JPH05186596A - Organosiloxane derivative having sugar residue and its production - Google Patents

Abstract

PURPOSE:To increase hydlophilicity, avoid coloration during aging, and improve biological safety by reacting a specific organohydrogensiloxane with a sugar deriv. in the presence of a catalyst. CONSTITUTION:1 equivalent of an organohydrogensiloxane of formula I (wherein R and R<a> are each a 1-8C hydrocarbon group; at least one of R<1a> to R<6a> is H and the rest are R; and the mean value of m and n is 0 or a positive integer provided that 1<=m+n<=1,000) is reacted with 0.1-1,000 equivalents of a sugar deriv. of formula II (wherein R<8> is a 2-20C org. group having a double bond in the molecule; and G is a glycosyl group derived from a mono-, oligo-, or polysaccharide) in the presence of a catalyst in an amt. of 1-10,000ppm at 40-150 deg.C for 0. 5-20hr to give an organosiloxane deriv. (mixture) of formula III [wherein at least one of R<1> to R<6> is an org. group of formula IV (wherein R<7> is a 2-20C org. group) and the rest are each a 1-8C hydrocarbon group or hydroxy].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 methyl polysiloxane are used as additives for foods or cosmetics because of their excellent physical properties such as heat resistance, weather resistance and low surface tension. However, because silicone oil is hydrophobic, its use is limited. Modified silicones in which various hydrophilic groups are introduced into silicone oil have been proposed as a device for enhancing the hydrophilicity of silicone oil while retaining the excellent properties of silicone oil.

(1) For example, in 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-52-14699. Modified silicone
JP-A-2-196862 discloses lactone-modified silicones.

However, since these modified silicones are ionic, they are easily affected by pH, which has a drawback that their applications are limited.

(2) In an attempt to improve the hydrophilicity of silicone by introducing a neutral hydrophilic group, for example, JP-A-57-
No. 149290 discloses a modified silicone in which a polyether type polyglycerin residue is introduced, but since the polyglycerin residue has a relatively small number of hydroxyl groups per unit molecular weight, it effectively imparts hydrophilicity to silicone oil. It is difficult to apply, and normally only modified silicones having a low HLB value can be obtained. Further, generally used polyether silicone has a polyoxyalkylene group as a hydrophilic group, but this polyether silicone is HL.
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 will be lost. Further, with the above-mentioned modified silicone having a polyether type hydrophilic group, odor is observed over time (see JP-A-2-302438), and it 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] Japanese Patent Laid-Open No. 63-139106 discloses a method of introducing a highly hydrophilic sugar residue by an amide bond for the purpose of eliminating such a drawback. According to this method, it is possible to significantly improve the hydrophilicity while maintaining the excellent physical properties of silicone oil by introducing a small amount of sugar residue, but introducing a sugar residue via the amino group. Therefore, there are the following problems.

[0007] Since a modified silicone having an amino group introduced is used as a raw material, it is necessary to carry out an amino group introduction reaction, which complicates the manufacturing process and increases the cost. * Since a modified silicone containing highly reactive amino groups is used, odor and coloration occur during the reaction or isolation / purification process.

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 a side reaction with the hydroxyl group.
Therefore, unreacted amino groups may remain, and the free amino groups may adversely affect the living body.

[0009]

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

[0010]

Means for Solving the Problems 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 sugar derivative having an unsaturated bond to form a glycoside bond. It was found that a modified silicone having a sugar residue bonded thereto was obtained.

That is, the present invention has the general formula (I):

[0012]

[Chemical 10]

[In the formula, R and R ^a are the same or different and each represents 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 the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of 0 is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000], or an organosiloxane derivative or a mixture thereof.

The present invention also has the general formula (II):

[0015]

[Chemical 11]

[In the formula, R and R ^a are the same or different and each represents 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 represent 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, and 1 ≦ m + n ≦ 1000] and the organohydrogensiloxane represented by the general formula (III): R ⁸ —O—G (III) [In the formula, 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, an oligosaccharide or a polysaccharide. ] It reacts with the sugar derivative represented by these in the presence of a catalyst, General formula (I):

[0017]

[Chemical 12]

[In the formula, R, R ^a , R ^{1 to} R ⁶ , m and n are the same as defined above. ] The manufacturing method of the organosiloxane derivative represented by these or its mixture is provided.

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

[0020]

[Chemical 13]

[In the formula, R and R ^a are the same or different and each represents 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 represent 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, and 1 ≦ m + n ≦ 1000] and the organohydrogensiloxane represented by the general formula (III): R ⁸ —O—G (III) [In the formula, 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, an oligosaccharide or a polysaccharide. ] It reacts with the sugar derivative represented by these in the presence of a catalyst, Then, an olefinic compound is added, General formula (I):

[0022]

[Chemical 14]

[Wherein R, R ^a , R ^{1 to} R ⁶ , m and n are the same as defined above. ] The manufacturing method of the organosiloxane derivative represented by these or its mixture is provided.

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

[0025]

[Chemical 15]

[In the formula, R and R ^a are the same or different and each represents 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 represent 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, and 1 ≦ m + n ≦ 1000] and the organohydrogensiloxane represented by the general formula (III): R ⁸ —O—G ₁ (III) [In the formula, 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 sugar derivative represented by the formula (I) is reacted in the presence of a catalyst, and then a deprotection reaction is carried out.

[0027]

[Chemical 16]

[In the formula, R, R ^a , R ^{1 to} R ⁶ , m and n are the same as defined above. ] The manufacturing method of the organosiloxane derivative represented by these or its mixture is provided.

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

[0030]

[Chemical 17]

[In the formula, R and R ^a are the same or different and each represents 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 represent 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, and 1 ≦ m + n ≦ 1000] and the organohydrogensiloxane represented by the general formula (III): R ⁸ —O—G ₁ (III) [In the formula, 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 sugar derivative represented by the formula (I) is reacted in the presence of a catalyst, unreacted hydrogen atoms are reacted by addition of an olefinic compound after the reaction is completed, and then a deprotection reaction is carried out. ):

[0032]

[Chemical 18]

[In the formula, R and R ^a are the same or different and each represents 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 the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of is 0 or a positive number which is the same or different, and 1 ≦ m + n ≦ 1000], and a method for producing the 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 )-, or other linear or branched hydrocarbon group,-(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]

[Chemical 19]

Cyclic hydrocarbon groups such as

[0037]

[Chemical 20]

Examples thereof include aromatic hydrocarbon groups which may have a substituent such as The preferred organic group represented by R ⁷ is an organic group having 2 to 20 carbon atoms, 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 20 organic group is not particularly limited as long as it has a double bond in the molecule, can be used for example, the following _{groups: CH 2 = CHCH 2 -O-} CH 2 C
_{H 2 -, CH 2 = CHCH} 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 = CHCH 2 -} , CH 2 = C (CH 3) CH
_{2 -, CH 2 = CHCH 2} CH 2 -, CH 2 = CHCH
_{2 CH 2 CH 2 -, CH} 2 = CH- (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]

[Chemical 21]

Unsaturated compounds such as CH ₂ = C (C
_{H 3) COOCH 2 CH 2 -} , CH 2 = CHCOOCH
₂ Compounds having an acrylic group such as CH ₂ —.

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.
The organic groups of

In the compound of general formula (I), m and n
The preferable range is 1 ≦ m + n ≦ 500, and the more preferable range is 1 ≦ m + n ≦ 150.

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

In the present invention, the glycosyl group having a protecting group derived from a monosaccharide, an oligosaccharide or a polysaccharide represented by G ₁ is a glycosyl group represented by G in which the free hydroxy group is usually a sugar group. It is protected by a group used as a protecting group. Examples of the protecting group include acetyl group, benzoyl group, benzyl group, t-butyl group, trityl group, methoxybenzyl group, methoxybenzoyl group, carbamoyl group, isopropylidene group, benzylidene group,
An acetylidene group etc. are mentioned.

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 is, for example, a methyl group, an ethyl group, an n-propyl group, i-
Propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, or other linear or branched carbon number 1 to 1
The hydrocarbon group of 8 is mentioned, and a preferable group is a hydrocarbon group of 1 to 6 carbon atoms, more preferably a hydrocarbon group of 1 to 4 carbon atoms or a phenyl group.

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

As a more preferable platinum catalyst, solid platinum is supported on a carrier such as chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and olefins, ketones, aldehydes, platinum chelate, platinum black or alumina. Some of them have been made.

In the present invention, the general formula (I):

[0050]

[Chemical formula 22]

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

The ratio of the reagent is 0.1 to 1 for the sugar derivative having an unsaturated bond of the general formula (III) with respect to 1 equivalent of the organohydrogensiloxane of the general formula (II).
About 100 equivalents are used, and the catalyst is 1-100 in the reaction system.
Use about 00 ppm. As the reaction solvent, solvent-free 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. , Dimethylsulfoxide, acetonitrile and 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.

Compounds of general formula (II) and general formula (II
When unreacted hydrogen atoms bonded to Si remain after the reaction of the compound I), it is preferable to add an olefin compound after completion of the reaction and allow the unreacted hydrogen atoms to react as much as possible. Examples of the olefin 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 and having one or more double bonds and having a straight chain or a branch is mentioned. The addition amount of this olefin compound is represented by the general formula (I
Although it depends on the number of hydrogen atoms of the compound 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, relative to the calculated amount of excess Si—H.
After the addition of the olefin compound, the reaction is carried out at a temperature of about 70 to 110 ° C. for 0.5 to 2 hours.

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

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

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

[0057]

According to the present invention, the following excellent effects are achieved.

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

(2) The organosiloxane derivative of the present invention is very stable and does not cause problems such as odor with time.

(3) The organosiloxane derivative of the present invention is highly safe because it is made of silicone oil and sugar, which are safe to the living body, and is highly safe. It is also used as a cosmetic product, a food additive, or a medical material that comes into direct contact with the human body. Are suitable.

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

(5) According to the method of the present invention, the content of the sugar residue in the product is controlled by the charging ratio of the sugar derivative.

It can be controlled by quantity.

The present invention will be described in more detail below 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 cooler and a thermometer was charged with the following formula:

[0065]

[Chemical formula 23]

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
Each r was charged and the reaction was carried out 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, and the solution in the dialysis tube was distilled off to give a grease-like silicone. 10.2 of the compound (1)
gr was obtained.

The structure of the product is 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 derived from the hydroxyl group of sugar is observed near 3500 cm ^-1 .

Absorption of Si--O is observed near 900 cm ^-1 .

As a raw material, 2100-2 derived from Si--H
A marked absorption at 300 cm ^-1 was observed, but the product did not have this absorption.

NMR analysis: Si-Me-derived peaks are found around 0 ppm, and sugar-derived peaks around 3.5-4.5 and 5 ppm.

Further, the raw material contains Si-
There is a peak derived from H, but not found 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 Element (%) XF40-A6099 (1) with complete addition of sugar Theoretical value C 30.2 39.4 40.0 H 8.1 7.3 7.3 Elemental analysis From the results and ¹ H-NMR analysis, the product 1 was obtained.
Was found to have 4 to 5 sugars added.

[0076]

[Embodiment 2] An apparatus similar to that of Embodiment 1 has the following formula:

[0077]

[Chemical formula 24]

Methyl hydrogen polysiloxane represented by: 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 the reaction was carried out 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 allyl glucoside, and the solution in the dialysis tube was distilled off,
4.9 gr of powdery silicone compound (2) was obtained. T
By LC, IR, NMR, elemental analysis and the like, it was found that the obtained product was a silicone compound having 4 or 5 sugars bonded.

[0079]

[Embodiment 3] An apparatus similar to that of Embodiment 1 is provided with the following formula:

[0080]

[Chemical 25]

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
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, and the solvent of the organic layer was distilled off to give an oily silicone compound (3).
8.8 gr was obtained. No silicone compound was obtained from the aqueous layer.

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

[0083]

[Embodiment 4] An apparatus similar to that of Embodiment 1 has the following formula:

[0084]

[Chemical formula 26]

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

No silicone compound was obtained from the aqueous layer.

The same analysis as in Example 1 revealed that the product (4) was a silicone compound having two sugars bonded.

[0088]

[Embodiment 5] A device similar to that of Embodiment 1 has the following formula:

[0089]

[Chemical 27]

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
Each r was charged and the reaction was carried out 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 allyl glucoside, 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 4 or 5 sugars bonded.

[0091]

[Embodiment 6] An apparatus similar to that of Embodiment 1 is provided with the following formula:

[0092]

[Chemical 28]

Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, 3-hexenyl glucoside 2.7 gr, dioxane 3.2 gr, chloroplatinic acid (0.2% solution) 2.
0 gr was charged for each and the reaction was carried out at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated, partitioned with an ethyl acetate / water system, and the solvent of the organic layer was distilled off to obtain 8.5 gr of an oily silicone compound (6).

No silicone compound was obtained from the aqueous layer.

By the same analysis as in Example 1, the product (6) was found to be a silicone compound having two sugars bonded.

[0096]

[Embodiment 7] An apparatus similar to that of Embodiment 1 has the following formula:

[0097]

[Chemical 29]

Methyl hydrogen polysiloxane represented by: XF40-A6100 (manufactured by Toshiba Silicone)
8.1 gr, 3-hexenyl glucoside 4.4 gr, dioxane 5.1 gr, chloroplatinic acid (0.2% solution) 2.
0 gr was charged for each and the reaction was carried out at 80 to 90 ° C. for about 3 hours. The reaction mixture was concentrated, partitioned with an ethyl acetate / water system, and the solvent of the organic layer was distilled off to obtain 8.2 gr of an oily silicone compound (7). No silicone compound was obtained from the aqueous layer.

By the same analysis as in Example 1, it was found that the product (7) was a silicone compound having two sugars bonded.

[0100]

Example 8 Allyl maltoside 4.5 as glycoside
The same operation as in Example 3 was performed except that gr was used 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 A polysiloxane having the following formula:

[0103]

[Chemical 30]

The same operation as in Example 3 was carried out except that 45.1 gr of the above 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 A commercially available polyether-modified silicone was used as Comparative Examples (1 to 3), and the solubility of the silicone compound obtained in the Example in various solvents was examined.

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

[0108] * Comparative Example 1: SH-3771 (Toray Dow Corning) * Comparative Example 2: SF-8410 (Toray Dow Corning) * Comparative Example 3: SH-8400 (Toray Dow Corning) the solubility of the measurement method About 10 mg of each silicone compound was added, 1 ml of a solvent was added, and the mixture was sufficiently stirred, allowed to stand, and after 10 minutes, the state of the solution was observed. The results are shown in Table 1 below.

[0109]

[Table 1]

In Table 1, x indicates insolubility.

A mark indicates that a part was dissolved.

◯ indicates that the substance was completely dissolved.

Further, since Examples 1, 2 and 5 are compounds obtained from the aqueous layer, they are collectively shown.

[0114]

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

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

(2) O / W system 2 mg of each silicone compound was accurately weighed in a test tube, 20 mg of silicone oil, 68 mg of water, and 10 mg of 1,3-butylene glycol were added in that order, and the mixture was sufficiently heated in a warm bath at 70 ° C. for 30 minutes. The mixture was stirred at room temperature and left overnight at room temperature, and then the state of the liquid phase was observed.

The results are shown in Table 2.

[0118]

[Table 2]

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

Δ indicates that the emulsion was partially emulsified.

◯ means emulsified.

⊚ indicates a completely emulsified and uniform state.

From Table 2, it was found that the oil-like silicone compound in the W / O system and the grease-like silicone compound in the O / W system showed good emulsifying properties.

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Okumura 5-1-1 Umei, Takasago-shi, Hyogo Nihon Seika Co., Ltd. Research Institute

Claims (5)

[Claims] 1. General formula (I): [In the formula, R and R ^a are the same or different and each represents 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 the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000]] or an organosiloxane derivative or a mixture thereof. 2. General formula (II): [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1a to} R ^6a are the same or different and at least one represents a hydrogen atom, and the rest represent 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, and 1
≦ m + n ≦ 1000] and the general formula (III): R ⁸ —OG (III) [wherein, R ⁸ has 2 to 10 carbon atoms having a double bond in the molecule] Two
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] It reacts with the sugar derivative represented by these in the presence of a catalyst, General formula (I): [In the formula, R and ^Ra are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1 to} R ⁶ are the same or different, and at least one is represented by the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Shows the organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of 0 is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000]. 3. General formula (II): [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1a to} R ^6a are the same or different and at least one represents a hydrogen atom, and the rest represent 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, and 1
≦ m + n ≦ 1000] and the general formula (III): R ⁸ —OG (III) [In the formula, R ⁸ has 2 to 2 carbon atoms having a double bond in the molecule. Two
0 represents an organic group, and G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] The sugar derivative represented by the formula [I] is reacted in the presence of a catalyst, and after the reaction is completed, an unreacted hydrogen atom is reacted by the addition of an olefinic compound. [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1 to} R ⁶ are the same or different, and at least one is represented by the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of 0 is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000]. 4. A compound represented by the general formula (II): [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1a to} R ^6a are the same or different and at least one represents a hydrogen atom, and the rest represent 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, and 1
≦ m + n ≦ 1000] and the general formula (III): R ⁸ —O—G ₁ (III) [In the formula, R ⁸ has 2 carbon atoms having a double bond in the molecule. ~ 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 sugar derivative represented by the formula (I) is reacted in the presence of a catalyst, and then a deprotection reaction is carried out. [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1 to} R ⁶ are the same or different, and at least one is represented by the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of 0 is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000]. 5. General formula (II): [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1a to} R ^6a are the same or different and at least one represents a hydrogen atom, and the rest represent 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, and 1
≦ m + n ≦ 1000] and the general formula (III): R ⁸ —O—G ₁ (III) [In the formula, R ⁸ has 2 carbon atoms having a double bond in the molecule. ~ 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 sugar derivative represented by the formula (I) is reacted in the presence of a catalyst, unreacted hydrogen atoms are reacted by addition of an olefinic compound after the reaction is completed, and then a deprotection reaction is carried out. ): [Chemical 9] [In the formula, R and R ^a are the same or different and have 1 to 1 carbon atoms.
8 shows a hydrocarbon group of 8. R ^{1 to} R ⁶ are the same or different, and at least one is represented by the general formula (A): —R ⁷ —OG (A) [In the formula, R ⁷ represents an organic group having 2 to 20 carbon atoms, G represents a glycosyl group derived from a monosaccharide, an oligosaccharide or a polysaccharide. ] Represents an organic group represented by
8 represents a hydrocarbon group or a hydroxy group. m and n
The average value of 0 is the same or different and represents 0 or a positive number, and 1 ≦ m + n ≦ 1000].