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A kind of synthetic method of o-nitrobenzaldehyde compound

An o-nitrobenzaldehyde and compound technology, which is applied in the field of organic compound synthesis, can solve problems such as different reaction steps, long reaction steps, strong acid safety issues, etc., and achieves good selectivity, simple reaction steps, and good substrate adaptability. Effect

Active Publication Date: 2016-02-24
徐州宏阳新材料科技股份有限公司
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Problems solved by technology

At present, o-nitrobenzaldehyde is mainly obtained from o-nitrotoluene through oxidation, hydrolysis or bromination, hydrolysis and other steps. However, o-nitrotoluene is obtained from toluene through mixed acid nitration, and excess nitric acid and sulfuric acid are required in the process. Strong acid is used as a reaction reagent and catalyst, and a large amount of heat is released during the reaction, which is likely to cause production hazards. At the same time, a large amount of waste gas and acid are produced in this process, causing serious environmental problems.
In addition, using benzaldehyde as the raw material, in the mixture of concentrated sulfuric acid and vinegar, slowly add benzylidene diacetic anhydride, the intermediate reacts with fuming nitric acid, and the yellow blocky solid can be separated by adding sodium carbonate aqueous solution. Nitrobenzaldehyde and p-nitrobenzaldehyde, but in most cases the ortho-para product is difficult to separate, which causes the yield and purity of the product o-nitrobenzaldehyde to be very low. A series of serious safety and environmental issues
[0003] At present, o-nitrobenzaldehyde compounds containing various substituents on the market are rare due to the limitation of the positioning rules of the benzene ring, which makes o-nitrobenzaldehyde compounds containing various substituents on the benzene ring more difficult. Regiospecific synthesis requires longer reaction steps to synthesize the corresponding o-nitrobenzaldehyde, and different substituents involve different reaction steps, so there is no general method for synthesis

Method used

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  • A kind of synthetic method of o-nitrobenzaldehyde compound
  • A kind of synthetic method of o-nitrobenzaldehyde compound
  • A kind of synthetic method of o-nitrobenzaldehyde compound

Examples

Experimental program
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Embodiment 1

[0045] Using benzaldehyde as raw material to synthesize 2-nitrobenzaldehyde

[0046]

[0047] (1) Add 0.530g (5.0mmol) of benzaldehyde, 1.12g (13.4mmol) of methoxyamine hydrochloride, 1.804g (22mmol) of anhydrous sodium acetate, 15ml of ethanol, and 45ml of water into a 100ml flask. The mixture was heated to reflux reaction, followed by TLC detection, the reaction was completed after 3 hours, the resulting mixed solution was extracted with 3×45mL ethyl acetate, the organic phase was taken and dried, and the solvent was removed under reduced pressure to obtain a light yellow liquid benzaldehyde-O-methyl Oxime 0.641g (95% yield).

[0048](2) Add 67.5 mg (0.5 mmol) of benzaldehyde O-methyloxime, 11 mg (0.05 mmol) of palladium diacetate, 154 mg (1.0 mmol) of silver nitrite, 270 mg (1.0 mmol) of potassium persulfate and 1,2-bis Ethyl chloride (5ml) was successively added to a 10ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 110°C, followed by T...

Embodiment 2

[0052] Synthesis of 4-trifluoromethyl-2-nitrobenzaldehyde from 4-trifluoromethylbenzaldehyde

[0053]

[0054] (1) Add 0.870g (5.0mmol) of 4-trifluoromethylbenzaldehyde, 1.12g of methoxyamine hydrochloride, 1.804g of anhydrous sodium acetate, 15ml of ethanol, and 45ml of water into a 100ml flask. The mixture was heated to reflux reaction, followed by TLC detection, and the reaction was completed after 3 hours. The resulting mixed solution was extracted with 3 × 45mL ethyl acetate, the organic phase was taken and dried, and the solvent was removed under reduced pressure to obtain a light yellow liquid 4-trifluoromethylbenzene Formaldehyde-O-methyloxime 0.995g (98% yield).

[0055] (2) 101.5mg (0.5mmol) of 4-trifluoromethylbenzaldehyde-O-methyloxime, 11mg (0.05mmol) of palladium diacetate, 154mg (1.0mmol) of silver nitrite, 270mg (1.0mmol) of potassium persulfate ) and 1,2-dichloroethane (5ml) were sequentially added to a 10ml sealed pressure vessel. The mixture was heated ...

Embodiment 3

[0059] Synthesis of 5-bromo-2-nitrobenzaldehyde from 3-bromobenzaldehyde

[0060]

[0061] (1) Add 0.915g (5.0mmol) of 3-bromobenzaldehyde, 1.12g of methoxyamine hydrochloride, 1.804g of anhydrous sodium acetate, 15ml of ethanol, and 45ml of water into a 100ml flask. The mixture was heated to reflux reaction, followed by TLC detection, the reaction was completed after 3 hours, the resulting mixed solution was extracted with 3 × 45mL ethyl acetate, the organic phase was taken and dried, and the solvent was removed under reduced pressure to obtain a light yellow solid 3-bromobenzaldehyde-O - Methyloxime 0.994 g (98% yield).

[0062] (2) 101.5mg (0.5mmol) of 3-bromobenzaldehyde-O-methyloxime, 11mg (0.05mmol) of palladium diacetate, 154mg (1.0mmol) of silver nitrite, 270mg (1.0mmol) of potassium persulfate and 1 , 2-dichloroethane (5ml) was sequentially added to a 10ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 110°C, followed by TLC detectio...

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Abstract

The invention provides a preparation method for an o-nitrobenzaldehyde compound. The method directly taking benzaldehyde compounds as starting raw materials comprises the following steps: firstly, converting a formyl group into an O-methyl oximido; secondly, taking divalent palladium salt as a catalyst, and realizing the carbon-hydrogen bond activation single nitration reaction on an o-position of an oximido under the condition that both an oxidant and a nitration agent exist; finally, removing the O-methyl oximido by using strong organic acid to obtain the o-nitrobenzaldehyde compound. The nitration method provided by the invention has the advantage of specificity in the o-position of a nitration position, the reaction process is safe and environment-friendly, the substrate is excellent in adaptability, and various substituents can realize o-position nitration; various benzaldehyde is directly taken as raw materials, so that the reaction steps are simple, and the synthesizing method is a novel route for synthesizing various o-nitrobenzaldehyde compounds containing substituents.

Description

technical field [0001] The invention relates to a method for synthesizing an organic compound, in particular to a method for preparing an o-nitrobenzaldehyde compound. Background technique [0002] O-nitrobenzaldehyde compounds are important pharmaceutical intermediates, which can be used to synthesize nitropyridine (Niafedin), nisoldipine, encaramide and other raw materials for the treatment of cardiovascular diseases, and are also important organic synthesis raw materials. It is widely used in chemical industry. At present, o-nitrobenzaldehyde is mainly obtained from o-nitrotoluene through oxidation, hydrolysis or bromination, hydrolysis and other steps. However, o-nitrotoluene is obtained from toluene through mixed acid nitration, and excess nitric acid and sulfuric acid are required in the process. Strong acids are used as reaction reagents and catalysts, and a large amount of heat is released during the reaction process, which is likely to cause production hazards. At ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C205/44C07C201/12
Inventor 刘运奎张巍徐振元
Owner 徐州宏阳新材料科技股份有限公司
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