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Preparation method of nitroolefin derivative with nitrate as nitro source

A technology for nitroalkene and nitrate, which is applied in the field of preparation of nitroalkene derivatives, can solve the problems of low product yield, unfavorable industrial preparation, poor substrate applicability, etc., and achieves cheap and easy-to-obtain raw materials and wide substrates. Applicability, the effect that is beneficial to industrial production

Active Publication Date: 2019-07-12
SHANGHAI NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Utilize cinnamaldehyde and nitrate (silver nitrate, copper nitrate and ferric nitrate) reaction, although this reaction is simple, substrate applicability is relatively poor, and product yield is low
Chinese patent (CN106995373A) discloses a method for the one-pot synthesis of α,β-unsaturated nitroolefin derivatives using ammonium iodide as a nitro source. The method utilizes porphyrin iron, ammonium iodide and tert-butyl peroxidation The hydrogen system directly nitrates olefins, and its peroxide oxidizes ammonium iodide, and then generates nitro radicals under the action of porphyrin iron, and then realizes nitration reaction on the substrate. The substrate has wide applicability, but the product yield The yield is not high, and porphyrin iron and tert-butyl hydroperoxide are expensive, which is unfavorable for industrial preparation

Method used

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  • Preparation method of nitroolefin derivative with nitrate as nitro source
  • Preparation method of nitroolefin derivative with nitrate as nitro source
  • Preparation method of nitroolefin derivative with nitrate as nitro source

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] React according to the following reaction equation:

[0045]

[0046] Olefins: Target product:

[0047] The specific operation steps are: olefin (100mmol), TMSCl (4 equivalents, 400mmol), guanidine nitrate (2.2 equivalents, 220mmol), copper sulfate pentahydrate (0.1 equivalents, 10mmol), triethylamine (2 equivalents, 200mmol) and acetonitrile (400mL) into a 1000mL Sneaker bottle. First add olefin, copper sulfate pentahydrate, and guanidine nitrate into the Sneck bottle, then add acetonitrile, and finally add TMSCl. The reaction was stirred well at room temperature for 24 hours and monitored by TLC. After the reaction was completed, filter, then add triethylamine to the filtrate, stir for 30 min, wash the mixture with water, and extract 3 times with DCM, then remove the solvent with a rotary evaporator to obtain nitrostyrene.

[0048] Yellow solid: Yield = 92%, 1 H NMR (400MHz, Chloroform-d) δ8.01(d, J=13.7Hz, 1H), 7.59(d, J=13.7Hz, 1H), 7.57-7.53(m, 2H), 7.53...

Embodiment 2-21

[0049] Embodiment 2-21 all reacts by following reaction equation:

[0050]

[0051] The specific operation steps are: olefin (0.5mmol), TMSCl (4 equivalents, 2mmol), guanidine nitrate (2.2 equivalents, 1.1mmol), copper sulfate pentahydrate (0.1 equivalents, 0.05mmol), triethylamine (2 equivalents, 1mmol ) and acetonitrile (3 mL) were added to a 10 mL Snicker tube. First, add olefin, copper sulfate pentahydrate, and guanidine nitrate into the snac tube, then add acetonitrile, and finally add TMSCl. The reaction was stirred well at room temperature for 8-36 hours and monitored by TLC. After the reaction was completed, triethylamine was added, and the mixture was stirred for 25 molecules, and the solvent was removed with a rotary evaporator, and petroleum ether (PE) / ethyl acetate (EA) was used as an eluent, and silica gel (200 mesh sieve) was used. Column chromatography purification.

Embodiment 2

[0053] Olefins: Target product:

[0054] Yellow solid: Yield = 99%, 1 H NMR (400MHz, Chloroform-d) δ8.17 (d, J = 13.7Hz, 1H), 8.03 (d, J = 1.8Hz, 1H), 7.89 (ddd, J = 9.0, 7.2, 3.0Hz, 3H) ,7.71(d,J=13.6Hz,1H),7.65-7.50(m,3H).

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Abstract

The invention relates to a nitroolefin derivative with nitrate as nitro source and a preparation method thereof. Under the atmosphere of nitrogen, an olefin compound, nitrate, trimethylchlorosilane (TMSC1) and copper salt are stirred in acetonitrile at 0-30 DEG C; in addition, the reaction degree is monitored by using a TLC point plate; after the olefin compound is completely consumed, alkali is added to an obtained mixture to be stirred for 20-30 min; then after a solvent is removed from an obtained mixture by using a rotary evaporator, the nitroolefin derivative can be obtained through silicagel column purification. Compared with the prior art, the nitroolefin derivative with the nitrate as the nitro source, provided by the invention, has the advantages of mild reaction condition, high yield, high E type selectivity and the like.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of nitroalkene derivatives using nitrate as a nitro source. Background technique [0002] Nitroalkenes are a class of biologically active compounds, which have important applications in antibacterial, anticancer, antitumor or as cell signal transduction factors. Lajollamycin, a novel antibiotic containing a nitroalkene structure isolated from marine sediments, exhibits antimicrobial activity against methicillin-resistant Staphylococcus aureus and activity against vancomycin-resistant enterococci, and it can also inhibit the growth of mouse melanoma cells grow. At the same time, nitroalkenes can also be used for Michael addition, especially asymmetrical Michael addition; the cycloaddition reaction of nitroalkenes can be used to construct cyclic compounds with various nitrogen-containing substituents; Nitroolefins are converted into various useful nitrogen-co...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C201/08C07C205/04C07C205/06C07C205/54C07C205/09C07C205/42C07C205/32C07C253/30C07C255/50C07D213/26C07D239/26C07D215/12C07D217/14C07D333/54C07J41/00
CPCC07C201/08C07C205/04C07C205/06C07C205/54C07C205/09C07C205/42C07C205/32C07C253/30C07C255/50C07D213/26C07D239/26C07D215/12C07D217/14C07D333/54C07J41/0072C07B2200/09
Inventor 邓清海李思源关振宇
Owner SHANGHAI NORMAL UNIVERSITY
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