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Synthetic method of phosphonyl methylene substituted five-membered cyclic compound

A technology for phosphonomethylene and cyclic compounds, which is applied in the field of simple synthesis of phosphono-containing heterocyclic compounds, can solve the problems of unavoidable heavy metal residues, and achieve the effect of simple and convenient operation and cheap and easy-to-obtain raw materials

Active Publication Date: 2020-04-28
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Existing synthetic methods all use transition metals as catalysts, and high-valent metal ions or peroxides as oxidants, so the synthesized heterocyclic compounds inevitably have heavy metal residues.

Method used

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  • Synthetic method of phosphonyl methylene substituted five-membered cyclic compound
  • Synthetic method of phosphonyl methylene substituted five-membered cyclic compound
  • Synthetic method of phosphonyl methylene substituted five-membered cyclic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Weigh 27.7mg (0.1mmol) of 4-methyl-N-(3-methyl-2-buten-1-yl)-N-propargylbenzenesulfonamide, 60.7mg (0.3mmol) of diphenylphosphine ) and organic dye photocatalyst eosin 3.4mg (5%mmol) in a 10mL colorless transparent reaction tube, add 2mL tetrahydrofuran solvent, under nitrogen, room temperature light stirring reaction, TLC detection reaction progress, after about 24h, after the reaction is complete, After separation and purification by column chromatography (petroleum ether: ethyl acetate = 1:1), a white solid was obtained with a yield of 83%.

[0017]

[0018] White solid (39.8mg, 83% yield); m.p.198-202℃; 1 H NMR (600MHz, CDCl 3 ): δ7.58(s,6H),7.43(s,2H),7.37(s,4H),7.19(s,2H),5.89(d,J=22.3Hz,1H),4.09(dd,J= 124.5,17.0Hz,2H),3.20–3.04(d,J=3.1Hz,2H),2.62(s,1H),2.33(s,3H),1.87(s,1H),0.90(s,3H), 0.71(s,3H); 13 C NMR (CDCl 3 ,150MHz): δ162.7,143.6,133.8(d,J=17.9Hz),133.1(d,J=18.9Hz),132.1,131.8(d,J=7.4Hz),130.7(q,J=6.2Hz), IR( neat):ν=2923,2860,2308,1639,1447,1338...

Embodiment 2

[0041] Using the same method and reaction conditions as in Example 1, when 1,6-enyne is 2-(3-methyl-2-buten-1-yl)-2-propargyl dimethyl malonate, The following target product 2 was obtained, yield: 94%.

[0042] The structure of product 2 is characterized as follows:

[0043]

[0044] colorless liquid; 1 H NMR (400MHz, CDCl 3 ):δ7.82–7.71(m,4H),7.58–7.46(m,6H),5.99(d,J=23.7Hz,1H),3.72(s,3H),3.66(s,3H),3.05( d,J=18.5Hz,1H),2.84(d,J=3.0Hz,1H),2.46(dd,J=12.9,8.0Hz,1H),2.12(td,J=13.2,6.6Hz,1H), 1.98(t, J=12.2Hz, 1H), 1.30(s, 1H), 1.03(d, J=6.8Hz, 3H), 0.88(d, J=6.7Hz, 3H); 13 C NMR (100MHz, CDCl 3)δ171.8, 171.5, 168.0, 131.4 (d, J = 2.3Hz), 130.9 (dd, J = 19.5, 9.8Hz), 128.5 (dd, J = 12.0, 6.7Hz), 113.0 (d, J = 104.9Hz) ,58.5,52.7,51.5(d,J=13.9Hz),40.6,40.5,32.8,29.6,21.3,16.3; 31 P NMR (243MHz, CDCl 3 )δ21.6; IR (neat): ν=2957,1736,1632,1439,1267,1192,1115,703cm -1 ; HRMS (ESI) Exact mass calculated for [C 25 h 29 NaO 5 P] + [M+Na] + :463.1645,found:463.1664.

Embodiment 3

[0046] Adopt the same method and reaction condition of embodiment 1, when R 3 When it is 3,5-dimethylphenyl, the following different target products 3 are obtained with a yield of 36%.

[0047] The structure of product 3 is characterized as follows:

[0048]

[0049] colorless liquid; 1 H NMR (400MHz, CDCl 3 ): δ7.65(d, J=8.1Hz, 2H), 7.26(d, J=6.8Hz, 4H), 7.22(s, 2H), 7.12(s, 2H), 5.93(d, J=22.0Hz ,1H),4.23(d,J=17.0Hz,1H),4.04(d,J=17.8Hz,1H),3.25–3.12(m,2H),2.70(s,1H),2.39(s,3H) ,2.30(s,12H),2.01–1.93(m,1H),0.96(d,J=6.8Hz,3H),0.83(d,J=6.8Hz,3H); 13 C NMR (CDCl 3 ,100MHz): δ162.1,143.5,138.3(dd,J=12.7,1.7Hz),133.5(dd,J=5.4,2.9Hz),129.6,128.267(d,J=17.8Hz),128.266(d,J=17.8Hz) 1.9Hz), 127.9, 114.3(d, J=101.0Hz), 51.8(d, J=13.5Hz), 51.5(d, J=6.3Hz), 47.8, 30.7(d, J=1.4Hz), 21.4, 21.214 (d, J=45.3Hz), 21.211, 21.0, 17.4; 31 P NMR (243MHz, CDCl 3 )δ21.7; IR (neat): ν=2959,2923,2866,1639,1458,1345,1170,1039,860cm -1 ; HRMS (ESI) Exact mass calculated for [C 31 h 38 NNa...

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Abstract

The invention discloses a synthetic method of a phosphonyl methylene substituted five-membered cyclic compound. According to the method, 1,6-enyne and diaryloxy phosphorus are taken as reaction raw materials, an organic dye is taken as a photocatalyst, a reaction solvent is added, an illumination reaction is carried out under a nitrogen protection condition, a target product is synthesized, and the structure of the target product is represented and analyzed through IR, 1H NMR, 13C NMR, HRMS and X-ray single crystal diffraction. The method does not need any additive, high temperature and otherharsh and complex reaction conditions, and has the advantages of mild reaction conditions, simple operation, convenient subsequent treatment, easily available raw materials, easy derivatization to obtain different types of organic compounds, and the like.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a convenient synthesis method for heterocyclic compounds containing phosphono groups. Background technique [0002] Organophosphorus compounds are widely used in the fields of organic synthesis and medicinal chemistry. Many organophosphorus compounds have physiological activities such as antitumor, antibacterial, anti-inflammatory and analgesic; pyrrolidine is commonly found in some natural products and drug molecules, and is also an important drug synthesis intermediate body. Therefore, the research on the synthesis of phosphono-pyrrolidine compounds is of great significance. [0003] In existing reports, metals such as nickel, copper, and silver can participate in the reaction of diaryl phosphine compounds to form phosphorus atom radicals to initiate radical addition / cyclization reactions (Hu G., Chen W., Ma D. , et al; Silver-Catalyzed, Aldehyde-inducedα-C–H functionalizatio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/53C07F9/572
CPCC07F9/572C07F9/5325
Inventor 侯虹孙月许月朱绍群
Owner YANGZHOU UNIV
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