JPS6310931B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 9-hydroxy-7-nonen-1-al and a method for producing the same. 9-Hydroxy-7-nonen-1-al provided by the present invention has the formula OHCCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH=
This is a new compound represented by CHCH ₂ OH that has not been described in any literature, and is extremely useful as a starting material for various industrially useful compounds. According to the present invention, 9-hydroxy-7-nonen-1-al is produced by hydroformylating 2,7-octadien-1-ol in an organic solvent with a mixed gas of carbon monoxide and hydrogen in the presence of a rhodium catalyst. By doing so, it can be easily manufactured. 2,7-octadiene-1- used in the above hydroformylation reaction
As previously proposed by the present inventors, ol can be easily produced by the reaction of butadiene and water using a palladium complex compound as the main catalyst (Japanese Patent Application No. 40989/1989). The rhodium catalyst used in the hydroformylation reaction of 2,7-octadien-1-ol in the present invention is a rhodium carbonyl complex compound known per se, or any rhodium compound that can form a rhodium carbonyl complex compound in the reaction system. It is. Many such rhodium complex compounds and rhodium compounds are known, but
rhodium oxide, rhodium acetylacetonate,
Dicarbonylacetylacetonato rhodium, rhodium chloride, rhodium acetate, Rh ₄ (CO) ₁₂ , Rh ₆
(CO) ₁₆ , RhCl(PPh ₃ ) ₃ [PPh ₃ represents triphenylphosphine], [RhCl(CO) ₂ ] ₂ , RhCl(CO)
(PPh ₃ ) ₂ and HRh(CO)(PPh ₃ ) ₃ can be cited as specific examples. In addition, it is also possible to provide a separate catalyst preparation tank, prepare the rhodium carbonyl complex compound therein by a known method, and feed the resulting mixed solution as it is to the hydroformylation reaction tank to carry out the reaction. The rhodium catalyst can be used uniformly dissolved in the reaction mixture, supported on a porous carrier such as activated carbon, alumina, or silica, or supported on an organic polymer such as styrene-divinylbenzene copolymer or polyvinyl alcohol. It can also be used by being fixed to the phosphine or amine atom. The rhodium catalyst is usually 0.01 to 10% rhodium metal per 1 part of the reaction mixture.
Used in the milligram atom concentration range. In the hydroformylation reaction of 2,7-octadien-1-ol, the compound of the present invention, 9-hydroxy-7- Nonen-1-al can be obtained in high yield. There are many monodentate tertiary organophosphorus compounds that can be used, but the general formula PR′R″R
Trisubstituted phosphines and trisubstituted phosphites represented by (R', R'' and R represent the same or different aryl group, aryloxy group, alkyl group and alkoxy group) are preferred, including triphenylphosphine, tritolylphosphine, Specific examples thereof include trinaphthylphosphine, diphenylpropylphosphine, triphenylphosphine, etc.The monodentate tertiary organophosphorus compound usually contains 5 to 500 equivalents per rhodium metal atom, preferably 5 to 500 equivalents per rhodium metal atom. The present inventors used the following general formula () in combination with a monodentate tertiary organophosphorus compound for the hydroformylation reaction of lower olefins. (In the formula, R ¹ and R ² represent an aryl group, and R ³
and R ⁴ represents an aryl group or a hydrocarbon group having 1 or more carbon atoms, and Z represents an alkylene group containing 2 to 5 carbon atoms in the straight chain and optionally substituted with a lower alkyl group or an alkylene group. 0.2 bidentate diphosphinoalkanes represented by
It was proposed to add at a ratio of ~5.0 equivalents (Japanese Patent Application Laid-Open No. 138511/1983 and Japanese Patent Application Laid-open No. 26830/1989).
(Refer to Japanese Patent Publication No. 2003-111011). Also in the hydroformylation reaction of 2,7-octadien-1-ol, the selectivity of 9-hydroxy-7-nonen-1-al can be improved by using the bidentate diphosphinoalkanes in combination. It is expected that the rhodium catalyst will be increased and the rhodium catalyst stabilized. In the bidentate diphosphinoalkanes represented by the general formula (), R ¹ and R ² are phenyl groups or aryl groups such as lower alkyl-substituted phenyl groups such as tolyl and xylyl.
Examples of R ³ and R ⁴ include aryl groups and saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and cyclohexyl. Specific examples of the alkylene group represented by Z include -CH ₂ CH ₂ -,

[Formula] − CH ₂ CH ₂ CH ₂ −,

[Formula] − CH ₂ CH ₂ CH ₂ CH ₂ −,

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] etc. In addition, in the above, for example

[Formula] shows that in the bidentate phosphine having such an alkylene group, P-CH ₂ - and CH ₂ -P are arranged in trans positions with respect to each other. Specific examples of preferred bidentate diphosphinoalkanes include the following. Ph ₂ PCH ₂ CH ₂ PPh ₂ (Ph represents a phenyl group), Ph ₂ PCH ₂ CH ₂ CH ₂ CH ₂ PPh ₂ ,

[Formula] 2,7-octadiene-1- according to the invention
In carrying out the hydroformylation reaction of ol, the reaction temperature is selected from room temperature to 130°C, preferably from 50°C to 110°C.
Partial pressure ratio of hydrogen/carbon monoxide is 1/2 in terms of input gas ratio
It is desirable that the ratio is in the range of ~10/1. The reaction pressure is selected from the atmospheric pressure to about 100 atmospheres, but the lower the pressure, the higher the selectivity for obtaining 9-hydroxy-7-nonen-1-al, the compound of the present invention. can. There is no problem in the coexistence of a gas inert to the hydroformylation reaction, such as nitrogen, helium, argon, methane, ethane, propane, butane, in the reaction system. When carrying out the hydroformylation reaction, the reaction raw materials and/or products and condensates thereof can serve as a reaction solvent, but it is also possible to use organic solvents that are inert to the reaction. Special organic solvents are used as long as they dissolve rhodium compounds and monodentate tertiary organophosphorus compounds (and bidentate diphosphinoalkanes) and do not adversely affect the hydroformylation reaction. Although not limited, examples of particularly preferred organic solvents include aromatic hydrocarbons, alcohols, ethers, and esters. 2,7-octadiene-1- according to the invention
The hydroformylation reaction of ol is industrially carried out in a continuous or batch process in a stirred reactor or a column reactor. After the reaction, the compound of the present invention, 9-
Hydroxy-7-nonen-1-al is separated and obtained, and the distillation residue containing catalyst components is recycled to the hydroformylation reactor and reused. The compound of the present invention, 9-hydroxy-7-nonen-1-al, can be easily converted to 1,9-nonanedial by a known isomerization reaction. 1,9-nonanedial can be easily converted into azelaic acid, which is industrially useful as a raw material for lubricating oils, polyesters, plasticizers, etc., through an oxidation reaction. Also, 9-hydroxy-7-nonen-1-al and its isomer 1,9
-Nonanediol can be easily converted into 1,9-nonanediol, which is useful as a raw material for polyesters, polyurethanes, etc., through a hydrogenation reaction. In addition, 1,9-nonanedial or 1,9-nonanediol can be made into industrially useful 1,9-nonanediol by reacting with ammonia and hydrogen.
Can be converted to nonanediamine. Conventionally,
Azelaic acid is produced, for example, by ozone oxidation of oleic acid obtained by hydrolyzing natural fats and oils, and 1,9-nonanediol is produced by catalytic hydrogenation of dimethyl azelate derived from azelaic acid. However, this conventional method uses natural products as raw materials, which limits the production volume, and requires complicated steps such as ozone oxidation of oleic acid.
This includes problems such as high production costs. In contrast, the compound of the present invention, 9-
By passing hydroxy-7-nonen-1-al, 1,9-nonanediol, azelaic acid, 1,9-nonanediol, 1,9 9-Hydroxy-7-nonene-
1-R is an extremely useful compound industrially. The present invention will be explained in more detail below using Examples. Example 1 In a four-necked flask with contents 1 equipped with a thermometer, a stirrer, a reflux condenser and a gas inlet,
HRh(CO)( _PPh3 ) ₃ 0.50 mmol, _PPh3 50 mmol and 1,4-bis(diphenylphosphino)
After charging 0.375 mmol of butane and replacing the inside of the system with hydrogen gas, 450 ml of dioctyl phthalate was added, and hydrogen/carbon monoxide mixed gas (mole ratio 3/
After replacing the system with 1), the internal temperature of the flask was set to 80℃.
I kept it. After that, hydrogen/carbon monoxide mixed gas (mole ratio 3/1) was passed through at a rate of 20/hour.
While stirring vigorously, 63.0 g (0.50 mol) of 2,7-octadien-1-ol was added to 30 g using a metering pump.
The mixture was charged continuously for 1 minute, and stirring was continued for an additional hour after the addition was completed. After a total of 1.5 hours of reaction, the reaction mixture was cooled and analyzed by gas chromatography, and the conversion rate of 2,7-octadien-1-ol was 80%, and 9-hydroxy-7
-Nonene-1-al selectivity was 76%.
Other products were mainly 8-hydroxy-2-methyl-6-octen-1-al and 1,9-nonanedial. The reaction mixture was then distilled under reduced pressure, resulting in a reduced pressure of approximately 0.5 mmHg.
9-Hydroxy-7-nonene-1 at boiling point 88-89℃
- Earl left. ^1H− in CDCl ₃ solution
The NMR spectrum was as follows (δ value with hexamethyldisiloxane as standard) OH ^g CCH ₂ ^f CH ₂ ^e CH ₂ ^e CH ₂ ^e CH ₂ ^d CH ^c = CH ^c CH ₂ ^b OH ^a H ^a : 2.73 (1H, s), H ^b : 4.02 (2H, d), H ^c : 5.60 (2H, m), H ^d : 2.01 (2H, q), H ^e : 1.30-1.68 (6H, m), H ^f : 2.38 (2H, td), H ^g : 9.73 (1H, t) IR spectra are 3400cm ^-1 , 2926cm ^-1 , 2857cm ^-1
and 1721 cm ^-1 respectively. Example 2 0.125 mmol of Rh ₄ (CO) ₁₂ and 75 mmol of tritolylphosphine were dissolved in a stainless steel autoclave with contents 1 equipped with a magnetic stirrer, a thermometer, a reflux condenser, a gas inlet and a gas outlet tube. After charging 450 ml of the toluene solution obtained above and thoroughly purging the system with hydrogen/carbon monoxide mixed gas (molar ratio 5/1), the internal temperature of the reactor was maintained at 85°C. Afterwards, 63.0 g (0.50 g) of 2,7-octadien-1-ol
mol) and introduced a hydrogen/carbon monoxide mixed gas into the autoclave, so that the pressure inside the autoclave was 4.0 Kg/cm ² (absolute pressure) and the exit gas flow rate was 20/hour. Adjustment was made and stirring was started. After 45 minutes, stirring was stopped and the reaction mixture was taken out from the autoclave and analyzed by gas chromatography.
The conversion rate of ol is 63% and 9-hydroxy-
The selectivity for 7-nonene-1-al was 64%. Example 3 The same procedure as in Example 2 was carried out except that 450 ml of a 1,8-octanediol diacetate solution in which 0.50 mmol of RhH(CO)(PPh ₃ ) ₃ and 100 mmol of triphenylphosphine were dissolved was used. A hydroformylation reaction of 2,7-octadien-1-ol was carried out. Analysis of the reaction mixture showed that the conversion of 2,7-octadien-1-ol was 60%, and the conversion of 9-hydroxy-7-nonene-1-ol was 60%.
The selectivity for 1-R was 70%.

Claims (1)

[Claims] 1 9-Hydroxy-7-nonen-1-al. 2 9-, characterized in that 2,7-octadien-1-ol is reacted with a mixed gas of carbon monoxide and hydrogen in an organic solvent in the presence of a rhodium catalyst.
Method for producing hydroxy-7-nonen-1-al.