JPS6039340B2 - Liquid branched chain higher aliphatic 1↓-ol and its production method - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula [1] X-C ratio -CH=CH-Z-CH20 days [1] (
In the formula, X is CQCH2CH2 or. ) and a method for producing the liquid branched higher aliphatic 1-ol. Generally, aliphatic monools having 11 to 25 carbon atoms are used as fragrances,
It is a useful compound that has a variety of uses, such as disinfectants or their intermediate raw materials, cosmetic raw materials, and surfactants. Conventionally, 1-ols having 11 to 25 carbon atoms have rarely been commercialized because the unsaturated hydrocarbons forming their basic skeletons are difficult to synthesize and separate. On the other hand, the present inventors succeeded in synthesizing alternating oligomers of Q-olefin and conjugated diolefin, and found that the number of carbon atoms is 10 to 31.
We have developed a method to easily produce polyene compounds with high yield and high selectivity. Among these, as one of the challenges for developing applications for polyene compounds having 10 carbon atoms, we have discovered a method for easily synthesizing a new 1-ol. The novel liquid branched chain higher aliphatic 1-ol of the present invention is useful as a raw material for antibacterial agents, fragrances, high-grade cosmetics, or intermediate raw materials thereof.
Specific examples of the 1-ols of the present invention include 3-methylene-5-decen-1-ol; 3-methyl-3,5-decadien-1-ol; 3-methylene-8-methyl-5nonen-1-ol; 3,8-dimethyl- It is 3,5 nonadiene-1-ol. 1-ol represented by the formula [1] of the present invention can be expressed by the following formula [
0]. ) is obtained by a Prins reaction, that is, a noncatalytic thermal reaction, between an unsaturated hydrocarbon, which is an alternating copolymerized oligomer of propylene and putadiene, and paraformaldehyde or formaldehyde. raw material formula

The alternating copolymerized oligomer represented by [0] has been disclosed in numerous patents already proposed by the present inventors, for example,
It is produced by the alternating copolymerization method described in No. 7-196, and the production method is publicly known, but it is also described in the lecture proceedings of the 24th Polymer Symposium (November 1930), pp. 587-590. ing. Since the molecular weight of the molecules contained in the alternating copolymerization reaction product changes stepwise, a desired oligomer can be easily separated, for example, by distillation. The reaction can be carried out without a solvent, but if it is without a solvent, paraformaldehyde powder will precipitate on the valves and piping of the reactor, causing operational troubles, so the reaction will run more smoothly if a solvent is used. It is done. As a solvent, methanol, etal/1,2-dichloroethane, etc. are used, but they dissolve paraformaldehyde well, are highly effective in preventing its precipitation, and have a boiling point convenient for the reaction. Therefore, ethanol is particularly preferred. The amount of solvent is 0.0% relative to the oligomer.
1 to 1.0 times by weight is preferable, more preferably 0.2 to 1.0 times by weight.
0. It is twice the mother weight. The reaction temperature is preferably 160~260oo, but 1
80-240qC is more preferred. The reaction time can be changed as appropriate depending on the reaction temperature, the type and amount of the solvent used, etc., but is usually 2 to 6 hours. The amount of formaldehyde or paraformaldehyde to be used is calculated as formaldehyde, and is 0.1 to 2.0% per mole of oligomer.
0 mol is preferred, and 0.5 to 1.5 mol is more preferred. The chemical structure of the liquid branched higher aliphatic 1-ol of the present invention is determined by determining the molecular weight from gas chromatography mass vector data, and by determining the skeletal structure by infrared absorption (IR) spectrum, proton and CI3 nuclear magnetic resonance (NMR) spectra, etc. It was decided. The minimum inhibitory concentration, which is a guideline for antibacterial agents, is measured using ordinary agar medium (OXID) for bacteria and potato dextrose Aio medium (Eiken) for fungi.
The coating was carried out using a conventional plate coating method at a concentration of 0.00 ppm. EXAMPLES The present invention will be described in more detail by way of Examples below, but these are merely for the purpose of illustration and the present invention should not be construed as being limited thereto. Note that unless otherwise specified, NMR was measured at room temperature. Example 1 In a stainless steel pressure-resistant container with a capacity of 50 cm and equipped with a spoiling layer, 2-methyl-1,4-nonadiene, 3
．． Add 0 quarts of paraformaldehyde and 7 quarts of ethyl alcohol as a solvent, and add 180 quarts of ethyl alcohol while stirring.
The reaction was carried out for 5 hours. After removing ethyl alcohol and unreacted formaldehyde from the reaction mixture, fractional distillation was carried out under reduced pressure to remove unreacted 2-methyl-1,4 nonadiene (boiling point 65oC/3).
A colorless and transparent liquid unsaturated alcohol mixture (boiling point 84-95 qo/2 qo/2 qo/2 qo) was obtained. When this was subjected to liquid chromatography, 2
．． It was separated into two parts, 0 evening and 4.5 evening. Gask these crabs. As a result of analysis using matograph mass vector, infrared absorption spectrum, proton nuclear magnetic resonance absorption spectrum, etc., the fraction of 2.0 fractions is 3-methylene-5-decen-1-ol, and the fraction of 4.5 fractions is 3-methyl. -3,5-decadien-1-ol. 3-methylene-5-decene-1-all 1R (C
-1) 33200-H stretching vibration 1650C=C<〃 1040C-○ 〃 970 trans-disubstituted olefin C-day bending angular vibration 89
0 Vinyl 1'' Den C-Day Angular Vibration NMR (8 ppm) 0.9 9 days CH3 - 1.1 to 1.54 days CH3-CH2 -CH2 -2.
0 2 days -CH2 -CH=CH-2.2 (triple line) 2.7 (triple line) 2 days I 'day go H-CH2-C go day 2 3.4 1 day -C ratio -OH 3. 6 (triplet) 2 days -CH20H I 4.8 (singlet) is cH2-c- 5.4 2 days -CH=CH- The IR spectrum of this compound is shown in Figure 1, and its NM
The R spectrum is shown in FIG. 3-Methyl-3,5-decadien-1-ol IR (skin-1) 33200 days stretching vibration 1040C-○ stretching vibration 970 trans disubstituted olefin C-day bending angular vibration NM
R (6 ppm) 0.9 3 days CH3 - 1.3 4 days C&-CH2 -CH2 -■,.
7 (-salt) lees'' day 3 1.9 2 days -CH2 -CH=CH-2.
2 (triple line) 2 days -C upper group -CQOH3.5 (triple line) group -CH20 days (unclear) IH -CH20 The IR spectrum of the Japanese compound is shown in Figure 3, and its NM
The R spectrum is shown in FIG. Example 2 The reaction was carried out in the same manner as in Example 1 except that 2,7-dimethyl-1,4-octadiene was used instead of 2-methyl-1,4 nonadiene. The reaction mixture was treated in the same manner as in Example 1 to remove 6.5 days of unreacted 2,7-dimethyl-1,4-octadiene and 6.
．． A mixture of colorless and transparent liquid unsaturated alcohols (boiling point 81-94°/2 days) was obtained. The mixture of the above unsaturated alcohols of 6.1 days was subjected to liquid chromatography to obtain two fractions, which were analyzed.The 1.8 fractions were 3-methylene-8-methyl-5nonen-1-ol, and the 4.3 fractions were analyzed. The liquid was 3,8-dimethyl-3,5-nonadien-1-ol. 3-methylene-8-methyl-5-/nen-1-ol I
R (arc-1) 33200-H stretching vibration 1650C=C<〃 1040C-○ 〃 970 trans-disubstituted olefin C-day bending angular vibration 89
0 Pinylidene C-day bending angular vibration NMR (6ppm) 0.9 set (CH3)2CH-1.5
1 day (C ratio)21CH-1.9 is (CH
3) 2-CH-CH2-CH=
・Chapter 2.2 2 days -
CH2 1C ratio OH2,7 is Go day 1 day 2 - Higo day 2
3.5, 2 days -CH20 days 4.7 Field CH2± Leaf CH2- 5.3 2 days -CH:CH- (unclear) IH -CH20 days 3,8-dimethyl-3,5-nonadiene-1-o -Le I
R(伽-1) 33200-H Stretching vibration 1040C-0 〃 970 Trans disubstituted olefin bending vibration NMR (6
ppm) 0.9 Group (CH3) 2CH- 1.3 1 day (C Melon) 21CH- 1, 7 Group CH3'' GoHI. 9 is (C ratio)2CH-CH2-2.2
2 days -CH2 -CH 20 days 3.5 3 days -CH 20 days 5.2 to 6.39 days -CH goH'' days go- (unclear) IH -CH 20 days Reference example 1 3-methylene- of Example 1 For the mixture of 5-decen-1-ol and 3-methyl-3,5-decadien-1-ol, and the mixture of 3-methylene-8-methyl-5-nonen-1-ol and 3,8-dimethyl-3,5-nonadien-1-ol of Example 2, respectively. When the various symptoms and minimum inhibitory concentration (MIC) of bacteria were measured, as is clear from Table 1, some symptoms and excellent efficacy against bacteria were observed. Table 1 Antibacterial properties (MIO)

[Brief explanation of drawings]

Figure 1 shows 3-methylene-5-decene-1 obtained in Example 1.
FIG. 3 is the IR spectrum of 3-methyl-3,5-decadien-1-ol obtained in Example 1, and FIG. 4 is its NMR spectrum. Hiiragi 2 drawings / collar 3 drawings Machii drawing

Claims (1)

[Claims] 1 Liquid branched chain higher aliphatic 1 represented by general formula [I]
-All. X-CH_2-CH=CH-Z-CH_2OH [I]
(In the formula, X is CH_3CH_2CH_2- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼Z is; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.) 2. 1-ol according to claim 1, wherein Z is ▲a mathematical formula, a chemical formula, a table, etc.▼. 3. 1-ol according to claim 1, wherein Z is ▲a mathematical formula, a chemical formula, a table, etc.▼. 4 General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is CH_3CH_2CH_2- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼.) General formula [I] X-CH_2-CH=CH-Z-C by reacting with formaldehyde in the absence of a catalyst
H_2OH [I] (wherein, X is CH_3CH_2C
H_2- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼Z is; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A method for producing a liquid branched chain higher aliphatic 1-ol. 5. The manufacturing method according to claim 4, wherein the reaction solvent is ethanol.