17872-98-9Relevant articles and documents
Synthesis of Aromatic and Olefinic Sodium Sulfonates by Electrophilic Destannylation with Trimethylsilyl Chlorosulfonate
Niestroj, Michael,Lube, Andreas,Neumann, Wilhelm P.
, p. 575 - 580 (2007/10/02)
A mild and effective method for the preparation of a variety of aromatic, olefinic, and acetylenic sodium sulfonates is described.The reaction of trialkylaryl- (2a-k) and -heteroarylstannanes (4a-d), bis-(1-alkenyl)dibutylstannanes (6a-f), or trialkylakynylstannanes with trimethylsilyl chlorosulfonate (1) followed by hydrolysis with aqueous NaHCO3 provides the sodium sulfonates in an ipso-specific and in the case of vinylic stannanes stereospecific manner.A comparision of the reactivity of stannylated and silylated olefinic compounds 13 and 14 underlines the greater leaving ability of the stannyl moiety.The in situ preparation of the stannanes makes it possible to apply the synthetic method to natural products such as N-substituted apocodeine (17). - Key Words: Electrophilic aromatic substitution/ Electrophilic vinylic substitution/ Trialkylstannanes, application of/ Arylsulfonates, sodium salts of/ Vinylsulfonates, sodium salts of
Anhydrides of Phosphorus and Sulfur Acids, 2. Mixed Anhydrides of Phosphoric, Phosphonic, and Phosphinic Acids with Sulfonic Acids and Sulfuric Monoimidazolide. New Methods of Synthesis, Novel Structures, Phosphorylating Properties
Dabkowski, Wojciech,Michalski, Jan,Skrzypczynski, Zbigniew
, p. 1809 - 1824 (2007/10/02)
New applications of methods leading to anhydrides RR'P(O)OSO2R'' (1) are described: a) Reaction of acids RR'P(O)OH (2) with sulfonic imidazolides. b) Reaction of phosphorus imidazolides 4 with sulfonic acids and sulfonic anhydrides.New methods of synthesis of anhydrides 1 have been developed. c) Reaction of phosphorus acid silyl esters RR'P(O)OSiMe3 (9) with methanesulfonic and trifluoromethanesulfonic anhydrides. d) Reaction of bis(trimethylsilyl) tert-butylphosphonate (10) with methanesulfonic acid leading to tBuP(O)(OSO2Me)2 (11). e) Reaction of stannyl phosphate (EtO)2P(O)OSnMe3 (15) with methanesulfonic anhydride. f) Reaction of phosphorus acid silyl esters 9 with trimethylsilyl trifluoromethanesulfonate.All methods result in high yields and can be adapted to a variety of anhydrides 1 derived from phosphoric, phosphonic, and phosphinic acids on the one hand and methanesulfonic, trifluoromethanesulfonic acids and sulfuric monoimidazolide on the other.Phosphonium intermediates have been demonstrated by low temperature FT 31P NMR spectroscopy for reaction b) and c).The anhydrides 1 are readily converted into imidazolides 4 by the reaction with N-(trimethylsilyl)imidazole which proceeds via two distinct phosphonium intermediates.With neutral and weakly basic nucleophiles, the anhydrides 1 behave as phosphorylating agents.
Sulfosilylation of Aromatic Hydrocarbons by Trimethylsilyl Chlorosulfonate
Hofmann, Karin,Simchen, Gerhard
, p. 282 - 297 (2007/10/02)
Aromatic hydrocarbons 2 ,6 ,8 ,9 ,13 ,16 ,18 ,19 ,22 react with trimethylsilyl chlorosulfonate (1) to give trimethylsilyl arenesulfonates 5, 7, 11, 12, 15, 23 or sulfonic acids 17, 20, 21.If trimethylsilyl sulfonates are obtained, working up of the sulfonation mixtures is possible by distillation.By hydrohalogenolysis of trimethylsilyl sulfonates 5 at 0-5 deg C anhydrous sulfonic acids 3 result.The pathways to diphenylsulfone (25a) in the reaction of benzene (2a) with 1 were investigated.In this connection we succeeded in synthesizing benzenepyrosulfonic acid (28) and trimethylsilyl benzenepyrosulfonate (29).
Le sulfate de bis (trimethylsilyle) reactif de sulfonation en chimie organique
Bourgeois, Paul,Duffaut, Norbert
, p. 195 - 199 (2007/10/02)
Trimethylsilyl chlorosulphonate 1 and di-(trimethylsilyl) sulphate 2 are obtained by reacting trimethylchlorosilane with chlorosulphonic acid and sulphuric acid respectively. 1 and 2 are thermally stable and soluble in most of the organic solvents.The silyl sulphonates are hydrolyzed at room temperature. 2 is less reactive than 1 and is adequate reagent when the molecule contains ether or ester groups as 1 reacts also as chlorination reagent.Thus, 2 when refluxed in the presence of an excess of methoxy benzene gives quantitatively trimethylsilyl 4-methoxybenzenesulphonate 3 which is hydrolyzed quantitatively into 4-methoxybenzenesulphonic acid. 2 reacts with acid chlorides and acid anhydrides in refluxing cyclohexane or carbon tetrachloride which leads to α-sulphonic carboxylic acids 4 by sulphonation in position α to the acyl function.When starting from chloroacetylchloride, a gem-disulphonic derivative 5 is formed.A common intermediate, acyl and trimethylsilyl sulphate 6, is put forward and easy preparation and isolation of sulphonic acids by this method is pointed out.
Synthetic Application of Iodo- and Bromotrimethylsilane in Saccharide Chemistry
Thiem, Joachim,Meyer, Bernd
, p. 3075 - 3085 (2007/10/02)
In simple model compounds an enhanced rate is observed in the reaction of iodotrimethylsilane with acetates and with cyclohexyl esters.Primary and secondary acetoxy-substituted saccharides show an exclusive formation of glycosyl iodides.Accordingly, pentaacetyl hexopyranoses and iodotrimethylsilane give in high yields the corresponding glycosyl iodides.Methyl glycosides can be transformed similarly, and with lactose octaacetate the formation of α-heptaacetyllactosyl iodide proceeds smoothly without rupture of the interglycosidic linkage.This procedure is particularly valuable for the synthesis of 2-deoxyglycosyl iodides.Corresponding reactions with bromotrimethylsilane are achieved in a similar way.By opening of epoxides with iodotrimethylsilane in the case of sterically fixed saccharide oxiranes the trans-diaxial, and with more flexible derivatives predominantly the trans-diequatorial iodohydrines are obtained.
