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Process for preparing allylic primary nitro compound

A technology of nitro compound and primary allylic position is applied in the field of preparation of primary nitro compound at allylic position, which can solve the problems of long reaction time, high toxicity and the like, and achieve simple steps, low corrosiveness, and economical and easy-to-obtain raw materials. Effect

Inactive Publication Date: 2004-09-15
HUBEI UNIV
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  • Description
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Problems solved by technology

[0002] The preparation method of existing allylic primary nitro compound mainly adopts under the existence of dimethylethylenediamine, ketone and nitromethane condensation preparation (Barton, D.H.R.; Motherwell, W.B., Zard, S.Z., J.Chem.Soc .Chem.Commun., 1982, 551; Barton, D.H.R,; Fernandez, I.; Ridard, C.S.; Zard, S.Z.Tetrahedron.1987, 43, 551; Tamura, R.; Chem.1986,51,4368), the specific method is to reflux aldehyde or ketone and nitromethane, dimethylethylenediamine in benzene for more than 20 hours, the reaction takes a long time, and the toxicity of solvent (benzene) is large, and the method It is not suitable for the preparation of allylic primary nitro compounds containing sensitive groups or active groups, such as ester groups, aldehyde groups, ketone groups, etc., because of the side reactions between carbonyl and amino groups

Method used

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  • Process for preparing allylic primary nitro compound
  • Process for preparing allylic primary nitro compound
  • Process for preparing allylic primary nitro compound

Examples

Experimental program
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Effect test

Embodiment 1

[0011] Example 1 From 5-nitro-6-methyl-6-hepten-2-one ( 1a ) to prepare 7-nitro-6-methyl-5-hepten-2-one ( 1b ), the reaction formula is as follows:

[0012]

[0013] Reaction formula (1)

[0014] Synthesis steps: introduce nitrogen oxide gas generated by mixing 10g (145mmol) sodium nitrite and 15ml (260mmol) glacial acetic acid into 30mL carbon tetrachloride, and add the resulting carbon tetrachloride solution dropwise to Contains 1.24g (7.3mmol) nitroketone 1a In 30ml of carbon tetrachloride, continue to stir at 60 ° C for 1 hour, then evaporate the solvent, and the crude product is obtained by silica gel column chromatography (elution condition: 2 / 8 ether / petroleum ether) 1b , 1.02g, yield 82%.

[0015] Infrared spectral analysis (IR, cm -1 , liquid film): 1716 (C=O), 1552 (NO 2 ).

[0016] NMR (90MHz) analysis:

[0017] δ H 5.54(t, 1H, CH=C), 4.76(s, 2H, -CH 2 NO 2 ), 1.76 (s, 3H, CH 3 C=C), 2.12(s, 3H, CH 3 C=O), 2.24-2.64 (m, 4H, -CH ...

Embodiment 2

[0018] Embodiment 2 By 5-nitro-5-acetic acid hydroxymethyl-6-methyl-6-hepten-2-ketone ( 2a ) to prepare 7-nitro-5-acetic acid hydroxymethyl-6-methyl-5-hepten-2-ketone ( 2b ). The reaction formula is as follows:

[0019]

[0020] Reaction formula (2)

[0021] Synthesis steps: 10g (145mmol) sodium nitrite and 15ml (260mmol) glacial acetic acid are mixed to generate nitrogen oxide gas into 25ml carbon tetrachloride, and the resulting carbon tetrachloride solution is added to the containing 1.16g (5mmol) nitroester ketone 2a In 30mL of carbon tetrachloride, continue to stir at 60°C for 1 hour, then evaporate the solvent, and the crude product is chromatographed on a silica gel column (elution condition: 1 / 2 ethyl ether / petroleum ether) to obtain 2b, 0.89g, and rate of 77%.

[0022] Infrared spectral analysis (IR, cm -1 , liquid film): 1743 (C=O, ester), 1714 (C=O, ketone), 1655 (C=C), 1558 (NO 2 ), 1234, 1048.

[0023] NMR (90MHz) analysis:

[0024]...

Embodiment 3

[0025] Embodiment 3 By 6-nitro-3,7-dimethyl-7-octenal ( 3a ) to prepare 8-nitro-3,7-dimethyl-6-octenal ( 3b )

[0026] The reaction formula is as follows:

[0027]

[0028] Reaction formula (3)

[0029] Synthesis steps: introduce nitrogen oxide gas generated by mixing 6.7g (100mmol) sodium nitrite and 10mL (174mmol) glacial acetic acid into 15ml carbon tetrachloride, and add the resulting carbon tetrachloride solution dropwise at 55-60°C To contain 0.95g (5mmol) nitroaldehyde 3a In 15ml of carbon tetrachloride, continue to stir at 60 ° C for 1 hour, then evaporate the solvent, and the crude product is obtained by silica gel column chromatography (elution condition: 1 / 3 ether / petroleum ether) 3b , 0.66g, yield 69%.

[0030] Infrared spectral analysis (IR, cm -1 , liquid film): 1724 (C=O), 1552 (NO 2 ).

[0031] NMR (300MHz) analysis: δ H : 9.76 (d, 1H, CHO), 5.63 (t, 1H, C=CH), 4.83 (s, 2H, -CH 2 NO 2 )1.77 (s, 3H, CH 3 ), 0.99 (d, CH 3 , CH ...

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Abstract

A process for preparing allytrinitro compound includes such steps as reaction of the allybinitro or ally tetranitro compound on excess nitrite and inorganic or organic acid in hydrocarbon or halohydrocarbon solvent to obtain NOX, and further reaction at 50-60 deg.c to obtain allytrinitro compound. Its advantages are simple process and high output rate (50-90%).

Description

technical field [0001] The invention belongs to a preparation method of an allyl primary nitro compound, in particular to a method for preparing an allyl primary nitro compound by using an allyl secondary or tertiary nitro compound as a raw material. Background technique [0002] The preparation method of existing allylic primary nitro compound mainly adopts under the existence of dimethylethylenediamine, ketone and nitromethane condensation preparation (Barton, D.H.R.; Motherwell, W.B., Zard, S.Z., J.Chem.Soc .Chem.Commun., 1982, 551; Barton, D.H.R,; Fernandez, I.; Ridard, C.S.; Zard, S.Z.Tetrahedron.1987, 43, 551; Tamura, R.; Chem.1986,51,4368), the specific method is to reflux aldehyde or ketone and nitromethane, dimethylethylenediamine in benzene for more than 20 hours, the reaction takes a long time, and the toxicity of solvent (benzene) is large, and the method It is not suitable for the preparation of allyl-positioned primary nitro compounds co...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C201/12C07C205/03C07C205/44
Inventor 张合胜钟传富陈祖兴杜颖珺
Owner HUBEI UNIV
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