Synthesis method of alpha-nitro-alpha-aryl ketone compound

A synthesis method and compound technology are applied in the field of synthesizing α-nitro-α-aryl ketone compounds, which can solve the problems of highly toxic organotin, high cost and the like, and achieve the effect of simple reaction operation.

Inactive Publication Date: 2018-12-21
LANZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] WO 2005087752 A2 discloses a synthesis of α-(4-tert-butylphenyl) with 2-nitrocyclohexanone substrate and tributylarylstannane as arylation reagent under the conditions of mercury acetate and lead acetate -α-nitrocyclohexanone, but the reaction requires expensive and highly toxic organotin, lead, mercury compounds

Method used

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  • Synthesis method of alpha-nitro-alpha-aryl ketone compound
  • Synthesis method of alpha-nitro-alpha-aryl ketone compound
  • Synthesis method of alpha-nitro-alpha-aryl ketone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Using 2-nitrocyclohexanone as raw material

[0029]

[0030] 2-Nitrocyclohexanone (28.6mg, 0.20mmol), K 2 CO 3 (82.9mg, 0.60mmol) and diphenyl iodotetrafluoroborate (Ph 2 IBF 4 , CAS: 313-39-3) (220.8mg, 0.60mmol), then add 2.0mL DCE under argon atmosphere, seal with a lid, and react in an oil bath at 100°C for 2 hours. When the raw materials were consumed, the system was cooled to room temperature, then diluted with 5.0 mL of petroleum ether, and directly subjected to column chromatography (petroleum ether / ethyl acetate=40:1). A pale yellow solid (16.2 mg, yield 37.0%) was finally obtained.

[0031] The product detection data are as follows:

[0032] 1 H NMR (400MHz, CDCl 3 ):δ7.48-7.46(m,3H),7.36-7.34(m,2H),3.10-3.03(m,1H),2.94-2.88(m,1H),2.70-2.64(m,1H),2.59 -2.52(m,1H),1.98-1.89(m,3H),1.80-1.74(m,1H); 13 C NMR (100MHz, CDCl 3 ): δ200.5, 131.8, 130.0, 129.0, 128.2, 100.9, 40.0, 35.0, 27.0, 21.8.

Embodiment 2

[0034] Using 2-nitrocyclohexanone as raw material

[0035]

[0036] 2-Nitrocyclohexanone (28.6mg, 0.20mmol), K 2 CO 3 (55.3mg, 0.30mmol) and diphenyliodotrifluoromethanesulfonate (Ph 2 IOTf, CAS: 66003-76-7) (172.1mg, 0.40mmol), then add 4.0mL DCE under an argon atmosphere, seal with a lid, and react in an oil bath at 85°C for 3 hours. When the raw materials were consumed, the system was cooled to room temperature, then diluted with 6.0 mL of petroleum ether, and directly subjected to column chromatography (petroleum ether / ethyl acetate=40:1). A pale yellow solid (30.3 mg, yield 69.0%) was finally obtained.

[0037] The spectral data of the product are the same as in Example 1.

Embodiment 3

[0039] Using 2-nitrocyclohexanone as raw material

[0040]

[0041] Add 2-nitrocyclohexanone (28.6 mg, 0.20 mmol), Cs 2 CO 3 (97.7mg, 0.30mmol) and diphenyl iodide bromide (Ph 2 IBr) (180.5 mg, 0.50 mmol), then 3.0 mL of DCE was added under an argon atmosphere, sealed with a lid, and reacted in an oil bath at 65° C. for 2 hours. When the raw materials were consumed, the system was cooled to room temperature, then diluted with 6.0 mL of petroleum ether, and directly subjected to column chromatography (petroleum ether / ethyl acetate=40:1). A pale yellow solid (24.4 mg, yield 55.6%) was finally obtained.

[0042] The spectral data of the product are the same as in Example 1.

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Abstract

The invention discloses a synthesis method of an alpha-nitro-alpha-aryl ketone compound. The method comprises the following steps: under the effect of alkali, enabling alpha-nitro ketone compound anddiaryliodonium salt to react, and obtaining the alpha-nitro-alpha-aryl ketone compound. The structural formula of the alpha-nitro ketone compound is as follows: (shown in the description) The structural formula of the diaryliodonium salt is as follows: (shown in the description). The structural formula of the alpha-nitro-alpha-aryl ketone compound is as follows: (shown in the description), whereinA is 5-ring to 12-ring, R is alkyl or aryl, R1 is alkyl or aryl, Ar is aryl, and X- is anions. On the premise of no transitional metal catalytic condition, the synthesis of the alpha-nitro-alpha-arylketone compound can be economically and efficiently realized, and the reaction operation is simple and safe.

Description

technical field [0001] The invention belongs to the field of synthesis of organic intermediates, in particular to a method for synthesizing α-nitro-α-aryl ketone compounds. Background technique [0002] In modern organic synthesis, material science and pharmaceutical research, α-nitro-α-aryl cyclic ketones with quaternary carbon centers are an important class of structural units. Compounds containing this skeleton can be widely used in agricultural production as herbicides. In addition, through further transformation of the nitro functional group and carbonyl functional group in the skeleton, key intermediates for the synthesis of natural products and organic functional molecules can also be prepared. Asymmetric catalytic Ligands - α-amino alcohol compounds, etc. [0003] Applicant (CN106632200A) disclosed a kind of synthetic method of α-nitrocycloalkanone before this, and this method is under the catalysis of copper-based or iron-based catalyst, React with nitrating agen...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C201/12C07C205/45
CPCC07C201/12C07C2601/08C07C2601/14C07C2601/18C07C2601/20C07C205/45
Inventor 张辅民安洋
Owner LANZHOU UNIVERSITY
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