JPS6338008B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula [] [In the formula, A is CH ₃ CH ₂ CH ₂ - or CH ₃ -

[Formula] E is

[Formula] (where G is H or -CH ₃ ) or -CH ₂ -

[Formula] (Here, G is the same as above, but when A is CH ₃ CH ₂ CH ₂ -, G is -
CH ₃ ). ] This relates to a liquid branched chain higher aliphatic aldehyde represented by: In general, aliphatic aldehydes having 11 to 20 carbon atoms are useful compounds as intermediate raw materials for perfumes, rubber vulcanization accelerators, higher fatty acids, higher alcohols, etc., and as raw materials for various synthetic resins. Conventionally, branched-chain aliphatic aldehydes having 11 to 20 carbon atoms have hardly been studied until now because it is difficult to synthesize and separate the hydrocarbons that form their basic skeletons. On the other hand, the present inventors succeeded in synthesizing alternating oligomers of α-olefin and conjugated diolefin, and have already developed a method for easily producing di- and triolefins having 10 to 19 carbon atoms with high yield and high selectivity. did. Among these, as one of the challenges of developing applications for diolefin compounds having 10 and 11 carbon atoms, we discovered a method for easily synthesizing new aldehydes, and succeeded in synthesizing the liquid branched chain higher aliphatic aldehyde of the present invention.
The invention has been completed. As mentioned above, the novel liquid branched chain higher aliphatic aldehyde of the present invention is useful as a synthetic intermediate for various chemical products, and is itself a substance useful as an antibacterial agent. Specifically describing the aldehyde of the present invention, 3-methyl-5-decenal; 3,8-dimethyl-5-
Nonenal; 3,8-dimethylnonanal; 3,
Mention may be made of 5-dimethyl-5-decenal; 3,5-dimethyldecanal; 3,5,8-trimethyl-5-nonenal; and 3,5,8-trimethyl-nonanal. Of the compounds of formula [] of the present invention, E is

[Formula] (G is H or -CH ₃ ) Unsaturated aldehyde has the following formula [] (In the formula, A is CH ₃ CH ₂ CH ₂ - or

[Formula] G is H or -CH ₃ . ) It can be obtained by hydroformylating a diolefin compound which is an adduct of propylene and butadiene or isoprene. The diolefin compound represented by the raw material formula [] is produced by the alternating copolymerization method described in numerous patents already proposed by the present inventors, for example, in Japanese Patent Publication No. 1969-19694, and the production method is well known. Proceedings of the 24th Polymer Symposium (November 1975) 587~
It is also described in detail on page 590. Since the molecular weight of the molecules contained in the alternating copolymerization reaction product changes stepwise, the desired adduct can be easily separated, for example, by distillation. Hydroformylation is carried out, for example, by combining the raw material diolefin compound [] with hydrogen and carbon monoxide at a temperature from room temperature to 400°C in the presence of a known oxo reaction catalyst.
The reaction can be carried out under pressure conditions ranging from normal pressure to 200 kg/cm ² . As a catalyst, Co(CO) ₈ , Ni(CO) ₄ , Mn(CO) ₈ ,
Rh carbon, RhH (CO) [Pφ ₃ ] ₃ , (π-
C ₅ H ₅ ) ₂ Zr(H)Cl etc. can be used. Of the compounds of formula [] of the present invention, E is

[Formula] (G is H or - CH ₃ , however, when A is CH ₃ CH ₂ CH ₂ -, G is -
The saturated aldehyde which is CH ₃ ) can be obtained by catalytically hydrogenating the unsaturated aldehyde obtained by the above method. Hydrogenation can be carried out using molecular hydrogen in the presence of a reducing catalyst. In addition, the compound of the formula [] of the present invention is the following formula [] [In the formula, A is CH ₃ CH ₂ CH ₂ - or

[Formula] E is

[Formula] (G is H or -CH ₃ ) or

[Formula] (G is the same as above, except that when A is CH ₃ CH ₂ CH ₂ -, G is -CH ₃ )] It can also be obtained by oxidizing an alcohol represented by the following using an oxidizing agent. For the oxidation of alcohol, various known oxidation methods applicable to oxidation of alcohol can be used. The alcohol represented by the raw material formula [] is a new substance discovered by the present inventors prior to the present invention (Japanese Patent Application Laid-Open No. 57-95927), and in the formula [], E is

The unsaturated alcohol represented by [Formula] (where G is H or -CH ₃ ) is []
By hydroaluminating the diolefin compound of the formula, reacting the resulting product with carbon dioxide, and then hydrolyzing and reducing the produced unsaturated carboxylic acid,

[Formula] (G is H or -CH ₃ , where A is CH ₃ CH ₂ -
A saturated alcohol represented by CH ₂ --, G is --CH ₃ ) can be obtained by catalytically hydrogenating the corresponding unsaturated alcohol obtained by the above method. The chemical structure of the liquid branched higher aliphatic aldehyde of the present invention was determined by determining the molecular weight from gas chromatography mass spectrum data, and determining the skeletal structure by infrared absorption spectrum, proton nuclear magnetic resonance spectrum, etc. To measure the minimum inhibitory concentration, which is a guide for antibacterial properties, use ordinary agar medium (OXID) for bacteria and potato dextrose agar medium (Eiken) for fungi, and use a regular plate at a concentration of 25 to 2000 ppm. This was done by the painting method. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but these are merely for the purpose of illustration, and the present invention should not be construed as being limited thereto. Example 1 38.5 g of 2,4-dimethyl-1,4-nonadiene was added to 100 ml of a benzene solution containing 0.176 mol of monochlorodicyclopentadienylzirconium hydride [(π-C ₅ H ₅ ) ₂ Zr(H)Cl]. After leaving it at room temperature for 16 hours, benzene and unreacted olefin were removed under reduced pressure, and a dark red viscous liquid [(π-C ₅ H ₅ ) ₂ Zr(n-C ₁₁ H ₂₁ )Cl] was obtained. It remained. Next, dissolve this in 350ml of benzene and add 1.5
was transferred to a glass autoclave. The autoclave was maintained at 3Kg/cm ² G with carbon monoxide, and while stirring,
The reaction was continued at 40°C for 3 hours. After the reaction, the contents were treated with dilute hydrochloric acid, and the aldehyde produced was extracted with ether. After processing the extract in a conventional manner and distilling it under reduced pressure, the result was 58℃/1.5mmHg.
3,5-dimethyl-5-decenal distilled by
15 g of C ₁₁ H ₂₁ CHO (d ²⁰ ₄ =0.864, n ²⁰ =1.453) was obtained. ^1H NMR spectrum (room temperature) Protons in a δ=0.8-1.1ppm b, C 〃 δ=1.1-1.8ppm d 〃 δ=1.58ppm (trans) e 〃 δ=1.8-2.1ppm f 〃 δ=2.3ppm Protons in g δ=4.9-5.3 ppm h 〃 δ=9.63ppm IR spectrum 2900cm ^-1 C-H stretching vibration 2720cm ^-1 C-H stretching vibration of aldehyde 1730cm ^-1 C=O stretching vibration 1460cm ^-1 ―CH ₂ ―Bending vibration 1380cm ^-1 ―CH ₃ Angular vibration mass spectrum m/e 167 (p-15) The IR spectrum of the product is shown in Figure 1, and its NMR spectrum is shown in Figure 2. Example 2 2,4-dimethyl-1,4- used in Example 1
The same procedure as in Example 1 was carried out except that 38.5 g of 2,4,7-trimethyl-1,4-octadiene was used instead of 38.5 g of nonadiene. 3,5,8-trimethyl-5-nonenal distilled at /2mmHg
11 g of C ₁₁ H ₂₁ CHO (d ²⁰ ₄ =0.860, n ²⁰ =1.449) was obtained. ^1H NMR spectrum (room temperature) Proton of a δ=0.8~1.1ppm b 〃 δ=1.1~1.7ppm c 〃 δ=1.57ppm (trans) d 〃 δ=1.7~2.1ppm e 〃 δ=2.2~2.3ppm f 〃 δ=4.8~5.2ppm g 〃 δ=9.6ppm IR spectrum 2900cm ^-1 C-H stretching vibration 2720cm ^-1 C-H stretching vibration of aldehyde 1730cm ^-1 C=O stretching vibration 1460cm ^-1 ―CH ₂ ―Bending vibration 1380cm ^-1 1360cm ^-1 Seminal dimethyl C-H bending vibration mass spectrum m/e 167 (p-15) Example 3 In a two-necked flask containing 19.4 g of Collins reagent (C ₅ H ₆ NO ₃ ClCr) and 150 ml of anhydrous methylene chloride, While stirring at room temperature, 32 ml of a methylene chloride solution containing 10.2 g of 3-methyl-5-decen-1-ol synthesized in Example 1 of JP-A-57-95927 was added dropwise over 30 minutes. Stirring was continued for an additional 1.5 hours at room temperature to complete the reaction, and then the product was extracted with ether. The ether solution was purified by washing with dilute aqueous sodium hydroxide solution, water, etc., and finally distilled under reduced pressure.
3-Methyl-5-decenal distilled at 0.5mmHg
6.1 g of C ₁₀ H ₁₉ CHO (d ²⁰ ₄ =0.842, n ^18.5 =1.444) was obtained. ^1H NMR spectrum (room temperature) Protons in a δ=0.8-1.0ppm b, c 〃 δ=1.0-1.7ppm d 〃 δ=1.8-2.1ppm Protons in e δ=2.1-2.3ppm f 〃 δ=5.2-5.4ppm g 〃 δ=9.8ppm IR spectrum 2900cm ^-1 C-H stretching vibration 2720cm ^-1 C-H stretching vibration of aldehyde 1730cm ^-1 C=O stretching vibration 1460cm ^-1 -CH ₂ -bending vibration 1380cm ^-1 -CH ₃ bending vibration 970cm ^-1 Trans disubstitution of olefin Out-of-plane bending vibration Mass spectrum m/e 153 (p-15) Example 4 In Example 3, 3-methyl-5-decene-
1-Example 2 of JP-A-57-95927 instead of all
3,8-dimethyl-5-nonene-1- synthesized in
An experiment was conducted in exactly the same manner as in Example 3 except that 10.2 g of 3,8-dimethyl-5-nonenal was distilled at 46-48°C/0.5 mmHg.
6.3 g of C ₁₀ H ₁₉ CHO (d ²⁰ ₄ =0.836, n ^18.5 =1.442) was obtained. ^1H NMR spectrum (room temperature) Proton of a δ=0.8~1.0ppm b 〃 δ=1.0~1.7ppm c 〃 δ=1.7~2.1ppm d 〃 δ=2.1~2.3ppm e 〃 δ=5.2~5.4ppm f 〃 δ=9.8ppm IR spectrum 2900cm ^-1 C-H stretching vibration 2710cm ^-1 C-H stretching vibration of aldehyde 1730cm ^-1 C=O stretching vibration 1460cm ^-1 -CH ₂ -bending vibration 1380cm ^-1 1360cm ^-1 Seminal dimethyl C-H bending vibration 970cm ^-1 Trans disubstitution of olefin Out-of-plane bending vibration Mass spectrum m/e 153 (p-15) The IR spectrum of the product is shown in Figure 3, and its NMR spectrum is shown in Figure 4. Example 5 In Example 3, 3-methyl-5-decene-
1-Example 5 of JP-A-57-95927 instead of all
3,8-dimethylnonan-1-ol synthesized by
An experiment was conducted in exactly the same manner as in Example 3 except that 10.0 g of 3,8-dimethylnonanal C ₁₀ H ₂₁ CHO (d ²⁰ ₄ =
0.825, n ^18.5 = 1.430) was obtained. ^1H NMR spectrum (room temperature) Proton of a δ=0.8~1.0ppm b, c 〃 δ=1.0~2.1ppm d 〃 δ=2.1~2.4ppm e 〃 δ=9.9ppm IR spectrum 2900cm ^-1 C-H stretching vibration 2720cm ^-1 C- of aldehyde H stretching vibration 1730cm ^-1 C=O stretching vibration 1460cm ^{-1 -} CH ₂ - Bending vibration 1380, 1360cm ^-1 Seminal dimethyl C-H Bending vibration 722cm ^-1 - CH ₂ - Lateral vibration Mass spectrum m/e 155 (p-15) Reference Example 1 The minimum inhibitory concentration (antibacterial As is clear from the table, it was found to have excellent efficacy against some molds and bacteria.

[Table] Reference Example 2 The aldehydes obtained in Examples 1 and 3 were each oxidized according to a conventional method to form 3,5-dimethyl-5-
Decenoic acid and 3-methyl-5-decenoic acid were obtained, respectively. The antibacterial properties of the obtained carboxylic acids were measured. Furthermore, a zinc salt of the above-mentioned 3-methyl-5-decenoic acid was also produced, and its antibacterial properties were also measured. The antibacterial properties of these compounds are shown in the table.

【table】

【table】 [Brief explanation of the drawing]

Figure 1 is the IR spectrum of the product obtained in Example 1, Figure 2 is its NMR spectrum; Figure 3 is the IR spectrum of the product obtained in Example 4,
Figure 4 shows its NMR spectrum.

Claims (1)

[Claims] 1 [In the formula, A is CH ₃ CH ₂ CH ₂ - or [formula] E is [formula] (where G is H or -CH ₃ ) or [formula] (where G is the same as above, except that A is
When CH ₃ CH ₂ CH ₂ -, G is -CH ₃ ). ] A liquid branched chain higher aliphatic aldehyde represented by 2. The aldehyde according to claim 1, wherein E is [Formula]. 3. The aldehyde according to claim 1, wherein E is [Formula].