Sulfur diimides are chemical compounds of the formula S(NR)2. Structurally, they are the diimine of sulfur dioxide. The parent member, S(NH)2, is of only theoretical interest. Other derivatives where R is an organic group are stable and useful reagents.
A particularly stable derivative is di-t-butylsulfurdiimide.[1] It is prepared by reaction of tert-butylamine with sulfur dichloride to give the intermediate "S(N-t-Bu)", which decomposes at 60 °C to give the diimide. A second route to sulfur diimides involve treatment of sulfur tetrafluoride with amines. A third route involves transimidation of disulfonylsulfodiimide:
S(NSO2Ph)2 + 2 RNH2 → S(NR)2 + 2 PhSO2NH2
N,N'-Bis(methoxycarbonyl)sulfur diimide (MeO2C-N=S=N-CO2Me) is obtained from methyl carbamate.[2]
Structure, bonding, reactionsedit
These compounds are related to SO2. They have planar C–N=S=N–C cores with bent C–N=S and N=S=N geometries, and various combinations of E and Z isomers are observed for the two N=S bonds.[3]
^ abKresze, G.; Wucherpfennig, W., "Organic synthesis with imides of sulfur dioxide", Angew. Chem. Int. Ed. Engl. 1967, volume 6, 149-167. doi:10.1002/anie.196701491
^Kresze, Günter; Braxmeier, Hans; Münsterer, Heribert (1987). "Allylcarbamates by the Aza-Ene Reaction: Methyl N-(2-Methyl-2-Butenyl)Carbamate". Organic Syntheses. 65: 159. doi:10.15227/orgsyn.065.0159.
^Lork, Enno; Mews, Ruëdiger; Shakirov, Makhmut M.; Watson, Paul G.; Zibarev, Andrey V. (2002). "The first N-alkyl-N′-polyfluorohetaryl sulfur diimide". Journal of Fluorine Chemistry. 115 (2): 165–168. doi:10.1016/S0022-1139(02)00047-7.
^Fleischer, R.; Stalke, D., "A new route to sulfur polyimido anions S(NR)nm-: reactivity and coordination behavior", Coord. Chem. Rev. 1998, 176, 431-450. doi:10.1016/S0010-8545(98)00130-1
April 13, 2024
sulfur, diimide, chemical, compounds, formula, structurally, they, diimine, sulfur, dioxide, parent, member, only, theoretical, interest, other, derivatives, where, organic, group, stable, useful, reagents, namesiupac, name, diimino, sulfaneother, names, 2λ4, . Sulfur diimides are chemical compounds of the formula S NR 2 Structurally they are the diimine of sulfur dioxide The parent member S NH 2 is of only theoretical interest Other derivatives where R is an organic group are stable and useful reagents Sulfur diimide NamesIUPAC name diimino l4 sulfaneOther names 2l4 Diazathia 1 2 dieneIdentifiers3D model JSmol Interactive imageChemSpider 298618PubChem CID 336934InChI InChI 1S H2N2S c1 3 2 h1 2HKey HQFYRKYAKZRZCJ UHFFFAOYSA NSMILES N S NPropertiesChemical formula H 2N 2SMolar mass 62 09 g mol 1Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Organic derivatives 2 Structure bonding reactions 3 See also 4 ReferencesOrganic derivatives edit nbsp Structure of S NBu t 2 A particularly stable derivative is di t butyl sulfurdiimide 1 It is prepared by reaction of tert butylamine with sulfur dichloride to give the intermediate S N t Bu which decomposes at 60 C to give the diimide A second route to sulfur diimides involve treatment of sulfur tetrafluoride with amines A third route involves transimidation of disulfonylsulfodiimide S NSO2Ph 2 2 RNH2 S NR 2 2 PhSO2NH2N N Bis methoxycarbonyl sulfur diimide MeO2C N S N CO2Me is obtained from methyl carbamate 2 Structure bonding reactions editThese compounds are related to SO2 They have planar C N S N C cores with bent C N S and N S N geometries and various combinations of E and Z isomers are observed for the two N S bonds 3 Sulfur diimides are electrophilic They undergo Diels Alder reactions with dienes 1 Organolithium reagents attack at the sulfur to give the corresponding nitrogen anion R Li S NR 2 R S NR NRLi The triimido analogues of sulfite can be generated by treating the sulfur diimides with a metal amide 4 4 LiNHBu t 2 S NBu t 2 2 Li2S NBu t 3 2 t BuNH2 dd See also editCarbodiimide the carbon analogue Disulfur dinitride Bis trimethylsilyl sulfur diimideReferences edit a b Kresze G Wucherpfennig W Organic synthesis with imides of sulfur dioxide Angew Chem Int Ed Engl 1967 volume 6 149 167 doi 10 1002 anie 196701491 Kresze Gunter Braxmeier Hans Munsterer Heribert 1987 Allylcarbamates by the Aza Ene Reaction Methyl N 2 Methyl 2 Butenyl Carbamate Organic Syntheses 65 159 doi 10 15227 orgsyn 065 0159 Lork Enno Mews Ruediger Shakirov Makhmut M Watson Paul G Zibarev Andrey V 2002 The first N alkyl N polyfluorohetaryl sulfur diimide Journal of Fluorine Chemistry 115 2 165 168 doi 10 1016 S0022 1139 02 00047 7 Fleischer R Stalke D A new route to sulfur polyimido anions S NR nm reactivity and coordination behavior Coord Chem Rev 1998 176 431 450 doi 10 1016 S0010 8545 98 00130 1 Retrieved from https en wikipedia org w index php title Sulfur diimide amp oldid 1161565910, wikipedia, wiki, book, books, library,
