CN1246292C - Disproportionation of nitro aromatic compounds - Google Patents

Disproportionation of nitro aromatic compounds Download PDF

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CN1246292C
CN1246292C CN 03157197 CN03157197A CN1246292C CN 1246292 C CN1246292 C CN 1246292C CN 03157197 CN03157197 CN 03157197 CN 03157197 A CN03157197 A CN 03157197A CN 1246292 C CN1246292 C CN 1246292C
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solution
nitro
acetonitrile
oil
mirbane
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CN1490301A (en
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高飞雪
华瑞茂
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Tsinghua University
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Abstract

The present invention discloses a method for the disproportionation of nitro aromatic compounds, which comprises: firstly, 0.4 to 10mM of acetate solution or water solution of heteropoly vanadate is prepared, and the acetate solution or the water solution of heteropoly vanadate and acetonitrile are prepared into uniform solution according to the volume ratio of 1: 0.5 to 30; secondly, nitro aromatic compounds are dissolved in the acetonitrile solution prepared in the first step, and hydrogen peroxide solution is added to make the final concentration reach 1.4 to 6.5 M; thirdly, the solution is heated to 50 to 90 DEG C and then reacts for 5 to 7 hours during stirring, dinitro aromatic compounds and corresponding aromatic compounds are generated through the disproportionation of the nitro aromatic compounds, and simultaneously, hydroxylated products of nitro aromatic compounds are generated as byproducts. The reaction method of the present invention has the advantages that the conversion rate of nitrobenzene reaches 20.5%, and the yield of p-dinitrobenzene reaches 6.6%; the conversion rate of p-nitrotoluene reaches 86.2%, and the yield of dinitrotoluene reaches 41.3%; after reaction ends, and an organic layer and a water layer separates at room temperature, which is convenient for the separation of catalysts and organic products.

Description

A kind of disproportionation method of nitro-aromatic compound
Technical field
The present invention relates to make in the synthetic field of compound for catalysis the method for nitro-aromatic compound generation disproportionation.
Background technology
Transition metal complex can catalysis C-N key formation or the fracture of C-N key, for example, at the title complex (PPh of transition metal Rh (I) 3) 3Under the catalysis of RhCl, the C-N bond rupture in the high enamine, the isomer of generation alkene and ketone (So-Hee Jang and Chul-Ho Jun.Bull.Korean Chem.Soc.1999, Vol.20,30-32).Again for example, the title complex [(o-MeC of palladium 6H 4) 3P] 2But the hybridization coupling of PdCl catalysis aryl bromide compound and tin aminocompound forms the C-N key, generates N, N-alkyl benzene amine (Paul, F.; Patt, J.; Hartwig, J.F.; J.Amer.Chem.Soc., 1994,116,5969).The method of traditional synthetic dinitrobenzene aromatic hydroxy compound, be by under the effect of the nitrosonitric acid and the vitriol oil, at 95 ℃, undertaken by electrophilic addition-elimination reaction the nitro-aromatic compound, the condition that this method requires is very harsh, need be just can carry out in the presence of the nitrosonitric acid and the vitriol oil in higher temperature and excessive nitration mixture, and reaction be very slow.
Summary of the invention
The purpose of this invention is to provide a kind of easy method that makes nitro-aromatic compound generation disproportionation.
A kind of method that makes nitro-aromatic compound generation disproportionation may further comprise the steps:
(1) preparation 0.4-10mM the hetero-vanadate aqueous solution or acetic acid solution, with volume ratio be 1: the acetonitrile of 0.5-30 is made into uniform solution;
(2) the nitro-aromatic compound is dissolved in the acetonitrile solution of step (1), adds superoxol, make the final concentration of hydrogen peroxide reach 1.4～6.5M;
(3) be heated to 50 ℃～90 ℃, under agitation reacted 5～7 hours, nitro-aromatic compound generation disproportionation generates dinitrobenzene aromatic hydroxy compound and corresponding aromatic hydroxy compound, and the while is with the hydroxylation product of nitro-aromatic compound.
Described hetero-vanadate is K 7NiV 13O 38And K 7MnV 13O 38
Dissolve hetero-vanadate with acetate, can improve nitro-aromatic conversion of compounds rate, the concentration of described acetate is 36%.
The volume ratio of described hetero-vanadate acetic acid solution and acetonitrile is preferably 1: 1.
The by weight/volume of described nitro-aromatic compound and acetonitrile solution is 1g: 10～60ml.
The final concentration of described hydrogen peroxide is preferably 3.0～6.0M.
It is synthetic that the present invention has creatively proposed to utilize nitro-aromatic compound for catalysis disproportionation to carry out the catalysis of dinitrobenzene aromatic hydroxy compound, can make the transformation efficiency of oil of mirbane reach 20.5%, and the productive rate of paradinitrobenzene is 6.6%; The transformation efficiency of para-nitrotoluene reaches 86.2%, and the productive rate of dinitrotoluene (DNT) is 41.3%.After reaction finished, under the room temperature, organic layer separated with water layer, was convenient to separating of catalyzer and organic product.
The present invention will be further described below in conjunction with specific embodiment.
Embodiment
Embodiment 1
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide (hydrogen peroxide), stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 3.3%, and the transformation efficiency of oil of mirbane is 7.8%.
Embodiment 2
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in 5ml 36% acetate and is made into uniform solution with the 10ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 5.0%, and the transformation efficiency of oil of mirbane is 14.3%.
Embodiment 3
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in 7.5ml 36% acetate and is made into uniform solution with the 7.5ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 6.6%, and the transformation efficiency of oil of mirbane is 20.5%.
Embodiment 4
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in 10ml 36% acetate and is made into uniform solution with the 5ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 2.6%, and the transformation efficiency of oil of mirbane is 9.1%.
Embodiment 5
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 12.5ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 1.5%, and the transformation efficiency of oil of mirbane is 5.6%.
Embodiment 6
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 10ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 1.1%, and the transformation efficiency of oil of mirbane is 2.7%.
Embodiment 7
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 7.5ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 0.5%, and the transformation efficiency of oil of mirbane is 2.1%.
Embodiment 8
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 5ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 0.5%, and the transformation efficiency of oil of mirbane is 1.5%.
Embodiment 9
Take by weighing 12rng K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 50 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 2.2%, and the transformation efficiency of oil of mirbane is 5.2%.
Embodiment 10
Take by weighing 12mg K 7MnV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of paradinitrobenzene is 2.8%, and the transformation efficiency of oil of mirbane is 6.9%.
Embodiment 11
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 2.2g (14mmol) p-Nitrophenyl chloride is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: p-Nitrophenyl chloride generation disproportionation generates dinitrochlorobenzene and chlorobenzene, and the while is with the hydroxylation product of nitro-chlorobenzene.2, the yield of 4-dinitrochlorobenzene is 0.6%, and the transformation efficiency of p-Nitrophenyl chloride is 2.8%.
Embodiment 12
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 2.3g (14mmol) p-nitroacetophenone is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: p-nitroacetophenone generation disproportionation generates dinitroacetophenone and methyl phenyl ketone, and the while is with the hydroxylation product of p-nitroacetophenone.The yield of dinitroacetophenone is 2.5% (2,4-dinitroacetophenone: 3,4-dinitroacetophenone=94: 6), and the transformation efficiency of p-nitroacetophenone is 12.5%.
Embodiment 13
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 2.5g (14mmol) methyl p-nitrobenzoate is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: methyl p-nitrobenzoate generation disproportionation generates dinitro-methyl benzoate and methyl benzoate, and the while is with the hydroxylation product of methyl p-nitrobenzoate.The yield of dinitro-methyl benzoate is 1.7% (2,4-dinitro-methyl benzoate: 3,4-dinitro-methyl benzoate=57: 43), and the transformation efficiency of methyl p-nitrobenzoate is 9.8%.
Embodiment 14
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.9g (14mmol) para-nitrotoluene is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: para-nitrotoluene generation disproportionation generates dinitrotoluene (DNT) and toluene, and the while is with the hydroxylation product of para-nitrotoluene.The yield of dinitrotoluene (DNT) is 41.3% (2,4-dinitrotoluene (DNT): 3,4-dinitrotoluene (DNT)=22: 78), and the transformation efficiency of para-nitrotoluene is 86.2%.
Comparison example 1
Take by weighing 14.3mg KVO 3Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: oil of mirbane generation disproportionation generates dinitrobenzene and benzene, and the while is with the hydroxylation product of oil of mirbane.The yield of dinitrobenzene only is 2.2%, and the transformation efficiency of oil of mirbane only is 6.4%.
Comparison example 2
Take by weighing 27.3mg NiSO 4Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.
Comparison example 3
Take by weighing 23mg H 3PW 12O 40Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.
Comparison example 4
Take by weighing 14.6mg H 3PMo 12O 40Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.
Comparison example 5
Take by weighing 23mg H 3SiW 12O 40Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.
Comparison example 6
In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the 15ml acetonitrile, add 15ml (30%) hydrogen peroxide, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.
Comparison example 7
Take by weighing 12mg K 7NiV 13O 38Catalyzer is dissolved in the 0.5ml water and is made into uniform solution with the 15ml acetonitrile.In 50ml two neck round-bottomed flasks, 1.5ml (14.7mmol) oil of mirbane is dissolved in the above-mentioned uniform solution, stir, reflux to 70 ℃ is reacted.Reaction times is 7 hours, and reaction result is: disproportionation does not take place.

Claims (6)

1, a kind of method that makes nitro-aromatic compound generation disproportionation may further comprise the steps:
(1) preparation 0.4-10mM the hetero-vanadate aqueous solution or acetic acid solution, with volume ratio be 1: the acetonitrile of 0.5-30 is made into uniform solution;
(2) the nitro-aromatic compound is dissolved in the acetonitrile solution of step (1), adds superoxol, make the final concentration of hydrogen peroxide reach 1.4～6.5M;
(3) be heated to 50 ℃～90 ℃, under agitation reacted 5～7 hours, nitro-aromatic compound generation disproportionation generates dinitrobenzene aromatic hydroxy compound and corresponding aromatic hydroxy compound, and the while is with the hydroxylation product of nitro-aromatic compound.
2, the catalysis disproportionation synthetic method of nitro-aromatic compound as claimed in claim 1, it is characterized in that: described hetero-vanadate is K 7NiV 13O 38And K 7MnV 13O 38
3, the method for claim 1 is characterized in that: the concentration of described acetate is 36%.
4, the method for claim 1 is characterized in that: the volume ratio of described hetero-vanadate acetic acid solution and acetonitrile is 1: 1.
5, the method for claim 1 is characterized in that: the by weight/volume of described nitro-aromatic compound and acetonitrile solution is 1g: 10～60ml.
6, the method for claim 1 is characterized in that: the final concentration of described hydrogen peroxide is 3.0～6.0M.
CN 03157197 2003-09-18 2003-09-18 Disproportionation of nitro aromatic compounds Expired - Fee Related CN1246292C (en)

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CN104529785A (en) * 2014-12-25 2015-04-22 甘肃银光化学工业集团有限公司 Method for preparing 2,4-dinitrotoluene by using mixed acid nitration method
CN113731400B (en) * 2021-09-02 2022-11-08 河海大学 K 7 [MnV 13 O 38 ]·18H 2 Application of O as catalyst in aromatic hydrocarbon hydroxylation reaction

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