Method for preparing beta-nitrostyrolene compound

Abstract

The invention discloses a method for preparing beta-nitrostyrolene compounds. The method uses cinnamic acid compounds and cupric nitrate as raw materials, the raw materials are heated in acetonitrile and finally the beta-nitrostyrolene compounds are obtained through decarboxylation coupling. The cupric nitrate not only is used as a reactant, but also is used as transition metal catalyst. The reaction does not need the participation of ligands, acid, alkali, oxidant and the like, and does not need microwave heating, either. The preparation method has the advantages that the raw materials are low-cost and easy to obtain, the reaction system is mild, the operation is simple, the yield is high and the industrialization prospect is good.

Description

technical field [0001] The invention belongs to the field of organic synthetic chemistry, and relates to a method for synthesizing β-nitrostyrene compounds, in particular to a method for preparing β-nitrostyrene compounds through decarboxylation coupling reaction of cinnamic acid compounds catalyzed by copper nitrate. Background technique [0002] The β-nitrostyrene compound itself has obvious bactericidal and anti-tumor activities; its structure has a double bond and is prone to conjugate addition reactions, and the nitro group contained in it can also be converted into amines, aldehydes, ketones, etc. through functional groups Other compounds, so β-nitrostyrene compounds are an important synthetic intermediate in the field of organic synthesis, and it has also been widely used in the fields of explosives, dyes and industrial solvents. [0003] The traditional synthetic method of β-nitrostyrene is formed by Henry reaction condensation of aromatic aldehyde and nitromethane u...

AI Technical Summary

Problems solved by technology

However, the raw material aromatic aldehyde is unstable, and nitromethane is relatively expensive

And under alkaline conditions, nitroalkene itself is prone to polymerization, has many side reactions, is difficult to separate, and is difficult to prepare on a large scale

[0004] In recent years, several methods for preparing β-nitrostyrene compounds through decarboxylation and coupling reactions have been developed with cinnamic acid compounds as reaction raw materials, mainly including: (1) under the catalysis of ABIN, cinnamic acid compounds and nitric acid Heating in acetonitrile solvent at 50°C for 2 to 29 hours to obtain the product (OrganicLetters, 2002, 4, 3055-3058.), this method has the characteristics of high yield and low reaction temperature, but the disadvantage is that the reaction time is long, and the raw material nitric acid is highly toxic , highly corrosive, easy to cause pollution, and the remaining nitric acid after the reaction is difficult to handle

(2) Cinnamic acid compounds and nitrates: (a) Cinnamic acid compounds and sodium nitrate react under the catalysis of ammonium cerium nitrate and under 600W microwave heating to obtain products, (RussianChemicalBulletin, 2008, 57, 118-123.), but Ceric ammonium nitrate is highly oxidizing, corrosive, flammable and explosive, and releases toxic gases when heated, which is not conducive to industrial production; (b) cinnamic acid compounds and Mg(NO 3 ) 2 , Sr(NO 3 ) 2 , Al(NO 3 ) 3 , Ca(NO 3 ) 2 , Ni(NO 3 ) 2 , Cd(NO 3 ) 2 , Zn(NO 3 ) 2 , Hg(NO 3 ) 2 , AgNO 3 , ZrO(NO 3 ) 2 , UO 2 (NO 3 ) 2 , Th(NO 3 ) 2 , NH 4 NO 3 β-Nitrostyrene compounds are produced by grinding with the participation of silica gel, solvent and polyethylene glycol, but Cu(NO 3 ) 2 Reacted! (Green and Sustainable Chemistry, 2011,1,132-148), the advantage of this method is that the required time is short and the yield is higher

But the amount that uses nitrate in the reaction is bigger, and it is 1:12 with the ratio of the amount of substance of cinnamic acid compound, and can not be recycled, and waste is serious, is unfavorable for suitability for industrialized production; (c) cinnamic acid compound and potassium nitrate or sodium nitrate in DMF / SOCl 2 or DMF / POCl 3 Microwave reaction in the system for 15 hours to the product (Organic Communications, 2012, 5, 42-49.)

The highest yield of this method is 75%, but solvent thionyl chloride and phosphorous trichloride all have strong acid and strong corrosion, strong volatility, easy to decompose when meeting water, the reaction time is long, and the yield is not high; (d) The reaction between cinnamic acid and ferric nitrate requires the addition of bipyridine as a ligand (International Journal of Chemical Kinetics, 2014, 46, 126-137.)

(3) tert-butyl nitrite is used as the source of nitro groups, and cinnamic acid is decarboxylated and coupled to construct a C-N bond to synthesize β-nitrostyrene compounds (Synthetic Communications, 2013, 43, 2672-2677; Organic & Biomolecular Chemistry, 2013,11,6713-6716.), the method has high yield, broad substrate expansion, and strong selectivity, but the raw material tert-butyl nitrite is easy to decompose when exposed to light, and the price is relatively expensive, which does not have good economic benefits

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