1,1-二甲氧基-2-(甲硫基)乙烷置于对甲苯磺酸体系中,用 二氯甲烷,水 用作溶剂,化学反应 4.0H,以59%的收率获得2-甲硫基乙醛 参考文献:Methylenomycin B: A New Synthesis From A β-Ketophosphonate 标题:Methylenomycin B: A New Synthesis From A β-Ketophosphonate 摘要:美克酮霉素b (1) 通过四个步骤从二乙基2-氧基丙烷磷酸酯 (5) 制备而成,产率为26%.该合成的关键步骤包括5与甲基硫醇乙醛 (7) 的威提希-霍尔纳反应,随后是丙酰阴离子当量对形成的α-烯酮4的1,4-加成,得到4-(甲基硫甲基)-庚-2,5-二酮 (3),该化合物是该抗生素的无环前体. Doi:10.1055/s-1987-28041
专利号:US-8202985-B2 优先权日:2005-10-31 标 题:Monomer compositions for the synthesis of polynucleotides, methods of synthesis, and methods of deprotection 发明人:DELLINGER DOUGLAS J; TIMAR ZOLTAN; SIERZCHALA AGNIESZKA; DELLINGER GERALDINO; CARUTHERS MARVIN H 权利人:DELLINGER DOUGLAS J; TIMAR ZOLTAN; SIERZCHALA AGNIESZKA; DELLINGER GERALDINO; CARUTHERS MARVIN H; AGILENT TECHNOLOGIES INC; UNIV COLORADO 摘要:Nucleotide monomers, polynucleotides, methods of making each, and methods of deprotecting each, are disclosed. An embodiment of the nucleotide monomer, among others, includes a nucleotide monomer having a heterobase protecting group selected from structures I through III as described herein. An embodiment of the polynucleotide, among others, includes a plurality of nucleotide moieties having a heterobase protecting group selected from one of structures I through III as described herein.
专利号:US-7759471-B2 优先权日:2005-10-31 标题 :Monomer compositions for the synthesis of RNA, methods of synthesis, and methods of deprotection 发明人:DELLINGER DOUGLAS J; TIMAR ZOLTAN; SIERZCHALA AGNIESZKA; DELLINGER GERALDINE; CARUTHERS MARVIN H 权利人:AGILENT TECHNOLOGIES INC; UNIV COLORADO 摘要:Nucleotide monomers, polynucleotides, methods of making each, methods of deprotecting each, and the like are disclosed herein.
专利号:US-4355184-A 优先权日:1980-05-02 标题:Synthesis of α, β-unsaturated-ketones 发明人:KAKU TSUTOMU; KATSUURA KIYOSHI; SAWAKI MIKIO 权利人:NIPPON SODA CO 摘要:alpha , beta -unsaturated-ketones are synthesized by reacting with an aldehyde and an alkali metal salt of acetoacetic acid in the presence of an aliphatic secondary amine in the mixture of heterogeneous solvents producing an oil layer and a water layer.
专利号:US-3901899-A 优先权日:1973-04-27 标题 :Synthesis of indoles from anilines and intermediates therein 发明人:GASSMAN PAUL G 权利人:UNIV OHIO STATE RES FOUND 摘要:Preparing indoles and intermediates therefor by reacting an Nhaloaniline with a Beta -carbonylic hydrocarbon sulfide to form an azasulfonium halide, reacting the azasulfonium halide with a strong base to form a thio-ether indole derivative, and then reducing the thio-ether indole, e.g. with Raney nickel, to form the indole compound. When an acetal or ketal of the Beta carbonyl hydrocarbon sulfide is used, the azasulfonium salt is treated with a base, and then with an acid to form the thio-ether indole derivative. When an Alpha -ethyl- Beta -carbonylic hydrocarbon sulfide is used, the resulting azosulfonium salt reacts with strong base to form a thio-ether indolenine derivative, which on reduction with Raney nickel or complex metal hydrides yields 3-substituted indoles. The aniline may be an aminopyridine to form an aza-indole compound in the process. The azasulfonium salts and thio-ether indole or thio-ether indolenine derivatives can be isolated and recovered from their respective reaction mixtures. The thio-ether-indole and thio-ether indolenine derivatives are useful as intermediates to make the indoles without the thio-ether group. The indoles are known compounds having a wide variety of uses, e.g., in making perfumes, dyes, amino acids, pharmaceuticals, agricultural chemicals and the like.
专利号:US-3992392-A 优先权日:1973-04-27 标题:Synthesis of indoles from anilines and intermediates therein 发明人:GASSMAN PAUL G 权利人:UNIV OHIO STATE RES FOUND 摘要:Preparing indoles and intermediates therefor by reacting an N-haloaniline with a β-carbonylic hydrocarbon sulfide to form an azasulfonium halide, reacting the azasulfonium halide with a strong base to form a thio-ether indole derivative, and then reducing the thio-ether indole, e.g. with Raney nickel, to form the indole compound. When an acetal or ketal of the β-carbonyl hydrocarbon sulfide is used, the azasulfonium salt is treated with a base, and then with an acid to form the thio-ether indole derivative. When an α-ethyl-β -carbonylic hydrocarbon sulfide is used, the resulting azosulfonium salt reacts with strong base to form a thio-ether indolenine derivative, which on reduction with Raney nickel or complex metal hydrides yields 3-substituted indoles. The aniline may be an aminopyridine to form an aza-indole compound in the process. The azasulfonium salts and thio-ether indole or thio-ether indolenine derivatives can be isolated and recovered from their respective reaction mixtures. The thio-ether-indole and thio-ether indolenine derivatives are useful as intermediates to make the indoles without the thio-ether group. The indoles are known compounds having a wide variety of uses, e.g., in making perfumes, dyes, amino acids, pharmaceuticals, agricultural chemicals and the like.
专利号:US-9284343-B2 优先权日:2011-04-04 标 题:2′-O-aminooxymethyl nucleoside derivatives for use in the synthesis and modification of nucleosides, nucleotides and oligonucleotides 发明人:BEAUCAGE SERGE L; CIESLAK JACEK 权利人:BEAUCAGE SERGE L; CIESLAK JACEK; US HEALTH 摘要:Disclosed are O-protected compounds of the formula (I): n nwherein B is an optionally protected nucleobase, and R 1 -R 3 are as described herein, wherein at least one of R 1 -R 3 is —CH 2 —O—Nâ• CHR. The compounds are useful as intermediates in oligonucleotide synthesis. Also disclosed is a method of preparing the compounds from nucleosides via a process comprising conversion of a hydroxyl group to a methylthiomethoxy group, and a method of preparing oligonucleotides such as RNA starting from the compounds. The —CH 2 —O—Nâ• CHR group is stable during oligonucleotide synthesis and can be easily removed after synthesis via, for example, treatment with a base.