JP3968983B2 - 2-aminocyclododecadienone oxime - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to 2-aminocyclododecadienone oxime that can be easily led to 12-aminododecanoic acid useful as a raw material such as 12 nylon.
Note that 2-aminocyclododecadienone oxime is a novel substance.
[0002]
[Prior art]
Techniques related to the present invention include Bull. Chem. Soc. Jpn. 39, 1129 (1966) describe various 2- (substituted amino) cyclododecadienone oximes. However, there is no description of 2-aminocyclododecadienone oxime of the present invention and it has not been known so far.
[0003]
[Problems to be solved by the invention]
The present invention provides a novel compound 2-aminocyclododecadienone oxime.
[0004]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0005]
2-Aminocyclododecadienone oxime can be produced, for example, by a reaction of 2-halocyclododecadienone oxime and ammonia.
Since 2-halocyclododecadienone oxime has two double bonds in the molecule, there are structural isomers of cis and trans isomers, but any case may be used. When 2-halocyclododecadienone oxime is a mixture of these isomers, 2-aminocyclododecadienone oxime is also obtained as a mixture of isomers.
[0006]
The 2-halocyclododecadienone oxime used as an example can be synthesized by the reaction of cyclododecatriene and nitrosyl chloride, and is usually obtained as a mixture of isomers. As a specific example, the preparation of 2-chlorocyclododecadienone oxime is described in Chim. Ind. (Milan), 49 (5), 494 (1967).
[0007]
As the ammonia used as an example of the present invention, a commercially available product can be used as it is. For example, gaseous, liquid, or dissolved in a solvent can be used.
[0008]
The amount of ammonia used can be 1 to 100 equivalents relative to 2-halocyclododecadienone oxime, for example. Preferably, it is 3 to 30 equivalents.
[0009]
The reaction of 2-chlorocyclododecadienone oxime and ammonia shown as an example is usually carried out with an aqueous ammonia solvent, but it can also be carried out in the presence of an organic solvent that does not affect the reaction. Examples of the organic solvent that can be used include lower aliphatic alcohols such as methanol and ethanol, cyclic ethers such as dioxane, lower aliphatic nitriles such as acetonitrile and propionitrile, and the like.
These solvents are usually 0 to 100 times by weight, preferably 0 to 50 times by weight, relative to 2-chlorocyclododecadienone oxime.
[0010]
Although reaction temperature is not specifically limited as long as it carries out below the boiling point of the solvent to be used, Usually, it can carry out at 40-110 degreeC.
[0011]
The reaction pressure is usually carried out under normal pressure. You may implement under some pressurization or a little decompression.
[0012]
The reaction time varies depending on the concentration and temperature, but is usually 0.01 to 24 hours.
[0013]
A mixture comprising 2-aminocyclododecadienone oxime and its isomer obtained in the present invention can be converted to 12-aminododecanoic acid by reduction, and is useful as a raw material intermediate of nylon 12.
[0014]
【Example】
Next, an Example is given and this invention is demonstrated concretely.
Example 1
Synthesis of 2-amino-5,9-cyclododecadienone oxime 30 ml of methanol was added to 60 ml of 25% by weight aqueous ammonia solution and kept at 3 ° C. or lower with ice cooling to give 2-chloro-5,9-cyclododecadienone oxime. A solution prepared by dissolving 3.00 g (13.2 mmol) in 30 ml of methanol was slowly added dropwise.
After stirring for 30 minutes at 3 ° C. or lower under ice cooling, ammonium chloride was filtered off and the solvent was distilled off under reduced pressure. 30 ml of water was added to the resulting residue, and extraction was performed three times with 30 ml of diethyl ether. The extraction solvent, diethyl ether, was washed twice with 30 ml of saturated brine and dried over anhydrous sodium sulfate. After filtration, diethyl ether was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (MS Gel D-150-60 A, methanol). 1 g (5.2 mmol) was obtained. This corresponds to a yield of 40 mol%.
The obtained white solid was subjected to the following melting point and various instrumental analyses.
(1) Melting point measurement m. p. 113-114 ° C
(2) Hydrogen nuclear magnetic resonance analysis ( ¹ H-NMR)
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 5.34 to 5.31 (4H, m), 3.39 to 3.35 (1H, m), 3.00 to 2.91 (1H, m) ),
2.51-1.50 (13H, m)
(3) Infrared spectroscopic analysis (IR)
IR (KBr): ν = 3344, 3288, 3165, 2902, 2849, 1583, 1446, 975, 951, 705 cm ⁻¹
(4) Mass spectrometry (MS)
MS (CI): m / z = 209 (MH ⁺ ), 191, 96, 67, 30
[0015]
【The invention's effect】
According to the present invention, a novel compound 2-aminocyclododecadienone oxime and its isomer mixture can be provided.
The compound of the present invention can be led to 12-aminododecanoic acid which is a raw material of nylon 12.
[Brief description of the drawings]
FIG. 1 is a mass analysis result of 2-amino-5,9-cyclododecadienone oxime. The upper row shows the results of mass spectrometry by EI-MS. The lower part showed the mass spectrometry result by CI-MS.
FIG. 2 is a result of hydrogen nuclear magnetic resonance analysis of 2-amino-5,9-cyclododecadienone oxime.
FIG. 3 is an infrared spectroscopic analysis result of 2-amino-5,9-cyclododecadienone oxime.

Claims (2)

The following formula (1):

2-aminocyclododecadienone oxime represented by A mixture comprising structural isomers of the compound of claim 1.

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