2-[(苯基氨基)羰基]-肼羧酸乙酯置于氢氧化钾 Dinitrogen Tetraoxide,Sodium Sulfate体系中,用 二氯甲烷,水 作为反应溶剂,化学反应 2.0H,反应生成 4-苯基-1,2,4-三唑啉-3,5-二酮 参考文献:1,2,4-三唑啉-3,5-二酮与双环烯烃的环加成反应导致重排乌唑的机理 标题:1,2,4-三唑啉-3,5-二酮与双环烯烃的环加成反应导致重排乌唑的机理 摘要:Mise En Evidence De L'Intervention D'Un Ion Aziridinium Dans La形成 Du Cycle Urazole Transpose Au Cours De La Cycloaddition Des Triazolinediones Avec Le Benzonorbornadiene,Les Norbornenes Et Des Bicycloalcenes尖 DOI:10.1021/ja00322A023
专利号:US-2022267266-A1 优先权日:2019-07-09 标 题 :Improved, cost effective process for synthesis of vitamin d3 and its analogue calcifediol from ergosterol 发明人:DATLA ANUPAMA; NAGRE PRASHANT; TAMORE JAGDISH; PRABHU MANOJKUMAR SADANAND; KADAM SACHIN VASANT 权利人:FERMENTA BIOTECH LTD 摘要:Disclosed herein is an improved and efficient process for synthesis of vitamin D3 and its analogue Calcifediol from Ergosterol. Particularly, the present invention discloses the synthesis of key intermediate 3β-tert-Butyldimethylsilyloxy-22-hydroxy-23,24-bisnorchola-5,7-diene (5), and novel intermediate β-tert-Butyldimethylsilyloxy-22-iodo-23,24-bisnorchola-5,7-diene (9) by a simple and cost effective process. The industrially viable processes for preparation of said intermediate(s) results in providing provitamins with various side chains and the desired products in high yield.
专利号:WO-9847910-A1 优先权日:1997-04-21 标题:Method for solution phase synthesis of oligonucleotides 发明人:PIEKEN WOLFGANG; MCGEE DANNY; SETTLE ALECIA; ZHAI YANSHENG; HUANG JIANPING; HILL KEN; SMITH RANDALL S 权利人:NEXSTAR PHARMACEUTICALS INC; PIEKEN WOLFGANG; MCGEE DANNY; SETTLE ALECIA; ZHAI YANSHENG; HUANG JIANPING; HILL KEN; SMITH RANDALL S 摘要:This invention discloses an improved method for the sequential solution phase synthesis of oligonucleotides. The method lends itself to automation and is ideally suited for large scale manufacture oligonucleotides with high efficiency.
专利号:US-4287129-A 优先权日:1980-07-28 标 题:Synthesis of 1α-hydroxy-7-dehydrosteroids 发明人:KLAUSMEIER WILLIAM H; JOHNSON RICHARD L; HIRSCH ARNOLD L 权利人:DIAMOND SHAMROCK CORP 摘要:Enol acetylation is carried out on a variety of 1,4,6-trien-3-ones to form 1,3,5,7 tetraene structures from which 1 alpha -hydroxy-7-dehydro steroids are obtained. The compounds are intermediates used in the preparation of vitamin D3 metabolites such as 1 alpha ,25-dihydroxyvitamin D3 and 1 alpha -hydroxyvitamin D3.
专利号:US-5087709-A 优先权日:1988-04-11 标 题 :Process for the preparation of 1α,25-dihydroxyvitamin D2 and the 24-epimer thereof 发明人:TSUJI MASAHIRO; YOKOYAMA SHINJI; TACHIBANA YOJI 权利人:NISSHIN FLOUR MILLING CO 摘要:(22E)-5,7,22-Ergostatriene-1α,3β,25-triol and the 24-epimer thereof which are new intermediates for the synthesis of 1α,25-dihydroxyvitamin D 2 and the 24-epimer thereof. A new process for the preparation of 1α,25-dihydroxyvitamin D 2 and the 24-epimer thereof is also described which comprises irradiation of (22E)-5,7,22-ergostatriene-1α,3β,25-triol or the 24-epimer thereof followed by isomerization.
专利号:US-6399767-B1 优先权日:1996-09-03 标 题 :Intermediates for the synthesis of vitamin D and steroid derivatives and process for preparation thereof 发明人:HORNE DAVID A; KUBODERA NOBORU; SUZUKI HIROSHI; SHIMIZU HITOSHI 权利人:UNIV COLUMBIA; CHUGAI PHARMACEUTICAL CO LTD 摘要:A process for preparing a compound having structure (I) wherein n is an integer from 1-5; each of R 1 and R 2 independently is optionally substituted C 1 -C 6 alkyl; each of W and X is independently hydrogen or C 1 -C 6 alkyl; Y is O, S or NR 3 where R 3 is hydrogen, C 1 -C 6 alkyl or a protective group; and Z is a CD ring structure, a steroid structure, or a vitamin D structure, each of which optionally having structure (IV) wherein W, X, Y and Z are defined above, in the presence of a base, with a compound having structure (V) or (v′) wherein n, R 1 and R 2 are as defined above, and E is an eliminating group.
专利号:US-9212137-B2 优先权日:2012-05-30 标题:Crystallization of (20R,22R)-2-methylene-19-nor-22-methyl-1α,25-dihydroxyvitamin D3 and related precursors 发明人:DELUCA HECTOR F; GRZYWACZ PAWEL; PLUM LORI A; FLORES AGNIESZKA; THODEN JAMES B; HOLDEN HAZEL M 权利人:WISCONSIN ALUMNI RES FOUND 摘要:Disclosed are methods of purifying the compound (20R,22R)-2-methylene-19-nor-22-methyl-1α,25-dihydroxyvitamin D 3 to obtain the compound in crystalline form. The methods typically include the steps of dissolving a product containing the compound in a solvent comprising hexane and 2-propanol, cooling the solvent and dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of crystals, and recovering the crystals. Certain diol precursors formed during the synthesis of the compound and its diasteromers also may be obtained in crystalline form using ethyl acetate as a solvent.
[参考文献]: Jiri Adamec, Et Al. Development And Optimization Of An Lc-Ms/ms-Based Method For Simultaneous Quantification Of Vitamin D2 , Vitamin D3 , 25-Hydroxyvitamin D2 And 25-Hydroxyvitamin D3. J Sep Sci. 2011 Jan;34(1):11-20.
合成参考文献
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