This reagent can be synthesized quickly and in near-quantitative yield by reacting phenyl thioacetate with tert-butyldichloroamine in hot benzene. After the reaction is complete, the product can be isolated as a yellow, moisture-sensitive solid by vacuum distillation.[2]
Mechanism
The first two steps in an oxidation reaction involving N-tert-butylbenzenesulfinimidoyl chloride are similar to a nucleophilic acyl substitution reaction. A nucleophile, such as an alkoxide (1), attacks the S=N bond in 2. The resulting intermediate (3) collapses and ejects chloride ion, which is a good leaving group. The resulting sulfimide has two resonance forms - 4a and 4b. Because of this, the nitrogen is basic, and via a five-membered ring transition state, it can abstract the hydrogen adjacent to the oxygen. This forms a new C=O bond and ejects a neutral sulfenamide (5), giving ketone6 as the product. N-tert-Butylbenzenesulfinimidoyl chloride reacts with enolates, amides, and primary alkoxides by the same general mechanism.
The Swern oxidation, which converts primary and secondary alcohols to aldehydes and ketones, respectively, also uses a sulfur-containing compound (DMSO) as the oxidant and proceeds by a similar mechanism. In the Swern oxidation, elimination also occurs via a five-membered ring transition state, but the basic species is a sulfur ylide instead of a negatively charged nitrogen. Several other oxidation reactions also make use of DMSO as the oxidant and pass through a similar transition state (see #See also).
Reactions
Reacting an aldehyde with a Grignard reagent or organolithium and treating the resulting secondary alkoxide with N-tert-butylbenzenesulfinimidoyl chloride is a convenient one-pot reaction for converting aldehydes to ketones. While Grignards can be used for this reaction, organolithium compounds give higher yields, due to the higher reactivity of a lithium alkoxide compared to the corresponding magnesium salt. In some cases, an equivalent of DMPU, a Lewis base, will increase yields. For example, treating benzaldehyde with n-butyllithium and N-tert-butylbenzenesulfinimidoyl chloride in THF gives 1-phenyl-1-pentanone in good yield.[3]
N-tert-Butylbenzenesulfinimidoyl chloride can also be used to synthesize imines from amines. Imines synthesized in this fashion have been shown to undergo a one-pot Mannich reaction with 1,3-dicarbonyl compounds, such as malonate esters and 1,3-diketones. In this example, Cbz-protected benzylamine is deprotonated using n-butyllithium, then treated with N-tert-butylbenzenesulfinimidoyl chloride to form the protected imine. Dimethyl malonate acts as the nucleophile and reacts with the imine to give the final product, a Mannich base.[4]
^ abcMatsuo, J.; Mukaiyama, T. (2001). "N-tert-Butylbenzenesulfinimidoyl Chloride". e-EROS Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X. hdl:10261/236866. ISBN9780470842898. Retrieved 30 June 2012.
^Barrett, A. G. M.; Gray, A. A.; Hill, M. S.; Hitchcock, P. B.; Procopiou, P. A.; White, A. J. P. (2006). "Imino Sulfinamidines: Synthesis and Coordination Chemistry of a Novel Class of Chiral Bidentate Ligands". Inorganic Chemistry. 45 (8): 3352–3358. doi:10.1021/ic052104m. PMID 16602794.
^Crawford, J. J.; Henderson, K. W.; Kerr, W. J. (2006). "Direct and Efficient One-Pot Preparation of Ketones from Aldehydes Using N-tert-Butylphenylsulfinimidoyl Chloride". Organic Letters. 8 (22): 5073–5076. doi:10.1021/ol061903l. PMID 17048846.
^Matsuo, J.; Tanaki, Y.; Ishibashi, H. (2006). "Oxidative Mannich Reaction of N-Carbobenzyloxy Amines with 1,3-Dicarbonyl Compounds". Organic Letters. 8 (19): 4371–4374. doi:10.1021/ol0618095. PMID 16956229.
External links
N-tert-butylbenzenesulfinimidoyl chloride on Organic Chemistry Portal
August 24, 2023
tert, butylbenzenesulfinimidoyl, chloride, useful, oxidant, organic, synthesis, reactions, good, electrophile, sulfimide, bond, attacked, nucleophiles, such, alkoxides, enolates, amide, ions, nitrogen, atom, resulting, intermediate, basic, abstract, hydrogen, . N tert Butylbenzenesulfinimidoyl chloride is a useful oxidant for organic synthesis reactions 1 It is a good electrophile and the sulfimide S N bond can be attacked by nucleophiles such as alkoxides enolates and amide ions The nitrogen atom in the resulting intermediate is basic and can abstract an a hydrogen to create a new double bond N tert Butylbenzenesulfinimidoyl chloride Ball and stick model of N tert butylbenzenesulfinimidoyl chloride Space filling model of N tert butylbenzenesulfinimidoyl chlorideNamesPreferred IUPAC name N tert Butylbenzenesulfinimidoyl chlorideSystematic IUPAC name 1 1 Dimethylethyl imino chloro phenyl l4 sulfaneOther names N tert Butylphenylsulfinimidoyl chlorideIdentifiersCAS Number 49591 20 03D model JSmol Interactive imageChemSpider 9542820ECHA InfoCard 100 189 718PubChem CID 11367903UNII JZE5325ZY8 YUN number 3261CompTox Dashboard EPA DTXSID00463732InChI InChI 1S C10H14ClNS c1 10 2 3 12 13 11 9 7 5 4 6 8 9 h4 8H 1 3H3SMILES CC C C N S C1 CC CC C1 ClPropertiesChemical formula C 10H 14Cl N SMolar mass 215 74 g mol 1Appearance Yellow to deep yellow red crystals or powderMelting point 51 to 53 C 124 to 127 F 324 to 326 K 1 Boiling point 112 to 116 C 234 to 241 F 385 to 389 K 1 0 5 mm HgSolubility in water DecomposesSolubility in other solvents Benzene THF DCM slightly soluble in tolueneHazardsOccupational safety and health OHS OSH Main hazards CorrosiveGHS labelling PictogramsSignal word DangerHazard statements H290 H314Precautionary statements P234 P260 P264 P280 P301 P330 P331 P303 P361 P353 P304 P340 P305 P351 P338 P310 P363 P405Safety data sheet SDS TCI MSDSExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Preparation 2 Mechanism 3 Reactions 4 See also 5 References 6 External linksPreparation EditThis reagent can be synthesized quickly and in near quantitative yield by reacting phenyl thioacetate with tert butyldichloroamine in hot benzene After the reaction is complete the product can be isolated as a yellow moisture sensitive solid by vacuum distillation 2 Mechanism EditThe first two steps in an oxidation reaction involving N tert butylbenzenesulfinimidoyl chloride are similar to a nucleophilic acyl substitution reaction A nucleophile such as an alkoxide 1 attacks the S N bond in 2 The resulting intermediate 3 collapses and ejects chloride ion which is a good leaving group The resulting sulfimide has two resonance forms 4a and 4b Because of this the nitrogen is basic and via a five membered ring transition state it can abstract the hydrogen adjacent to the oxygen This forms a new C O bond and ejects a neutral sulfenamide 5 giving ketone 6 as the product N tert Butylbenzenesulfinimidoyl chloride reacts with enolates amides and primary alkoxides by the same general mechanism The Swern oxidation which converts primary and secondary alcohols to aldehydes and ketones respectively also uses a sulfur containing compound DMSO as the oxidant and proceeds by a similar mechanism In the Swern oxidation elimination also occurs via a five membered ring transition state but the basic species is a sulfur ylide instead of a negatively charged nitrogen Several other oxidation reactions also make use of DMSO as the oxidant and pass through a similar transition state see See also Reactions EditReacting an aldehyde with a Grignard reagent or organolithium and treating the resulting secondary alkoxide with N tert butylbenzenesulfinimidoyl chloride is a convenient one pot reaction for converting aldehydes to ketones While Grignards can be used for this reaction organolithium compounds give higher yields due to the higher reactivity of a lithium alkoxide compared to the corresponding magnesium salt In some cases an equivalent of DMPU a Lewis base will increase yields For example treating benzaldehyde with n butyllithium and N tert butylbenzenesulfinimidoyl chloride in THF gives 1 phenyl 1 pentanone in good yield 3 N tert Butylbenzenesulfinimidoyl chloride can also be used to synthesize imines from amines Imines synthesized in this fashion have been shown to undergo a one pot Mannich reaction with 1 3 dicarbonyl compounds such as malonate esters and 1 3 diketones In this example Cbz protected benzylamine is deprotonated using n butyllithium then treated with N tert butylbenzenesulfinimidoyl chloride to form the protected imine Dimethyl malonate acts as the nucleophile and reacts with the imine to give the final product a Mannich base 4 See also EditSwern oxidation Pfitzner Moffatt oxidation Corey Kim oxidation Parikh Doering oxidationReferences Edit a b c Matsuo J Mukaiyama T 2001 N tert Butylbenzenesulfinimidoyl Chloride e EROS Encyclopedia of Reagents for Organic Synthesis John Wiley amp Sons doi 10 1002 047084289X hdl 10261 236866 ISBN 9780470842898 Retrieved 30 June 2012 Barrett A G M Gray A A Hill M S Hitchcock P B Procopiou P A White A J P 2006 Imino Sulfinamidines Synthesis and Coordination Chemistry of a Novel Class of Chiral Bidentate Ligands Inorganic Chemistry 45 8 3352 3358 doi 10 1021 ic052104m PMID 16602794 Crawford J J Henderson K W Kerr W J 2006 Direct and Efficient One Pot Preparation of Ketones from Aldehydes Using N tert Butylphenylsulfinimidoyl Chloride Organic Letters 8 22 5073 5076 doi 10 1021 ol061903l PMID 17048846 Matsuo J Tanaki Y Ishibashi H 2006 Oxidative Mannich Reaction of N Carbobenzyloxy Amines with 1 3 Dicarbonyl Compounds Organic Letters 8 19 4371 4374 doi 10 1021 ol0618095 PMID 16956229 External links EditN tert butylbenzenesulfinimidoyl chloride on Organic Chemistry Portal Retrieved from https en wikipedia org w index php title N tert Butylbenzenesulfinimidoyl chloride amp oldid 1105298130, wikipedia, wiki, book, books, library,
