JPS58167547A - Preparation of nonandiamine - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for various kinds of nylons, polyurethanes, etc. in high yield, by reducing and aminating a dialkyl hemiacetal of 1,9-nonanedial with hydrogen and ammonia in the presence of a Ni-based or Co-based catalyst. CONSTITUTION:A novel dialkyl hemiacetal of 1,9-nonanedial shown by the formula (R is 5-10C straight-chain saturated aliphatic hydrocarbon) is reacted with hydrogen and ammonia in the presence of anickel-based catalyst and covalt-based catalyst (e.g., Raney nickel, Raney cobalt, etc.) at 60-275 deg.C, preferably at 100-250 deg.C at 60-300atm. to give the desired substance. The amount of ammonia used is 3-300 times, preferably 10-100 times the molar quantity of the compound shown by the formula. The compound shown by the formula is easily obtained by bringing 1,9-nonanedial in a solution into contact with at least two times the molar quantity of a corresponding straight-chain fatty primary alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 1,9-nonanediamine.
This invention relates to a method for producing a dialkyl hemiacetal of nonane dial by reducing it with hydrogen and ammonia.

1.9-Nonanediamine is an extremely useful compound industrially as a raw material for various nylons and polyurethanes, and as a starting material for various organic synthetic leathers, but until now no industrial manufacturing method has been established. Not yet. First, the present inventors isomerized 2,7-octarenin-1-ol obtained by reacting butadiene and water in the presence of a palladium catalyst in the presence of a copper thread catalyst or a chromium-based catalyst,
1. Hydroformylation of the resulting 7-octen-1-al with a hydrogen/carbon oxide mixed gas in the presence of a rhodium complex compound and a trisubstituted phosphine yields 1.9-nonanedial in high yield; By contacting 9-nonanedial with a saturated aliphatic primary alcohol having an IK chain having 5 to 10 carbon atoms, the following general formula (1) (wherein, R is a straight chain having 5 to 10 carbon atoms) It has been found that 1,9-nonanedial dialkyl hemiasecure crystals are formed as saturated fats.

In addition, the dialkyl hemiacetal of 1,9-nonanedial represented by the above general formula (1) is Ill which is not described in the literature.
ll gold compound. In the case of 2-methyl-1,8-octanedial, which is a by-product in the hydroformylation reaction of 7-octen-1-al, crystals of this dialkyl hemiacetal do not form under the same conditions, so if this property is used, In this case, the dialkyl hemiacetal of 1,9-nonane dial, which can be obtained from the above general formula (1), can be obtained with extremely high purity.

Against this background, the present inventors have extensively investigated the effective use of the dialkyl hemiacetal of 1,9-nonanedial represented by the above general formula (1). Alternatively, it has been discovered that 1,9-nonanediamine can be obtained in high yield by reductive amination with hydrogen and ammonia in the liquid phase in the presence of a cobalt catalyst, and the present invention has been completed. Conventionally, synthesis of the corresponding diamine by reductive amination of dialdehyde with hydrogen and ammonia has been described, for example, in AngeWandte Mountain 1.
emie (Anguevante Hemie) Volume 62 1o5-
118 (1950), the yield of 1,9-nonanediamine when this method is applied to the reductive amination of 1,9-nonanediamine is as shown in Comparative Example 1 below.
As shown in , it is only 26%.

In the dialkyl hemiacetal of 1,9-nonanedial represented by the general formula (1) used as a reaction raw material, Rldn-pentyl group, n-hexyl group, n-
heptyl group, n-octyl group, n-nonyl group and n-
It represents a linear saturated aliphatic hydrocarbon group having 5 to 10 carbon atoms selected from the decyl group. The dialkyl hemiacetal of 1,9-nonanedial represented by the general formula (1) is a dialkyl hemiacetal of 1,9-nonanedial in which 1,9-nonanedial is dissolved in a solution containing the 1,9-nonanedial.
. and!
& Can be easily synthesized by touching.

As a reaction solvent, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, the above linear fatty acids &
Specific examples include primary alcohols and mixtures thereof. Fi Murobuchi ~ approx. 80 as reaction i degree
It is advantageous to choose a temperature within the range 0°C 1.
After contacting 9-nonane dial with a linear aliphatic primary alcohol, if the solution is allowed to stand at a temperature below or below the Vi chamber, the dialkyl hemiacetal represented by the general formula (1) becomes colorless. 0 precipitates as crystals of
In the reductive amination reaction according to the method of the present invention, the solution containing the crystals obtained in this way can also be used as is.
Alternatively, crystals separated from the solution by normal operations such as filtration, sedimentation, and centrifugation may be used. General formula (1)
In the synthesis of the dialkyl hemiacetal of 1,9-nona/dial represented by Dihemiacetal crystals do not precipitate, and when the carbon number of the primary alcohol exceeds 01&:, the primary alcohol itself is mixed with the poly-primary alcohol crystallized under the operating conditions. Since their boiling points are close to that of 9-nonanediamine, it is difficult to separate the two from the reaction mixture after the reductive amination reaction, which is undesirable from a technical standpoint. In addition, when a branched aliphatic primary alcohol, secondary alcohol, or tertiary alcohol is used, the corresponding crystal of dialkyl hemiacetal of 1,9-nonanedial is! ! Not formed qualitatively.

Nickel-based catalysts and cobalt-based catalysts used as catalysts in the reduction 7-mination reaction according to the method of the present invention include Raney nickel catalyst, Raney copal) M medium, copper, silver, chromium, mankan, iron, cobalt, nickel, titanium,) Gold such as magnesium, zinc, tungsten, molybdenum, rhenium and zirconium
Modified Raney nickel catalyst modified with at least one kind of gold maple, modified Raney cobalt catalyst, and nickel in which these nickel-based catalysts and cobalt-based catalysts are supported on silica, alumina, diatomaceous earth, magnesia, crude lead oxide, etc. Examples include cobalt-based catalysts and cobalt-based catalysts. This reaction is carried out at 60-275°C, preferably at 10
It is carried out at a temperature within the range of 0 to 250°C. Since the reaction system needs to be kept in a liquid phase at the above reaction temperature,
The reaction pressure is usually selected to be within the range of 30 to 500 atm, preferably 60 to 300 atm. Liquid ammonia or ammonia aqueous solution is used as the ammonia source. The amount of ammonia used is 1,9-
3 to nonane dial dialkyl hemiacetal
A suitable range is 300 times by mole, preferably 10 to 100 times by mole #'i. Although ammonia can serve as a solvent, other organic solvents that are inert under the in-situ N reaction conditions can also be used together. Examples of organic solvents that can be used include alcohols such as ethanol, hexanol, 2-ethylhexanol, octatool, and ethylene glycol; Examples include aliphatic hydrocarbon chains such as hexane, octane, decane, liquid paraffin, and cyclohexane. As in the case of general reductive amination reactions, this reaction is carried out in a continuous or batchwise manner in a stirred reactor, a bubble column reactor, or a packed column reactor packed with a supported catalyst.

The crude 1,9-nonanediamine separated from the reaction mixture according to conventional methods may be subjected to 111 trade, or after forming the corresponding salt with a mineral acid or an organic carboxylic acid, if necessary. It is possible to purify the grade salt by subjecting it to a noble crystal operation.

Hereinafter, the method of the present invention will be specifically explained with reference to Examples.

LP Example 1 111 Synthesis of 1.9-nonanedialdialkyl hemiacetal Finally 1. 9-nonanedial and 2-methyl-1,8-octanedial mixture (1,9-nonanedial/2-methyl-1,8-octanedial-89
, 1710, 9) was isolated and obtained.

A Mitsuro flask with a content of 200d was charged with 20f of the above mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial, n-octatool 332, and 25f of n-hexane, and heated at 30°C under a nitrogen gas atmosphere. Stirred for 30 minutes. However, when this solution was allowed to stand still while being cooled to 5° C., colorless crystals were precipitated. After leaving this reaction mixture at 5°C for 3 hours, the precipitated crystals were
It was separated and washed with 50 d of n-hexane. After drying with ¥m) and weighing it, the colorless crystal's value was 44.1.
12%. The melting point of this colorless product was 42.6° (a part of the crystals was dissolved in ethanol) and analyzed by gas chromatography, and it was found that 2-methyl-1
, 8-octanedial was found to contain only about 1 root, and it was found that there was 2 times as much n-octatool as 1,9-nonanedial and 1,9-nonanedial. Further, when the crystal was subjected to infrared absorption spectrum measurement using the KBf tablet method, the following characteristic absorption was observed.

3160-3400cm” (broad), 29
55m', 2889cy'.

2845m-1,1468 pictures-1,1375m-1,1
150cm 1°1118m-1,1100m 1. l
(190m', 10003-".

958crn, 870ω.

Indeed, the elemental analysis values of the crystals closely matched the composition formula of C26H5204.

From the above analysis results, the above crystal is expressed by the following formula 1,
It was identified as 9-nonanedialdioctyl hemiacetal.

When the same reaction and operation as above was carried out using n-pentanol or n-decanol instead of 11-octatool, colorless crystals of the corresponding dialkyl hemiacetal of 1,9-nonanedial were obtained. Obtained. The melting points of these dialkyl hemiacetal crystals are 27.5°C (n-pentyl) and 48.5°C (
(n-decyl) was 0 (2) Reductive amination reaction of 1,9-nonanedialdialkyl hemiacetal. Commercially available Raney nickel was deployed in a stainless steel electromagnetic stirring autoclave of 811 equipped with a gas inlet and outlet at a temperature of 1.
．． 4F with 20 ml of ethanol and 1,9-nonanediardioctyl hemiacetal 10? obtained by the procedure of Example 1. After charging (24 mmol) and 200+++/liquid ammonia, hydrogen gas was pressurized to 60 atmospheres at a constant temperature. While stirring, the mixture was heated to 120°C (internal temperature) over about 30 minutes. Under these conditions, 6 more
Stirring was continued for 0 minutes. After cooling the autoclave and releasing hydrogen and ammonia, ethanol 1001
was added and the contents were taken out. Gas chromatography analysis of the ethanol solution after P was removed from the catalyst revealed that 1,9-nonanediamine was present in the charged 1,9
-79 based on nonane dial dioctyl hemiacetal standard
% yield.

Preparation 1, when the reductive amination reaction of 1,9-nonanedialsialgyl to other 1,9-nonanedialsialgyl was carried out by the same operation while gradually changing the catalyst and reaction temperature.
9-nonanedialdialkyl hemiacetal standard 1
, 9-nonanediamine yields are shown in Table 1 below.

Table 1 Di< y f yv 4% Cr modification 1.5
120 75 Hemiacetal Raney nickel didel 2% Mn modified 1.5 130
? .

Hemiacetal Raney Cobalt Example 2 In (2) of Example 1, liquid ammonia 200w1
The reductive amination reaction of 1,9-nonanedialdioctyl miacetal was carried out under the same conditions as in Example 1 (2) except that a 60% ammonia water bath solution was used for the 01,9 -The yield of nonanediamine is 76
%Met.

Comparative Example 1 In (2) of Example 1, 3.7f (2
4 mmol) of 1,9-nonanedial dissolved in ethanol'/f! Example 1 except that L8d was added (
One reductive amination reaction was carried out under the same conditions as in 2).

The yield of 1,9-nonanediamine based on the charged 1,9-nonanedial was 26%, indicating that a considerable amount of insoluble polymeric material was produced in this case.

Patent applicant: RiRashi Co., Ltd. Agent: Patent Attorney Important Ken

Claims (1)

[Scope of Claims] A dialkyl hemiacetal of 1,9-nonanedial represented by the following general formula (1) (wherein RL represents a linear saturated aliphatic hydrocarbon group having 5 to 10 carbon atoms) A process for producing 1,9-nonanediamine, which comprises reducing and aminating 1,9-nonanediamine with hydrogen and ammonia in a liquid phase in the presence of a nickel-based catalyst or a metal-based catalyst.