2519-12-2Relevant academic research and scientific papers
Novel bisphosphonate compound and synthetic method thereof
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Paragraph 0029; 0034-0038; 0041-0043; 0046-0047, (2021/02/06)
The invention provides a novel diphosphonate compound, and further provides a synthesis method of the novel diphosphonate compound. The synthesis method comprises the following steps: adding dichloroethylene, triethyl phosphate and a catalyst 1 in a nitrogen environment, carrying out sealed reaction at 180 to 200 DEG C, and carrying out column chromatography to obtain a product compound 3 disubstituted phosphonate compound; adding the compound 3 into a drying container, adding a catalyst 2, water and an organic solvent in a nitrogen environment, heating to 60 to 80 DEG C, adding a compound 4 substituted phenylboronic acid, and after the reaction is finished, carrying out vacuum-pumping solvent column chromatography to obtain a product. The diphosphonic acid compound generated after the product is hydrolyzed is a good metal ligand, can react with metal salts such as aluminum salt and the like, and can be used for developing a novel organophosphorus flame retardant with better performance; compared with a traditional Michael addition reaction, the synthetic method disclosed by the invention is simpler to operate, higher in yield and more suitable for large-scale production.
Addition, Substitution, and Deoxygenation Reactions of α-Phenyl-β-nitrostyrenes with the Anions of Thiols and Diethyl Phosphite: Formation of Indoles by Reaction with Ethyl Phosphites
Russell, Glen A.,Yao, Ching-Fa,Tashtoush, Hasan I.,Russell, June E.,Dedolph, Douglas F.
, p. 663 - 669 (2007/10/02)
Reaction of excess RS- (R=Ph, t-Bu) with Ph2C=C(SPh)NO2 in Me2SO form Ph2C=CHSR via conversion of the initial Michael-type adducts into Ph2C(SR)CH=NO2- and Ph2C=CHNO2.In a similar fashion, reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 forms initially mainly PhSP(O)(OEt)2 and Ph2CCH=NO2-, which upon acidic workup will yield the nitroalkane or the Nef reaction product, Ph2CCHO.The reaction of (EtO)2PO- with Ph2C=C(SPh)NO2 also produces Ph2CCN via a Perkow-type reaction of the Michael adduct to yield Ph2CCH=N(O)OP(O)(OEt)2 as an intermediate.The nitrile is also formed from Ph2CCH(NO2)2 with (EtO)2PO- in (EtO)2P(O)H or Me2SO at 30 deg C and in >95percent yield by the reaction of (EtO)3P with Ph2CCH(NO2)2 at 150 deg C.Reaction of Ph2C=CHNO2 or Ph2CCH2NO2 with excess (EtO)PO- in Me2SO or (EtO)2P(O)H forms 3-(diethoxyphosphinyl)-2,2-diphenylaziridine by a process postulated to involve Ph2C=CHN(O-)OP(O)(OEt)2, Ph2C=CHNOP(O)(OEt)2-, and 2,2-diphenyl-2H-azirine.Similarly, Ph2C=C(SBu-t)NO2 and (EtO)2PO- give 3-(tert-butylthio)-2,2-diphenyl-2H-azirine in Me2SO or 2-(tert-butylthio)-3-phenylindole in (EtO)2P(O)H solution.Deoxygenation of Ph2C=C(X)NO2 to form the 2-X-3-phenylindoles occurs in high yield at 150 deg C in (EtO)3P with X=H, PhS, or t-BuS while 2-nitrro-3-phenylindole is formed from Ph2C=C(NO2)2 in (EtO)2P(O)H at 150 deg C.
Substitution Reactions in the β-Styryl and Phenylethynyl Systems
Russell, Glen A.,Ngoviwatchai, Preecha
, p. 1836 - 1842 (2007/10/02)
Substitution for Q in the systems PhCH=CHQ, Ph2C=CHQ, and PhCCQ can occur by a free-radical chain mechanism where the attacking radical is alkyl (Q = HgX, Bu3Sn, PhSO2, PhSO, PhS, Cl, Br, I) or (EtO)2PO. (Q = HgX, Bu3Sn, I).The Q. radicals formed by β-elimination can generate t-Bu. or (EtO)2PO. by reaction with t-BuHgCl, Hg2, ClHg or by electron transfer between .HgCl and (EtO)2PO-.With Q = PhS or PhSO2, relative reactivity data indicates that the free radical addition-elimination sequence occurs for t-BuLi at 0 or 45 deg C andthat this process may also be involved in reactions of t-BuMgCl or tert-butyl cuprates with some of the substrates.Ionic reaction of (EtO)2PO- with the three substrates with Q = PhSO2 or halogen are examined.With Q = PhSO2, PhCHCH2P(O)(OEt)2, Ph2C=CHP(O)(OEt)2, and PhCCP(O)(OEt)2 are formed in good yield.
