JPH1087593A - Primary dioxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primary dioxime which is a useful intermediate for synthesizing a heat-resistant polyamide which can be melt-molded and a primary diamine which is a raw material of an amorphous / transparent polyamide. SOLUTION: General formula (I) (Wherein, R represents an aliphatic or alicyclic hydrocarbon group having 5 to 10 carbon atoms).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a synthetic intermediate for producing an aliphatic primary diamine or an alicyclic primary diamine. Aliphatic primary diamine is used as a raw material for synthesizing a heat-resistant polyamide that can be melt-molded by condensation polymerization with a dicarboxylic acid such as terephthalic acid,
The alicyclic primary diamine is used as a raw material for synthesizing an amorphous and transparent polyamide by condensation polymerization with a dicarboxylic acid such as terephthalic acid.

[0002]

2. Description of the Related Art A method for synthesizing an aliphatic primary diamine or an alicyclic primary diamine using a dialdehyde or a derivative directly derived therefrom as a synthetic intermediate is known. For example, a method of reductive amination of a dialdehyde in the presence of a hydrogenation catalyst in the presence of ammonia and hydrogen (see US Pat. No. 2,636,051), a method of converting a dialdehyde or its hemiacetal in the presence of a hydrogenation catalyst For reductive amination in the coexistence of ammonia and hydrogen
135, and a method of hydrogenating a Schiff base formed from a dialdehyde and a monoamine in the presence of ammonia (see Japanese Patent Publication No. 58-26902).

[0003]

SUMMARY OF THE INVENTION US Patent No. 2,63
The reductive amination method described in US Pat. No. 6,051 and Japanese Patent Publication No. 1-49135 and the method using a Schiff base described in Japanese Patent Publication No. Sho 58-26902 both use ammonia. 250 kg / cm ²
However, there is a problem that a device which can withstand the high pressure has to be used. Therefore, without using ammonia
0 kg / cm ² or less total pressure, preferably 10 kg / cm 2
There has been a demand for providing a dialdehyde derivative as a synthetic intermediate that can be used when synthesizing a diamine at a low pressure of ² or less.

[0004]

A method generally known as a synthesis method of a monoamine has a large difference in reactivity between a monoamine and a diamine. Therefore, if the method is directly applied to the synthesis of a diamine, it will undergo intramolecular reaction by a secondary reaction or the like. Due to cyclization or formation of polyamine, the desired primary diamine is obtained only in low yield, which is not industrially satisfactory. As shown in Reference Examples 9 and 10,
When a reductive amination reaction of an aldehyde compound was actually attempted, a monoamine reaction yielded a monoamine with a yield of 80% or more, whereas a primary dialdehyde reaction yielded a low yield of only 30% or less. No primary diamine was obtained. Therefore, the present inventors have focused on oximes which are known to be converted to amines and are utilized as useful reaction intermediates in the synthesis of various nitrogen-containing compounds, and as a result of intensive studies, have found that the general formula ( I)

[0005]

Embedded image

The above object has been achieved by finding a primary dioxime represented by the formula (wherein, R represents an aliphatic or alicyclic hydrocarbon group having 5 to 10 carbon atoms). The primary dioxime represented by the above general formula (I) is reduced in the presence of a hydrogenation catalyst to give a compound of the general formula (II)

[0007]

Embedded image

(Wherein R is as defined above)
In high yield.

R in the general formulas (I) and (II) represents an aliphatic or alicyclic hydrocarbon group having 5 to 10 carbon atoms. When R represents an aliphatic hydrocarbon group having 5 to 10 carbon atoms, specific examples of the dioxime represented by the general formula (I) include 1,7-heptanediol dioxime,
8-octanedialdioxime, 2-methyl-1,8
-Octanedialdoxime, 1,9-nonandialdioxime, 1,10-decandialdioxime,
1,11-undecandial dioxime, 1,12-
Dodecandial dioxime, 3,8-dimethyl-1,
10-decandial dioxime, 3,7-dimethyl-
Examples include 1,10-decandial dioxime and mixtures thereof. When R represents an alicyclic hydrocarbon group having 5 to 10 carbon atoms, specific examples of the dioxime represented by the general formula (I) include cyclohexane-1,3.
(4) -Dicarbaldehyde dioxime, bicyclo [2.
2.1] Heptane-2 (3), 5 (6) -dicarbaldehydedioxime, bicyclo [2.2.2] octane-2
(3), 5 (6) -dicarbaldehyde dioxime, tricyclo [5.2.1.0] decane-3 (4), 8 (9)
-Dicarbaldehyde dioxime and mixtures thereof.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The primary dioxime represented by the general formula (I) has the general formula (III)

[0011]

Embedded image

(Wherein R is as defined above), which is obtained almost quantitatively by a condensation reaction between a primary dialdehyde and hydroxylamine. The amount of the primary dialdehyde to be used relative to hydroxylamine is 0.25 to 1.0 mol of hydroxylamine.
０．５0.5 mol. This reaction is preferably performed in a solvent. Water or an organic solvent can be used as the solvent. As the organic solvent, any solvent can be used as long as it does not react irreversibly with hydroxylamine or primary dialdehyde. For example, alcohols such as methanol, ethanol and isopropyl alcohol; hydrocarbon solvents such as benzene and toluene; ether solvents such as tetrahydrofuran, dioxane and diethylene glycol dimethyl ether; and secondary or tertiary amine solvents such as morpholine, pyridine and triethylamine. And the like, but are not limited to these.

Specifically, this reaction is preferably carried out by dissolving hydroxylamine in a solvent, dropping a primary dialdehyde, and completing the condensation reaction. The dropping temperature of the primary dialdehyde is a temperature in the range of 0 ° C to 100 ° C. After dropping, the mixture is stirred at a temperature of 100 ° C. or less for 5 minutes to 10 hours, depending on the type of primary dialdehyde and the reaction temperature. At this time, the temperature of the dropping or the reaction was set to 100 ° C.
In this case, the decomposition of hydroxylamine occurs, and the yield of primary dioxime decreases. By the above operation, primary dioxime is produced almost quantitatively. The primary dioxime is isolated and purified by distilling off the solvent after the reaction treatment and, if necessary, recrystallization. As the hydroxylamine, a commercially available aqueous solution can be used, or one prepared by treating a salt such as a sulfate or a hydrochloride with an alkali can be used as it is. However, when producing a diamine from the dioxime of the present invention, the coexistence of water causes a decrease in yield, so when a primary dioxime is prepared using an aqueous hydroxylamine solution, it is necessary to dehydrate after preparing the oxime. preferable. In addition, when a primary dioxime is prepared using a salt such as a sulfate or a hydrochloride of hydroxylamine, a dehydration treatment may be performed after removing a salt such as an alkali sulfate by-produced as necessary after the preparation of the dioxime. preferable.

Dioximes can be produced by a conventionally known method for producing a monooxime, for example, a method by reduction of a nitro compound (J. Org. Chem., Vol. 28, p. 266; 1963
), A method by addition reaction of nitrosyl chloride to olefins (Journal of Organic Chemistry (J. Org. Chem.), 36, 1169, 197).
1 year), by the oxidation of hydroxylamine (Justus Libig Annaren del Chemie)
tus Liebigs Ann. Chem.), 83, 679, 19
1964), a method by a nitrite transfer reaction (J. Am. Chem. Soc., Vol. 82, 2640).
Page, 1960). The primary dioxime obtained by the above method may be used in the reaction system as it is, without isolation and purification, as it is in the reaction system.

[0015]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Isopropyl alcohol 50 was placed in a 200 ml three-necked flask.
ml and 13.8 g of 50% aqueous hydroxylamine solution
(0.21 mol), and 1,9-nonandial / 2-methyl-1,8-octanediol = 70 under water cooling.
15.6 g (0.10 mol) of a / 30 mixture was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, and then cooled with ice to precipitate white crystals. The precipitated crystals were collected by filtration under reduced pressure and washed three times with 30 ml of ether.
The crystals were dried under reduced pressure to obtain 7.94 g of white crystals. When the obtained crystal was subjected to structural analysis by mass spectrometry, infrared absorption and NMR, it was found to be a 1,9-nonandialal dioxime mixture having an average cis / trans composition ratio of 1/1 (molar ratio). Was. The yield based on the charged 1,9-nonandial was 73.7%. The physical properties of 1,9-nonandial dioxime are as follows. Melting point 150 ° C mass spectrometry M ⁺ = 186 infrared absorption 1665 cm ^-1 NMR data δ = 7.40 (1H, t), 6.75
(1H, t), 4.85 (2H, bs), 2.35 (2
H, m), 2.20 (2H, m), 1.50 (4H,
m), 1.35 (6H, bs)

Example 2 The recrystallized mother liquor from which crystals had been removed by filtration in Example 1 was further recrystallized to remove 1,9-nonandioxime, and concentrated to dryness to give 2-methyl-1,8 having the following physical properties. -Octanedial dioxime was obtained. Mass spectrometry M ⁺ = 186 Infrared absorption 1665 cm ^-1 NMR data δ = 7.40 (0.5H, t), 7.2
0 (0.7H, d), 6.75 (0.5H, t), 6.
40 (0.3H, d), 4.85 (2H, bs), 2.
35 (2H, m), 2.20 (1H, m), 1.35
(8H, bs), 1.10 (2.1H, d), 0.90
(0.9H, d)

Example 3 Isopropyl alcohol 50 was placed in a 200 ml three-necked flask.
ml and 13.8 g of 50% aqueous hydroxylamine solution
(0.21 mol) and tricyclo [5.
2.1.0] 19.2 g (0.10 mol) of a mixture of decane-3 (4), 8 (9) -dicarbaldehyde was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours.
The solvent was distilled off under reduced pressure to obtain 22.0 g of a colorless oil. The structure of the obtained product was analyzed by mass spectrometry, infrared absorption and NMR, and it was found that tricyclo [5.2.
1.0] Decane-3 (4), 8 (9) -dicarbaldehyde dioxime mixture was found to have formed.
The physical properties of the dioxime mixture are as follows. Mass spectrometry M ⁺ = 222 Infrared absorption 1664 cm ^-1 NMR data δ = 7.30 (1H, m), 6.60
(1H, m), 2.55 (2H, m), 1.10-2.
30 (12H, m)

EXAMPLE 4 Isopropyl alcohol 50 was placed in a 200 ml three-necked flask.
ml and 13.8 g of 50% aqueous hydroxylamine solution
(0.21 mol), and under water cooling, 14.2 g (0.10 mol) of 1,8-octanedial was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, and then cooled with ice to precipitate white crystals. The precipitated crystals were collected by filtration under reduced pressure, washed three times with 30 ml of ether, and dried under reduced pressure to obtain 12.0 g of white crystals. The structure of the obtained crystal was confirmed by mass spectrometry and infrared absorption. As a result, it was found that 1,8-octanedialdioxime having the following physical properties was formed. Mass spectrometry M ⁺ = 172 Infrared absorption 1665 cm ^-1

EXAMPLE 5 Isopropyl alcohol 50 was placed in a 200 ml three-necked flask.
ml and 13.8 g of 50% aqueous hydroxylamine solution
(0.21 mol) and 1,10-decandial / 2-methyl-1,9-nonandial = 80 under water cooling.
/ 20 (weight ratio) of a mixture of 17.0 g (0.10 mo
l) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, and then cooled with ice to precipitate white crystals. The precipitated crystals were collected by filtration under reduced pressure, washed three times with 30 ml of ether, and dried under reduced pressure to obtain 15.2 g of white crystals. When the structure of the obtained crystal was confirmed by mass spectrometry and infrared absorption, it was found that a mixture of 1,10 decanedial dioxime and 2-methyl-1,9-nonandial dioxime was formed. The physical properties of the dioxime mixture are as follows. Mass spectrometry M ⁺ = 200 Infrared absorption 1665cm ^-1

EXAMPLE 6 Isopropyl alcohol 50 was placed in a 200 ml three-necked flask.
ml and 13.8 g of 50% aqueous hydroxylamine solution
(0.21 mol), water-cooled, and bicyclo [2.
2.1] Heptane-2 (3), 5 (6) -dicarbaldehyde 12.8 g (0.10 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 2 hours, and then the solvent was distilled off under reduced pressure to obtain 15.9 g of a colorless oil. The structure of the obtained product was confirmed by mass spectrometry and infrared absorption. As a result, a mixture of bicyclo [2.2.1] heptane-2 (3), 5 (6) -dicarbaldehyde dioxime having the following physical properties was obtained. Was generated. Mass spectrometry M ⁺ = 158 Infrared absorption 1664 cm ^-1

Reference Example 1 1.0 g of nonandial dioxime synthesized in Example 1
(5.38 mmol) in 8.8 g of morpholine,
Placed in a 50 ml autoclave. 100 mg of Fe—Cr-modified Raney nickel and 100 mg of a 10% NaOH methanol solution were added, and the mixture was pressurized with hydrogen at 10 kg / cm ² and reacted at 100 ° C. for 15 hours. Analysis of the reaction mixture revealed that all primary dioximes had disappeared and 0.72 g of 1,9-nonanediamine had been produced. The yield of diamine based on primary dioxime is 85.0%.

Reference Example 2 Terephthalic acid 327.3 g (1.97 mol), 1,9
-316.6 g (2.0 mol) of nonanediamine, 7.33 g (0.06 mol) of benzoic acid, 0.65 g of sodium hypophosphite monohydrate and 600 ml of distilled water.
A 0 L autoclave was charged and replaced with nitrogen. 100 ℃
After stirring for 30 minutes at an internal temperature of 210
The temperature was raised to ° C. After continuing the reaction for 1 hour,
The reaction was carried out while maintaining the pressure at 22 kg / cm ² while gradually removing water vapor. Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and further reacted for 1 hour.
A prepolymer having an intrinsic viscosity [η] of 0.25 dl / g was obtained. After drying at 100 ° C. under reduced pressure for 12 hours,
It was pulverized to a size of 2 mm or less. This is 230 ° C,
Solid phase polymerization was performed at 0.1 mmHg for 10 hours, and the melting point was 31
A white polyamide having an intrinsic viscosity [η] of 1.35 dl / g and a terminal sealing rate of 90% at 7 ° C. was obtained. Next, this polyamide was injection molded at a cylinder temperature of 340 to 350 ° C and a mold temperature of 100 ° C. The obtained polyamide had a melting point of 350 ° C. or less, and could be melt-molded.

Reference Examples 3 to 8 In Reference Example 2, instead of 1,9-nonanediamine, equimolar numbers of 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, and 1,10-decane were used. Diamine, 1,11-undecanediamine and 1,
A polyamide was synthesized in the same manner except that 12-dodecanediamine was used. Table 1 summarizes the melting point, decomposition temperature, and melt moldability of the obtained polyamide. The melting point of 1,6-hexanediamine was higher than the decomposition temperature, so that melt molding was impossible, but the diamine having 7 to 12 carbon atoms had a melting point lower than the decomposition temperature and was melt-moldable.

[Table 1]

Reference Example 9 10.0 g (0.10 mol) of hexyl aldehyde, 29.5 g of methanol and 0.5 g of Raney nickel catalyst
Was charged into a 100 ml autoclave, and the inside of the autoclave was replaced with hydrogen. After returning to normal pressure, ammonia 10.
After feeding 0 g, the hydrogen pressure was increased to 100 kg / cm ² and the reaction was carried out at 120 ° C. for 4 hours. When the obtained reaction solution was analyzed, all of hexylaldehyde disappeared, and 8.2 g of hexylamine and 0.7 g of dihexylamine were used.
It was found that 7 g had been produced. The conversion based on hexylaldehyde was 100%, and the selectivities were 81.2% for hexylamine and 15.3% for dihexylamine.

Reference Example 10 15.6 g of 1,9-nonandial (0.10 mol)
1), 23.9 g of methanol and 0.5 g of Raney nickel catalyst were charged into a 100 ml autoclave, and the inside of the autoclave was replaced with hydrogen. After returning to normal pressure, 10.0 g of ammonia was pumped in, and then the hydrogen pressure was increased to 100 kg / cm.
² and reacted at 120 ° C. for 4 hours. When the obtained reaction solution was analyzed, it was found that all the 1,9-nonandial had disappeared, and 4.1 g of 1,9-nonanediamine and a large amount of polyamine had been formed. 1,
The conversion based on 9-nonandial is 100%,
The selectivity for 1,9-nonanediamine was 26.0%. It was revealed that the selectivity of the reductive amination reaction of dialdehyde with respect to the reductive amination reaction of monoaldehyde was extremely low.

[0027]

The primary diamine in which R in formula (II) is an aliphatic hydrocarbon having 5 to 10 carbon atoms, that is, a primary diamine having 7 to 12 carbon atoms, is melt-molded by condensation polymerization with inexpensive terephthalic acid. As described in Table 1, these polyamides can be melt-molded at a melting point of at least 10 ° C. lower than the decomposition temperature of the polyamide, and the polyamide has excellent heat resistance. . On the other hand, a polyamide comprising an aliphatic primary diamine having 6 or less carbon atoms and terephthalic acid has high crystallinity and has a melting point higher than the decomposition temperature of the polyamide, so that it cannot be melt-molded. Further, a primary diamine in which R in the general formula (II) is an alicyclic hydrocarbon having 5 to 10 carbon atoms, that is, an alicyclic primary diamine having 7 to 12 carbon atoms is subjected to condensation polymerization with a dicarboxylic acid such as terephthalic acid. Can be converted to an amorphous transparent polyamide. For example, 3 (4),
8 (9) -Bisaminomethyltricyclo [5.2.1.
0] A polyamide comprising decane and terephthalic acid is amorphous and has excellent transparency.
No. 44 discloses this. According to the present invention, there has been provided a primary dioxime which is a useful intermediate for synthesizing a heat-resistant polyamide which can be melt-molded and a primary diamine which is a raw material of an amorphous / transparent polyamide.

Claims (4)

[Claims] 1. A compound of the general formula (I) (In the formula, R represents an aliphatic or alicyclic hydrocarbon group having 5 to 10 carbon atoms.) 2. A 1,9-nonandial dioxime 3. 2-Methyl-1,8-octanedialdioxime 4. Tricyclo [5.2.1.0] decane-
3 (4), 8 (9) -dicarbaldehyde dioxime