1,2-二硝基苯置于甲醇,Sodium Disulfide体系中,化学反应生成双(2-硝基苯基)二硫化物 参考文献:Hodgson; Ward,Journal Of The Chemical Society,1949,P. 1316 标题:Hodgson; Ward,Journal Of The Chemical Society,1949,P. 1316
专利信息
专利号:US-7015176-B2 优先权日:2003-06-03 标题 :Process for the synthesis of aryl sulfurpentafluorides 发明人:BAILEY III WADE H; CASTEEL JR WILLIAM J; PESARESI RENO J; PROZONIC FRANK M 权利人:AIR PROD & CHEM 摘要:A process is described for the synthesis of an aryl sulfur pentafluoride compound. In one embodiment of the present invention, there is provided a process for preparing an aryl sulfurpentafluoride compound comprising: combining an at least one aryl sulfur compound with a fluorinating agent to at least partially react and form an intermediate aryl sulfurtrifluoride product; and exposing the intermediate aryl sulfurtrifluoride product to the fluorinating agent and optionally a fluoride source to at least partially react and form the aryl sulfurpentafluoride compound.
专利号:US-3759935-A 优先权日:1969-11-03 标题 :Azoles method for the preparation of 2-alkyl substituted thiazoles and selen 发明人:DE CAT A; MANSSENS L 权利人:AGFA GEVAERT NV 摘要:WHEREIN: Alk stands for C1-C5 alkyl for example methyl and ethyl, X stands for sulphur or selenium, Y stands for nitro or amino, Z1 stands for the atoms necessary to complete a benzene or naphthalene ring including a substituted benzene or naphthalene ring for instance substituted by alkyl including substituted alkyl for example methyl, ethyl, trifluoromethyl, acyloxymethyl, and hydroxymethyl, alkenyl for example allyl, aryl including substituted aryl, halogen such as chlorine, alkyloxy, alkylthio, alkylsulphonyl, haloalkyloxy, haloalkylthio, haloalkylsulphonyl, carboxy, sulpho, amino, (di)alkylamino, acylamino, nitro, alkoxycarbonyl, etc., and Z2 stands for the atoms necessary to complete a benzene or naphthalene ring optIonally carrying substituents, which are either identical to the substituents present in Z1 or are derived forms thereof converted under the reaction conditions of the invention such as amino where Z1 carries nitro, acetyloxymethyl where Z1 carries hydroxymethyl, propyl where Z1 carries allyl, etc. Under the reaction conditions of the invention it would be possible to prepare the benzothiozoles starting from 2nitrothiophenols instead of using bis(2nitrophenyl)disulphides; however, 2-nitrothiophenols as compared with bis(2-nitrophenyl)-disulphides disulphides are difficult to prepare. The method of the present invention comprises more especially the steps of admixing an aromatic disulphide or diselenide carrying in the 2-positions relative to the disulphide or diselenide group nitro groups or amino groups with an aliphatic carboxylic anhydride and a catalytic amount of a rhenium sulphide, charging the reaction vessel with a sufficient hydrogen pressure, heating the reaction mixture to a temperature at which hydrogen is readily absorbed until absorption of hydrogen ceases, cooling the reaction mixture to a temperature below the boiling temperature of the aliphatic carboxylic acid formed, filtering off the rhenium sulphide catalyst and isolating the 2-alkyl heterocyclic base formed from the filtrate by any suitable means e.g., by concentrating the filtrate by evaporation if necessary under rpduced pressure and filtering off the precipitate formed or distilling the residue. The rhenium sulphide catalyst is generally used in amounts comprised between 0.25 g and 10 g, preferably from 1 g to 5 g per mole of disulphide or diselenide compound. The amount of aliphatic carboxylic anhydride used may vary between wide limits. The most effective amount can easily be determined by some simple tests. The required minimum theoretical amount depends on whether there is stated from a 2,2''-dinitro aromatic disulphide or diselenide or from a 2,2''-diaminoaromatic disulphide or diselenide and from the optional presence of further nitro and amino groups. The minimum amount of aliphatic carboxylic anhydride is 3 moles of anhydride per nitro group present and 2 moles of anhydride per amino group present. Solubility considerations may necessitate the use of larger amounts and also supplemental amounts may be required to convert other groups present in the starting material. Indeed, the 2,2''-dinitro (or 2,2''-diamino)phenyl (or naphthyl) disulphide or diselenide might comprise in addition to the 2,2''dinitro (or diamino) groups, groups known to those skilled in the art of preparative organic chemistry to undergo alteration under the reaction conditions of the method of the invention either by reaction with the carboxylic anhydride used or by being itself hydrogenated so that the resulting thiazole or selenazole compounds comprise in the fused-on aromatic ring substituents of a nature different from those of the starting materials. For instance when the 2,2''-dinitro (or 2,2''-diamino)phenyl (or naphthyl) disulphide or diselenide comprises further nitro or amino groups, the heterocyclic base formed will carry an acyl amino group, by reaction of the amino or reduced nitro group with the aliphatic acarboxylic anhydride; as known by those skilled in the art of preparative organic chemistry the acyl amino group can be converted into amino by boiling with hydrochloric acid. In the same way, substituents in the starting products carrying hydroxyl groups such as hydroxymethyl, will also react with the carboxylic anhydride to form ester groups; as is illustrated hereinafter it is possible to hydrolyse the ester group formed by treating the reaction mixture afterwards with hydrochloric acid so that the hydroxyl group is formed again. The exact working conditions of the method oF the invention are of course dependent on the nature of the starting material used and the optimum combination of temperature, pressure, amount of catalyst used and the reaction time. A hydrogen pressure of 1,000 to 1,500 psi generally suffices to obtain fast hydrogenation rates at temperatures comprised between 100 and 175* C. In many cases the hydrogen is readily absorbed at temperatures of 130140* C. Once the absorption of hydrogen ceases, the reaction mixture is cooled below the boiling temperature of the lower aliphatic carboxylic acid formed. The rhenium sulphide of use according to the present invention can be prepared by methods well known to those skilled in the art and described in literature. For instance rhenium(VII) sulphide can be prepared as described in J1.Am.Chem.Soc. 76, 151923(1954). The following preparations illustrate the method of the present invention. A method of preparing 2-alkylthiazoles or 2-alkylselenazoles is described wherein an aromatic disulphide or diselenide having amino groups or nitro groups in the 2-positions relative to the disulphide or diselenide group is catalytically hydrogenated using a rhenium sulphide as catalyst in the presence of an aliphatic carboxylic anhydride. The method is a one-step synthesis and high yields of 2-alkyl thiazoles or selenazoles are obtained having a high degree of purity. The present invention relates to a new method for the preparation of a 2-alkyl substituted thiazoles or selenazoles with fused-on aromatic group. As is known 2-alkyl-benzothiazoles, 2-alkyl-naphthothiazoles, 2alkyl-benzoselenazoles and 2-alkylnaphthoselenazoles are important heterocyclic bases for use in the preparation of methine dyes (see e.g., F.M. Hamer ''''The Cyanine Dyes and related compounds'''' Interscience Publishers 1964, New-York/London, and P.Glafkides, Photographic Chemistry, Vol. II, Chapter XXXVI, Fountain press, London), which are used amongst others as spectrally sensitizing agents for photosensitive systems such as photographic silver halide material and electrophotographic material. It has now been that 2-alkyl substituted thiazoles or selenazoles having a fused-on 6-carbon mononuclear or 10-carbon dinuclear aromatic ring can be prepared by catalytic hydrogenation under pressure of an aromatic disulphide or diselenide comprising in the 2-positions relative to the disulphide or diselenide group, amino groups or nitro groups, said hydrogenation taking place in the presence of an aliphatic carboxylic anhydride using as catalyst a rhenium sulphide, more particularly rhenium(VII)sulphide. The said aliphatic carboxylic anhydride may serve also as the reaction medium. The general one step synthesis of 2-alkyl substituted thiazoles or selenazoles having a fused-on 6-carbon mononulcear or 10carbon dinuclear aromatic ring according to the present invention is time-saving and gives high yields with a high degree of purity. Moreover, the method of the invention can be carried out very easily, even on an industrial scale without giving rise to technological difficulties. The rhenium sulphide used according to the present invention is not poisoned by the sulphur-containing starting products used in the method of the invention and cause no fission of the carbonsulphur bond, while being resistant to carboxylic anhydrides. The method of the invention can be represented by the following reaction scheme:
专利号:US-8580998-B2 优先权日:2008-12-11 标题 :Preparation of alkenes by mild thermolysis of sulfoxides 发明人:LONG TIMOTHY EDWARD; PATEL SRAVAN KUMAR 权利人:LONG TIMOTHY EDWARD; PATEL SRAVAN KUMAR; UNIV GEORGIA 摘要:Embodiments of this disclosure, among others, encompass methods for generating alkenes under mild thermolytic conditions that can provide almost total conversion of a precursor compound to an alkene without isomerization or the need to chromatographically purify the final product By selectively blocking the amino and carboxy groups of the derivatized amino acid, the methods of the disclosure provide for the synthesis of a peptide having the vinylglycine moiety at either the carboxy or the amino terminus of the peptide The mild conditions for the thermolytic removal of an o-NO 2 -phenyl substituted aryl group ensure that there is minimal if any damage to thermally sensitive conjugates such as a peptide bearing the vinylglycine The methods of the present disclosure have practical applications for the preparation of unsaturated compounds under mild, thermolytic conditions.
专利号:US-7408023-B2 优先权日:2001-04-06 标 题 :Peptoids incorporating chemoselective functionalities 发明人:HORN THOMAS; ZUCKERMANN RONALD N 权利人:NOVARTIS VACCINES & DIAGNOSTIC 摘要:Molecules having potential biological activity, particularly peptoids, that are conjugated to solid phase supports, spacer groups, and/or ligation moieties, and methods of their preparation, are described. In some instances, the molecules of the invention are made entirely by solid phase synthesis. In other instances, the spacer groups are hydrophilic and compositions containing them, and to solid phase synthesis of varied structure peptoids using chemoselective ligation moieties.
专利号:US-11471537-B2 优先权日:2017-04-05 标题 :Oligomer extended insulin-Fc conjugates 发明人:MOELLER TAGMOSE TINA; MADSEN PETER; KJELDSEN THOMAS BOERGLUM; PRIDAL LONE; DE MARIA LEONARDO; LIN ZHAOSHENG; Wan zhe; ZHANG YUANYUAN; LYKKE LENNART; MUENZEL MARTIN WERNER BORCHSENIUS; KODRA JANOS TIBOR 权利人:NOVO NORDISK AS 摘要:This invention is in the field of protein conjugates. More specifically the invention relates to oligomer extended insulins with covalently attached Fc monomer polypeptides, for use in the treatment of a metabolic disorder or condition, and to methods of producing such oligomer extended insulin-Fc conjugates. The invention also relates to novel Fc fragments, to intermediate products, and to the use of such intermediate products in processes for the synthesis of the oligomer extended insulin-Fc conjugates of the invention. Finally the invention provides pharmaceutical compositions comprising the oligomer extended insulin-Fc conjugates of the invention, and relates to the use of such compositions for the treatment or prevention of medical conditions relating to metabolic disorders or conditions.
专利号:EP-1484318-A1 优先权日:2003-06-03 标题:Process for the synthesis of aryl sulfurpentafluorides
参考标题:Synthesis Of Sulfonimidamides From Sulfenamides Via An Alkoxy‐amino‐λ 6 ‐sulfanenitrile Intermediate 作者:Edward L. Briggs,Arianna Tota,Marco Colella,Leonardo Degennaro,Renzo Luisi,James A. Bull |发布日期:2019.10 摘要:Few Operationally Simple Methods For Their Preparation. Here, The Synthesis Of Nh-Sulfonimidamides Is Achieved Directly From Sulfenamides, Themselves Readily Formed In One Step From Amines And Disulfides. A Highly Chemoselective And One-Pot Nh And O Transfer Is Developed, Mediated By Phio In Iproh, Using Ammonium Carbamate As The Nh Source, And In The Presence Of 1 Equivalent Of Acetic Acid. A Wide
合成参考文献
摘要:Kleoff, M.; Omoregbee, K.; Zimmer, R., Science of Synthesis Knowledge Updates, (2018) 4, 220. 摘要:Kaneda, K.; Mitsudome, T., Science of Synthesis: Catalytic Reduction in Organic Synthesis, (2017) 1, 351.