JP2671389B2 - Sorbitol compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel sorbitol compound.

The compound of the present invention acts to solidify a liquid such as oil,
It has so-called gelling ability and is useful as a gelling agent, and also has the effect of increasing the transparency and rigidity of the resin, the effect of increasing the viscosity of paints, and the effect of stabilizing emulsions such as emulsions.

[Conventional technology]

Conventionally, dibenzylidene sorbitol and the like have been known as sorbitol compounds, and they have been used as gelling agents and the like. The gelling agent has a function of causing the fluidity of the fluid to be lost and solidifying into a jelly, and for example, it can be used as an oil gelling agent such as a recovering agent for oil spilled at sea or a coagulating agent for waste oil. Is used in the fields of food, cosmetics, etc.

In addition to sorbitols such as diberylidene sorbitol, the main known agents include fatty acid metal salts such as aluminum stearate, hydroxystearic acids, amino acids such as dibutylamide N-lauroyglutamic acid, Etc.

[Problems to be solved by the invention]

However, the performance of these gelling agents is still insufficient, and the advent of higher performance gelling agents has been desired. The present invention is intended to provide a sorbitol compound having a novel structure and having performances selected from conventional gelling agents.

[Means for solving the problem]

The present invention provides a sorbitol compound having a novel structure represented by the following general formula [I].

[In the formula, _one of R ₁ and R ₂ is an alkyl, aryl, or aralkyloxycarbonyl group, and the other is a hydrogen atom, a chlorine atom, or a hydroxyl group, a group selected from an alkyl group and an alkoxy group. is there. In the above general formula [I], it is essential that either one of R ₁ and R ₂ is an ester group of a carboxylic acid represented by CO ₂ R ′, and R ₁ and R _{2 in} the benzene nucleus are The substitution position may be an ortho position, a meta position, or a para position. −CO ₂ R ′
The ester group R ′ represented by is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
And an aralkyl group having 7 to 20 carbon atoms, specifically,
Examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, cyclohexylphenyl, and naphthyl ester. When the other of R ₁ and R ₂ is an alkyl group, it is preferably an alkyl group having 1 to 8 carbon atoms, specifically, methyl, ethyl, propyl,
Examples thereof include butyl, hexyl, octyl and cyclohexyl groups. Further, when it is an alkoxy group, it is preferable that the alkyl part thereof has 1 to 8 carbon atoms, and specifically,
Methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, cyclohexyloxy groups and the like can be mentioned.

As a typical example of the compound of the present invention represented by the above general formula [I], one in which the other of R ₁ and R ₂ is a hydrogen atom is 1,3
-(P-Methoxycarbonylbenzylidene) -2,4-benzylidene sorbitol, 1,3-benzylidene-2,4-
Examples of the alkyl group such as (p-methoxycarbonylbenzylidene) sorbitol include 1,3- (p-methoxycarbonylbenzylidene) -2,4- (p-methylbenzylidene) sorbitol and 1,3- (p- Methoxycarbonylbenzylidene) -2,4- (p-ethylbenzylidene) sorbitol, 1,3- (p-methylbenzylidene) -2,4- (p-methoxycarbonylbenzylidene)
Sorbitol, 1,3- (p-ethylbenzylidene) -2,4
Examples of alkoxy groups such as-(p-methoxycarbonylbenzylidene) sorbitol include 1,3- (p-methoxycarbonylbenzylidene) -2,4- (p-methoxybenzylidene) sorbitol and 1,3- (p- Methoxybenzylidene) -2,4- (p-methoxycarbonylbenzylidene) sorbitol and the like have a hydroxyl group as 1,3- (p-methoxycarbonylbenzylidene)-
2,4- (p-hydroxybenzylidene) sorbitol,
1,3- (p-hydroxybenzylidene) -2,4- (p-methoxycarbonylbenzylidene) sorbitol, etc.
The chlorine atom includes 1,3- (p-methoxycarbonylbenzylidene) -2,4- (p-chlorobenzylidene) sorbitol, 1,3- (p-chlorobenzylidene) -2,4- ( p-methoxycarbonylbenzylidene) sorbitol and the like.

Among the compounds represented by the general formula [I],
It is preferable that _{one of} R ₁ and R ₂ is an alkyloxycarbonyl group, particularly a lower alkyl ester group, and the other is a hydrogen atom or an alkyl group.

〔Production method〕

The compound of the present invention represented by the above general formula [I] can be produced, for example, by the reaction shown in the following formula.

Specifically, first, sorbitol and 1 equivalent of benzaldehyde with respect to sorbitol. To obtain a compound [II] by subjecting the compound to a compound [II]
To 1 equivalent of benzaldehyde To produce the compound [I] of the present invention. still,
R ₁ and R ₂ have the same meaning as in formula [I], and one of the benzaldehydes having a —CO ₂ R ′ substituent is used. In the above two-step reaction, once the compound [II]
It is also possible to produce the compound [I] of the present invention by continuously performing the same in the same reactor without isolation.

In the reaction of the formula (1), the amount of benzaldehydes used is 0.8 to 1.1 molar equivalents to sorbitol, and an acid such as hydrochloric acid, sulfuric acid or p-toluenesulfonic acid is used as a catalyst, and 0.5 to 10 mols relative to sorbitol. %. As the solvent, water or a mixed solvent of water and an organic solvent such as dioxane or tetrahydrofuran, which is miscible with water, and water is used, and the amount thereof is 0.2 to 50 times by weight that of sorbitol. The reaction temperature is 20 ° C to 60 ° C, and the reaction time is about 3 to 12 hours.

In the reaction of the formula (2), the amount of benzaldehydes is 0.8 to 1.1 molar equivalents with respect to the compound [II], the acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid is used as the catalyst, and the compound [II] is used. ] To 0.5 to 10 mol%. As the solvent, benzene, toluene, cyclohexane, an organic solvent such as dialkyl ether, or a mixed solvent of these and water is used, and the amount thereof is 0.
2 to 50 times the weight. The reaction temperature is 40 to 100 ° C, and the reaction time is about 3 to 12 hours. In the above reaction, the condensation reaction of the first step occurs selectively at the positions of sorbitol 2 and 4 as shown in the above reaction.
Confirmed by NMR spectrum analysis.

〔The invention's effect〕

The sorbitol compound represented by the above general formula [I] of the present invention forms a gel even in a small addition amount as compared with a conventional gelling agent, and particularly, N, N-dimethylformamide, dimethyl sulfoxide and other highly polar compounds are used. It is a compound having a high gelling ability, which is not a conventional gelling agent capable of solidifying the organic solvent described above. Further, in general, a gelling agent having a high gelling ability does not have good solubility, but the sorbitol compound of the present invention is also one of the notable features that the solubility is extremely good.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to experimental examples.

Example 1 [1,3- (p-methoxycarbonylbenzylidene) -2,4
-Benzylidene sorbitol] In a 200 ml flask, 36.4 g (0.2 mol) of D-sorbitol, 24 ml of water, 21.2 g (0.2 mol) of benzaldehyde and 2.3 g (0.012 mol) of p-toluenesulfonic acid hydrate were placed and placed under a nitrogen atmosphere. The mixture was stirred at 35 ° C for 6 hours. After cooling to 20 ° C, water is added to the white creamy reaction mixture.
0 ml and 0.5 g of sodium hydroxide were added, and the mixture was stirred at room temperature. The white slurry was filtered, the obtained white solid was thoroughly washed with water and ether, and dried to obtain 46.4 g of a white powder of 2,4-benzylidenesorbitol (yield 85.9.
%).

Next, in a flask No. 2 equipped with a Dean-Stark type fractionating tube and a powerful stirrer, 46.4 g (0.17 mol) of the above 2,4-benzylidene sorbitol and 2 parts of methyl p-formylbenzoate were added.
7.9 g (0.17 mol), benzene 800 ml, and p-toluenesulfonic acid monohydrate 0.32 g (1.7 mmol) were added, and the mixture was heated with stirring at a benzene reflux temperature (77 ° C.) for 6 hours under a nitrogen atmosphere. During the reaction, water distilled out of the fractionating tube was withdrawn as needed. After the reaction, after cooling to room temperature, 300 ml of water and 70 ml of sodium hydroxide were added to the reaction solution showing a white gel form.
Was added and the mixture was stirred at room temperature. The white slurry is filtered,
The obtained white solid was washed with warm water of about 70 ° C. and ethanol and dried to obtain 65.8 g of a white powder of the target 1,3- (p-methoxycarbonylbenzylidene) -2,4-benzylidenesorbitol. 92.0%) Total yield from D-sorbitol 79.0%.

 The measurement results of the physical properties are as follows.

Melting point 204.0 to 208.5 ° C ¹ H-NMR (DMSO-d ₆ ) δ (ppm) 7.98 (2H, d), 7.61 (2H, d), 7.44 to 7.48 (2H, m), 7.
35 ~ 7.39 (3H, m), 5.76 (1H, s), 5.67 (1H, s), 4.81
(1H, d), 4.77 (1H, t), 3.45 ~ 4.36 (8H, m), 3.86
(3H, s).

Mass spectrum m / e (relative intensity) 416 (4.0, M ⁺ ), 385 (3.5), 355 (6.8), 267 (6.
8), 267 (6.8), 207 (14), 149 (78), 105 (10
0), 91 (76), 77 (35).

Example 2 [1,3- (p-methoxycarbonylbenzylidene) -2,4
-(P-Methylbenzylidene) sorbitol] D-sorbitol 54.6 g (0.3 mol), water 36 ml, p-tolualdehyde 36.0 (0.3 mol) and p-toluenesulfonic acid hydrate 3.4 g (0.018 mol) were used, The same operation as in Example 1 was performed to obtain 75.5 g of white powder of 2,4- (p-methylbenzylidene) sorbitol (yield 88.6%).

Next, 2,4- (p-methylbenzylidene) sorbitol 7
5.5g (0.27mol), methyl p-formylbenzoate 44.3g
Example 1 using (0.27 mol), 1,200 ml of benzene and 0.51 g (2.7 mmol) of p-toluenesulfonic acid monohydrate.
The same operation was performed to obtain 107.4 g of white powder of 1,3- (p-methoxycarbonylbenzylidene) -2,4- (p-methylbenzylidene) sorbitol (yield 94.5%). D
-Total yield from sorbitol 83.3%.

 The physical properties were as follows.

Melting point 216.0 to 219.0 ° C ¹ H-NMR (DMSO-d ₆ ) δ [ppm] 7.99 (2H, d), 7.61 (2H, d), 7.35 (2H, d), 7.19 (2
H, d), 5.75 (1H, s), 5.62 (1H, s), 4.81 (H, d), 4.
77 (1H, t), 3.41 to 4.37 (8H, m), 3.87 (3H, s) 2.30
(3H, s).

Mass spectrum m / e (relative intensity) 430 (8.1, M ⁺ ), 399 (3.5), 369 (6.2), 250 (4.
3), 207 (23), 163 (49), 119 (100), 105 (57).

Application Examples 1 and 2 and Comparative Example 1 To r-butyrolactone, a predetermined amount of 1,3: 2,4-dibenzylidene sorbitol as the compound of the present invention and the comparative compound obtained in Examples 1 and 2 was added and heated. Once dissolved, the mixture was cooled to room temperature and left standing overnight to form a gel.
The minimum amount required to form a gel, the temperature and time required to once dissolve it, and the shape of the gel produced are summarized in Table 1.

Application Examples 3 and 4 and Comparative Example 2 In place of γ-butyrolactone, N, N-dimethylformamide is used, and gelation results are shown in Table 2 in the same manner as in Application Examples 1 and 2. It should be noted that 1,3: 2,4-dibenzylidene sorbitol did not form a gel even with the addition amount of 10 wt%.

Claims (1)

(57) [Claims] 1. A compound of the formula [I] [In the formula, _one of R ₁ and R ₂ is an alkyl, aryl, or aralkyloxycarbonyl group, and the other is a hydrogen atom, a chlorine atom, or a hydroxyl group, a group selected from an alkyl group and an alkoxy group. is there. ] The sorbitol compound represented by these.