JP3172787B2 - Organosiloxane derivative having sugar residue and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organosiloxane derivative having a sugar residue and a method for producing the same.

[0002]

2. Description of the Related Art Silicone oils such as methylpolysiloxane are used as additives for foods or cosmetics because of their excellent properties such as heat resistance, weather resistance and low surface tension. However, the use of silicone oil is limited because of its hydrophobicity. Modified silicones in which various hydrophilic groups are introduced into silicone oil have been proposed as a device for increasing the hydrophilicity of the silicone oil while maintaining the excellent properties thereof.

(1) For example, as an attempt to improve hydrophilicity by introducing an ionic group, a pyrrolidone-carboxylic acid-modified silicone is disclosed in JP-A-51-59852, and an amino acid is disclosed in JP-A-52-114699. The modified silicone
Japanese Unexamined Patent Publication (Kokai) No. 2-196682 discloses lactone-modified silicones.

[0004] However, these modified silicones have the disadvantage that they are ionic and thus are susceptible to pH, which limits their use.

(2) As an attempt to increase the hydrophilicity of silicone by introducing a neutral hydrophilic group, see, for example,
No. 149290 discloses a modified silicone in which a polyether-type polyglycerin residue is introduced, but the polyglycerin residue has a relatively small number of hydroxyl groups per unit molecular weight, so that the silicone oil can effectively impart hydrophilicity to silicone oil. It is difficult to apply, and usually only a modified silicone having a low HLB value can be obtained. Further, generally used polyether silicones have a polyoxyalkylene group as a hydrophilic group.
If the ratio of the polyether residue to the entire modified silicone is increased to obtain a modified silicone having a high B value, the excellent physical properties of the silicone oil are lost. Further, with the above-mentioned modified silicone having a polyether type hydrophilic group, odor is recognized over time (see JP-A-2-302438), and is not suitable for use in cosmetics and the like. Various improvements have been made to solve the problem, but satisfactory results have not yet been obtained.

[0006] JP-A-63-139106 discloses a method of introducing a sugar residue having a high hydrophilicity through an amide bond for the purpose of solving such a drawback. According to this method, the introduction of a small amount of a sugar residue has the advantage that the hydrophilicity can be greatly improved while maintaining the excellent physical properties of the silicone oil, but the introduction of the sugar residue via an amino group is advantageous. Therefore, there are the following problems.

* Since a modified silicone having an amino group introduced therein is used as a raw material, it is necessary to carry out an amino group introduction reaction, which complicates the production process and increases the cost. * Since a modified silicone containing a highly reactive amino group is used, odor and coloring occur during the reaction or in the process of isolation and purification.

[0008] Since the polyfunctional sugar residue is bonded to the amino group of the modified silicone in one step, it is necessary to use relatively mild reaction conditions in order to avoid side reactions with the hydroxyl group.
Therefore, unreacted amino groups remain, and the free amino groups may adversely affect the living body.

[0009]

DISCLOSURE OF THE INVENTION The present invention improves the hydrophilicity of a silicone oil while maintaining the excellent physical properties of the silicone oil.
Another object of the present invention is to provide a novel modified silicone which is highly safe for a living body and a method for producing the same.

[0010]

As a result of intensive studies to achieve the above object, the present inventor has found that a siloxane having a hydrogen atom is reacted with a saccharide derivative having an unsaturated bond to form a saccharide derivative via a glycosidic bond. It has been found that a modified silicone having a sugar residue bonded thereto can be obtained.

That is, the present invention provides a compound represented by the general formula (I):

[0012]

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Wherein R and ^Ra are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], or a mixture thereof.

Further, the present invention provides a compound represented by the general formula (II):

[0015]

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[Wherein, R and R ^a are the same or different and each represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average values of m and n are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], and an organohydrogensiloxane represented by the general formula (III): R ⁸ -OG (III) [wherein, R ⁸ has 2 to 2 carbon atoms having a double bond in the molecule.
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. A sugar derivative represented by the general formula (I):

[0017]

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Wherein R, R ^a , R ^{1 to} R ⁶ , m and n are the same as above. And a method for producing the organosiloxane derivative or a mixture thereof.

Further, the present invention provides a compound represented by the general formula (II):

[0020]

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Wherein R and ^Ra are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average values of m and n are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], and an organohydrogensiloxane represented by the general formula (III): R ⁸ -OG (III) [wherein, R ⁸ has 2 to 2 carbon atoms having a double bond in the molecule.
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. A saccharide derivative represented by the formula (I):

[0022]

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Wherein R, R ^a , R ^{1 to} R ⁶ , m and n are as defined above. And a method for producing the organosiloxane derivative or a mixture thereof.

Furthermore, the present invention provides a compound of the general formula (II):

[0025]

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Wherein R and ^Ra are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average values of m and n are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], and an organohydrogensiloxane represented by the general formula (III): R ⁸ -OG ₁ (III) [wherein, R ⁸ has 2 to 2 carbon atoms having a double bond in the molecule.
0 represents an organic group, and G ₁ represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide having a protecting group. ]
Reacting with a sugar derivative represented by the following formula in the presence of a catalyst, and then performing a deprotection reaction, characterized by the general formula (I):

[0027]

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Wherein R, R ^a , R ^{1 to} R ⁶ , m and n are the same as above. And a method for producing the organosiloxane derivative or a mixture thereof.

Further, the present invention provides a compound represented by the general formula (II):

[0030]

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Wherein R and ^Ra are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average values of m and n are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], and an organohydrogensiloxane represented by the general formula (III): R ⁸ -OG ₁ (III) [wherein, R ⁸ has 2 to 2 carbon atoms having a double bond in the molecule.
0 represents an organic group, and G ₁ represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide having a protecting group. ]
A saccharide derivative represented by the formula (I), and after completion of the reaction, an unreacted hydrogen atom is reacted by adding an olefinic compound, followed by a deprotection reaction. ):

[0032]

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[Wherein, R and R ^a are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000]. The present invention provides a method for producing an organosiloxane derivative or a mixture thereof.

In the present invention, the number of carbon atoms represented by R ⁷ is 2
As 20 organic group, for example _{- (CH 2) 2 -,} - (CH 2) 3 -, - CH 2 CH
_{(CH 3) CH 2 -,} - (CH 2) 4 -, - (CH 2)
_{5 -, - (CH 2)} 6 -, - (CH 2) 7 -, - (CH
₂ ) ₈ -,-(CH ₂ ) ₂ -CH (CH ₂ CH ₂ C
_{H 3) -, - CH 2} -CH (CH 2 CH 3) - hydrocarbon radicals having straight or branched, such as, - (CH _{2) 3} -O
— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O— (CH ₂ ) ₂
—O— (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —O—CH ₂ C
H (CH ₃₎ - straight or branched group having an ether bond such _{as, -CH 2 -CH (CH 3)} -COO (CH
₂ ) a group having an ester bond such as _2- ,

[0035]

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A cyclic hydrocarbon group such as

[0037]

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And an aromatic hydrocarbon group which may have a substituent. Preferred organic radicals represented by R ^7, an organic group having 2 to 20 carbon atoms, or more preferably an organic group having 2 to 10 carbon atoms.

In the present invention, the number of carbon atoms represented by R ⁸ is 2
The organic group to -20 is not particularly limited as long as it has a double bond in the molecule, and for example, the following groups can be used: CH ₂ ＣＨCHCH ₂ —O—CH ₂ C
H ₂ —, CH ₂ ＣＨCHCH ₂ —O—CH ₂ CH ₂ —O—
_{CH 2 CH 2 -, CH 2} = CHCH 2 -O-CH 2 CH
_{(CH 3) -, CH 2} = CHCH 2 -O-CH 2 CH
(OH) CH ₂ - allyl compounds such as, CH ₂ = CH
—, CH ₂ ＣＨCHCH ₂ —, CH ₂ ＣC (CH ₃ ) CH
_{2 -, CH 2 = CHCH 2} CH 2 -, CH 2 = CHCH
₂ CH ₂ CH ₂ —, CH ₂ ＣＨCH— (CH ₂ ) ₄ —, C
_{H 2 = CH- (CH 2)} 5 -, CH 2 = CH- (C
_{H 2) 6 -, CH 3} CH 2 CH = CHCH 2 CH 2 -,

[0040]

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Unsaturated compounds such as CH ₂ ＣC (C
H ₃ ) COOCH ₂ CH ₂ —, CH ₂ ＣＨCHCOOCH
Compounds having an acryl group such as ₂ CH ₂ — and the like.

The preferred organic group represented by R ⁸ is an organic group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
Organic groups.

In the compounds of the general formula (I), m and n
Is preferably 1 ≦ m + n ≦ 500, and more preferably 1 ≦ m + n ≦ 150.

In the present invention, the glycosyl group derived from the monosaccharide, oligosaccharide or polysaccharide represented by G includes, for example, glucosyl, mannosyl, galactosyl, ribosyl, arabinosyl, xylosyl, fructosyl and the like. Monosaccharide group, maltosyl group, cellobiosyl group, lactosyl group, oligosaccharide group such as maltotriosyl group, cellulose, polysaccharide group such as starch, and preferred groups include monosaccharide group and oligosaccharide group. .

In the present invention, the glycosyl group having a protecting group derived from a monosaccharide, oligosaccharide or polysaccharide represented by G ₁ is a compound in which a free hydroxy group in the glycosyl group represented by G is usually It is protected by a group used as a protecting group. As the protecting group, acetyl group, benzoyl group, benzyl group, t-butyl group, trityl group, methoxybenzyl group, methoxybenzoyl group, carbamoyl group, isopropylidene group, benzylidene group,
Acetylidene group and the like.

In the present invention, the hydrocarbon group represented by any of R, R ^a , R ^{1 to} R ⁶ and R ^{1a to} R ^6a includes, for example, methyl, ethyl, n-propyl, i-
A straight-chain or branched carbon number of 1 to 1 such as propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group.
And a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms or a phenyl group.

Examples of the catalyst used in the present invention include peroxides, amines and phosphines, transition metals of Group VIII such as Ni, Rh, Pd and Pt, and compounds thereof, and preferably a platinum-based catalyst. Can be

More preferred platinum catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, ketones, aldehydes, etc., and solid platinum supported on a carrier such as platinum chelate, platinum black or alumina. And the like.

In the present invention, general formula (I):

[0050]

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Wherein R, R ^a , R ^{1 to} R ⁶ , m and n are the same as above. The reaction conditions of the above method for producing the organosiloxane derivative represented by the formula [1] are as follows.

The ratio of the reagent is such that the sugar derivative having an unsaturated bond of the general formula (III) is 0.1 to 1 per equivalent of the organohydrogensiloxane of the general formula (II).
The catalyst is used in an amount of about 1 to 100 equivalents in the reaction system.
Use about 00 ppm. Examples of the reaction solvent include no solvent or alcohols such as methanol, ethanol, and isopropanol; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as ethyl ether and dioxane; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; and dimethylformamide. , Dimethyl sulfoxide, acetonitrile or the like or a mixed solvent thereof. The reaction time is about 0.5 to 20 hours, preferably about 1 to 5 hours, and the reaction temperature is about 40 to 150 ° C, preferably about 70 to 110 ° C.

The compound of the general formula (II) and the compound of the general formula (II)
I) When unreacted hydrogen atoms bonded to Si remain after the reaction of the compound, it is preferable to add an olefinic compound after the reaction and react the unreacted hydrogen atoms as much as possible. Examples of the olefinic compound used for this purpose include ethylene, propylene, 1-butylene, 2-butylene, isobutylene, butadiene, 1-pentene, 1,3-pentadiene, 1-hexene, cyclohexene, 1-heptene, 1-octene and styrene. An aliphatic hydrocarbon compound having 1 to 8 carbon atoms, containing at least one double bond, and having a straight or branched chain is exemplified. The addition amount of this olefinic compound is represented by the general formula (I
Although it depends on the number of hydrogen atoms of the compound of I) and the conditions of the condensation reaction with the compound of the general formula (III), it is used in an amount of 2 equivalents or more, preferably an excess amount, based on the calculated amount of excess Si-H.
After the addition of the olefinic compound, the mixture is reacted at a temperature of about 70 to 110 ° C for 0.5 to 2 hours.

The purification of the organosiloxane derivative can be carried out by using known purification means such as solvent extraction, column chromatography, membrane separation, and reprecipitation.

When the sugar derivative of the general formula (III) has a protecting group, a deprotection reaction is then performed. The deprotection reaction can be carried out under the same conditions as those of a sugar deprotection reaction which is usually performed, for example, by adding an alkali such as sodium hydroxide or sodium methoxide in a solvent such as methanol. Can be performed.

The siloxane of the general formula (I) of the present invention may be obtained as a single product in the case where the compound of the general formula (II) as a raw material has one Si—H group. It is obtained as a mixture of compounds differing in the number of residues and the substitution position of the residue with respect to siloxane. The siloxane derivative of the present invention may be used alone or in a mixture as long as it is within the range represented by the general formula (I), as long as the siloxane derivative has increased the water solubility of the siloxane by introducing a sugar residue. Can be suitably used.

[0057]

According to the present invention, the following excellent effects can be achieved.

(1) Since a highly water-soluble saccharide residue is introduced into silicone oil, the introduction of a relatively small proportion of saccharide residues is effective while maintaining excellent properties such as heat resistance and weather resistance of the silicone oil. In this way, the hydrophilicity of the silicone oil can be increased.

(2) The organosiloxane derivative of the present invention is very stable, and does not cause a problem such as odoration over time.

(3) The organosiloxane derivative of the present invention is highly safe because it uses silicone oil and sugar which are safe for living organisms as raw materials, and can be used as cosmetics, food additives and medical materials which come into direct contact with the human body. Are suitable.

(4) According to the method of the present invention, a sugar residue can be easily introduced into silicone oil, and its water solubility can be remarkably increased.

(5) According to the method of the present invention, the content of saccharide residues in the product is determined by the

It can be controlled by a quantity.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0064]

Example 1 A 1-liter four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with the following formula:

[0065]

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Methyl hydrogen polysiloxane represented by: XF40-A6099 (manufactured by Toshiba Silicone)
8.3 gr, allyl glucoside 11.0 gr, dioxane 12.9 gr, chloroplatinic acid (0.2% solution) 5.0 g
r were charged and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated and partitioned with ethyl acetate / water system,
The aqueous layer was concentrated and dialyzed for 3 days using a dialysis tube (manufactured by Union Carbide; 27/32) to remove unreacted allyl glucoside, distill off the solution in the dialysis tube, and obtain a grease-like silicone. Compound (1) was 10.2
gr was obtained.

The structure of the product was determined by TLC, IR, NMR,
It was confirmed by elemental analysis and the like.

TLC: It was confirmed that sugar and hydrogen polysiloxane raw materials were not contained in the product.

IR analysis: Absorption at around 3500 cm ^{-1 due} to the hydroxyl group of sugar is observed.

The absorption of Si—O is observed at around 900 cm ⁻¹ .

The raw materials are 2100-2 derived from Si—H.
A noticeable absorption at 300 cm ^-1 was observed, but the product did not.

NMR analysis; peaks derived from Si-Me are found at around 0 ppm, and sugar-derived peaks are found around 3.5 to 4.5 and around 5 ppm, respectively.

Further, the raw material contains Si-
There is a peak derived from H, but not in the product.

Elemental analysis: As shown in Table 1 below, it can be confirmed that the contents of carbon and hydrogen are increased as compared with the raw material silicone.

Table 1 Elements to which sugar is completely added (%) XF40-A6 099 (1) Theoretical value at the time of C 30.2 39.4 40.0 H 8.1 7.3 7.3 Elemental analysis According to the results and ¹ H-NMR analysis, product 1 was obtained.
Was found to have 4-5 sugars added.

[0076]

Example 2 In the same apparatus as in Example 1, the following formula:

[0077]

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Methyl hydrogen polysiloxane represented by the following formula: XF40-A6098 (manufactured by Toshiba Silicone)
9.25 gr, 60.0 gr of allyl glucoside, 200 gr of isopropyl alcohol, and 3.0 gr of chloroplatinic acid (0.2% solution) were charged, and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated, partitioned with an ethyl acetate / water system, the aqueous layer was concentrated, dialyzed to remove unreacted allylglucoside, and the solution in the dialysis tube was distilled off.
4.9 gr of a powdery silicone compound (2) was obtained. T
LC, IR, NMR, elemental analysis, and the like revealed that the obtained product was a silicone compound having four or five sugars bonded.

[0079]

Example 3 The same apparatus as in Example 1 was replaced by the following formula:

[0080]

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Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, allyl glucoside 22.0 gr, dioxane 126 gr, chloroplatinic acid (0.2% solution) 2.5 gr
And reacted at 80 to 90 ° C. for about 3 hours.
The reaction mixture was concentrated and partitioned with an ethyl acetate / water system, and the solvent in the organic layer was distilled off to form an oily silicone compound (3).
Was obtained in an amount of 8.8 gr. No silicone compound was obtained from the aqueous layer.

According to the same analysis as in Example 1, it was found that the product (3) was a silicone compound having two sugars bonded.

[0083]

Example 4 The same apparatus as in Example 1 was replaced with the following formula:

[0084]

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Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, allyl glucoside 4.4 gr, dioxane 5.2 gr, and 2.0 gr of chloroplatinic acid (0.2% solution) were respectively charged and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated and partitioned with an ethyl acetate / water system, and the solvent in the organic layer was distilled off to obtain 8.0 g of an oily silicone compound (4).

No silicone compound was obtained from the aqueous layer.

According to the same analysis as in Example 1, it was found that the product (4) was a silicone compound having two sugars bonded.

[0088]

Example 5 An apparatus similar to that of Example 1 was replaced with the following formula:

[0089]

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Methyl hydrogen polysiloxane represented by: XF40-A6099 (manufactured by Toshiba Silicone)
8.3 gr, allyl glucoside 22.0 gr, dioxane 25.9 gr, chloroplatinic acid (0.2% solution) 5.0 g
r were charged and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated and partitioned with ethyl acetate / water system. The aqueous layer was concentrated and dialyzed to remove unreacted allylglucoside, and the solution in the dialysis tube was distilled off to obtain 15.5 gr of a grease-like silicone compound (5). The same analysis as in Example 1 revealed that the product (5) was a silicone compound having four or five sugars bonded thereto.

[0091]

Example 6 The same apparatus as in Example 1 was replaced by the following formula:

[0092]

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Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, 2.7 g of 3-hexenyl glucoside, 3.2 gr of dioxane, chloroplatinic acid (0.2% solution)
0 gr each was charged and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated and partitioned with an ethyl acetate / water system, and the solvent of the organic layer was distilled off to obtain 8.5 g of an oily silicone compound (6).

No silicone compound was obtained from the aqueous layer.

The analysis in the same manner as in Example 1 revealed that the product (6) was a silicone compound having two sugars bonded.

[0096]

[Embodiment 7] In the same apparatus as in Embodiment 1, the following formula:

[0097]

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Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, 4.4 gr of 3-hexenyl glucoside, 5.1 gr of dioxane, chloroplatinic acid (0.2% solution)
0 gr each was charged and reacted at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated and partitioned with an ethyl acetate / water system, and the solvent of the organic layer was distilled off to obtain 8.2 g of an oily silicone compound (7). No silicone compound was obtained from the aqueous layer.

The analysis in the same manner as in Example 1 revealed that the product (7) was a silicone compound having two sugars bonded thereto.

[0100]

Example 8 Allyl maltoside 4.5 as glycoside
The same operation as in Example 3 was performed except for using gr, to obtain 7.8 gr of an oily silicone compound (8).

The same analysis as in Example 1 revealed that the product (8) was a silicone compound having two sugars bonded.

[0102]

Example 9 As a polysiloxane, the following formula:

[0103]

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The same operation as in Example 3 was carried out except that 45.1 gr of the silicone compound was used, to obtain 6.6 gr of an oily silicone compound (9).

The same analysis as in Example 1 revealed that the product (9) was a silicone compound having two sugars bonded.

[0106]

Example 10 Commercially available polyether-modified silicones were used in Comparative Examples (1 to 3), and the solubility of the silicone compounds obtained in the examples in various solvents was examined.

The polyether-modified silicone used as a comparative example is shown below.

* Comparative Example 1: SH-3771 (Toray Dow Corning) * Comparative Example 2: SF-8410 (Toray Dow Corning) * Comparative Example 3: SH-8400 (Toray Dow Corning) Solubility Measurement Method About 10 mg of each silicone compound was taken, 1 ml of a solvent was added, and the mixture was sufficiently stirred. The results are shown in Table 1 below.

[0109]

[Table 1]

In Table 1, X indicates insoluble.

The symbol "△" indicates that the substance was partially dissolved.

○ indicates complete dissolution.

Examples 1, 2, and 5 are compounds obtained from the aqueous layer, and are shown together.

[0114]

Example 11 The same polyether-modified silicone as used in Example 10 was used in Comparative Examples 1 to 3, and
The emulsifiability of the silicone compounds obtained in 2, 3 and 5 in a silicone oil / water system was examined.

Measurement method of emulsifying property (1) 2 mg of each W / O silicone compound was precisely weighed in a test tube, and 10 m of water was measured.
g, 10 mg of 1,3-butylene glycol, and 78 mg of silicone oil were sequentially added, and the mixture was sufficiently stirred in a warm bath at 70 ° C. for 30 minutes, allowed to stand at room temperature for 24 hours, and the state of the liquid phase was observed.

(2) O / W system 2 mg of each silicone compound was precisely weighed in a test tube, and 20 mg of silicone oil, 68 mg of water and 10 mg of 1,3-butylene glycol were added in this order, and the mixture was sufficiently placed in a 70 ° C. warm bath for 30 minutes. And left at room temperature for 24 hours to observe the state of the liquid phase.

Table 2 shows the results.

[0118]

[Table 2]

[0119] In Table 2, x indicates a state where no emulsification was performed.

The symbol “△” indicates that the emulsion was partially emulsified.

○ indicates emulsification.

◎ indicates complete emulsification and a uniform state.

From Table 2, it was found that the oily silicone compound in the W / O system and the grease-like silicone compound in the O / W system exhibited good emulsifiability.

From the results shown in Tables 1 and 2, in the organosiloxane derivative of the present invention, the sugar moiety in the molecule shows an action as a hydrophilic group, and the organosiloxane group shows an action as a hydrophobic group. Therefore, the silicone compound of the present invention is a type of surfactant having both hydrophilic and hydrophobic functions, and is widely used in various fields including cosmetics, toiletries, paints, plastic additives, and the like. It turns out that it is applicable.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masakazu Okumura 5-1-1, Umei, Takasago City, Hyogo Pref. Japan Research Institute, Ltd. (56) References JP-A-63-139106 (JP, A) 62-68820 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 77/38 C08G 77/14 C08G 77/16

Claims (5)

(57) [Claims] 1. A compound of the general formula (I): [Wherein, R and ^Ra are the same or different and each represent a hydrocarbon group having 1 to 8 carbon atoms. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different, and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000], or a mixture thereof. 2. A compound of the general formula (II): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average value of m and n is the same or different and represents 0 or a positive number;
≦ m + n ≦ 1000 and is] in the organohydrogensiloxane and the general formula represented ^{(III): R 8 -O-} G (III) [ wherein, R ⁸ is 2 to carbon atoms having a double bond in the molecule 2
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And a sugar derivative represented by the following general formula (I): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different and each represent 0 or a positive number, and 1 ≦ m + n ≦ 1000]. 3. A compound of the general formula (II): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average value of m and n is the same or different and represents 0 or a positive number;
≦ m + n ≦ 1000 and is] in the organohydrogensiloxane and the general formula represented ^{(III): R 8 -O-} G (III) [ wherein, R ⁸ is 2 to carbon atoms having a double bond in the molecule 2
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. Wherein the unreacted hydrogen atom is reacted by the addition of an olefinic compound after the completion of the reaction to react with the sugar derivative represented by the general formula (I): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different, and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000]. The method for producing an organosiloxane derivative or a mixture thereof. 4. A compound of the general formula (II): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average value of m and n is the same or different and represents 0 or a positive number;
≦ m + n ≦ 1000 and is] in the organohydrogensiloxane and the general formula represented ^{(III): R 8 -O-} G 1 (III) [ wherein carbon atoms R ⁸ has the double bond in the molecule 2 ~ 2
0 represents an organic group, and G ₁ represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide having a protecting group. ]
Reacting with a sugar derivative represented by the following formula in the presence of a catalyst, and then performing a deprotection reaction, characterized by the following general formula (I): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different, and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000]. The method for producing an organosiloxane derivative or a mixture thereof. 5. A compound of the general formula (II): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1a to} R ^6a are the same or different, and at least one represents a hydrogen atom, and the rest represents a hydrocarbon group having 1 to 8 carbon atoms. The average value of m and n is the same or different and represents 0 or a positive number;
≦ m + n ≦ 1000 and is] in the organohydrogensiloxane and the general formula represented ^{(III): R 8 -O-} G 1 (III) [ wherein carbon atoms R ⁸ has the double bond in the molecule 2 ~ 2
0 represents an organic group, and G ₁ represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide having a protecting group. ]
A saccharide derivative represented by the formula (I), and after completion of the reaction, an unreacted hydrogen atom is reacted by adding an olefinic compound, followed by a deprotection reaction. ): [Wherein, R and ^Ra are the same or different and have 1 to 1 carbon atoms;
8 represents a hydrocarbon group. R ^{1 to} R ⁶ are the same or different, and at least one is represented by a general formula (A): —R ⁷ —OG (A) wherein R ⁷ represents an organic group having 2 to 20 carbon atoms; G represents a glycosyl group derived from a monosaccharide, oligosaccharide or polysaccharide. And an organic group represented by the formula:
8 represents a hydrocarbon group or a hydroxy group. m and n
Are the same or different, and represent 0 or a positive number, and 1 ≦ m + n ≦ 1000]. The method for producing an organosiloxane derivative or a mixture thereof.