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6-nitroacetophenone compound, preparation method and application thereof

A technology for nitroacetophenone and cyanoacetophenone, applied in the field of 6-nitroacetophenone compounds, can solve the problems of harsh reaction conditions, environmental pollution, adverse effects and the like

Inactive Publication Date: 2009-12-16
TOPHARMAN SHANGHAI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The reaction conditions used are relatively harsh, and the yield is low, only 40 to 50%, and the unavoidable volatilization of high boiling point solvents such as Dowtherm at high temperature has adverse effects on the working environment and the health of operators, and has a negative impact on the environment. Pollution, not suitable for large-scale industrial production

Method used

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  • 6-nitroacetophenone compound, preparation method and application thereof
  • 6-nitroacetophenone compound, preparation method and application thereof
  • 6-nitroacetophenone compound, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0133] Example 1 3-acetamido-4-ethoxyacetophenone (Compound B, R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) Synthesis

[0134] (1) Preparation of 3-nitro-4-hydroxyacetophenone

[0135] In an ice bath, add p-hydroxyacetophenone (136.2g, 1.0mol) to concentrated sulfuric acid (1000ml), stir for 10min, add potassium nitrate (96.0g, 0.95mol), stir for 2h, then add potassium nitrate (7.1 g, 0.07mol), stirred for 1h, and the reaction was over. The reaction solution was poured into 3000 ml of crushed ice to separate out a large amount of solids, filtered with suction, washed with water, and dried to obtain 171.2 g of light yellow powder of 3-nitro-4-hydroxyacetophenone with a yield of 94.5%.

[0136] (2) Preparation of 3-amino-4-hydroxyacetophenone

[0137] At room temperature, 3-nitro-4-hydroxyacetophenone (171.2g, 0.945mol) was dissolved in THF (1500ml), Raney Ni 20g was added, and the hydrogenation reaction was carried out at atmospheric pressure for 24h, and the reaction was completed. After ...

Embodiment 2

[0142] Example two 3-acetamido-4-ethoxy-6-nitroacetophenone (compound D, R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) Synthesis

[0143] Compound B (R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) (88.5g, 0.4mol) dissolved in nitromethane (1000ml), add fuming nitric acid (17.7ml, 0.4mol), stir at 40℃ for 12h, add fuming nitric acid (15.5ml, 0.35mol), stirring for 10h, the reaction is over. Pour the reaction solution into saturated sodium bicarbonate solution (1000ml), stir, separate, wash the organic layer with water, dry, filter, add 10g activated carbon to the filtrate, reflux for 20min, hot filter, and concentrate to obtain a red oil, 40℃ normal pressure Dry 3-acetamido-4-ethoxy-6-nitroacetophenone (compound D, R 1 = Acetyl, R 2 =ethyl, Z=-NH-) 86.5g, yield 81.2%. 1 HNMR(300MHz, CDCl 3 )δ1.52(t, 3H), 2.24(s, 3H), 2.52(s, 3H), 4.22(q, 2H), 7.53(s, 1H), 7.98(s, 1H), 8.52(s, 1H) ). ESI-MS (m / z) 265 (M-1).

Embodiment 3

[0144] Example three 3'-acetamido-4'-ethoxy-6'-nitro-2-bromoacetophenone (Compound II, R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) Synthesis

[0145] The compound D(R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) (79.9g, 0.3mol) dissolved in dichloromethane (1000ml), add liquid bromine (14.6ml, 0.285mol), stir for 12h at room temperature, the reaction liquid turns from light red to light Yellow, make up liquid bromine (1.1ml, 0.021mol), stir for 2h, the reaction is over. 3'-acetamido-4'-ethoxy-6'-nitro-2-bromoacetophenone (Compound II, R 1 = Acetyl, R 2 = Ethyl, Z = -NH-) 110.0g, can be used directly in the next reaction. 1 HNMR(300MHz, CDCl 3 )δ1.55(t, 3H), 2.24(s, 3H), 4.27(q, 2H), 4.30(s, 2H), 7.64(s, 1H), 8.01(s, 1H), 8.58(s, 1H) ). ESI-MS (m / z) 346 (M+1), 368 (M+23).

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Abstract

The invention relates to a 6-nitroacetophenone compound of the formula I, a preparation method and application thereof in preparing a 3-substitute-4-hydroxyquinoline compound, a 3-substitute-4-chloroquinoline compound and an intermediate of the compound of the formula I. In the formula I, X is a cyano-group, trifluoromethyl, nitryl, -NHCOR3, -NHCOOR3, -CONER3R3', -N=CHR3 or -CO2R3, wherein R3 and R3' are hydrogen, C1-C10 alkyl, C1-C10 alkenyl, aryl or the C1-C10 alkyl substituted by the aryl and the same or different; Z is -NH- or -O- or the formula II; R1 and R1' are formyl radicals, the C1-C10 alkyl, the C1-C10 alkenyl, the aryl, the C1-C10 alkyl substituted by the aryl, C1-C10 lauroyl groups, aroyl groups, the C1-C10 lauroyl groups substituted by the aryl, C1-C10 alkoxy carbonyl or the C1-C10 alkoxy carbonyl substituted by the aryl the same or different; R2 is the C1-C10 alkyl, the C1-C10 alkenyl or the aryl; the alkyl does not need to be substituted by halogen, alkoxy, the aryl or a heterocyclic radical containing 1-2 O or N, wherein the heterocyclic radical does not need to be substituted by the C1-C10 alkyl or the C1-C10 alkoxy; and when Z is -O- and R1 is methyl, R2 is not the methyl.

Description

Technical field [0001] The present invention relates to 6-nitroacetophenone compounds which can be used to prepare 3-substituted-4-hydroxyquinoline compounds and 3-substituted-4-chloroquinoline compounds, as well as preparation methods and uses thereof, and the intermediate body. More specifically, it relates to a 6-nitroacetophenone compound represented by the following formula I, a preparation method thereof, and its use in the preparation of 3-substituted-4-hydroxyquinoline compounds (compounds represented by formula A) And the use of 3-substituted-4-chloroquinoline compounds (compounds represented by formula A'). Background technique [0002] [0003] 3-substituted-4-hydroxyquinoline compounds (formula A) and 3-substituted-4-chloroquinoline compounds (formula A') are important pharmaceutical intermediates for the preparation of 3,4-disubstituted quinolines An important intermediate of such compounds. For example, 3,4-disubstituted quinolines are irreversible small molecule ...

Claims

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Application Information

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IPC IPC(8): C07C233/33C07C231/12C07C255/60C07C253/30C07D215/56C07D295/08
CPCC07C211/51C07D215/26C07C205/36C07C211/46C07C215/76
Inventor 茆勇军李剑峰谢凯李海泓张容霞段宏亮郭洪利沈敬山
Owner TOPHARMAN SHANGHAI
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