in
the molecule thereof), from polyhydric alcohols (see U.S. Pat. No.
2,258,892, Japanese Patent Publication No. 18170/1977, and Japanese
Laid-open Application Nos. 137,905/1978 and 145,224/1979). The resulting
polyol ether compounds show the w/o type emulsifying characteristics and
are employed as a substrate for cosmetics (see West Germany OS No. 24 55
287) and also as an antimicrobial and fungicidal agent as well as an
ordinary emulsifier.
The present inventors payed attention to such utility of polyol ether
compounds and derived mono- and di-alkyl ethers of diglycerine, which
ethers are polyol ether compounds, from alkyl glycidyl ethers which can
readily be prepared from alcohols. Some patent applications have already
been made on the application of such mono- and di-alkyl ethers of
diglycerine as cosmetics substrates (Japanese Patent Application Nos.
81456/1981, 81457/1981 and 113404/1981).
SUMMARY OF THE INVENTION
We have made further studies and, as a result, found that novel polyol
ether compounds of the general formula (I) have excellent surface active
properties:
##STR2##
in which R represents a saturated or unsaturated, straight-chain or
branched aliphatic hydrocarbon group having 8 to 24 carbon atoms, and R'
represents a saturated or unsaturated, straight-chain or branched
hydrocarbon group having 1 to 24 carbon atoms.
Accordingly, an object of the present invention is to provide novel polyol
ether compounds represented by the above formula (I).
Another object of the invention is to provide a process for preparing the
compounds (I).
A further object of the invention is to provide cosmetics comprising the
compounds (I).
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
The polyol ether compounds of the invention represented by the formula (I)
are readily prepared in high yield and high purity from alkyl glycidyl
ethers (II), which can be readily prepared from alcohols, by the following
two processes (processes A and B).
##STR3##
(in which R.sub.1 represents hydrogen or a hydrocarbon group, R.sub.2
represents a hydrocarbon group, R" represents a hydrocarbon group having 1
to 5 carbon atoms, X represents a halogen atom, and R and R' have the same
meanings as defined above, respectively.)
Process A
An alcohol is added to the alkyl glycidyl ether (II) in the presence of an
acid or base catalyst according to a known method (e.g. Germany OS No.
2535778), thereby forming 1,3-di-O-alkyl glycerine (III), followed by
interacting an epihalohydrin and the 1,3-di-O-alkyl glycerine (III)
according to Williamson's synthesis of ether to obtain an epoxide compound
(IV). An acid anhydride is then added to the epoxide compound (IV)
according to the method proposed by us (Japanese Patent Application No.
16061/1982) to obtain a diester compound (V). This diester compound (V) is
hydrolyzed (saponified) to obtain an intended polyol ether compound (I).
Process B
To the epoxide compound (IV) obtained in the same manner as in the above
process A is added a carbonyl compound according to the method proposed by
us (Japanese Patent Application No. 133281/1981) to obtain a dioxolan
compound (VI). The thus obtained dioxolan compound (VI) is hydrolyzed
thereby obtaining an intended polyol ether compound (I).
In the above reactions, the 1,3-di-O-alkyl glycerine (III) which is an
adduct of the alkyl glycidyl ether (II) and an alcohol has the reactive
hydroxyl group at the 2 position. Alkylene oxides such as ethylene oxide,
propylene oxide and the like are added to the reactive hydrogen whereby
1,3-di-O-alkyl-2-O-polyoxyalkylene glycerines which are nonionic active
agents are obtained. The processes for preparing these compounds and
applications thereof as an emulsifier have been already proposed such as
in Japanese Laid-open Application No. 63936/1981, Germany OS Nos. 2139447
and 2139448, and the like. However, the polyol ether compounds of the
present invention are completely different from the above compounds from
the structural and preparatory aspects.
The reactions indicated above will now be described in detail.
The process A is first described. The alkyl glycidyl ether (II) used as one
of starting materials in the process of the invention should have a
saturated or unsaturated, straight-chain or branched aliphatic hydrocarbon
group having from 8 to 24, preferably from 8 to 20 carbon atoms. Specific
examples of the ether include: primary straight-chain alkyl glycidyl
ethers such as n-octyl glycidyl ether, n-decyl glycidyl ether, n-dodecyl
glycidyl ether, n-tetradecyl glycidyl ether, n-hexadecyl glycidyl ether,
n-octadecyl glycidyl ether, n-octadecenyl glycidyl ether (oleyl glycidyl
ether), docosyl glycidyl ether, and the like; primary branched alkyl
glycidyl ethers such as 2-ethylhexyl glycidyl ether, 2-hexyldecyl glycidyl
ether, 2-octyldodecyl glycidyl ether, 2-heptylundecyl glycidyl ether,
2-(1,3,3-trimethylbutyl)octyl glycidyl ether, 2-decyltetradecyl glycidyl
ether, 2-dodecylhexadecyl glycidyl ether, 2-tetradecyloctadecyl glycidyl
ether, 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octyl glycidyl ether,
methyl-branched isostearyl glycidyl ethers of the following formula:
##STR4##
in which m is an integer of from 4 to 10, and n is an integer of from 5 to
11 provided that m+n=11 to 17 with a distribution having vertexes at m=7
and n=8; secondary alkyl glycidyl ethers such as sec-decyl glycidyl ether,
sec-octyl glycidyl ether, sec-dodecyl glycidyl ether, and the like; and
tertiary alkyl glycidyl ethers such as t-octyl glycidyl ehter, t-dodecyl
glycidyl ether, and the like.
In recent years, there have been developed processes for preparing alkyl
glycidyl ethers in high yield from alcohols (ROH) without isolation of
halohydrin ethers (e.g. in Japanese Laid-open Application Nos.
141708/1979, 141709/1979, 141710/1979, 63974/1981, 108781/1981, and
115782/1981).
The alcohol (R'OH) which is added to the alkyl glycidyl ether (II) should
have a saturated or unsaturated, straight-chain or branched hydrocarbon
group having carbon atoms of from 1 to 24, preferably from 1 to 18 and
most preferably from 1 to 10. Examples of the alcohol include:
straight-chain aliphatic alcohols such as methyl alcohol, ethyl alcohol,
propyl alcohol, butyl alcohol, octyl alcohol, decyl alcohol, hexadecyl
alcohol, octadecyl alcohol, octadecenyl (oleyl) alcohol, and the like;
branched aliphatic alcohols such as isopropyl alcohol, isobutyl alcohol,
2-ethylhexyl alcohol, 2-heptylundecyl alcohol,
5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)octyl alcohol, and methyl-branched
isostearyl alcohols represented by the following formula:
##STR5##
in which m is an integer of from 4 to 10, and n is an integer of from 5 to
11 provided that m+n=11 to 17 with a distribution having vertexes at m=7
and n=8; and alicyclic alcohols such as cyclohexyl alcohol, cyclopentyl
alcohol, and the like.
The reaction at the first stage in which the alkyl glycidyl ether (II) and
the alcohol are used to prepare 1,3-di-O-alkyl glycerine (III) is
considered as an addition reaction of the alcohol with the epoxide bond
derived from the terminal olefin. This addition reaction proceeds in the
presence of either an acid or an alkali accompanied by the cleavage of the
epoxide bond. However, when an acid catalyst is used, there is the danger
that the cleavage takes place in two ways at alpha and beta positions, so
that the alcohol is added at the alpha and beta positions, thereby giving
two adducts. On the other hand, with an alkali catalyst, selective
cleavage of the epoxide bond occurs at the alpha position, thereby
selectively producing a product in which the alcohol is added at the alpha
position i.e. the alcohol is added at the end portion of the molecule
(see, for example, "KOGYO KAGAKU ZASSHI" Vol. 68, No. 4, pp. 663-669
(1965)). In this sense, it is preferable to use an alkali catalyst for the
purpose of the present invention. Examples of the alkali catalyst include
alkali metals such as Li, Na, K and the like, alkali metal hydroxides such
as LiOH, NaOH, KOH and the like, and alkali metal alcoholates such as
NaOMe, NaOEt, KOtBu and the like, tertiary amines such as triethylamine,
tributylamine, tetramethylethylenediamine, tetramethyl-1,3-diaminopropane,
tetramethyl-1,6-diaminohexane, pyridine, dimethylaniline, quinoline and
the like.
The above reaction is effected by reacting the alkyl glycidyl ether (II)
and 1 to 10 moles, preferably 1 to 5 moles of an alcohol in the presence
of 0.001-0.2 mole, preferably 0.01 to 0.1 mole of an alkali catalyst, each
based on per mole of the ether (II), under conditions of 70.degree. to
150.degree. C., preferably 70.degree. to 120.degree. C.
The resulting 1,3-di-O-alkyl glycerine (III) is then reacted with an
epihalohydrin which is prepared by Williamson's synthesis of ether,
thereby obtaining an epoxide compound (IV). This etherification reaction
is preferably effected in the presence of a catalytic amount of a
quaternary ammonium salt. The quaternary ammonium salts used for these
purposes are preferably ammonium salts because of ease in industrial
availability. Specific examples of the quaternary ammonium salts include
tetraalkylammonium salts such as, for example, tetrabutylammonium
chloride, tetrabutylammonium hydrogensulfate, trioctylmethylammonium
chloride, lauryltrimethylammonium chloride, stearyltrimethyltriammonium
chloride, benzyltrimethylammonium chloride, and the like, a group of
alkylammonium salts having a polyoxyalkylene group such as, for example,
tetraoxyethylene stearyldimethylammonium chloride, bistetraoxyethylene
stearylmethylammonium chloride, and the like, betaine compounds, crown
ethers, amine oxide compounds, and ion-exchange resins. These quaternary
onium salts may be used in catalytic amounts but it is convenient to use
0.005 to 0.5 mole per mole of the 1,3-di-O-alkyl glycerine (III).
The reaction is effected in the presence of the quaternary onium salt
catalyst using 1 to 10 moles, preferably 3 to 6 moles, per mole of the
1,3-di-O-alkyl glycerine (III), of an alkaline substance in the form of an
aqueous solution (having a concentration of 10 to 80%, preferably 30 to
60%) in a reaction solvent such as an inert hydrocarbon such as, for
exaple, hexane, benzene, toluene, xylene or the like at a reaction
temperature of 30.degree. to 70.degree. C., preferably 40.degree. to
60.degree. C. The alkaline substance includes, for example, sodium
hydroxide, potassium hydroxide, lithium hydroxide or the like. Of these,
sodium hydroxide is conveniently used from the industrial standpoint.
To the resulting epoxide compound (IV) is added an acid anhydride in the
presence of an acid or base catalyst, thereby giving a diester compound
(V), followed by hydrolysis (saponification) to obtain an intended polyol
ether compound.
The acid anhydrides used in the present invention include ordinary acid
anhydrides. From the industrial standpoint and in view of ease in
availability and after-treatment, anhydrides of lower acids are preferred.
Specific examples of the anhydride include acetic anhydride, propionic
anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride,
isovaleric anhydride, and the like. Of these, acetic anhydride is
particularly preferred.
Other type of acid anhydride which is inexpensively available and important
as an industrial meterial includes an anhydride of dibasic acid. For
instance, the dibasic acid anhydrides are phthalic anhydride, succinic
anhydride, maleic anhydride and the like. However, when these dibasic acid
anhydrides are added to the glycidyl ether at 1,2 positions within the
molecule thereof, the resulting adducts become unstable because they have
such a highly-distorted structure as of the eight-membered ring and are
thus unstable. In this connection, there is the possibility that the
addition reaction takes place intermolecularly rather than the case where
the eight-membered structure added at 1,2 positions within the molecule is
formed, thereby causing the reaction to proceed so as to give a so-called
polyester structure. From this, it is considered difficult to apply the
dibasic acid anhydrides to the process of the present invention.
The acid catalysts used for the preparation of the diester compound (V) are
conveniently Lewis acids. Examples of the Lewis acid include boron
trifluoride ether complex, boron trifluoride acetate complex, boron
trifluoride phenol complex, aluminum chloride, aluminum bromide, zinc
chloride, tin tetrachloride, antimony chloride, titanium tetrachloride,
silicon tetrachloride, ferric chloride, ferric bromide, cobalt(III)
chloride, cobalt(III) bromide, and the like. The base catalysts are
preferably tertiary amines. Examples of the tertiary amine include
triethylamine, tripropylamine, tributylamine, trioctylamine,
tetramethylethylenediamine, tetramethyl-1,3-diaminopropane,
tetramethyl-1,6-diaminohexane, pyridine, quinoline, dimethylaniline, and
the like.
In order to prepare the diester compound (V) from the epoxide compound
(IV), it is usual to react an epoxide compound (IV) with 1 to 30 moles of
an acid anhydride per mole of the epoxide compound (IV) in the presence of
0.001 to 0.2 mole of a Lewis acid or tertiary amine catalyst per mole of
the epoxide compound (IV) at a temperature of 0.degree. to 70.degree. C.
for the Lewis acid and 100.degree.-150.degree. C. for the tertiary amine.
The amount of the acid anhydride is theoretically sufficient to be
equimolar with the epoxide compound (IV). However, the reaction smoothly
proceeds with higher yield when the acid anhydride is used in excess.
Thus, it is effective to use the acid anhydride in amounts ranging from 2
to 20 moles, preferably 8 to 16 moles, per mole of the epoxide compound
(IV).
The reaction using Lewis acids is an exothermic reaction and thus it is
effective to control the reaction temperature in the range below
60.degree. C., preferably 20.degree. to 40.degree. C., by suitable means
such as cooling upon addition of the epoxide compound (IV) to an acid
anhydride coexisting with a Lewis acid. Higher reaction temperatures may
cause side reactions by the Lewis acid, e.g. polymerization of the epoxide
compound (IV) or ring cleavage of the ether bond, to occur. With epoxide
compounds (IV) having unsaturated bonds, there may occur the isomerization
of the unsaturated bonds and the Wagner-Meerwein transfer reaction in
combination. Accordingly, the reaction temperature should be accurately
controlled.
On the other hand, when tertiary amines are used as the catalyst, no
generation of heat takes place as is experienced in the use of Lewis
acids. It is rather necessary to keep the reaction temperature high by
application of heat. Preferably, a mixture of a tertiary amine and an acid
anhydride is maintained at a temperature of 100.degree. to 150.degree. C.,
preferably 100.degree. to 120.degree. C., to which an epoxide compound
(IV) is dropwise added. In this procedure, there is recognized no
generation of heat and hence, it is necessary to maintain the temperature,
for example, by application of heat during the course of the dropping of
the epoxide compound (IV).
The reaction proceeds in the absence of any reaction solvent and it is the
most suitable to use an excess of an acid anhydride serving also as a
solvent. However, in order to suppress occurrence of the side reactions
and control the reaction temperature, solvents may be used, if necessary.
The reaction solvents may be any compounds which do not give any adverse
influence on the reaction. Hydrocarbon solvents are suitably used.
Examples of the hydrocarbon include aliphatic hydrocarbons such as
pentane, hexane, heptane, octane and the like, aromatic hydrocarbons such
as benzene, toluene, xylene and the like, alicyclic hydrocarbons such as
cycloheptane, cyclohexane and the like, and mixtures thereof.
When the above reaction is carried out under such conditions as indicated
above, the diester compound (V) is ordinarily obtained in a yield as high
as about over 90% and may be purified using a technique such as
distillation.
The hydrolysis reaction of the diester compound (V) in the subsequent step
may be performed any known techniques. It is preferable to heat the
compound in an aqueous solution of an alkaline substance such as sodium
hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide,
sodium carbonate, calcium carbonate or the like. The amount of the
alkaline substance is not critical. It is general to use 2 moles or more,
preferably 2 to 5 moles, of the substance per mole of the diester compound
(V). The hydrolysis proceeds in the absence of any reaction solvent but it
is convenient to use a water-soluble solvent including, for example, a
lower alcohol such as methanol, ethanol, isopropanol or the like, or an
ether such as tetrahydrofuran, dioxane or the like and to reflux the
mixture at a temperature of 50.degree. to 100.degree. C.
Upon hydrolysis of the diester compound (V) under conditions as indicated
above, the 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine (I) which is
a final product of the invention is quantitatively obtained.
Next, the process B is described. In the process B, a carbonyl compound is
added to the epoxide compound (IV) obtained in the process A in the
presence of an acid catalyst to obtain a dioxolan compound, followed by
hydrolysis of the dioxolan compound thereby obtaining an intended polyol
ether compound. The carbonyl compounds used in the practice of the
invention include ordinary ketones and aldehydes. Examples of the ketone
include aliphatic ketones such as acetone, methyl ethyl ketone, diethyl
ketone, methyl propyl ketone, dipropyl ketone, ethyl propyl ketone, methyl
hexyl ketone and the like, alicyclic ketones such as cyclobutanone,
cyclopentanone, cyclohexanone, cyclooctanone and the like, and aromatic
ketones such as acetophenone, benzophenone and the like. Examples of the
aldehyde include aliphatic aldehydes such as formaldehyde, acetoaldehyde,
propionaldehyde, octylaldehyde and the like, alicyclic aldehydes such as
cyclopentyl aldehyde, cyclohexyl aldehyde and the like, and aromatic
aldehydes such as benzaldehyde, naphthyl aldehyde and the like. Because of
the ease in aftertreatment, lower carbonyl compounds having a small number
of carbon atoms are preferably used. Most preferably, compounds having 6
or less carbon atoms are used.
The acid catalyst used for preparing the dioxolan compound (VI) may be
either proton-donative acids or Lewis acids. Examples of the
proton-donative acid include sulfuric acid, hydrochloric acid, phosphoric
acid and the like, and examples of the Lewis acid include boron
trifluoride etherate complex, boron trifluoride acetate complex, aluminum
chloride, aluminum bromide, zinc chloride, tin tetrachloride, antimony
chloride, titanium tetrachloride, silicon tetrachloride, ferric chloride,
ferric bromide, cobalt(III) chloride, cobalt(III) bromide, zirconium
chloride, boron oxide, acidic active alumina, and the like.
In order to prepare the dioxolan compound (VI) from the epoxide compound
(IV), it was found convenient to react the epoxide compound (IV) with 1 to
30 moles of a carbonyl compound, based on unit mole of the epoxide
compound (IV), in the presence of an acid catalyst in an amount of 0.001
to 0.2 mole per mole of the epoxide compound (IV) at a temperature of
0.degree. to 70.degree. C. Although it is theoretically sufficient to use
equimolar amounts of the carbonyl compound and the epoxide compound (IV),
the reaction proceeds more smoothly in higher yields when the carbonyl
compound is used in larger amounts. Accordingly, it is convenient to use
the carbonyl compound in amounts 2 to 15 moles, preferably about 7 moles,
per mole of the epoxide compound (IV). The acid is used in catalytic
amounts, i.e. in an amount of 0.001 to 0.3 mole, preferably 0.01 to 0.1
mole, per mole of the epoxide compound. Because this reaction is an
exothermic reaction, the epoxide compound (IV) is added to a carbonyl
compound coexisting with an acid catalyst during which a suitable
operation such as cooling is applied to the reaction mixture thereby
controlling the temperature below 60.degree. C., preferably 20.degree. to
40.degree. C. Similar to the process A, higher temperatures may cause
undesirable side reactions with acid catalysts. For instance,
polymerization of the epoxide compound (IV) or cleavage of the bonds may
take place. With epoxide compounds (IV) having unsaturated bonds, the
isomerization of the unsaturated bonds with the acid catalyst may occur as
well as the Wagner-Meerwein transfer reaction. Accordingly, the reaction
temperature has to be severely controlled. The reaction proceeds in the
absence of any solvent and it is most suitable to use an excess of a
carbonyl compound for use also as a solvent for the reaction. However,
solvents may be used in order to suppress the side reactions from
occurrence and to suitably control the reaction temperature. The solvents
for the reaction may be any ordinary solvents which do not give any
adverse influence on the reaction. Conveniently, hydrocarbon solvents are
used. Examples of the hydrocarbon solvents include aliphatic hydrocarbons
such as pentane, hexane, heptane, octane and the like, aromatic
hydrocarbons such as benzene, toluene, xylene and the like, alicyclic
hydrocarbons such as cyclopentane, cyclohexane and the like, and mixtures
thereof.
Under such reaction conditions as indicated above the dioxolan compound
(VI) can be ordinarily obtained in yields over 90% and may be purified by
any suitable means such as distillation.
The hydrolysis reaction of the dioxolan compound (VI) may be effected by
any known procedures. It is convenient to heat the dioxolan (VI) in water
using a proton-donative acid catalyst such as sulfuric acid, hydrochloric
acid, phosphoric acid, benzenesulfonic acid, acetic acid or the like. The
amount of the acid catalyst is not critical and is usually in the range of
0.01 to 2N, preferably 0.05 to 0.5N. Preferably, the water is admixed with
water-soluble organic solvents including lower alcohols such as methanol,
ethanol, isopropanol and the like, tetrahydrofuran, dioxane, and the like
and the hydrolysis is effected at a temperature of 50.degree. to
100.degree. C. The hydrolysis of the dioxolan compound (VI) under
conditions indicated above almost quantitatively gives a final product of
1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine (I).
The final product (I) can be recovered, for example, by a method which
comprises allowing the reaction mixture to stand so as to separate the
product from the aqueous phase, collecting the separated product, and
extracting the product dissolved in the water with a water-insoluble
organic solvent.
The 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine has no decomposable
bonds such as an ester group in the molecule thereof, so that it is very
chemically stable and has surface activity only a slight degree of skin
irritativeness. Thus, this product is useful as an emulsifier, oil
(emolient), humectant, thickener or the like and is particularly effective
as an ingredient of cosmetics.
Properties of typical 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine
compounds are shown in Table 1 below.
TABLE 1
______________________________________
Physical Properties of Polyol Ether Compounds (I)
In Formula (I)
Form Solubility in Water
R' R (25.degree. C.)
(10%)* (25.degree. C.)
(30%)*
______________________________________
CH.sub.3
C.sub.8 H.sub.17
Liquid opaque dissolved
CH.sub.3
C.sub.12 H.sub.25
Liquid formation of
formation of
liquid crystal
liquid crystal
CH.sub.3
C.sub.14 H.sub.29
Liquid formation of
formation of
liquid crystal
liquid crystal
CH.sub.3
C.sub.18 H.sub.37
waxy formation of
formation of
liquid crystal
liquid crystal
CH.sub.3
C.sub.18 H.sub.37
liquid formation of
formation of
(methyl-branched liquid crystal
liquid crystal
isostearyl)
C.sub.4 H.sub.9
C.sub.18 H.sub.37
liquid separated
separated
(methyl-branched
isostearyl)
______________________________________
*Concentrations of the product.
The 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine products of the
formula (I) in which R' represents a group having only one carbon atom are
all very hydrophilic in nature, and especially the products of the formula
(I) in which R represents a group having 12 to 18 carbon atoms form a
liquid crystal even in an aqueous solution of low concentration. In
contrast, when the number of carbon atoms of R' becomes larger, little or
no solubility in water is recognized.
Although all the 1,3-di-O-alkyl-2-O-2',3'-dihydroxypropyl glycerine
compounds exhibit hygroscopicity, the compounds of the formula (I) in
which the number of carbon atoms of R' is one show better hygroscopicity.
Of these, the compounds of the formula (I) in which R represents a
hydrocarbon group having 12-18 carbon atoms are very useful as a humectant
of cosmetics. Moreover, the compounds of the formula (I) in which R'
represents a hydrocarbon group having only one carbon atom and R
represents a hydrocarbon group having 12 to 18 carbon atoms exhibit very
high emulsifying force and show excellent properties when used as an
emulsifier for cosmetic emulsion.
Additionally, the compounds of the formula (I) in which R' represents a
hydrocarbon group having 4 to 8 carbon atoms and R represents a
hydrocarbon group having 8 or more carbon atoms have the strong tendency
of being oily in nature and are thus suitable as an oil for cosmetics,
serving also as an emolient which not only is hygroscopic, but also has
high affinity for skin.
The amount of these compounds in cosmetics may, more or less, vary
depending on various factors. When used as an emulsifier, the amount is in
the range of about 0.2 to 15 wt%. Upon application as an oil or humectant,
the amount is conveniently in the range of 5 to 50 wt%.
The present invention is particularly described by way of examples, which
should not be construed as limiting the present invention to these
examples.
REFERENCE 1
Synthesis of methyl-branched isostearyl glycidyl ether
To a 1 liter round bottom flask equipped with a reflux condenser, a
dropping funnel and an agitator were added, in the following order, 120 g
of an aqueous 50% sodium hydroxide solution (60 g as pure sodium hydroxide
(1.5 moles), 68 g (0.25 mole) of the monomethyl-branched isostearyl
alcohol obtained in Reference 2, 200 ml of n-hexane, and 25.1 g (0.0075
mole) of stearyltrimethylammonium chloride. The reaction mixture was
maintained at a reaction temperature of 25.degree. C. on a water bath,
into which was dropped 93 g (1 mole) of epichlorohydrin while violently
agitating at an agitation speed of 400 r.p.m. The epichlorohydrin was
dropped in about 1.5 hour, after which the temperature of the reaction
mixture was raised to 50.degree. C., followed by agitating for further 8
hours at the temperature. After completion of the reaction, the reaction
solution was treated as usual, thereby obtaining 68 g (yield 83%) of
monomethyl-branched isostearyl glycidyl ether.
Boiling point 142.degree.-175.degree. C. (0.08 mmHg).
IR Spectrum (liquid film cm.sup.-1): 3050, 3000, 1250, 1100, 920, 845
##STR6##
in which m is an integer of from 4 to 10, and n is an integer of from 5 to
11 provided that m+n=11 to 17 with a distribution having vertexes at m=7
and n=8.
REFERENCE 2
Synthesis of methyl-branched isostearyl alcohol
Into a 20 liters autoclave were charged 4770 g of isopropyl isostearate
[Emery 2310, isopropyl isostearate, available from the Emery Co., Ltd. of
U.S.A.) and 239 g of a copper-chromium catalyst (Nikki Co., Ltd.).
Thereafter, hydrogen gas was charged into the autoclave at a pressure of
150 kg/cm.sup.2, followed by heating the reaction mixture to 275.degree.
C. After the hydrogenation under conditions of 150 m kg/cm.sup.2 and
275.degree. C. for about 7 hours, the resulting reaction product was
cooled, from which the solid catalyst was removed thereby obtaining 3500 g
of a crude product. The crude product was distilled under reduced pressure
to obtain 3300 g of colorless, transparent isostearyl alcohol as a
distillate of 80.degree. to 167.degree. C./0.6 mmHg. The thus obtained
isostearyl alcohol (monomethyl-branched isostearyl alcohol) had an acid
value of 0.05, a saponification value of 5.5, and a hydroxyl group value
of 181.4. The alcohol had absorption peaks at 3340 and 1055 cm.sup.-1 in
the IR analysis and at delta 3.50 (broad triplet, --CH.sub.2 --OH) in the
NMR analysis (CCl.sub.4 solvent). It was found from the gas chromatography
that the alcohol was a mixture of alcohols which had about 75% of an alkyl
group containing 18 carbon atoms in total with the remainder having 14 to
16 carbon atoms in total and whose branched methyl groups were positioned
almost at the central portion of the alkyl main chain.
EXAMPLE 1
Synthesis of 1-O-methyl-branched isostearyl-3-O-methyl glycerine
1000 g (31.3 moles) of methanol and 11 g (0.2 mole) of MeONa were added to
a 3 liters reaction vessel equipped with a reflux condenser, dropping
funnel, thermometer and agitator, and were then heated. The reaction
mixture was maintained at 60.degree. C., into which 654 g (2.0 moles) of
the methyl-branched isostearyl glycidyl ether obtained in Reference 1 was
dropped from the dropping funnel over about 3 hours. After completion of
the dropping, the reaction mixture was agitated at 60.degree. C. for 8
hours. From the gas chromatography of the reaction mixture it was
confirmed that the glycidyl ether completely disappeared. The mixture was
cooled and the methanol was distilled off under reduced pressure.
By the removal of the methanol and the distillation under reduced pressure,
there was obtained 650 g of a colorless, transparent liquid of
1-O-methyl-branched isostearyl-3-O-methyl glycerine.
Yield: 91%, Boiling point: 180.degree. C.-210.degree. C./0.7 mmHg,
Elementary analysis: calculated for C.sub.22 H.sub.46 O.sub.3 in
parentheses, C: 73.6% (73.69%); H: 12.7% (12.93%); O: 13.4% (13.38%),
Hydroxyl value: 150 (157), Average molecular weight (VPO
method/HCCl.sub.3): 350 (359) IR spectrum (cm.sup.'1, liquid film):
3100-3600, 1190, 1000-1150.
NMR (CDCl.sub.3, delta, TMS internal standard):
##STR7##
EXAMPLE 2-11
The general procedure of Example 1 was repeated using various alkyl
glycidyl ethers and various alcohols, thereby obtaining 1,3-di-O-alkyl
glycerines. The yield and physical properties of these compounds are shown
in Tables 2 and 3.
TABLE 2
__________________________________________________________________________
1,3-Di-O Alkyl Glycerines
##STR8##
Other Characteristics
Boiling Elementary Analysis
(Calcd)
Example Point Yield
(Calcd) Hydroxyl
Molecular
Iodine
No. R R' (mm Hg)
(%) C (%)
H (%)
O (%)
Value
Weight
Value
IR (cm.sup.-1,
__________________________________________________________________________
liq)
2 n-C.sub.8 H.sub.17
CH.sub.3
110-120.degree. C.
70 65.9
12.0
22.2
250 215 -- 3100-3650
(1.0) (66.01)
(12.00)
(21.98)
(257)
(218) 1195-970
1000-1170
3 n-C.sub.12 H.sub.25
CH.sub.3
153-155.degree. C.
85 69.4
12.5
18.0
200 270 -- 3100-3650
(1.0) (70.02)
(12.49)
(17.49)
(205)
(274) 1195, 965
1000-1170
4 n-C.sub.14 H.sub.29
CH.sub.3
170-180.degree. C.
99 71.0
12.1
15.3
181 -- -- 3100-3650
(0.55) (71.47)
(12.66)
(15.87)
(186) 1200, 970
1000-1180
5 n-C.sub.16 H.sub.33
CH.sub.3
190-195.degree. C.
96 72.8
12.4
14.2
163 -- -- 3100-3650
(0.5) (72.67)
(12.81)
(14.52)
(169.7) 1195, 965
1000-1180
6 n-C.sub.18 H.sub.37
CH.sub.3
41-41.8.degree. C.
95 73.5
12.7
13.6
157 -- -- 3100-3650
(Melting (73.69)
(12.93)
(13.38)
(156.5) 1200, 970
Point) 1000-1180
7 C.sub.18 H.sub.35
CH.sub.3
189-200.degree. C.
85 73.8
12.6
13.4
160 352 68.2
3100-3650
(Oleyl) (0.9) (74.10)
(12.44)
(13.46)
(157)
(357) (71.2)
1190, 960
1000-1110
8 C.sub.18 H.sub.37
C.sub.4 H.sub.9
197-238.degree. C.
80 74.5
12.8
12.5
133 401 -- 3100-3600
(Methyl-branched
(0.4) (74.94)
(13.08)
(11.98)
(140)
(409) 1000-1160
isostearyl
9 C.sub.18 H.sub.35
C.sub.4 H.sub.9
210-230.degree. C.
85 75.2
12.0
12.5
144 397 62.1
3100-3650
(Oleyl) (0.9) (75.32)
(12.64)
(12.04)
(141)
(399) (63.7)
1000-1170
10 C.sub.18 H.sub.37
C.sub.8 H.sub.17
216-240.degree. C.
80 76.0
13.4
11.0
130 450 -- 3100-3650
(Methyl-branched
(0.3) (76.25)
(13.24)
(10.51)
(123)
(457) 1000-1180
isostearyl)
11 C.sub.18 H.sub.35
C.sub.8 H.sub.17
240-260.degree. C.
85 76.6
12.8
11.0
124 450 52.2
3100-3600
(1.0) (76.59)
(12.86)
(10.55)
(123)
(455) (55.8)
1000-1170
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
1,3-Di-O-Alkyl Glycerines
##STR9##
Example NMR Data (CDCl.sub.3, .delta., TMS)
No. R R' O .sub.--H
CHOH Others
__________________________________________________________________________
2 n-C.sub.8 H.sub.17
CH.sub.3
2.90 (d,1H)
3.67 (m,1H)
3.33 (s,3H,C .sub.--H.sub.3 O)
3.10.about.3.60
##STR10##
3 n-C.sub.12 H.sub.25
CH.sub.3
2.80 (d,1H)
3.00 (m,1H)
3.32 (s,3H,C .sub.--H.sub.3 O)
3.15.about.3.65
##STR11##
4 n-C.sub.14 H.sub.29
CH.sub.3
2.85 (d, 1H)
3.70 (m,1H)
3.31 (s,3H,C .sub.--H.sub.3 O)
3.10.about.3.60
##STR12##
5 n-C.sub.16 H.sub.33
CH.sub.3
2.83 (d,1H)
3.68 (m,1H)
3.30 (s,3H,C .sub.--H.sub.3 O)
3.10.about.3.65
##STR13##
6 n-C.sub.18 H.sub.37
CH.sub.3
2.85 (d,1H)
3.65 (m,1H)
3.33 (s,3H,C .sub.--H.sub.3 O)
3.05.about.3.60
##STR14##
7 C.sub.18 H.sub.35
CH.sub.3
2.80 (d,1H)
3.85 (m,1H)
5.30 (t,2H,cis-Olefin)
(Oleyl) 3.33 (s,3H,C .sub.--H.sub.3 O)
3.3.about.3.70
##STR15##
8 C.sub.18 H.sub.37
C.sub.4 H.sub.9
2.75 (d,1H)
3.73 (m,1H)
3.20.about.3.70
(Methyl- branched isostearyl)
##STR16##
9 C.sub.18 H.sub.35
C.sub.4 H.sub.9
2.70 (d,1H)
3.85 (m,1H)
5.30 (t,2H,cis Olefin)
(Oleyl) 3.25.about.3.70
##STR17##
10 C.sub.18 H.sub.37
C.sub.8 H.sub.17
2.65 (d,1H)
3.84 (m,1H)
3.20.about.3.70
(Methyl- branched isostearyl
##STR18##
11 C.sub.18 H.sub.35
C.sub.8 H.sub.17
2.65 (d,1H)
3.80 (m,1H)
5.32 (t,2H,cis Olefin)
(Oleyl) 3.25.about.3.70
##STR19##
__________________________________________________________________________
*s: singlet
d: doublet
t: triplet
m: multiplet
EXAMPLE 12
Synthesis of 1-O-methyl-branched
isostearyl-3-O-methyl-2-O-2',3'-epoxypropyl glycerine
(1) Into a 3 liters reaction vessel equipped with a reflux condenser,
thermometer, dropping funnel and agitator were charged 416 g of an aqueous
50% sodium hydroxide solution (208 g as NaOH [5.2 moles]), 1.5 liters of
hexane, and 467 g (1.3 moles) of the 1-O-methyl-branched
isostearyl-3-O-methyl glycerine obtained in Example 1, followed by
charging 33.1 g (0.097 mole) of tetrabutylammonium hydrogensulfate and
violently agitating at 25.degree. C. Thereafter, 301 g (3.25 moles) of
epichlo | | |
