J Toluenesulfonyl chloride

The reaction of a quinolizidine enamine, 6-dehydrodeoxynupharidine (188) with /j-toluenesulfonyl chloride in benzene gave two epimeric indolizidine carboxaldehydes (189).247... 

Fig. 4. Glaxo synthesis of T3 and T4 where p-TsCl = j -toluenesulfonyl chloride and Py = pyridine (24).

The submitters used j)-toluenesulfonyl chloride obtained from Badische Anilin- und Soda-Fabrik, 67 Ludwigshafen, Rhein, Germany. Very impure />-toluenesulfonyl chloride can be purified by recrystallization from ether. The checkers used material from Matheson, Coleman and Bell without further purification. 

The remaining heterocyclic compounds with oxygen in the bridge are ethers of the types 37 and 38. The parent compound (37 R = R = H) has been obtained by treatment of l,l -di(hydroxy-methyl)ferrocene with j-toluenesulfonyl chloride in refluxing benzene or with 10% hydrochloric acid in ether. The ring protons appear as a singlet in the NMR spectrum of 37 (R = R = H). In a similar manner other diols have been dehydrated with -toluene-sulfonyl chloride, acid alumina, dilute hydrochloric acid, dilute acetic acid, and silica to give 37 (R = R = R = R =... 

The bis-tosylate 47 is commonly preferred in synthetic sequences over the bis-mesylate 38. Treating 37 with excess j -toluenesulfonyl chloride in pyridine affords excellent yield of (2 S, 3 S)-l,4-bis-tosyl-2,3-0-isopropylidene-L-threitol (47) [24]. Nucleophilic displacement of the tosyl groups with potassium thiolacetate followed by deacetylation provides (2S,3S)-l,4-dithio-2,3-0-isopropylidene-L-threitol (48). 

D. Todd Whitaker Wayne State University, Detroit, MI, USA /J-Toluenesulfonyl Chloride 480... 

Toluenesulfonyl Chloride. Toluene reacts with chlorosulfonic acid to yield both ortho- and j )i7n7-toluenesulfonyl chlorides, of which Monsanto is the only producer. The ortho isomer is converted to saccharin. 

The p-toluenesulfonyl chloride should be free of j-toluenesulfonic acid, otherwise potassium p-toluenesulfonate will be formed and will result in the formation of tosylates, rather than thiotosylates. The reagent used by the checkers was obtained from British Drug Houses Ltd. and was purified according to the following procedure.4 A benzene solution of the tosyl chloride was washed with 5% aqueous sodium hydroxide, dried with magnesium sulfate, and then distilled under reduced pressure, b.p. 146° (15 mm.). 

DV Kashelikar, C Ressler. An oxygen-18 study of the dehydration of asparagine amide by N,N -dicyclohexylcarbodiimide and p-toluenesulfonyl chloride. J Am Chem Soc 86, 2467, 1964. 

J.D. White et al. reported the total synthesis of ( )-ibogamine via the catalytic asymmetric Diels-Alder reaction of benzoquinone. The azatricyclic framework of the molecule was established by converting the bicyclic ketone to the anti oxime and then subjecting it to a Beckmann rearrangement in the presence of p-toluenesulfonyl chloride to afford the 7-membered lactam. Elaboration of this lactam into the azatricyclic core of ibogamine and later to the natural product itself was accomplished in a few additional steps. 

Ethoxynaphthalene. Ethyl (5 naphthyl ether ethyl d-naphtholate nerolin "new -naphthyl ethyl ether Bromelia, Cl2H]20 mol wt 172.22. C 83.09%, H 7.02%, O 9.29%. Prepd by heating d-naphthol with potassium ethyl sulfate, or with alcohol and HjS04 Yokoyama et of.. Yaku-%aku Zasshi 78, 123 (1958) C.A. 52, ]0986c (1958) from d-naphthol + p-toluenesulfonyl chloride + ethyl alcohol Drakowzal, Klamann, Monatsh 82, 5S8 (1951) from d-naphthol + H2S04 + ethyl acetate Patai, Bentov, J. Am. Cfiem. Soc. 74, 6118 (1952) From 6 -naphtha] + triethyl -phosphate + p-toluenesulfonic acid Bell, US. pat. 2,683,-748 (1954 ro Eastman Kodak). 

NaH-mineral oil added to N-benzoyl-O-benzylhydroxylamine in dry benzene, p-toluenesulfonyl chloride in benzene added to the resulting precipitate, and refluxed 3 days benzyl p-toluenesulfonylbenzimino ether. Y 73%. F. method and e. s. J. H. Cooley et al., J. Med, Chem. 11, 196 (1968). 

Formation of Sulfonyl Cyanide. Tosylmethylene phosphorane reacts readily with nitrosyl chloride to provide /j-toluenesulfonyl cyanide via a Wittig-like fragmentation of the a-nitroso phosphonium intermediate with expulsion of Ph3PO (eq7).22... 

J ry pyridine added to a suspension of a-anilino-a,a-diphenylacetic acid and p-toluenesulfonyl chloride in dry benzene, and refluxed 7 hrs. benzo-phenone anil. Y 62.4%.—No reaction occurs with aq. NaOH in place of pyridine. J.G. Sheehan and J. W. Frankenfeld, J. Org. Ghem. 27, 628 (1962). 

Bromo-N -dimethyladenosine and di-n-butyltin oxide refluxed 1 hr. in methanol 2, 3 -0-dibutylstannylene-8-bromo-N -dimethyladenosine (Y 90%) suspended in methanol, triethylamine and p-toluenesulfonyl chloride added, and stirred 18 hrs. at room temp. 2 -0-tosyl-8-bromo-N -dimethyladenosine (Y 81%). M. Ikehara and T. Maruyama, J. Carbohyd. Nucleos. Nucleot. 2, 335 (1975) preferential 2-acylation of carbohydrates s. a. R. M. Munavu and H. H. Szmant, J. Org. Chem. 41, 1832 (1976) preferential protection of carbohydrate hydroxyl by acylation or alkylation cf. M. A.Nashed and L. Anderson, Tetrah. Let. 1976, 3503. 

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