Chlorides camphorsulfonyl

Form Supplied in both enantiomers and the racemic sulfonyl chloride are commercially available. 

Preparative Methods can be prepared from 10-Camphorsul-fonic Acid upon treatment with Phosphorus(V) Chloride or Thionyl Chloride.  

Purification crystallized from hexane or from MeOH. 

Handling, Storage, and Precautions corrosive and moisture-sensitive. This reagent should be handled in a fume hood. 

Reagent for Determination of Enantiomeric Excesses and for Chemical Resolution of Alcohols and Amines. 10- 

Camphorsulfonyl chloride has been widely used as a chiral deriva-tizing agent for the assay of enantiomeric purity of alcohols and amines by NMR techniques. A typical procedure for the 

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Calcium carbonate as support for palladium catalyst, 46, 90 Calcium hydride, 46, 58 D,L-Camphor, sulfonation to d,l-10-camphorsulfonic acid, 46,12 10-Camphorchlorosulfoxide, 46, 56 d,l-10-Camphorsulfonic acid, 46,12 conversion to acid chloride, 45,14 10-Camphorsulfonyl chloride, 45, 56 d,l-10-Camphorsulfonyl chloride,... 

Oxidation, of d,l 10-camphorsulfonyl chloride to d,l ketopime acid with potassium permanganate, 46, 55... 

The reaction of chiral sulfones 161, derived from (lS)-( + )-10-camphorsulfonyl chloride, with cyclopentadiene gives predominantly the endo adduct in a diastereomeric ratio of 91 9 from which one diastereomer 162 can be isolated in pure form by recrystallization (equation 115)109. 

D,L-10-Camphorsulfonyl chloride may be oxidized to ketopinic acid (p. 55). The optically active forms of the sulfonyl chloride are useful for resolving alcohols and amines into optical antipodes. 

D,L-Ketopinic acid has been prepared by oxidation of bornyl chloride with nitric acid at 20° or with perbenzoic acid in acetic acid from 10,10-dinitrocamphan-2-on or apocamphan-2-ol-l-carboxylic acid with alkaline permanganate and from the oxidation of 10-camphorchlorosulfoxide, obtained from 10-camphorsulfonyl chloride by the action of pyridine, with potassium permanganate. The present procedure represents a simplification of the latter and gives as high an overall yield. ... 

Camphorsulfonyl chloride is rather rapidly hydrolyzed by warm water. The procedure here provides for complete hydrolysis of phosphorus oxychloride and excess phosphorus pentachloride without local heating and loss of product due to hydrolysis. For best results, the whole hydrolysis operation should be carried out quickly and steadily. It is well to have additional quantities of crushed ice on hand because the mixture may become quite hot if all of the ice added initially melts. 

D-lO-Camphorsulfonyl chloride, 48, 107 reaction with diazomethane and triethylamine, 48, 106 d,i,-10-Camphorsulfonyl chloride,... 

Camphorsulfonyl chloride Bicyclo[2.2.1]heptane-1-methanesulfonyl chloride,... 

Calythrone, 430,431 Camphoric acid, 317, 318 10-Camphorsulfonyl chloride, 290 Canadaline, 214, 215 Cannivonine, 10 Cantharanthine, 456 e-Caprolactam, 316 Carbamates, 254 Carbamoylation, 279... 

Synthesis of Chiral Auxiliaries. Their availability and crystalline nature has made camphor derivatives the precursors of choice for the design and synthesis of chiral auxiliaries. 10-Camphorsulfonyl chloride is the starting material for the synthesis... 

Synthesis of Chiral Reagents. An efficient chiral a-chloro-a-nitroso reagent derived from 10-camphorsulfonyl chloride (1, Cy2NH 2, NH2OH 3. t-BuOCl 70-78%) has been developed for the asymmetric a-amination of ketone enolates (eq 7). The resulting p-keto /V-hydroxylamine can be converted to the anti-1,2-hydro y amine under reducing conditions (NaBHt Zn, HCl, AcOH),... 

Preparative Methods crystalline, enantiomerically pure 10-diisopropyl- and 10-dicyclohexylsulfonamidoisobomeol auxiliaries are readily prepared from the appropriate enantiomer of 10-Camphorsulfonyl Chloride by successive amidation and cxtr selective reduction (eq 1). ... 

Preparative Methods both enantiomers of the a-methyl sultam may be prepared on a multigram scale in optically pure form by asymmetric hydrogenation of imine (2a) followed by simple crystallization (eq 1). The (7 )-enantiomer of the a-f-butyl sultam may also be prepared in enantiomerically pure form by asymmetric reduction of imine (2b) followed by fractional crystallization. However, multigram quantities of either enantiomer of the a-t-butyl sultam may be prepared by derivati-zation of the racemic auxiliary (obtained in 98% yield from reaction of (2b) with Sodium Borohydride in MeOH) with 10-Camphorsulfonyl Chloride, separation of the resulting diastere-omers by fractional crystallization, and acidolysis. Prochi-ral imines (2a) and (2b) are readily prepared from inexpensive Saccharine by treatment with Methyllithium (73%) and t-Butyllithium (66%), respectively. 

Resolution 3t3-Acetoxy-A. etienic add. T-Acid from a tetranitrofluorenone and an optically active hydroxylamine. i><—>Butane-2,3-diol. L.(+)-Butane-2,3-dithiol. (By crystallization Silver acetate). 10-Camphorsulfonic acid. 10-Camphorsulfonyl chloride. 4-(4-Carboxy-phenyl) semicarbazide. Complex from ethylene, platinous chloride, and (- -)-l-phenyi-2-aminopropane. Debydroataetylamine. Diisopinocampheylborane. Di-p-toluoyl-o-tartrate. d- and /-u-Phenylethylamiiie. L-Pyrrolidonecarboxylic add. a-(2,4,S,7-Tetianitro-9-fluorenyl-ideneaminooxy)-propionic acids. 

In our laboratories, we have used a related approach to covalently attach chiral camphorsulfonate groups to N centers of PAn, by the reaction of EB with (lS)-(+)-10-camphorsulfonyl chloride in NMP/pyridine.153 The optically active product 13, isolated as the HC1 salt, is believed to preferentially adopt a one-handed helical conformation for its polymer chains. This provides the first example of chiral induction in a PAn species through a covalently attached group. A significant advantage for the product 13 compared to the chiral PAn/HCSA salts described earlier is that it consequently retains its optical activity upon alkaline dedoping in solution to its EB form. 

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