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Method of using nitrate hydrate to prepare bisphosphonate nitro compound

A technology for dinitro compounds, which is applied in the preparation of nitro compounds, the formation/introduction of nitro/nitroso groups, and organic chemistry, etc., can solve the problems of waste in industrial production, a large number of strong bases, and the environment is not friendly enough to achieve The effect of good application prospect, less additive dosage and simple preparation method

Inactive Publication Date: 2019-04-05
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of this method is that it needs to start from nitro compounds, and requires a large amount of strong base, which is not friendly to the environment.
[0004] Another method for preparing gem-dinitro compounds is to carry out tandem nitrosation-oxidation to oximes. This method generally uses a large amount of concentrated nitric acid as a solvent, which is relatively wasteful in industrial production.

Method used

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  • Method of using nitrate hydrate to prepare bisphosphonate nitro compound
  • Method of using nitrate hydrate to prepare bisphosphonate nitro compound
  • Method of using nitrate hydrate to prepare bisphosphonate nitro compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031]

[0032] In a dry Schlenk tube, add 92 mg of the above diacetylene, 81 mg of Fe(NO 3 ) 3 9H 2 O and 9 mg of pyridine N-oxide. The Schlenk tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 0.5 mL of nitromethane was added to the Schlenk tube, and the resulting reaction solution was stirred at room temperature for 4 hours. After the reaction was completed, it was filtered with diatomaceous earth, concentrated, and passed through a silica gel column (the volume ratio of petroleum ether to ethyl acetate was 20:1), and 97 mg of the product was obtained with a yield of 85%.

[0033] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0034] 1 H NMR (400MHz, CDCl 3 )δ7.80(d, J=8.8Hz, 2H), 7.70(d, J=8.4Hz, 2H), 7.40(d, J=8.0Hz, 2H), 7.04(d, J=8.8Hz, 2H) ,6.82(d,J=8.8Hz,2H),6.59(d,J=8.8Hz,2H),4.42(s,2H),4.12(s,2H),3.83(s,3H),3.64(s, 3H), 2.49(s, 3H).

[0035] 13 C NMR (100MHz, CDCl 3 )δ...

Embodiment 2

[0037]

[0038] In a dry Schlenk tube, add 80 mg of the above diacetylene, 81 mg of Fe(NO 3 ) 3 9H 2O and 4mg p-benzoquinone. The Schlenk tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 0.5 mL of acetonitrile was added to the Schlenk tube, and the resulting reaction solution was stirred at room temperature for 26 hours. After the reaction was completed, the mixture was filtered with diatomaceous earth, concentrated, and passed through a silica gel column (the volume ratio of petroleum ether to ethyl acetate was 20:1) to obtain 60 mg of the product with a yield of 59%.

[0039] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0040] 1 H NMR (400MHz, CDCl 3 )δ7.77(d, J=8.4Hz, 2H), 7.72(d, J=8.4Hz, 2H), 7.51(t, J=7.6Hz, 1H), 7.44(d, J=8.0Hz, 2H) ,7.37(t,J=7.6Hz,2H),7.09-7.05(m,5H),4.46(s,2H),4.18(s,2H),2.50(s,3H).

[0041] 13 C NMR (100MHz, CDCl 3 )δ193.76, 145.50, 145.09, 134.63, 13...

Embodiment 3

[0043]

[0044] In a dry Schlenk tube, add 85 mg of the above diyne and 162 mg of Fe(NO 3 ) 3 9H 2 O. The Schlenk tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 0.5 mL of acetonitrile solution containing 2.5 μl of concentrated nitric acid was added to the Schlenk tube, and the resulting reaction solution was stirred at room temperature for 8 hours. After the reaction was completed, it was filtered with diatomaceous earth, concentrated, and passed through a silica gel column (the volume ratio of petroleum ether to ethyl acetate was 20:1), to obtain 44 mg of the product with a yield of 42%.

[0045] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0046] 1 H NMR (400MHz, CDCl 3 )δ7.71-7.68 (m, 4H), 7.43 (d, J = 8.4Hz, 2H), 7.17 (d, J = 8.4Hz, 2H), 6.98-6.85 (dd, J 1 =8.4Hz,J 2 =43.2Hz,4H),4.43(s,2H),4.13(s,2H),2.49(s,3H),2.35(s,3H),2.13(s,3H).

[0047] 13 C NMR (100MHz, CDCl 3 )δ1...

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Abstract

The invention discloses a method of using nitrate hydrate to prepare a bisphosphonate nitro compound. The method includes: in an organic solvent, taking nitrate hydrate as a nitro source, an oxygen-containing compound as an additive and 1, 6-diyne as a substrate for nitration-cyclization-oxidation tandem reaction, and performing aftertreatment after reaction is finished to obtain the bisphosphonate nitro compound. The compound is synthesized by direct nitration of 1, 6-diyne; the method is simple, and the nitrate hydrate is used as the nitro source, so that the compound is low in cost, easy toobtain, safe and stable. The method can be used for synthesizing a series of bisphosphonate nitro compounds, and nitric oxide release ability and drug activity of synthesized products can be furtherstudied.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for preparing gem-dinitro compounds with nitrate hydrate. Background technique [0002] Gem-dinitro compounds are widely used in the production of various energetic materials due to their suitable energy, stability, and good performance (Zhang, J.; Hou, T. Tetrahedron Lett., 2018, 59, 28802883). In recent years, gem-dinitro compounds have also been confirmed to have pharmaceutical activity (Blangetti, M.; Rolando, B. ACS Med. Chem. Lett. 2017, 8, 1054-1059). Therefore, the research on the preparation methods of gem-dinitro compounds is of great significance. [0003] The traditional method for synthesizing gem-dinitro compounds is to oxidize and nitrate nitroalkanes under strong alkaline conditions. The disadvantage of this method is that it needs to start from nitro compounds, and requires a large amount of strong base, which is not environmentally friendly. [0004]...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D211/96C07D309/28C07D409/14C07C201/08C07C205/55C07B43/02
CPCC07B43/02C07C201/08C07C2601/16C07D211/96C07D309/28C07D409/14C07C205/55
Inventor 陈万芝衣晓飞
Owner ZHEJIANG UNIV
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