JP3014631B2 - Novel ether compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel ether compound and a method for producing the same. More specifically, a cosmetic or detergent composition that is colorless and odorless, does not color or change odor over time, has a low oily feeling, has an excellent feel, has a moderately low viscosity, and has no irritating feeling to the eyes. New ether compounds that can be used widely as oils such as lubricants, lubricants, or surfactants such as penetrants, emulsifiers, solubilizers, dispersants, and detergents that have moderately low viscosity and low stickiness. It relates to the manufacturing method.

[0002]

2. Description of the Related Art
As liquid oil agents widely used as oil agents for cosmetics, detergent compositions, lubricants, etc., oils and fats and hydrocarbons obtained by animals and plants or by chemical synthesis are known. The ideal properties that such general-purpose liquid oils should have are: (1) no odor or color; (2) no coloring or unpleasant odor over time; (3) excellent feel; (4) For example, the viscosity is appropriately low. However, oils and fats are not preferable because they are hydrolyzed upon contact with water and have an oily feeling when touched, and hydrocarbons have high stability but are not preferable because they have high stability. As described above, none of the liquid oils known so far satisfy all of the above properties.

[0003] Conventionally, the above-mentioned fats and oils, hydrocarbons, and esters have been used as liquid oil agents that can be used for removing makeup cosmetics. However, these liquid oils have the ideal properties that liquid oils for removing make-up cosmetics should have, that is, excellent feel (less oiliness) and excellent removability to makeup cosmetics. There is no one that satisfies all of the properties such as the presence of the subject and no irritation to the eyes.

On the other hand, it is known that ether compounds are also used as oils for cosmetics and the like. For example, JP-A-48-5941 discloses a saturated β-side chain monoether compound having 24 or more carbon atoms, JP-A 48-33037 discloses a higher chain ether compound having 20 or more carbon atoms, JP-A-63-122612 and JP-A-6-507654 disclose that one alkyl group of a monoether has 6 to 6 carbon atoms.
An ether compound of No. 22 and US Pat. No. 4,092,254 discloses an ether compound in which one alkyl group has 1 to 3 carbon atoms and the other alkyl group has 8 to 20 carbon atoms.
However, these ether compounds also do not satisfy all of the above properties as an oil agent for removing makeup cosmetics.

[0005] Conventionally, a penetrant, an emulsifier, a solubilizer,
Dispersants, surfactants used in detergents, etc., are classified into anionic, cationic, amphoteric, non-ionic types, but for anionic, cationic and amphoteric surfactants, they have a charge, There are drawbacks such as high viscosity, strong hygroscopicity and easy stickiness,
In addition, most of nonionic surfactants have a hydroxyl group partially or entirely, which also causes problems such as high viscosity, high hygroscopicity and stickiness. In addition, there are nonionic surfactants having no hydroxyl group, but since they mainly have an ester bond or the like, they are hydrolyzed under acidic or alkaline conditions and cannot be used in most cases.

Accordingly, an object of the present invention is to solve the above-mentioned problems, to be colorless and odorless, not to be colored or unpleasant with time, to have an excellent feel, to have a moderately low viscosity, Oils such as cosmetics, detergents, lubricants, etc., which are less hygroscopic and less sticky, and are stable under various conditions,
Novel compounds that can be widely used as surfactants such as penetrants, emulsifiers, solubilizers, dispersants, detergents, etc., especially those with little oiliness, excellent removability to makeup cosmetics, and irritating to eyes Another object of the present invention is to provide a novel compound useful as an oil agent for removing makeup cosmetics.

[0007]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found a novel asymmetric ether compound which can solve the above-mentioned problems, and have completed the present invention. That is, the present invention provides an ether compound represented by the general formula (I). R ¹ -O- (AO) _n -R ² (I) wherein R ¹ is a formula

[0008]

Embedded image

[0009] a group represented by, R ² is a straight or branched chain alkyl group or alkenyl group having 10 to 30 carbon atoms. A represents an alkylene group having 2 to 12 carbon atoms, and n
May be the same or different. n shows the number of 0-30. Where R ¹ is the formula

[0010]

Embedded image

When a group represented by the n = 0 in [0011], the total number of carbon atoms in R ¹ and R ² Ri 16 to 36 der, R ¹ has the formula

[0012]

Embedded image

When n = 0, the total carbon number of R ¹ and R ² is 17 to 34. Further, the present invention has the general formula (VI)

[0014]

Embedded image

[ Wherein R ⁹ and R ¹⁰ are those wherein R ⁹ is a methyl group ;
¹⁰ is the formula

[0016]

Embedded image

Wherein R ⁹ and R ¹⁰ both represent a group of the formula

[0018]

Embedded image

Wherein R ⁹ is a hydrogen atom,
R ¹⁰ is the formula

[0020]

Embedded image

The group represented by ] And a carbonyl compound represented by the general formula _{(VII) HO- (AO) n} -R 2 (VII) wherein, R ^2, A, n have the same meanings as defined above. A method of producing an ether compound represented by the above general formula (I), wherein the reaction is carried out in a hydrogen atmosphere using a palladium catalyst supported on C (carbon) powder. To provide.

[0022]

Embodiments of the present invention will be described below in detail. In the ether compound represented by the general formula (I) in the present invention, the alkyl or alkenyl group of a straight-chain or branched-chain carbon atoms from 10 to 30 represented by R ^2, decyl, undecyl, dodecyl, tridecyl, tetradecyl , pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, triacontyl, oleyl, hexyl decyl, groups such as octyl decyl or coconut oil, or the like mixed alkyl groups derived from tallow and the like. Among these,
A linear or branched alkyl group is preferred, and a linear alkyl group is particularly preferred.

The alkylene group having 2 to 12 carbon atoms represented by A includes ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, 2-methylpropylene, 2,2 Although groups such as' -dimethylpropylene and 3-methylpentylene are mentioned, an ethylene group is preferable. n represents a number of 0 to 30, preferably 0 to 20, and particularly preferably 0.

The ether compound represented by the general formula (I) of the present invention includes a compound represented by the following general formula (II) or (V) .

R ³ -O- (EO) _n -R ⁴ (II) wherein R ³ is

[0026]

Embedded image

Wherein R ⁴ represents a linear or branched alkyl group having a total of 16 to 28 carbon atoms of R ³ and R ⁴ ; E represents an ethylene group; n has the same meaning as described above. ] R ⁷ -O- (BO) _m -R ⁸ (V) [where R ⁷ is a formula

[0028]

Embedded image

Wherein R ⁸ is a straight-chain or branched-chain alkyl or alkenyl group having 10 to 30 carbon atoms , particularly preferably a straight-chain or branched-chain alkyl group, more preferably a straight-chain or branched-chain alkyl group. Represents an alkyl group. B has 2 to 3 carbon atoms,
It preferably represents 2 alkylene groups, and m B may be the same or different. m is a number of 1 to 30, preferably 1 to 20 indicating the average number of added moles of the alkylene oxide. In the asymmetric ether compound represented by the general formula (II), the total number of carbon atoms of R ³ and R ⁴ is 16 to 28, preferably
17-24. If the total carbon number of R ³ and R ⁴ is less than 16, irritation to the eyes occurs, and if it exceeds 28, the removability of the makeup cosmetic becomes poor, and it tends to be solid at room temperature. It is not preferred when used.

Preferable examples of the asymmetric ether compound represented by the general formula (II) include, for example, the following general formula (II)
Compounds represented by ( I) or (IV) are listed. Particularly, when used as an oil agent for removing makeup cosmetics, the general formula
The compound represented by (III) is preferred.

[0031]

Embedded image

[Wherein R ⁵ has 10 to 22 carbon atoms, preferably 12 carbon atoms.
Represents up to 18 linear or branched alkyl groups, E and n
Has the same meaning as described above. ]

[0033]

Embedded image

Wherein R ⁶ has 13 to 24 carbon atoms, preferably 14 carbon atoms.
Represents up to 20 linear or branched alkyl groups, and E and n have the same meaning as described above. As the linear or branched alkyl group having 10 to 22 carbon atoms represented by R ⁵ in the general formula (III), decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Examples thereof include groups such as eicosyl and docosyl, and mixed alkyl groups derived from coconut oil, tallow, and the like, and straight-chain alkyl groups are preferred because appropriate viscosity is obtained.

The number of carbon atoms represented by R ⁶ in the general formula (IV)
As a straight-chain or branched alkyl group of 13 to 24, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
Examples thereof include groups such as behenyl, docosyl, and tetracosyl, and mixed alkyl groups derived from coconut oil, tallow, and the like, and straight-chain alkyl groups are preferred because appropriate viscosity is obtained. Among the compounds represented by the general formula (III ) or (IV) , those having n = 0 are particularly preferred.

As a method for synthesizing the ether compound represented by the general formula (I) of the present invention, a method generally used for synthesizing a lower alkyl ether, for example, a method of reacting an alkyl halide with a metal alkoxide by Wilson (Wilson).
liamson), a method in which a carbonyl compound such as an alcohol and a ketone is reacted under a hydrogen atmosphere using a catalyst, an addition reaction of an alcohol and an olefin under an acid catalyst, or a method by reduction of an ester compound, and the like. The synthesis method is not limited to these.

Specifically, for example, as shown in the following reaction formula 1, a metal alkoxide represented by the formula (VIII) and a metal alkoxide represented by the formula (I
X) or a method of reacting a compound represented by the formula (VI) with a carbonyl compound represented by the formula (VII) using a catalyst as shown in the following reaction formula 2. The ether compound represented by the general formula (I) can be obtained by, for example, a method of reacting under a hydrogen atmosphere.

[0038]

Embedded image

(Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , A, and n have the above-mentioned meanings, M represents an alkali metal, and X represents a halogen atom.) A metal alkoxide represented by the formula (VIII) (hereinafter metal alkoxide (VIII)
Abbreviated) as 4-methyl-2-pentanol, 2
- butanol, 3,7-dimethyl octanol, 2,6
- dimethyl-4-heptanol, 2-sodium alcohol octanol le such as lithium, include metal alkoxides such as potassium, the compound represented by the formula (IX) as (hereinafter abbreviated as compound (IX)) is dodecyl bromide,
Examples include tetradecyl bromide, hexadecyl bromide, and octadecyl bromide.

In Reaction Scheme 1, the metal alkoxide (VII
Instead of reacting I) with compound (IX) , 4-methyl-
2-pentanol, 2-butanol , 3,7-dimethyloctanol, 2,6-dimethyl-4-heptanol,
An alcohol such as 2-octanol and the compound (IX) are
Particulate sodium hydroxide, particulate potassium hydroxide, 20-
The ether compound represented by the general formula (I) can also be obtained by reacting in the presence of an alkali such as a 50% by weight aqueous sodium hydroxide solution. Metal alkoxide (V
The reaction molar ratio of ( III) to compound (IX) is (VIII) :( IX) =
About 1: 1 to 1:10 is preferable. Reaction temperature is 50 ~ 150
C. and the reaction time are preferably about 5 to 20 hours. Further, a phase transfer catalyst such as tetrabutylammonium may be added.

In the method shown in the above-mentioned reaction formula 2, as a catalyst, a conventionally known hydrogenation catalyst, for example, a palladium catalyst appropriately supported on a carrier such as carbon, silica alumina, zeolite, alumina, silica, etc. Although palladium compounds such as palladium and palladium oxide can be used, a carbonyl compound represented by the formula (VI) and a carbonyl compound represented by the formula (VII) under a hydrogen atmosphere using a palladium catalyst supported on C (carbon) powder. The method of reacting with the represented hydroxy compound is particularly preferable since the ether compound can be produced in a very high yield, and the ether compound can be produced easily and inexpensively on an industrial level.

In the present invention, the catalyst is usually used by supporting it at a ratio of 2 to 10% by weight based on a carrier such as carbon, but may be used as it is without being supported on the carrier. Further, it may be a water-containing product of about 20 to 60% by weight. If the catalyst is, for example, 5% by weight supported on the carrier, the catalyst is used in an amount of 0.1 to 0.1% based on the hydroxy compound (VII) used.
It is preferred to use 10% by weight. If the amount is less than 0.1% by weight, the reaction proceeds, but the reaction is unfavorably slow. When the amount is more than 10% by weight, the reaction is fast, but on the contrary, a side reaction proceeds, which is not preferable. More preferably, it is 0.5 to 5% by weight.

Although the catalyst can be used in all pH ranges,
Since an appropriate reaction rate can be obtained, it is preferable that the pH be 1
-8, more preferably 3-7 catalysts.
The pH of the catalyst as used herein refers to the pH of an aqueous solution obtained by dispersing 2 g of the catalyst powder in 30 g of ion-exchanged water. Commercially available palladium catalysts can be used, and those previously adjusted to pH 1 to 8 can be used as they are. Further, even if the pH is higher than 8, the catalyst may be washed well with water and the alkali content may be removed. In some cases, the pH may be adjusted to 1 to 8 with an acid or the like before use. As a method for adjusting the pH of the catalyst to 1 to 8, for example, the following (a) or
A method of supporting palladium by the method (b) is exemplified. (a) A method in which a predetermined amount of activated carbon is added to an aqueous solution of palladium chloride or palladium nitrate containing hydrochloric acid, water and hydrochloric acid are removed under reduced pressure, and then dried and fired in air. (b) A method in which a predetermined amount of activated carbon is added to an aqueous solution of palladium chloride or palladium nitrate containing hydrochloric acid, water and hydrochloric acid are removed under reduced pressure, and a reduction treatment is performed in a hydrogen atmosphere.

Specifically, a predetermined amount of palladium chloride or palladium nitrate and a small amount of concentrated hydrochloric acid or dilute hydrochloric acid are dissolved in water, activated carbon is added thereto, and the mixture is sufficiently stirred, and then under reduced pressure of 1 to 200 torr. Heat-treated and then 50-150
Dried at ℃ to obtain a precursor of activated carbon supported palladium catalyst,
Then, dry in air at 200-400 ° C for 1-5 hours.
Firing or under hydrogen atmosphere for 1-5 hours, 80
By performing a reduction treatment at ~ 300 ° C, a palladium catalyst supported on activated carbon is obtained.

The formula used in the method shown in the above reaction formula 2
Examples of the carbonyl compound represented by (VI), main Chirue <br/> ethyl ketone, methyl isobutyl ketone (4-methyl-2
- pentanone), diisobutyl ketone, methylheptenone, include citronellal like.

[0046] As specific examples of the hydroxy compound represented by formula (VII), n- de sills alcohol, n- undecyl alcohol, n- dodecyl alcohol, n- tridecyl alcohol, n- tetradecyl alcohol, n -Pentadecyl alcohol, n-hexadecyl alcohol,
Linear saturated alcohols such as n-octadecyl alcohol and n-eicosyl alcohol, 2- hexyldecyl alcohol, 2-heptylundecyl alcohol, 2-octyldodecyl alcohol, 2-decyltetradecyl alcohol, 2- (1,3, 3-trimethylbutyl) -5
7,7-trimethyloctyl alcohol, the following formula

[0047]

Embedded image

(Where a and b are a + b = 14, and a = b
= A saturated branched alcohol such as methyl-branched isostearyl alcohol represented by the formula:
Octadecenyl alcohol, farnesyl alcohol,
Alkenyl alcohols such as abiethyl alcohol and oleyl alcohol, ethylene glycol monodecyl ether
Le, ethylene glycol mono dodecyl ether, ethylene glycol mono hexadecyl ether, ethylene glycol mono octadecyl ether, mono ethers of ethylene glycol such as ethylene glycol monomethyl eicosyl ether, diethylene glycol mono-decyl ether
Le, diethylene glycol dodecyl ether, diethylene glycol mono ethers such as diethylene glycol octadecyl ether, triethylene glycol
Monoethers of triethylene glycol such as ethylene glycol monodecyl ether , triethylene glycol monododecyl ether, triethylene glycol monotetradecyl ether, triethylene glycol monooctadecyl ether, propylene glycol monodecyl ether , propylene glycol monododecyl ether, propylene glycol mono hexadecyl ether, propylene glycol mono octadecyl ether, monoethers of propylene glycol such as propylene glycol monomethyl eicosyl ether, dipropylene glycol mono-decyl Agent
Ter , dipropylene glycol monododecyl ether,
Dipropylene glycol monoethers such as dipropylene glycol monooctadecyl ether ;
Monoethers of tripropylene glycol such as lenglycol monodecyl ether , tripropylene glycol monododecyl ether, tripropylene glycol monotetradecyl ether and tripropylene glycol monooctadecyl ether, and ethylene oxide, propylene oxide or butylene oxide adducts of the above alcohols And the like, but are not necessarily limited to these.

The reaction molar ratio between the carbonyl compound (VI) and the hydroxy compound (VII) is as follows : (VI) :( VII) = 1: 1 to 2
The ratio is preferably about 0: 1, more preferably 1: 1 to 5: 1. This reaction is carried out in a hydrogen atmosphere. The hydrogen pressure is preferably 5 to 250 kg / cm ² , and 5 to 150 kg / cm ² , since an appropriate reaction rate is obtained and the reduction of the carbonyl group is small.
cm ² is more preferred. The reaction temperature is preferably from 10 to 200 ° C, more preferably from 50 to 180 ° C. The reaction time is 3-25
Time is preferred, and 3-15 hours is more preferred.

In this reaction, the reaction can be carried out without using a solvent, but it can be used in the form diluted with a suitable solvent. Examples of such solvents include, for example,
hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, petroleum ether,
Inert organic solvents such as ether solvents such as n-butyl ether and n-hexyl ether can be used, but are not necessarily limited thereto.

The ether compound of the present invention represented by the general formula (I) is colorless and odorless, does not color or change its odor over time, has an excellent feel, and has a moderately low viscosity. , As a detergent composition, as an oil such as a lubricant, or moderately low viscosity, less sticky feeling, penetrant,
It is highly useful as a surfactant such as an emulsifier, solubilizer, dispersant, and detergent. Among them, the asymmetric ether compound represented by the general formula (II) has a low oily feeling, has excellent removability to makeup cosmetics, and has no irritating feeling to eyes. Particularly useful. Further, the ether compound represented by the general formula (V) is particularly useful as a surfactant such as a penetrant, an emulsifier, a solubilizer, a dispersant, and a detergent.

[0052]

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.

Example 1 Synthesis of 1,3-dimethylbutyl dodecyl ether

[0054]

Embedded image

500 equipped with a hydrogen gas inlet tube and a stirrer
93 g (0.5 mol) of dodecyl alcohol, 100 g (1.0 mol) of 4-methyl-2-pentanone in a ml autoclave,
As a catalyst, 1.9 g of 5% Pd-C (pH 6.6) was charged, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-
Methyl-2-pentanone was removed. Furthermore, vacuum distillation (1
20-122 ° C / 1 Torr) to obtain 108 g (0.40 mol) of the target 1,3-dimethylbutyl dodecyl ether as a colorless transparent liquid. The isolation yield was 80%.

The ¹ H-NMR data of the obtained 1,3-dimethylbutyl dodecyl ether are shown below. ^{· 1 H-NMR (δ:} ppm, CDCl 3) 0.82~0.98 ( overlapping doublets and triplets, 9H; a) 1.12 (2 doublets, 3H; b) 1.20~1.40 (broad singlet, 18H; c) 1.40 to 1.65 (complex multiplex, 4H; d) 1.65 to 1.87 (complex multiplex, 1H; e) 3.24 to 3.40 (complex multiplex, 1H; f) 3.38 to 3.60 (complex multiplex Wire, 2H; g)

[0057]

Embedded image

Example 2 Synthesis of 1,3-dimethylbutyl dodecyl ether 4-methyl-2-pentanol was placed in a 500 ml flask equipped with a dropping funnel, a nitrogen gas inlet tube, a cooling tube and a stirrer.
71.4 g (0.7 mol) and 36 g (0.9 mol) of particulate sodium hydroxide were charged and stirred at 80 ° C. for 1 hour under nitrogen gas introduction. Thereafter, 224 g (0.9 mol) of dodecyl bromide was added to 1
The mixture was added dropwise over time, and the temperature was further raised to 100 ° C., and the mixture was stirred for 16 hours. After completion of the reaction, the reaction mixture was washed with water to remove excess sodium hydroxide and generated salts, further, excess 4-methyl-2-pentanol and dodecyl bromide were removed under reduced pressure, and further distilled under reduced pressure (102 ° C). /0.25 Torr) and the desired 1,3-dimethylbutyl dodecyl ether 40
g (0.15 mol) was obtained as a clear, colorless liquid. The isolation yield was 21%. ¹ H-NMR data of the obtained 1,3-dimethylbutyl dodecyl ether was consistent with that obtained in Example 1.

Example 3 Synthesis of 1,3-dimethylbutyltetradecyl ether

[0060]

Embedded image

A 500 equipped with a hydrogen gas inlet tube and a stirrer
107 g of tetradecyl alcohol in a ml autoclave
(0.5 mol), 100 g (1.0 mol) of 4-methyl-2-pentanone, and 2.1 g of 5% Pd-C (pH 6.6) as a catalyst were stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ^2. Was. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, distillation under reduced pressure (143 ° C./1 Torr) was performed to obtain 112 g (0.38 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 75%.

The ¹ H-NMR data of the obtained 1,3-dimethylbutyltetradecyl ether are shown below. ^{· 1 H-NMR (δ:} ppm, CDCl 3) 0.85~1.05 ( overlapping doublets and triplets, 9H; a) 1.15 (2 doublets, 3H; b) 1.20~1.45 (broad singlet, 22H; c) 1.45 to 1.65 (complex multiplex, 4H; d) 1.65 to 1.90 (complex multiplex, 1H; e) 3.25 to 3.45 (complex multiplex, 1H; f) 3.37 to 3.10 (complex multiplex Wire, 2H; g)

[0063]

Embedded image

Example 4 Synthesis of 1,3-dimethylbutyltetradecyl ether 107 g (0.5 mol) of tetradecyl alcohol was placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
-Methyl-2-pentanone 100 g (1.0 mol), 2% Pd (OH) ₂ -C 5.35 g as a catalyst were charged, and the hydrogen pressure was 100 kg.
The mixture was stirred at 150 ° C. for 8 hours under / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2 was removed under reduced pressure.
Pentanone was removed. Further, distillation under reduced pressure (same as in Example 3) was performed to obtain 39 g (0.13 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless and transparent liquid. The isolation yield was 26%. The catalyst used here was washed well with water in advance, further washed with ethanol, and dried well before use.

Example 5 Synthesis of 1,3-dimethylbutyltetradecyl ether 107 g (0.5 mol) of tetradecyl alcohol was placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
100 g (1.0 mol) of -methyl-2-pentanone and 2.1 g of 5% Pd-zeolite (pH 6.47) were charged as a catalyst, and the mixture was stirred at 150 ° C for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-
Methyl-2-pentanone was removed. Further, vacuum distillation (the same as in Example 3) was performed to obtain 28 g (0.095 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless and transparent liquid. The isolation yield was 19%.

Example 6 Synthesis of 1,3-dimethylbutyltetradecyl ether 107 g (0.5 mol) of tetradecyl alcohol was placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
100 g (1.0 mol) of -methyl-2-pentanone and 2.1 g of 5% Pd-silica alumina (pH 7.97) were charged as a catalyst, and the mixture was stirred at 150 ° C for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, by silica gel column chromatography,
3.0 g of 3-dimethylbutyltetradecyl ether (0.01
Mol) was obtained as a clear, colorless liquid. The isolation yield was 2%.

Example 7 Synthesis of 1,3-dimethylbutyltetradecyl ether 107 g (0.5 mol) of tetradecyl alcohol was placed in a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer.
100 g (1.0 mol) of -methyl-2-pentanone and 2.1 g of 5% Pd-alumina (pH 5.00) were charged as a catalyst, and the mixture was stirred at 150 ° C for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, distillation under reduced pressure (same as in Example 3) was performed to obtain 33 g (0.11 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless transparent liquid. The isolation yield was 22%.

Example 8 Synthesis of 1,3-dimethylbutyltetradecyl ether In a 500 ml autoclave equipped with a hydrogen gas inlet tube and a stirrer, 107 g (0.5 mol) of tetradecyl alcohol,
100 g (1.0 mol) of methyl-2-pentanone, 2.1 g of 5% Pd-C (pH 10.26) were charged as a catalyst, and hydrogen pressure was 100
The mixture was stirred at 150 ° C. for 8 hours under kg / cm ² . After the reaction,
The catalyst was removed by filtration and the excess 4-methyl-
2-Pentanone was removed. Further, distillation under reduced pressure (same as in Example 3) was performed to obtain 28 g (0.094 mol) of the target 1,3-dimethylbutyltetradecyl ether as a colorless and transparent liquid. The isolation yield was 19%.

Example 9 Synthesis of 1,3-dimethylbutylhexadecyl ether

[0070]

Embedded image

A 500 equipped with a hydrogen gas inlet tube and a stirrer
Hexadecyl alcohol 121g in ml autoclave
(0.5 mol), 100 g (1.0 mol) of 4-methyl-2-pentanone and 2.4 g of 5% Pd-C (pH 6.6) as a catalyst were stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ^2. Was. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. Further, vacuum distillation (142 ° C./0.6 Torr) was performed to obtain 114 g (0.35 mol) of the target 1,3-dimethylbutylhexadecyl ether as a colorless and transparent liquid. The isolation yield was 70%.

The ¹ H-NMR data of the obtained 1,3-dimethylbutylhexadecyl ether are shown below. ¹ H-NMR (δ: ppm, CDCl ₃ ) 0.80 to 1.05 (overlap of doublet and triplet, 9H; a) 1.11 (doublet, 3H; b) 1.17 to 1.40 (wide singlet, 26H; c) 1.40 to 1.65 (complex multiplex, 4H; d) 1.65 to 1.90 (complex multiplex, 1H; e) 3.20 to 3.40 (complex multiplex, 1H; f) 3.35 to 3.60 (complex multiplex Wire, 2H; g)

[0073]

Embedded image

Example 10 Synthesis of 1,3-dimethylbutyloctadecyl ether

[0075]

Embedded image

A 500 equipped with a hydrogen gas inlet tube and a stirrer
108 g of octadecyl alcohol in a ml autoclave
(0.4 mol), 80 g (0.8 mol) of 4-methyl-2-pentanone, 2.2 g of 5% Pd-C (pH 4.0) as a catalyst, and stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ^2. Was. After completion of the reaction, the catalyst was removed by filtration, and excess 4-methyl-2-pentanone was removed under reduced pressure. further,
Purification by silica gel column chromatography to 1,3-dimethylbutyl octadecyl ether 106
g (0.30 mol) was obtained as a clear, colorless liquid. The isolation yield was 75%.

The ¹ H-NMR data of the obtained 1,3-dimethylbutyl octadecyl ether are shown below. ¹ H-NMR (δ: ppm, CDCl ₃ ) 0.85 to 0.95 (overlap of doublet and triplet, 9H; a) 1.12 (doublet, 3H; b) 1.20 to 1.40 (wide singlet, 30H C) 1.40 to 1.65 (complex multiplex, 4H; d) 1.65 to 1.87 (complex multiplex, 1H; e) 3.28 to 3.40 (complex multiplex, 1H; f) 3.37 to 3.60 (complex multiplex , 2H; g)

[0078]

Embedded image

Example 11 Synthesis of 1,3-dimethylbutyl octadecyl ether 4-methyl-2-pentanol was placed in a 500 ml flask equipped with a dropping funnel, a nitrogen gas inlet tube, a condenser tube and a stirrer.
51 g (0.5 mol) and 26 g (0.65 mol) of particulate sodium hydroxide were charged and stirred at 80 ° C. for 1 hour under nitrogen gas introduction. Thereafter, 216 g (0.65 mol) of octadecyl bromide was added dropwise over 1 hour, and the temperature was further raised to 100 ° C.
Stirring was performed for hours. After completion of the reaction, the reaction mixture is washed with water,
Excess sodium hydroxide and generated salts were removed, and excess 4-methyl-2-pentanol and octadecyl bromide were removed under reduced pressure. This was further purified by silica gel column chromatography to obtain the desired 1,1
27 g of 3-dimethylbutyl octadecyl ether (0.075
Mol) was obtained as a clear, colorless liquid. The isolation yield was 15%. ¹ H-NMR data of the obtained 1,3-dimethylbutyl octadecyl ether was consistent with that obtained in Example 10.

Example 12 Synthesis of 1-methylpropyltetradecyl ether

[0081]

Embedded image

500 equipped with a hydrogen gas inlet tube and a stirring device
107 g of tetradecyl alcohol in a ml autoclave
(0.5 mol), 72 g (1.0 mol) of methyl ethyl ketone, and 2.1 g of 5% Pd-C (pH 4.0) as a catalyst.
The mixture was stirred at 150 ° C. under 100 kg / cm ² for 8 hours. After completion of the reaction, the catalyst was removed by filtration, and excess methyl ethyl ketone was removed under reduced pressure. Further, the residue was purified by silica gel column chromatography to obtain 103 g (0.38 mol) of the target 1-methylpropyltetradecyl ether as a colorless transparent liquid. The isolation yield was 76%.

The ¹ H-NMR data of the obtained 1-methylpropyltetradecyl ether are shown below. ¹ H-
NMR (δ: ppm, CDCl ₃ ) 0.72-0.98 (two triplets, 6H; a) 1.13 (doublet, 3H; b) 1.20-1.40 (broad singlet, 22H; c) 1.40-1.70 ( Complex multiplet, 4H; d) 3.20 to 3.40 (Complex multiplet, 2H; e) 3.35 to 3.55 (Complex multiplet, 1H; f)

[0084]

Embedded image

Example 13 Synthesis of 1-methylpropyltetradecyl ether 37 g (0.5 mol) of 2-butanol and 32 g of particulate sodium hydroxide were placed in a 500 ml flask equipped with a dropping funnel, a nitrogen gas inlet tube, a condenser tube and a stirrer. (0.8 mol), and the mixture was stirred at 80 ° C. for 1 hour under nitrogen gas introduction. afterwards,
222 g (0.8 mol) of tetradecyl bromide was added dropwise over 1 hour, the temperature was further raised to 100 ° C., and the mixture was stirred for 20 hours. After the completion of the reaction, the reaction mixture was washed with water to remove excess sodium hydroxide and generated salts, excess 2-butanol and tetradecyl bromide were removed under reduced pressure, and further purified by silica gel column chromatography.
35 g of desired 1-methylpropyltetradecyl ether
(0.13 mol) was obtained as a colorless transparent liquid. The isolation yield is
25%. The ¹ H-NMR data of the obtained 1-methylpropyltetradecyl ether was consistent with that obtained in Example 12 .

Example 14 Synthesis of 1-methylpropyl octadecyl ether

[0087]

Embedded image

A 500 equipped with a hydrogen gas inlet tube and a stirrer
135 g of octadecyl alcohol in a ml autoclave
(0.5 mol), 100 g (1.0 mol) of methyl ethyl ketone and 2.7 g of 5% Pd-C (pH 4.0) as a catalyst were stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess methyl ethyl ketone was removed under reduced pressure. Furthermore, distillation under reduced pressure (160 ° C / 0.35
Torr) to obtain 109 g (0.33 mol) of the desired 1-methylpropyl octadecyl ether as a colorless and transparent liquid. The isolation yield was 66%.

The ¹ H-NMR data of the obtained 1-methylpropyl octadecyl ether are shown below. ¹ H-NMR (δ: ppm, CDCl ₃ ) 0.84 to 1.00 (two triplets, 6H; a) 1.13 (doublet, 3H; b) 1.20 to 1.43 (wide singlet, 30H; c) 1.43 to 1.70 (complex multiplex, 4H; d) 3.20 to 3.43 (complex multiplex, 2H; e) 3.36 to 3.57 (complex multiplex, 1H; f)

[0090]

Embedded image

Example 15 Synthesis of triethylene glycol-1-methylpropyl dodecyl ether

[0092]

Embedded image

500 equipped with a hydrogen gas inlet tube and a stirring device
127 g (0.4 mol) of triethylene glycol monododecyl ether and methyl ethyl ketone 58
g (0.8 mol) and 2.5 g of 5% Pd—C (pH 4.0) as a catalyst were stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess methyl ethyl ketone was removed under reduced pressure. Further, the target triethylene glycol-1-methylpropyl dodecyl ether was subjected to silica gel column chromatography.
112 g (0.3 mol) were obtained as a clear, colorless liquid. The isolation yield was 75%.

¹ H-NMR data of the obtained triethylene glycol-1-methylpropyl dodecyl ether are shown below. ^{· 1 H-NMR (δ;} ppm, CDCl 3) 0.85~1.10 (2 three doublets; 6H, a) 1.10~1.20 (2 doublets; 3H, b) 1.20~1.85 (and complex broad singlet Multiplet; 22H, c) 3.25 to 3.90 (Complex multiplet; 15H, d)

[0095]

Embedded image

Example 16 Synthesis of triethylene glycol-1,3-dimethylbutyl dodecyl ether

[0097]

Embedded image

500 equipped with a hydrogen gas inlet tube and a stirring device
127 g (0.4 mol) of triethylene glycol monododecyl ether, 80 g (0.8 mol) of methyl isobutyl ketone, 5% Pd-C (pH 4.0) 2.5
g, and the mixture was stirred at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess methyl isobutyl ketone was removed under reduced pressure. Further, by silica gel column chromatography, 112 g (0.28 mol) of the target triethylene glycol-1,3-dimethylbutyl dodecyl ether was obtained as a colorless and transparent liquid. The isolation yield was 70%.

The obtained triethylene glycol-1,3
¹ H-NMR data of -dimethylbutyl dodecyl ether is shown below. ¹ H-NMR (δ; ppm, CDCl ₃ ) 0.80 to 1.05 (overlap of doublet and triplet; 9H, a) 1.10 (doublet; 3H, b) 1.17 to 1.40 (wide singlet; 18H, c) 1.40 to 1.90 (complex multiplex; 5H, d) 3.25 to 3.90 (complex multiplex; 15H, e)

[0100]

Embedded image

Example 17 Synthesis of polyoxyethylene (average number of moles of added ethylene oxide: 9) -1-methylpropyl dodecyl ether

[0102]

Embedded image

In a 1-liter autoclave equipped with a hydrogen gas inlet tube and a stirrer, 200 g (0.34 mol) of ethylene oxide adduct of dodecyl alcohol (average number of moles of ethylene oxide added: 9 mol), methyl ethyl ketone
97 g (1.34 mol), anhydrous magnesium sulfate 5.8 g (0.05
Mol) and 4 g of 5% Pd-C (pH 4.0) as a catalyst, and reacted at 150 ° C. for 7 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess methyl ethyl ketone was removed under reduced pressure to obtain 202 g of the desired polyoxyethylene (average number of moles of ethylene oxide added: 9) -1-methylpropyl dodecyl ether. The isolation yield was 98%.

[0104]

Embedded image

¹ H-NMR (δ; ppm, CDCl ₃ ) 0.83 (m, 6H, a), 1.15 (d, 3H, b), 1.27 (broad, 18H,
c), 1.58 (broad, 4H, d), 3.51 (broad, 3H, e), 3.65 (m, 36
H, f) Example 18 Synthesis of polyoxyethylene (average number of moles of ethylene oxide added 9) -1,3-dimethylbutyl dodecyl ether

[0106]

Embedded image

In a 1-liter autoclave equipped with a hydrogen gas inlet tube and a stirring device, 150 g (0.26 mol) of ethylene oxide adduct of dodecyl alcohol (average number of moles of ethylene oxide added: 9 mol), 350 g (3.5 mol) of methyl isobutyl ketone , Anhydrous magnesium sulfate 8.6
g and 5 g of Pd-C (pH 4.0) as a catalyst were charged and reacted at 150 ° C. for 7 hours under a hydrogen pressure of 100 kg / cm ² .
After completion of the reaction, the catalyst was removed by filtration, and excess methyl isobutyl ketone was removed under reduced pressure to obtain the desired polyoxyethylene (average number of moles of ethylene oxide added: 9) -1,3-dimethylbutyl dodecyl ether 17
1 g was obtained. The isolation yield was 97%.

[0108]

Embedded image

¹ H-NMR (δ; ppm, CDCl ₃ ) 0.81 (m, 9H, a), 1.12 (d, 3H, b), 1.25 (broad, 18H,
c), 1.55 (broad, 4H, d), 1.70 (m, 1H, e), 3.50 (broad, 3
H, f), 3.61 (m, 36H, g) Example 19 Synthesis of polyoxyethylene (average number of moles of ethylene oxide added: 12) -3,7-dimethyloctyldodecyl ether

[0110]

Embedded image

In a 1-liter autoclave equipped with a hydrogen gas inlet tube and a stirrer, 200 g (0.28 mol) of ethylene oxide adduct of dodecyl alcohol (average number of added ethylene oxide; 12 mol), citronellal 345
g (2.24 mol), 8.5 g of anhydrous magnesium sulfate, and 6 g of 5% Pd-C (pH 4.0) as a catalyst.
The reaction was carried out at 150 ° C. for 6 hours under 0 kg / cm ² . After the reaction,
The catalyst was removed by filtration, and excess citronellal was removed under reduced pressure to obtain 224 g of the objective polyoxyethylene (average number of moles of added ethylene oxide: 12) -3,7-dimethyloctyldodecyl ether. The isolation yield was 94%.

[0112]

Embedded image

¹ H-NMR (δ; ppm, CDCl ₃ ) 0.81 (m, 12H, a), 1.27 (broad, 24H, b), 1.55 (broad,
4H, c), 1.72 (m, 2H, d), 3.51 (m, 4H, e), 3.65 (m, 48H, f) Example 20 Polyoxyethylene (average number of moles of ethylene oxide added 9) -1-isobutyl Synthesis of -3-methylbutyl dodecyl ether

[0114]

Embedded image

In a 1-liter autoclave equipped with a hydrogen gas inlet tube and a stirrer, 150 g (0.26 mol) of ethylene oxide adduct of dodecyl alcohol (average number of moles of ethylene oxide added: 9 mol), diisobutyl ketone
293 g (2.1 mol), 8.4 g of anhydrous magnesium sulfate and 6 g of 5% Pd-C (pH 4.0) were charged as a catalyst, and reacted at 150 ° C. for 8 hours under a hydrogen pressure of 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess diisobutyl ketone was removed under reduced pressure, whereby the desired polyoxyethylene (average number of moles of ethylene oxide added 9) -1
-Isobutyl-3-methylbutyldodecyl ether 165
g was obtained. The isolation yield was 92%.

[0116]

Embedded image

¹ H-NMR (δ; ppm, CDCl ₃ ) 0.87 (m, 15H, a), 1.29 (broad, 18H, b), 1.57 (broad,
6H, c), 1.69 (m, 2H, d), 3.50 (m, 3H, e), 3.63 (m, 36H, f) Example 21 Polyoxyethylene (average number of moles of ethylene oxide added 9) -1-methyl Synthesis of heptyldodecyl ether

[0118]

Embedded image

In a 1-liter autoclave equipped with a hydrogen gas inlet tube and a stirrer, 150 g (0.26 mol) of ethylene oxide adduct of dodecyl alcohol (average number of moles of ethylene oxide added: 9 mol), methylheptenone 2
62 g (2.1 mol), 8.5 g of anhydrous magnesium sulfate, 6 g of 5% Pd-C (pH 4.0) as a catalyst were charged, and hydrogen pressure was adjusted.
The reaction was carried out at 150 ° C. for 7 hours under 100 kg / cm ² . After completion of the reaction, the catalyst was removed by filtration, and excess methylheptenone was removed under reduced pressure, whereby the desired polyoxyethylene (average number of moles of ethylene oxide added 9) -1-
165 g of methylheptyldodecyl ether were obtained. The isolation yield was 92%.

[0120]

Embedded image

¹ H-NMR (δ; ppm, CDCl ₃ ) 0.81 (m, 6H, a), 1.14 (d, 3H, b), 1.26 (broad, 26H,
c), 1.55 (broad, 4H, d), 3.49 (broad, 3H, e), 3.60 (broa
d, 36H, f) Test Example 1 With respect to the asymmetric ether compound of the present invention obtained in Examples 1, 3, 9, 10, 12, 14, and 17 , the odor, color, change over time of odor, feel, and viscosity are as follows. Was evaluated.
In addition, general-purpose oil agents shown in Table 1 were similarly evaluated as comparative products. Table 1 shows the results.

<Evaluation Method> (1) Odor was evaluated according to the following criteria. ：: Odorless Δ: Slightly odor X: Smell (2) After standing at 50 ° C. for 1 week, color and odor were evaluated according to the following criteria. ：: no change Δ: slight change ×: change (3) Feeling was evaluated according to the following criteria. ：: Not sticky Δ: Slightly sticky X: Sticky (4) The viscosity was evaluated according to the following criteria. ○: less than 10 cps (good spread) △: 10 to 20 cps (slightly poor spread) ×: bigger than 20 cps (poor spread)

[0123]

[Table 1]

As is clear from Table 1, the asymmetric ether compound of the present invention has no odor, does not color or change its odor over time, has no stickiness, has a moderately low viscosity, and has good spreadability. Understand.

Test Example 2 Using the asymmetric ether compounds obtained in Examples 1, 3, 9, 10, 12, 14 , and 17 , the removability of oily mascara and the feeling of irritation to eyes were evaluated by the following methods. As a comparative product, a conventional general-purpose oil agent was similarly evaluated. Table 2 shows the results.

<Evaluation method> (1) Removal of oily mascara: An oily mascara having the following composition was applied to a slide glass with a radius of about 2
Approximately 20 mg is applied in a circle of cm, and left overnight to dry.
A mascara-free slide glass is placed on white paper, and the color is measured with a colorimeter CR-300 (manufactured by Minolta) (E ₀ ).
Next, a slide glass coated with mascara is placed, and the color of the mascara stain before washing is measured (E ₁ ). Thereafter, 200 μl of each oil (asymmetric ether compound of the present invention and comparative general oil) is applied to the mascara stain, massaged 40 times to float the stain, and wiped off with tissue paper. Finally, the colorimetry is performed at the place where the colorimetry was performed first (E ₂ ). Using the color difference thus measured, the removal rate was determined by the following formula.

[0127]

(Equation 1)

(Oil-based mascara composition) Carnauba wax 7.0 (%) Beeswax 2.0 Microcrystalline wax 20.0 Lanolin 0.4 Light fluid polyisobutene 60.6 Carbon black 10.0 ────────── Total 100.0 (2) Eye irritation: Have the above-mentioned oily mascara applied to eyelashes by 5 specialized panelists and let it dry for 6 hours. After drying, 0.5 g of each oil agent (asymmetric ether compound of the present invention and comparative general oil agent) was impregnated into absorbent cotton, and the eyelids were massaged from above the closed eyes to remove mascara. During the massage around the eyes, the presence or absence of irritation to the eyes was evaluated according to the following criteria. None: All five people answered that there was no irritation Yes: One person answered that there was irritation

[0129]

[Table 2]

As is clear from Table 2, the asymmetric ether compound of the present invention is excellent in removing oily mascara and has no irritating effect on eyes.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideharu Morimoto 2-1-3 Bunka, Sumida-ku, Tokyo Kao Co., Ltd. (72) Inventor Mitsuru Uno 1334 Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd. ) References Justus Liebigs Ann. Chem. (1973), (7), p. 1156-p. 1178 (58) Field surveyed (Int.Cl. ⁷ , DB name) C07C 43 / 04,43 / 11 C07C 43 / 15,43 / 18 C07C 41 / 01,41 / 05 B01J 23 / 44,29 / 068 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. An ether compound represented by the general formula (I). R ¹ —O— (AO) _n —R ² (I) wherein R ¹ is a group of the formula Wherein R ² represents a linear or branched alkyl or alkenyl group having 10 to 30 carbon atoms. A represents an alkylene group having 2 to 12 carbon atoms, and n A's may be the same or different. n shows the number of 0-30. Where R ¹ is of the formula When n = 0 in the group represented by the formula, the total carbon number of R ¹ and R ² is 16 to
36 and R ¹ is of the formula When n = 0 in the group represented by the formula, the total carbon number of R ¹ and R ² is 17 to
34. Further, R ¹ and R ² is ## STR4 ## In the group represented by, A is an alkylene group having 5 to 12 carbon atoms,
And and n is 1, and R ¹ is embedded image Wherein R ² is an alkyl group having 9 to 14 carbon atoms,
Excluding those for which n is 0. ] 2. An ether compound represented by the general formula (I) is represented by the general formula (II): R ³ —O— (EO) _n —R ⁴ (II)
R ³ is of the formula Wherein R ⁴ has a total carbon number of R ³ and R ⁴ of 16 to
A linear or branched alkyl group such as 28,
Represents an ethylene group, and n has the same meaning as described above. The ether compound according to claim 1, which is an asymmetric ether compound represented by the formula: 3. The ether compound according to claim 2, wherein the asymmetric ether compound represented by the general formula (II) is a compound represented by the general formula (III). Embedded image [In the formula, R ⁵ represents a linear or branched alkyl group having 10 to 22 carbon atoms, and E and n have the same meaning as described above. ] 4. The ether compound according to claim 2, wherein the asymmetric ether compound represented by the general formula (II) is a compound represented by the general formula ( IV) . Embedded image [ Wherein , R ⁶ represents a linear or branched alkyl group having 13 to 24 carbon atoms, and E and n have the same meanings as described above. ] 5. An ether compound represented by the general formula (I) is represented by the general formula (V): R ⁷ -O- (BO) _m -R ⁸ (V) wherein R ⁷ is a group represented by the formula: Wherein R ⁸ is a linear or branched alkyl or alkenyl group having 10 to 30 carbon atoms. B represents an alkylene group having 2 to 3 carbon atoms, and m B may be the same or different. m is a number of 1 to 30 indicating the average number of added moles of alkylene oxide. The ether compound according to claim 1, which is a compound represented by the formula: 6. A compound of the general formula (VI) [ Wherein R ⁹ and R ¹⁰ are such that R ⁹ is a methyl group and R ¹⁰ is a compound of the formula: Wherein R ⁹ and R ¹⁰ both represent a group of the formula Or R ⁹ is a hydrogen atom, and R ¹⁰ is a group represented by the formula Represents a group represented by ] And a carbonyl compound represented by the general formula _{(VII) HO- (AO) n} -R 2 (VII) wherein, R ^2, A, n have the same meanings as defined above. The reaction of the ether compound according to any one of claims 1 to 5 , wherein the reaction is carried out under a hydrogen atmosphere using a palladium catalyst supported on C (carbon) powder. Production method.