JPS6039333B2 - Process for producing liquid branched chain higher aliphatic 2- or 3-ols - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula

[0] Liquid branched chain unsaturated higher aliphatic 2- or 3 represented by
-ol and a method for producing a liquid branched chain saturated higher aliphatic 2- or 3-ol represented by the general formula [RO']
In the formula, A is or CH3-(CH2)a+2-; E is (where G is H or -C); E' is (where G is the same as above); n is 0, 1, 2 or 3 and a is 0 or 1
It is. ]. In general, aliphatic monools having 10 to 40 carbon atoms have a variety of uses, such as fragrances, antibacterial agents, or their intermediate raw materials, cosmetic raw materials, textile oils, surfactants, metal processing oils, resin softeners, and printing ink auxiliaries. It is a useful compound. Conventionally, monools having 10 to 40 carbon atoms have rarely been commercialized because it is difficult to synthesize and separate the unsaturated hydrocarbons that form their basic skeletons. For example, in the case of linalool and geraniol, which are alcohols with 10 carbon atoms, they are synthesized from isoprene or acetylene through complicated reaction steps, which cannot be said to be an industrially advantageous method. On the other hand, the present inventors have succeeded in synthesizing an alternating copolymerized oligomer of a olefin and a conjugated diolefin, and have developed a method for easily producing polyene compounds having 10 to 40 carbon atoms with high yield and high selectivity. developed. As a challenge for developing uses for these polyethylene compounds having 10 to 40 carbon atoms, we have discovered a method for easily synthesizing 2- or 3-ol. Most of the 2- or 3-ols obtained by the method of the present invention are new compounds. Both unsaturated and saturated liquid branched chain higher aliphatic 2- or 3-ols obtained by the method of the present invention are useful as antibacterial agents, fragrances, or intermediate materials thereof. Typical examples of monools obtained by the method of the present invention include 2-methyl-2-nonanol; 2-methyl-4
Nonen-2-ol; 2,7-dimethyl-2-octanol; 2,7-dimethyl-4-octen-2-ol; 2,4-dimethyl-2-nonanol; 2,4-dimethyl-4-nonen-2-ol; 2,4,7-trimethyl −
2-octanol; 2,4,7-trimethyl-4-octen-2-ol: 3-methyl-3-undecanol;
3-Methyl-5-undecen-3-ol; 3,8-dimethyl-3-decanol; 3,8-dimethyl-5-decen-3-ol; 3,5-dimethyl-3-undecanol; 3,5-dimethyl-5-undecen-3-ol;
2,8-dimethyl-2-pentadelene-2-ol; 2,8-dimethyl-4,10-bentadediene-2-ol; 2,
8.13-trimethyl-2-tetradecanol; 2,8
,13-trimethyl-4,10-tetradecadien-2
-ol; 2,4,8,10-tetramethyl-2-bentadecanol; 2,4,8,10-tetramethyl-4,
10-Pentadecadien-2-ol; 2,4,8,1
0,13-pentamethyl-2-tetradecanol: 2,
4,8,10,13-bentamethyl-4,10-tetradecadien-2-ol; 9-ethyl-3-methyl-3
-heptadecanol; 9-ethyl-3-methyl-5,1
1-heptadecadien-3-ol; 9-ethyl-3,
14-dimethyl-3-hexadecanol; 9-ethyl-3,14-dimethyl-5,11-hexadecadiene-3
-ol; 9-ethyl-3,5,11-trimethyl-3
-heptadecanol; 9-ethyl-3,5,11-trimethyl-5,11-hebutadecadien-3-ol; 9
-ethyl-3,5,11,14-tetramethyl-3-hexadecanol; 9-ethyl-3,5,11,14-tetramethyl-5,11-hexadecadien-3-ol; 2,8,14-trimethyl-2-heneicosanol: 2,8,14-trimethyl-4,10,16-heneicosatrien-2-ol; 2,8,14,19-tetramethyl-2-eicosanol; 2,8,14,19
-tetramethyl-4,10,16-eicosatrien-2-ol; 2,4,8,10,14,16-hexamethyl-2-heneicosanol; 2,4,8,10,1
4,16-hexamethyl-4,10,16-heneicosatrien-2-ol; 2,4,8,10,14,1
6,19-heptamethyl-2-eicosanol; 2,4
,8,10,14,16,19-heptamethyl-4,1
0,16-eicosatrien-2-ol; 9,15-diethyl-3-methyl-3-tricosanol; 9,15
-diethyl-3-methyl-5,11,17-tricosatrien-3-ol; 9,15-diethyl-3,20-dimethyl-3 docosanol; 9,15-diethyl-3
,20-dimethyl-5,11,17 docosatrien-3-ol;9,15-diethyl-3,5,11,17
-tetramethyl-3-tricosanol; 9,15-diethyl-3,5,11,17-tetramethyl-5,11,
17 Tricosatrien-3-ol; 9,15-diethyl-3,5,11,17,20-pentamethyl-3-
Docosanol; 9,15-diethyl-3,5,11,1
Examples include 7,20-bentamethyl-5,11,17 docosatrien-3-ol; and the like. The unsaturated monool represented by the general formula [D] obtained by the method of the present invention has the following general formula [1] [wherein A is or CH3-(CH2)a+2-; E is (here G is H or -CH3); n is 0, 1, 2 or 3 and a is 0 or 1. ] It is obtained by contacting an unsaturated hydrocarbon which is an alternating copolymerized oligomer of a Q-olefin and a conjugated diolefin with an organic acid or an inorganic salt, and then hydrolyzing it. The alternating copolymerized oligomer represented by the raw material formula [1]' is produced by the alternating copolymerization method described in numerous patents already proposed by the present inventors, for example, in Japanese Patent Publication No. 47-19694, and the production method is well known. , and further Proceedings of the 24th Polymer Symposium (November 1930, Sanno) 587-590
It is also written on the page. Since the molecular weight of the molecules contained in the alternating copolymerization reaction product changes stepwise, oligomers having a desired specific molecular weight can be easily separated, for example, by distillation. Formic acid, acetic acid, chloroacetic acid, etc. can be used as an organic acid, and hydrochloric acid, hydrobromic acid, etc. can be used as an inorganic salt. The amount of acid used is 0.2 to 1.5 mol, preferably 0.8 to 1.0 mol, per 1 mol of the raw material. If 1.5 mol or more of acid is used, hydration will occur in double bonds other than the terminal double bond, increasing the risk of polyol by-products, and if the acid is 0.2 mol or less, the selectivity will be low. Although it is high, the yield is low and it is not preferable. The reaction is usually carried out without a solvent, but may be carried out in the presence of a solvent depending on the case. Water or aliphatic hydrocarbons such as pentane, n-hexane and petroleum benzene, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride and ethylene dichloride are preferably used as the solvent. The reaction temperature is 0 to 50 qo, preferably 20 to 30 qo. The reaction time can be changed as appropriate depending on the type and amount of acid used, reaction temperature, etc. Hydrolysis is carried out by treatment with an alkaline aqueous solution in a conventional manner. The saturated monool represented by the general formula [0'] obtained by the method of the present invention can be obtained by catalytically hydrogenating the above-mentioned unsaturated monool obtained by hydroxylation of an alternating copolymerized oligomer. . The type of catalyst is not particularly regulated, but Ni, Co, Pt, P
Metal catalysts such as d, metal oxide catalysts of Cr, V, Ni, M
Sulfide metal catalysts such as O and W, and reduction catalysts such as carbonyl such as Co are usually used, and metal catalysts, particularly nickel catalysts, are preferably used. Although the reaction pressure is arbitrary, it is usually carried out under hydrogen pressure of about 20 to 150 kg/2, and the reaction temperature is 20 to 200°C, preferably 50 to 150 qo. The reaction time varies depending on the conditions used, but is generally 0.1 to 2
4 hours, and typically ranges from 0.5 to 1 anchor hour.
The chemical structure of the liquid branched higher aliphatic monool of the present invention was determined by determining the molecular weight from gas chromatography mass vector data, infrared absorption spectrum, proton and CI
The skeletal structure was determined by 3-nuclear magnetic resonance spectroscopy. The minimum inhibitory concentration, which is a guide for antibacterial properties, is measured using an ordinary agar medium (OXID) for bacteria and a potato dextrose agar medium (Eiken) for fungi, mainly at a concentration of 25 to 1,000 pPm. This was done using the usual flat plate coating method. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but these are merely for illustrative purposes and the present invention should not be construed as being limited thereto. In addition, all mass spectrometry analyzes were carried out after methylsilylation of alcohols. In addition, unless otherwise specified, nuclear magnetic resonance results are obtained at room temperature.
Example 1 2,7-dimethyl-4-octen-2-ol dropping funnel
2,7-dimethyl-1,4 in 1 part 20 flask with
-Prepare 69 mols of octadiene (0.5 mol) and set the temperature to 2.
A benzene solution of trichloroacetic acid under 0 to 25 q○ (
A concentration of 2 mol/ml was added dropwise over a period of 1 hour. After further heating at the same temperature for 4 hours, the benzene was distilled off after washing with an aqueous potassium carbonate solution, and then hydrolyzed with a 50% aqueous sodium hydroxide solution. The product was extracted with ether, treated in a conventional manner, and then distilled under reduced pressure to obtain 2,7-dimethyl-4, which is a colorless and transparent liquid.
-Octen-2-ol (b.p: 56-60 qo/2
Willow Hg, d reed o: 0.8404) was obtained for 35 days. The product had a strong floral odor. Mass spectrometry m/e213 (P-15) m/e131 (P-97)
Infrared absorption (IR) spectrum 3330-1 -○ day stretching vibration (intensity strong) 2960 skin-1 Methyl group stretching vibration (〃 〃) 1460c-1 Methylene group bending vibration (〃 medium) 1380 skin-1 }Methyl group bending vibration (〃 〃)1360ｽ-11150c-I
C-○ stretching vibration (〃 strong) 970 skin-1 trans C-diurnal angular vibration (〃 〃) Nuclear magnetic resonance (NMR) spectrum The IR spectrum of the product is shown in Figure 1 and the NM old spectrum is shown in Figure 2. Indicated. Example 2 2-Methyl-4nonen-2-ol Instead of 2,7-dimethyl-1,4-octadiene 69 in Example 1, 2-methyl-1,4 nonadiene 69 (0.5 mol) was used. The reaction was carried out under the same conditions except that 2-methyl-4-nonen-2-ol (b.p: 58-6yo/2, Hg, dO: 0.8334), which is a colorless and transparent liquid, was obtained for 36 days. I got it. The product had a floral odor. Mass spectrometry m/e213 (P-15) m/e131 (P-97)
Infrared absorption (IR) spectrum 3330 arc-1 -○ day stretching vibration (intensity strong) 2960 skin-1 Methyl group stretching vibration ('' 〃) 2930 arc-1 Methylene group stretching vibration (〃 〃) 1460c-1 Methylene Radical bending angle vibration (〃 Medium) 1375 Kay-1 Methyl radical bending angle vibration (〃 〃) 1150 Skin-IC-○Stretching vibration
(〃 Medium) 970 Skin-1 Trans C-Day Angular Vibration (
(Strong) Nuclear Magnetic Resonance (NMR) Spectrum The IR spectrum of the product is shown in FIG. 3 and the NMR spectrum is shown in FIG. 4. Example 3 2,4-dimethyl-4nonen-2-ol 2,4-dimethyl-1,4-nonadiene 76 instead of 2,7-dimethyl-1,4-octagene 69 in Example 1
The reaction was carried out under the same conditions except that 2,4-dimethyl-4-nonen-2-ol (b.p = 58 qC/1.5 Hg), a colorless and transparent liquid, was used at 45 I got it. The product had a citrus odor. Mass spectrometry m/e227 (P-15) m/e131 (P-111
) Infrared absorption (IR) spectrum 3330 skin-1 -○ day stretching vibration (intensity strong) 2960 skin-1 Methyl group stretching vibration (〃 〃)2930c-1 Methylene group stretching vibration (〃 〃)1460 C-1 Methylene group bending vibration (〃 Medium) 1375 Skin-1 Methyl group bending vibration (〃 〃) 1140 佽-IC-○Stretching vibration
( 〃 〃) Nuclear Magnetic Resonance (NMR) Spectrum The IR spectrum of the product is shown in FIG. 5, and the original spectrum is shown in FIG. 6. Example 4 2,8-dimethyl-4,10-pentadecadien-2-ol and 2,8,13-trimethyl-4,10-tetradecadien-2-ol 2,7- in Example 1
Dimethyl-1,4-octadiene 69 instead of 2,
8-dimethyl-1,4,10-bentadecatriene and 2
, 8,13-trimethyl-1,4,10-tetradecatriene (60:40) was reacted under the same conditions except that a mixture of 119 (about 0.5 mol) of 1,8,13-trimethyl-1,4,10-tetradecatriene (60:40) was used, and a colorless and transparent liquid was obtained. 2,8-dimethyl-4,10-pentadecadien-2-ol and 2,8,13-trimethyl-4.1
Mixture of 0-tetradecadien-2-ol (60:40) (b.p: 103-106q0/2 skin Hg, d poly:
0.8293) was obtained. The composition ratio of the product, 60:40, was determined by gas chromatography. Mass spectrometry m/e309 (P-15) Infrared absorption spectrum 3370c -1 1 day stretching vibration (strong intensity)
2960C-1-CQ 〃 ( 〃 〃)
1460 skin-1 -C mountain bending angle vibration (〃 medium) 1
360~ CH3, 1377cm-1 〃(〃〃) 1150c -IC-○Stretching vibration (〃 〃)9
70 skin-IC=C bending vibration (''strong) nuclear magnetic resonance spectrum Example 5 2,7-dimethyl-2-octanol; 2,7-dimethyl-4- synthesized in Example 1 in a micro autoclave with an internal volume of 40 mm. Octene-2-all 5.
3 tert, 1 part methanol and 0.0% Raney nickel.
Prepared for 5 nights, temperature 70-90qo, hydrogen pressure 60k9/
Hydrogenation was carried out under the Medenawa Ocean for 2 hours. After the reaction, 2,7-dimethyl-2-octanol (b.p57-60℃/2 skin H
g) was obtained in an amount of 4.1 ta. The product had a citrus odor. Mass spectrometry m/e215 (P-15) m/e131 (P-99)
Infrared absorption (IR) spectrum 3330ka-1 -○-H
Stretching vibration (strength strong) 2960-1 Methyl group stretching vibration (〃 〃) 2930 skin-1 Methylene group bending vibration (〃 〃) 1460 佽-1 Methylene group bending vibration (〃 medium) 1380 skin-1} methyl Radical angular vibration (〃 〃)1360ｽ-I1150ｽ-IC-0
Stretching vibration (〃 middle) Nuclear magnetic resonance (NMR) spectrum The IR spectrum of the product is shown in Figure 7, and the NMR
The spectrum is shown in FIG. Example 6 2,8-dimethyl-2-bentadecanol and 2,8
, 13-trimethyl-2-tetradecanol Example 5
2,8-dimethyl-4,10-pentadecadien-2-ol synthesized in Example 4 and 2,8
,13-trimethyl-4,10-tetradecadiene-2
- using a mixture of 48:30 and 30:40
2,8-dimethyl-2-bentadecanol, which is a colorless and transparent liquid, and 2,8,13 -Trimethyl-2-tetradecanol (60:40) mixture (b.p: 105-10
800/3.5 Yanagi Hg) was obtained. The composition ratio of the product, 60:40, was determined by gas chromatography. Mass spectrometry m/e313 (P-15) Infrared absorption spectrum 3350cm-1 -○ One day stretching vibration (strong intensity)
2910 佽-1 -CH3 〃 ( 〃 〃)
1460 Skin-1 -CQ-Angle Vibration (Medium) 1
-IC-○ stretching vibration (〃 〃) of 150c Nuclear magnetic resonance absorption spectrum Example 7 3-Methyl-5-undecen-3-ol Instead of 2,7-dimethyl-1,4-octagene69 in Example 1, 2-ethyl-1,4-decadiene 66.4 hours (
(approximately 0.36 mol) and trichloroacetic acid in benzene (concentration 2 mol/night) instead of 250
The reaction was carried out under the same conditions except that 3-methyl-5-undecen-3-ol (
b. p: 88-9000/2 legs Hg, d reed o: 0.84
22) Obtained 32 evenings. Infrared absorption (IR) spectrum 3360cm-1 -○ One day stretching vibration (strong intensity) 2960cm-1 Methyl group stretching vibration (〃 〃) 2930cm-1 Methylene group stretching vibration (〃 〃) 1460 skin-1 Methyl group bending angle Vibration (〃 Medium) 1375 Kaya-1 Methyl radical bending vibration (〃 〃) 1140cm-IC-0 stretching vibration (〃 Strong) 970 Kaya-1 Trans C one-day bending vibration (〃 〃) Nuclear magnetic resonance (NMR) Spectrum Example 8 3-Methyl-3-undecanol A microautoclape with an internal volume of 70 cm was charged with 3-methyl-5-undecen-3-ol synthesized in Example 7, 1 part of methanol, and 0.5 parts of Raney nickel, and the temperature 70-9000, hydrogen pressure 60k9/Medetaka Azusa 3
Hydrogenated for hours. After the reaction, 3-methyl-undecanol (b.p: 89~
9100/2 Yanagi Hg, d army o: 0.8330) Obtained 6.4 evening. Infrared absorption (IR) spectrum 3360c -1 -○ day stretching vibration (strong intensity)
2960 arc-1 Methyl group stretching vibration (〃 〃)2
930c-1 Methylene group stretching vibration (〃 〃)1
460 arc-1 Methylene group bending vibration (〃 medium) 13
75c-1 Methyl group bending vibration (〃 〃)11
-IC-○ stretching vibration (〃 〃) nuclear magnetic resonance (NMR) spectrum of 40c The IR spectrum of the product is shown in FIG. 9, and the NMR spectrum is shown in FIG. Reference Examples 2,7-dimethyl-4-octen-2-ol of Example 1, 2-methyl-4-nonen-2-ol of Example 2,
For each of 2,4-dimethyl-4-nonen-2-ol of Example 3 and 2,7-dimethyl-2-octanol of Example 5, the minimum inhibitory concentration (antibacterial property, MIC ), and as is clear from Table 1, excellent efficacy against some ruts and bacteria was observed. Table 1 shows antibacterial data. Table 1 Antibacterial properties (MIO)

[Brief explanation of the drawing]

Figure 1 is the IR spectrum of the product of Example 1; Figure 2 is its NMR spectrum; Figure 3 is the I spectrum of the product of Example 2.
R spectrum, Figure 4 is its NM old spectrum; Figure 5 is the IR spectrum of the product of Example 3; Figure 6 is its N
Figure 7 is the IR spectrum of the product of Example 5, Figure 8 is its NMR spectrum; Figure 9 is its IR spectrum of the product of Example 8, and Figure 10 is its NM spectrum. be. Answer'Prisoner's screen 2 Legs 3 Shihiragi 4 Figure ekkuzu nerazu turtle et al. 7 Prisoner mia Figure name? Kyota’o diagram

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] consisting of reacting an unsaturated hydrocarbon represented by with an organic acid or an inorganic acid and then hydrolyzing it. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼ Liquid branched chain unsaturated higher aliphatic 2- or 3
-Production method of all [In the formula, A is ▲ mathematical formula, chemical formula, table, etc. ▼ or CH_3-(CH_2)_a_+_2-: E is ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (Here, G or H or -
CH_3): n is 0, 1, 2 or 3 and a is 0 or 1. ]. 2. The manufacturing method according to claim 1, wherein the organic acid is formic acid, acetic acid, or chloroacetic acid. 3. The manufacturing method according to claim 1, wherein the inorganic acid is hydrochloric acid or hydrobromic acid. 4 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II′] consisting of reacting an unsaturated hydrocarbon represented by with an organic or inorganic acid, hydrolyzing it, and then hydrogenating it. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼ Liquid branched chain unsaturated higher aliphatic 2- or 3
-Production method of all [In the formula, A is ▲ mathematical formula, chemical formula, table, etc. ▼ or CH_3-(CH_2)_a_+_2-; E is ▲ mathematical formula,
There are chemical formulas, tables, etc.▼ (Here, G is H or -CH
＿３）;E' is ▲a mathematical formula, chemical formula, table, etc.▼(here, G is the same as above);n is 0, 1, 2 or 3 and a is 0 or 1
It is. ]. 5. The production method according to claim 4, wherein the organic acid is formic acid, acetic acid, or chloroacetic acid. 6. The production method according to claim 4, wherein the inorganic salt is hydrochloric acid or hydrobromic acid. 7. The production method according to any one of claims 4 to 6, wherein the hydrogenation catalyst is Raney nickel.