JPH02243639A - Production of 1,9-nonanediol and/or decanetriol - Google Patents

Abstract

PURPOSE:To industrially advantageously obtain the title compound without producing a catalyst-poisoning substance as a by-product by subjecting a specific compound to hydroformylation reaction with H2 and CO in the presence of a rhodium catalyst and then successively subjecting the resultant reaction product to H2 reduction reaction and hydrolysis reaction, etc. CONSTITUTION:A compound expressed by formula I [R<1> is formula II, formula III, formula IV, (CH3)2C- or R<2>CO- (R<2> is 1-6C hydrocarbon group)] is subjected to hydroformylation reaction with H2 and CO in the presence of a rhodium catalyst such as dicarbonylacetylacetonato rhodium, preferably together with an unidentate ligand tert. organophosphorus compound, preferably such as a complex expressed by formula V and then resultant reaction product is successively or simultaneously subjected to reduction reaction with H2 in the presence of a hydrogenation catalyst such as Raney nickel and hydrolysis reaction by water in the presence of an acidic catalyst such as active Chinese clay or to alcohol exchange reaction with a 1-6C lower alcohol to provide the aimed compound useful as a production raw material for polyester and polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 1,9-nonanediol and decanetriol.

1.9-Nonanediol and decanetriol are useful as molecular modifiers, acrylate synthesis agents, organic synthesis intermediates, etc., and are particularly useful as raw materials for producing polyesters and polyurethanes. 1,9-nonanediol and decane) IJol are 1,4-butanediol and decane, respectively, which are industrially produced on a large scale.
It has a longer carbon number than diols such as 1.6-hexanediol and trimethylolpropane, and therefore has superior physical properties such as hydrolysis resistance, softness, flexibility, and low-temperature properties compared to these existing compounds. A polymer compound having the following properties is obtained.

[Prior art]

It is known that 1,9-nonanediol can be produced by hydroformylating octa-2,7-renin-1-ol and then reducing the resulting compound with hydrogen (Japanese Patent Publication No. 63-10931 No. Publication, JP-A-57-19
No. 7238, Japanese Unexamined Patent Publication No. 140030/1983.

[Problem to be solved by the invention]

Oct-2,7-renin-1-ol has double bonds at the 2- and 7-positions that can be hydroformylated, and theoretically, if only the 7-position is hydroformylated, 1,9-nonanediol can be produced. Furthermore, if the 2-position is also hydroformylated, decanetriol can be produced. However, when octa-2,7-renin-1-ol is hydroformylated, only the 7-position double bond is selectively hydroformylated, and both the 2-position and 7-position double bonds are hydroformylated. This is impossible, and the production of oct-2-formyl-7-en-1-ol, which is a hydroformylated internal olefin, is inevitable. This product was found to dehydrate under one reaction condition to form 2-methylene-oct-7-en-1-al, which tended to deactivate the hydroformylation catalyst.

This deactivation not only prevents the reaction from progressing, but also causes problems such as an increase in the amount of expensive rhodium catalyst used.
1,9-nonanediol and/or decanetriol cannot be produced industrially advantageously.

Therefore, the object of the present invention is to avoid producing 2-methylene-oct-7-en-1-al, which is a catalyst poisoning substance, by producing octa-2,7-diene-1-ol or 1, The purpose is to produce 9-nonane diol or decanetriol.

[Means to solve the problem]

According to the present invention, the above object is achieved by the following general formula % formula % () () (wherein R2 represents a hydrocarbon group having 1 to 6 carbon atoms) derived from octa-2,7-renin-1-ol. After hydroformylating the compound represented by hydrogen and carbon monoxide in the presence of a rhodium catalyst, the resulting reaction product is subjected to a reduction reaction with hydrogen in the presence of a hydrogenation catalyst, and then in the presence of an acidic catalyst. Hydrolysis reaction with water or carbon number 1
This can be achieved by providing a method for producing 1,9-nonanediyl and/or decanetriol, which is characterized in that the alcohol exchange reaction with the lower alcohol of ~6 is carried out sequentially but also simultaneously. I found out.

In the present invention, the compound represented by general formula (1) is:

Octa-2,7-renin-1-ol and 2-hydroxy-4-methyl-tetrahydro-2H-pyran, tetrahydro-2H-bilane, tetrahydro-2H-furan, t
- Butanol or an organic carboxylic acid having 1 to 6 carbon atoms such as acetic acid, propionic acid, butanoic acid, hexanoic acid, benzoic acid, etc. as an acidic catalyst, tertiary acid, hydrochloric acid, phosphoric acid, p
-Synthesized by condensation reaction in the presence of toluenesulfonic acid, cation exchange resin, activated clay, etc., or octa-2,7
-renin-1-ol t-2,3-dihydro-4-methyl-2H-pyran, 2,3-dihydro-2H-bilane,
It can be synthesized by addition reaction of 2<3>-dihydro-2H-furan or isobutyne in the presence of an acidic catalyst similar to that described above.

As the rhodium catalyst used in the hydroformylation reaction of the heptaarsensate represented by general formula (1), known rhodium compounds having a hydroformylation catalytic action can be used. Many such rhodium compounds are known, including rhodium oxide, rhodium chloride, rhodium acetylacetonate, rhodium dicarbonylacetylacetonate, rhodium acetate, Rh4(Co)1□, gha(C
o)16. (Rh(Co)z C/') 2゜ji-μm
Chlorobis(cyclooctadiene)nirodium, Rh
α(PPb3)3 [PPh3 represents triphenylphosphine:], Rhα(Co) (PPb3)2. )
Specific examples include LRh(Co)(PPh3)3. The rhodium catalyst can be used by being uniformly dissolved in the reaction mixture, or can be used by being fixed on a polymeric compound containing activated carbon, alumina, silica, or phosphine. The rhodium catalyst is used at a concentration of 0.001 to 10 milligram atoms per 1 j of the reaction mixture in terms of rhodium metal.

In the present invention, rhodium 1 is used together with the above rhodium compound.
The stability of the rhodium catalyst and the selectivity of the reaction can be increased by carrying out the reaction in the presence of 5 to 500 equivalents per gram atom of a monodentate tertiary phosphorous compound. As a monodentate tertiary organophosphorus compound,
General formula PR'RNR'''(R',R'' and R'' are each the same or different aryl group, aryloxy group,
Specific examples of phosphine compounds or phosphite compounds represented by (representing an alkyl or alkoxy group) include triphenylphosphine, tritolylphosphine, tricyclohexylphosphine, tris(4
-methoxyphenyl)phosphine, diphenylglobylphosphine, triphenylphosphite, tris(2-
methylphenyl) phosphite, tris(2-t-7”
tylphenyl) phosphite.

Tris(3-methyl-6-t-7'terphenyl)phosphite, tris(2,4-di-t-butylphenyl)
Examples include phosphite, tris(4-chlorophenyl)phosphite, and the like.

Furthermore, the following general formula (n) or general formula (■) (
In the formula 31. H2, R3 and R4 represent an aryl group or an alkyl group which may be different if they are the same;
2 has 2 to 5 carbon atoms in the straight chain.

and optionally a lower alkyl group (9 represents an alkylene group which may be substituted with a lower alkylene group) at a rate of 0.2 per gram atom of rhodium. It is preferable to add the rhodium catalyst at a ratio of ~3% to improve the thermal stability of the rhodium catalyst and the reaction yield.
In the secondary coordinating diphosphine alkanes represented by II), the groups represented by R3, H4, R5 and R6 include lower alkyl-substituted phenyl groups such as phenyl, tolyl and xylyl, methyl, ethyl, clovir, hexyl, octyl, Also includes saturated hydrocarbon groups such as cyclohexyl.

Specific examples of the alkylene group represented by 2 are as follows.

-(CH2)n -(n=2.3, 4 is 5),
-CH-CHz-CH3 -CH2-CH-(:H2--CH2CH2CHCH2
CH2-Hs CH3 are mentioned. Specific examples of preferred bidentate diphosphinoalkanes include the following.

1.2-Bis(diphenylphosphino)ethane.

1,3-bis(diphenylphosphino)furonokun.

14-bis(diphenylphosphino)butane.

(CsHs)2PCH2CH2P(CsHs)2゜(C
6′kIs)2 PCt12CkLzCHzCH2P(
CtsH5)2Ckh-CH2 In carrying out the hydroformylation reaction of the present invention,
The reaction temperature is from room temperature to 120°C, preferably 50°C.
and 100°C.

The partial pressure ratio of hydrogen/carbon oxide is 1/2 to 10 in terms of input gas ratio.
It is desirable that it be in the range of /1. The reaction pressure can be selected from within the range of atmospheric pressure to 200 atm, but when the reaction is carried out at low pressure, it is preferable to use a rhodium catalyst modified with a modifier. Hydroformylation reaction? In carrying out the reaction, the reaction raw material and/or product can serve as a reaction solvent, but there is no problem even if the reaction is carried out in the presence of an inert organic solvent.

Specific examples of such solvents include benzene and toluene.

Aromatic hydrogens such as xylene; Alcohols such as methanol, ethanol, butanol, and octatool;
Diethyl ether, cyphthyl ether, tetraethylene glycol dimethyl ether.

Ethers such as tetrahydrofuran and dioxane;
Esters such as methyl acetate, butyl acetate, dioctyl phthalate, and dimethyl adipate can be mentioned.

The hydroformylation reaction of the present invention can be carried out continuously or batchwise in a stirred reaction tank or a column-type reaction tank.

In the hydroformylation reaction of the compound represented by the general formula (1), the reaction rate of the terminal olefin is higher than that of the internal olefin, so as the reaction progresses, the proportion ti of the decanetriol precursor can be added. The catalyst component can be separated from the reaction mixture after the reaction by evaporation. When a rhodium catalyst modified with an organic phosphorus compound is used, the evaporation residue containing catalyst components can be recycled and used in the hydroformylation reaction.

In the present invention, the hydroformylation product is reduced with hydrogen in the presence of a hydrogenation catalyst.

As the hydrogenation catalyst that can be used in the present invention, known catalysts that have the ability to reduce olefins and aldehyde groups with hydrogen can be used. These catalysts include Raney nickel, Raney cobalt, and palladium black.

Examples include copper-chromite, etc., as well as nickel diatomaceous earth in which such metals are supported on activated carbon, diatomaceous earth 1, etc., palladium carbon, ruthenium carbon, and the like.

There is no problem even if these catalysts are partially modified with molybdenum, tungsten, iron, rhenium, manganese, or tungsten sodium. The amount of catalyst used is 0.01 to 10 percent by weight in terms of metal relative to the reaction mixture when the reaction is carried out in a liquid phase suspension type.

The hydrogen pressure is selected from the atmospheric pressure to 100 atm, and the reaction temperature is selected from the range of 20 to 150°C.

In the present invention, in the reduction, the raw material and/or the product can function as a reaction solvent, but an inert organic solvent can be used for one reaction. Specific examples of such solvents include alcohols such as methanol, ethanol, propatool, butanol, and octatool; ethers such as diptyl ether, tetrahydrofuran, and dioxane; hexane, heptane, and octane.

Examples include hydrocarbons such as benzene.

The hydrogenation reaction of the present invention can be carried out in any of a stirred reaction tank, a fixed bed type reaction tank, and a bubble column type reaction tank, and can be carried out in a batch type or continuous type.

In the present invention, the hydrogen-reduced product is further alcohol-exchanged using a lower alcohol having 1 to 6 carbon atoms in the presence of an acidic catalyst, and then hydrolyzed with water.
．． 9-nonanediol and/or decanetriol is obtained.

As the acidic catalyst used, organic or inorganic acidic catalysts can be used. Specific examples include mineral acids such as sulfuric acid, phosphoric acid, and hydrochloric acid; Lewis acids such as calcium chloride, ferric chloride, and zinc chloride; organic acids such as p-toluenesulfonic acid and cation exchange resins; activated clay, and cation exchange resins; The amount of catalyst used is 1 when used in a normal stirring tank.

The amount is 0.001 to 10% by weight based on the reaction mixture.

The amount of water or alcohol used to obtain 1.9-nonanediol and/or decanetriol can range from a stoichiometric amount to 100 times the molar amount relative to the unreacted raw material and oxo product. . Specific examples of alcohols having 1 to 6 carbon atoms used for this purpose include methanol, ethanol, n-propanol, ingropanol, n-butanol, and i-butanol.

Examples include n-heptatool, n-hexanol, etc.
Among these, methanol is particularly preferred.

During the reaction, there is no problem in using an inert solvent in combination with the reaction. Specific examples of such solvents include hydrocarbons such as hexane, heptane, octane, benzene, and toluene; and acetone.

Examples include ketones such as methyl ethyl ketone; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane; and nitriles such as acetonitrile.

The reaction is carried out in a stirred or fixed bed reactor.

The reaction can be carried out at a temperature within the range of 10-150°C.

After filtering or neutralizing the catalyst, the reaction mixture can be distilled to fractionate 1,9-nonanediol or decanetriol. Decanetriol obtained in the present invention Fi,l,1.7-)limeterolhebutane, 1,1.6-trimethylolhebutane, 1,2.
A mixture of 7-) rimeterol hebutane and 1.2.6-) rimeterol hebutane.

These can usually be used as is as a mixture.

In the present invention, the above-mentioned hydrogen reduction and hydrolysis or alcohol exchange reaction can also be carried out simultaneously. In this case, activated clay is used as the acidic catalyst.

Preferably, diatomaceous earth or the like is used in conjunction with the hydrogenation catalysts described above.

〔Example〕

Hereinafter, the present invention will be fully explained in detail with reference to Examples, but the present invention is not limited in any way by these Examples.

Reference Example 1 Octa-2,7-di-s7-ly? -639. 85 f of n-hexane and 1.5 f'i of activated clay were charged and refluxed. Here 2-hydroxy-4-methyltetrahydro-
The mixture was added dropwise to 2H-pilaf 58f1 over 2 hours. As soon as the dropping started, water was distilled out into the liquid-liquid separator by azeotropy with hexane. After the dropwise addition was completed, the reaction was continued until no water was distilled out azeotropically (about 2 hours). After the reaction is completed, the activated clay is separated from F, and after distilling hexane from the F solution, the remaining liquid is heated to 10 μHf.
2-(octa-2,7-dininoxy)-4-methyltetrahydro-2H-bilane%) as a fraction with a boiling point of 141-142°C. The proton NMR spectrum of this compound is shown in FIG.

Reference Example 2 Same reactor K as Reference Example 1, octa2,7-dinin-1-ol 53f, n- to #f An 51 cation conversion resin (Amberlyst 15) 1.5f and 2,3-dihydro- 35f of 2H-furan was charged and reacted in the same manner as in Example 2. The reaction product was distilled under reduced pressure of l Q ymHf, and the 2-
(Octa-2,7-dininoxy)-tetrahydrofuran (5 △ mehahe) was obtained (89F) (yield 91%). The proton NMR spectrum of this compound is shown in FIG.

Reference Example 3 Octa-2,7-renine-1 was added to the same apparatus as Reference Example 1.
-All 63f, n-hexane 85f ion exchange resin (
Amberlyst 15% Organo) 1.5F and 3
．． 4-dihydro-2H-pyran 42f was charged, and after stirring at room temperature for 5 hours, the reaction was continued for an additional hour while heating and refluxing hexane. After the reaction, exchange resin t-
F was separated and removed, and hexane was distilled from the F solution. Next, the residual liquid was distilled under reduced pressure of 10-rinds, resulting in 2-(octa-2, 7-
94.5F of dininoxy)-tetrahydro-2H-bilane (Ω0) was obtained (yield: 90 qb). The proton NMR spectrum of this compound is shown in FIG.

Example 1 Contents 300d with gas inlet and sampling port
1. Rhodium dicarbonylacetylacetonate in a magnetically stirred autoclave. 2q (0.0047 mmol), tris(2,4-di-t-butylphenyl)phosphite 3001FC0.47 mmol), (C6ns
)2P(CHz)4P(Co)is)21. 0 1'
19 (0. O O 2 35 mmol) and 150 mmol of 2-(octa-2.7-dininoxy)-4-methyltetrahydro-2H-pyran were charged without introducing air, and the autoclave was heated with hydrogen/- Carbon oxide =
The pressure was maintained at 90 K4/dG with a 1/1 mixed gas. Offgas was flowed at a rate of t-5 J/hr, and the internal temperature was raised to 80° C. without stirring. When reacted in this state for 7 hours, the reaction rate Fi of the raw materials was 99%. After the reaction is complete,
Take out the contents and use a molecular distillation device 1. Owax
Separate the product and catalyst components at 160°C under reduced pressure of H9.

An evaporated component of 168.6F was obtained.

Into an autoclave with the same contents as the above reaction, 160F of the vaporized component obtained in the hydroformylation reaction, 2102 of methanol, and 3.72 of Raney nickel were charged,
After replacing the system with hydrogen gas, heat the system to 25K with hydrogen gas.
The pressure was maintained at g/ctAG.

The internal temperature was raised to 80° C. without stirring. Internal pressure 25V4/
The reaction was carried out at 80°C for 6 hours while maintaining dGK.

The feedstock was 100% hydrogen reduced. After the reaction was completed, one reaction mixture was taken out and the catalyst was removed by filtration.

Next, the F solution was charged into a three-necked flask with a capacity of 1j equipped with a condenser, a thermometer, and a stirring device, and activated clay 42 was further charged therein, and the flask was reacted at 65° C. for 6 hours. After the completion of the reaction, a part of the reaction mixture was acetylated with an acetylating agent and analyzed by gas chromatography.
-methoxy-4-methyltetrahydro-2H-pyran 8
5.3 F.

1.9-nonanediol 30.5F, 2-methyl-1°8-octanediol l 6.5? , 1,1.7
-) Rimethylolheitane 23.6 f, 1,
1.6-Dolinoterolhebutane 12.7 ? , 1.2
．． 7-) Rimeterol Hebutane 12.7 W and 1
, 6.8y of butane to 2,6-trimethylol were produced.

After removing the activated clay from this reaction mixture by filtration, it was added to methanol and 2-methoxy-4-methyltetrahyde.
Rho 2H-pyran was distilled off on a rotary evaporator. The result of vacuum distillation of the residual liquid.

127~b tendiol 19.3F was obtained, 155~b/l,
Decanetriol mixture 40 as a fraction of Q mH9
．． 5f' was obtained.

Comparative Example 1 In a reactor similar to Example 1, 1.2 μ (0,0047 mmol) of dicarbonylacenaracetonate rhodium was added.
Tris(2,4-di-t-butylphenyl)phosphite 300”9 (0,47 mmol) (C6Hs)2P(
CMsu4P (C6)is)2 1.0■(0,002
35 (remole) and 150 ft of octa-2,7-renin-1-ol were charged, and the reaction was carried out in the same manner as in Example 1.

Sample the reaction mixture every 30 minutes.

Analysis revealed that one reaction completely stopped after 1.5 hours.
The conversion rate of octa-2,7-renin-1-ol up to this time was 35%.

Example 2 Rh4(Co)120.
Cape 88.

) IJ su(3-methyl-6-t-butylphenyl phosphite 240y, 2-(octa-2,7-dininoxynotetrahydro 2H-furan 150y) was prepared,
Hydrogen/-carbon oxide = 1/1. 90 Kf/d with mixed gas
The reaction was carried out in the same manner as in Example 1 at 80° C. for 8 hours. The reaction rate of the raw materials was 98%.

This reaction mixture was treated in the same manner as in Example 1 to obtain evaporated component 1.
I got 72F. In the same hydrogenation apparatus as in Example 1, 230 y of methanol, 42 y of activated clay, and 4 ft. of nickel were added.
The inside of the charging system was maintained at 50 to 410 AG with hydrogen gas. The internal temperature was raised to 80° C., and while maintaining this temperature, the product 1702 obtained by the hydroformylation reaction was fed into the autoclave at 2 Br/hr using a feed pump.

After the feeding was completed, the reaction was continued for an additional 15 minutes.

A portion of the reaction mixture was acetylated and analyzed by gas chromatography to find 2-methoxy-4-methyltetrahydro-2H-furan 57.2F.

1,4-butanediol 18.8F, 1.9-7nanediol 36.2F, 2-methyl-1,8-octanediol 19.5f, 1,1.7-)limethylolhebutane 28. Of, 1,1.6-)trimethylolhebutane 15, Of, 1,2.7-trimethylolhebutane/15. Of and 1,2.6-)limethylol to butane 8.12 were produced. After removing the catalyst from this reaction mixture by filtration, it was treated in the same manner as in Example 1 to obtain 19-
A mixture of 23.5 F of nonanediol and 50 F of decanetriol was obtained.

Example 3 HRh(GO)((Ca
Hs)3P)3216jlv, triphenylphosphine 616■ and 2-(octa-2,7-dienexy)tetrahydro-2H-bilane 150f were charged, and hydrogen/-
Maintain at 10K4/crAG with carbon oxide mixed gas, 8
The reaction was carried out at 0° C. for 5 hours in the same manner as in Example 1. The reaction rate of the raw materials was 86%. This reaction mixture was treated in the same manner as in Example 1 to obtain evaporated fraction 141. In a hydrogenation apparatus similar to Example 1, 5 wt % Baladicum carbon 2F and water 1
002 and the evaporated fraction 1302 obtained above were charged,
While keeping the inside of the system at 25Kq/crAG with hydrogen gas,
The reaction was carried out at 0°C for 6 hours. After completion of reaction P, the catalyst was filtered off. To the F solution, 2r of sulfonic acid type cation exchange resin (Amberlyst 15 manufactured by Organo) was added and reacted in the same apparatus as in Example 1 at 30°C for 10 hours.

After acetylating a portion of the reaction mixture, gas chromatography analysis revealed 2-hydroxytetrahydro-2H-bilane 65.5F, 1.9-nonanediol 6
5. Of, 2-methyl-1,8-octanediol 10
．． 5f was being generated. From this reaction mixture, the catalyst ′(l
After filtration, distillation was carried out in the same manner as in Example 1 to obtain 1.
．． 9-nonanediol 56F was obtained.

Example 4 In the same reactor as in Example 1, dicarbonylacetylacetonate rhodium 1.2y9. ) Lis(2-t-butylphenyl) phosphite 225 ■.

(C6H5)2P(CH2)2P(C6H5)21.0
+ay, and commercially available octa-2,7-dininyl acetate) 140F were charged, maintained at 90 VcIAG with hydrogen/carbon oxide = 1/l mixed gas, and reacted at 80° C. in the same manner as in Example 1 for 7 hours. The reaction rate of the raw materials was 98%.

This reaction mixture was heated to 1 vmHf using the same apparatus as in Example 1.
The mixture was treated at 145° C. under reduced pressure to obtain evaporation fraction 165f. Raney nickel 4.5 was added to the same hydrogenation equipment as in Example 1.
F, 320v of ethanol and 1502 of the evaporated fraction obtained above were charged, and the system was heated to 50 Kf/dG with hydrogen gas.
The reaction was carried out at 80° C. for 5 hours while maintaining K. After the reaction was completed, the catalyst was removed by filtration. F liquid and ion exchange resin (
Amberlyst 15) 52 was charged into the same three-necked flask as in Example 1 and reacted at 30°C for 10 hours. After acetylating a portion of the reaction mixture, analysis by gas chromatography revealed that 60.7 F of ethyl acetate, 35.8 F of 1,9-nonanediol, 19.3 F of 2-methyl-1,8-octanediol, 1,1.7-trimethylolheptane 26.7M, 1.1.6-)rimeterolheptane 14.9F, 1,2.7-trimethylolheptane 14.82, and 1.2.6-trimethylolheptane 14.9F, 8.0 ml of butane to methylol was produced. After removing the catalyst from this reaction mixture by filtration, it was distilled in the same manner as in Example 1 to obtain 22.5 F of 19-nonanediol and 47.2 F of a mixture of decanetriol.

Example 5 In the same reactor as in Example 1, 1.2 my of dicarbonylacetylacetonate rhodium, )lith(2,4-di-t)
-butylphenyl) phosphite 225 cape, (Cs
t-Butylocl'-2,7-dininyl ether 130F synthesized by addition reaction of Hs)2P(CHz)4P(CaHs)21.0■ and offta-2,7-thien-1-old isobutylene according to a conventional method. Prepare.

Water
The mixture was maintained at rAG and reacted at 80° C. for 7 hours in the same manner as in Example 1. The reaction rate of the raw materials was 98%.

This reaction mixture was treated at 145° C. under a reduced pressure of 1 mHf in the same apparatus as in Example 1 to obtain an evaporated fraction 150F.

32 ft of Raney nickel, 180 f of methanol, and 130 ft of the evaporated fraction obtained above were placed in the same hydrogenation apparatus as in Example 1.
The mixture was charged and reacted at 80° C. for 6 hours while maintaining the pressure at 25 KIi/dG with gold-hydrogen gas within the system. After the reaction was completed, the catalyst was removed by t-filtration. P solution and sulfuric acid 102 were charged into the same three-necked flask as in Example 1, and reacted at 50°C for 5 hours.

After acetylating a portion of the reaction mixture, analysis by gas chromatography revealed that 1,9-nonanediol 25.22.2-Methyl-1,8-octanediol 1
3.6-1,1,7-trimethylolbutane17.
5f.

1.1.6-) Listyrol to butane 10.5f, 1,
2゜7-trimethylolhbutane 10.4 F and 1
．． 5.62 of butane to 2°6-trimethylol was produced. After neutralizing this reaction mixture with ethanolic KOH, it was distilled in the same manner as in Example 1 to obtain 15.5 F of 1,9-nonanediol and 34.69 F of a mixture of decanetriol.
I got it.

〔Effect of the invention〕

According to the present invention, even if an internal olefin undergoes a hydroformylation reaction, α,β-unsaturated aldehyde compounds that become catalyst poisoning substances are not produced, so that it is industrially advantageous to use 1,9-nonanediol and/or decanetriol. can be manufactured.

[Brief explanation of drawings]

Figures 1 to 3 are diagrams showing proton NMR spectra of the compounds obtained in Reference Examples 1 to 3, respectively.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, (CH_3)_3C- or R^2
CO- (R^2 represents a hydrocarbon group having 1 to 6 carbon atoms)
] The compound represented by is subjected to a hydroformylation reaction with hydrogen and carbon monoxide in the presence of a rhodium catalyst, and the resulting reaction product is subjected to a reduction reaction with hydrogen in the presence of a hydrogenation catalyst and a reduction reaction with hydrogen in the presence of an acidic catalyst. A method for producing 1,9-nonanediol and/or decanetriol, characterized in that a hydrolysis reaction with water or an alcohol exchange reaction with a lower alcohol having 1 to 6 carbon atoms are carried out sequentially or simultaneously.