氯磷酸二异丙酯置于氨,Sodium体系中,用 四氢呋喃 用作溶剂,化学反应 0.5H,以84%的收率获得亚磷酸二异丙酯 参考文献:Reductive Cleavage Of The Halogen-Phosphorus,Oxygen-Phosphorus And Phosphorus-Phosphorus Bonds With Alkali Metals 标题:Reductive Cleavage Of The Halogen-Phosphorus,Oxygen-Phosphorus And Phosphorus-Phosphorus Bonds With Alkali Metals 摘要:The Reduction Of Phosphorus Acid Chlorides As Well As Hypophosphates,Pyrophosphates And Mixed P(III)-P(V) Anhydrides With Alkali Metals (Li,Na,K) In Nh3 Liq. / Thf Solution And Potassium Naphthalenide Was Investigated. It Was Found That This Type Of Phosphorus Compounds Easily Undergo Reduction: A) >P(O)Cl To >P(O)H; B) >P(O)P(O)< To >P(O)H; C) >P(O)-O-P(O)< To >P(O)Oh And >P(O)H; D) >P(O)-O-P< To >P(O)O-And >P-. The Results Of Our Experiments Strongly Suggest That The Mixed P(III)-P(V) Anhydride Is Reduced By Potassium Naphthalenide In Thf With The Cleavage Of The P(III)-Oxygen Bond. Doi:10.1080/10426500008042094
专利号:US-2024287520-A1 优先权日:2021-06-30 标题:Method for synthesis of linkage modified oligomeric compounds 发明人:RODRIGUEZ ANDREW A 权利人:IONIS PHARMACEUTICALS INC 摘要:The present disclosure provides methods of synthesizing modified oligonucletodies and oligomeric compounds (including oligomeric compounds that are antisense agents or portions thereof) comprising a modified oligonucleotide having at least one modified internucleoside linking group. In certain embodiments, the present disclosure provides stabilized formulations of certain sulfonyl azides for use in the synthesis of olignonucleotides comprising one or more sulfonyl phosphoramidate linkages. Some embodiments provide stabilized compositions of high energy reagents that may be used in the synthesis of modified oligonucleotides, allowing for safe process scale preparation thereof.
专利号:US-5512668-A 优先权日:1991-03-06 标 题 :Solid phase oligonucleotide synthesis using phospholane intermediates 发明人:STEC WOJCIECH J; GRAJKOWSKI ANDRZEJ; UZNANSKI BOGDAN 权利人:POLISH ACADEMY OF SCIENCES 摘要:Methods and compounds are provided for solid phase synthesis of oligonucleotides and related polymers by condensing protected monomer-O- 1,3,2-dichalcogen-substituted-phospholane! synthons in the presence of a catalytic base. Compounds of the invention include 2-N-substituted-1,3,2-dichalcogen-substituted-phospholane precursors of the above synthons, the protected monomer-O- 1,3,2-dichalcogen-substituted-phospholane! synthons, and P-chiral oligonucleotides and related P-chiral polymers.
专利号:US-4092316-A 优先权日:1975-02-03 标题:Synthesis of C-alkyl-triethylenediamines 发明人:NIEH EDWARD C Y 权利人:TEXACO DEVELOPMENT CORP 摘要:A liquid phase synthesis of C-alkyl-triethylenediamines involves heating to elevated temperatures of from about 200° C to 300° C a suitable N-(2-hydroxyalkyl) piperazine feedstock in the presence of a catalytic amount of a pentavalent acidic phosphorus compound and then recovering the C-alkyl-triethylenediamine product from the resulting reaction product mixture.
专利号:US-8785629-B2 优先权日:2009-06-18 标题 :Phosphonates synthons for the synthesis of phosphonates derivatives showing better bioavailability 发明人:AGROFOGLIO LUIGI A; ROY VINCENT; PRADERE UGO 权利人:AGROFOGLIO LUIGI A; ROY VINCENT; PRADERE UGO; CENTRE NAT RECH SCIENT; UNIV ORLEANS 摘要:Synthons for the synthesis of phosphonates prodrugs POM and POC, especially for direct Cross Metathesis.
专利号:US-5646267-A 优先权日:1991-08-05 标 题:Method of making oligonucleotides and oligonucleotide analogs using phospholanes and enantiomerically resolved phospholane analogues 发明人:STEC WOJCIECH J; GRAJKOWSKI ANDRZEJ; UZNANSKI BOGDAN 权利人:POLISH ACADEMY OF SCIENCES 摘要:Methods and compounds are provided for solid phase synthesis of oligonucleotides and related polymers by condensing protected monomer-O-[1,3,2-dichalcogen-substituted-phospholane] synthons in the presence of a catalytic base. Compounds of the invention include 2-N-substituted-1,3,2-dichalcogen-substituted-phospholane precursors of the above synthons, the protected monomer-O-[1,3,2-dichalcogen-substituted-phospholane] synthons, and P-chiral oligonucleotides and related P-chiral polymers.
专利号:US-6147245-A 优先权日:1998-07-13 标题:Preparation and use of α-Keto Bisphosphonates 发明人:MCKENNA CHARLES E; KASHCMIROV BORIS A 权利人:UNIV SOUTHERN CALIFORNIA UNIVE 摘要:A unique method for the synthesis of substantially pure α-keto bisphosphonate esters and the usage of these esters in reactions with C, N, O, or P nucleophiles for synthesis of α-functionalized bisphosphonates. The method starts with a reaction mixture formed of an α-diazo methanediphosphonate ester, including tert-butylchlorite, a polar aprotic organic solvent, and an effective amount of water. After synthesis is complete, a water trapping reagent may be added to remove any excess water. The present invention provides a versatile pathway to new α-substituted bisphosphonate derivatives and could be readily adapted to combinatorial drug discovery synthetic strategies. The α-keto bisphosphonate esters can be converted to the corresponding acids by acid hydrolysis or mild silyldealkylation.
摘要:Gagnon, A.; Benoit, E.; Le Roch, A., Science of Synthesis Knowledge Updates, (2018) 4, 81. 摘要:Tomé, A. C., Science of Synthesis Knowledge Updates, (2015) 2, 110. 摘要:Silva, V. L. M.; Pinto, D. C. G. A.; Santos, C. M. M.; Rocha, D. H. A., Science of Synthesis Knowledge Updates, (2022) 3, 419. 摘要:Aitken, R. A., Science of Synthesis Knowledge Updates, (2018) 3, 340. 摘要:Cacciarini, M.; Larsen, M. H.; Brøndsted Nielsen, M., Science of Synthesis Knowledge Updates, (2015) 2, 304.