P-Toluenesulfonamides

In addition to alcohols, some other nucleophiles such as amines and carbon nucleophiles can be used to trap the acylpalladium intermediates. The o-viny-lidene-/j-lactam 30 is prepared by the carbonylation of the 4-benzylamino-2-alkynyl methyl carbonate derivative 29[16]. The reaction proceeds using TMPP, a cyclic phosphite, as a ligand. When the amino group is protected as the p-toluenesulfonamide, the reaction proceeds in the presence of potassium carbonate, and the f>-alkynyl-/J-lactam 31 is obtained by the isomerization of the allenyl (vinylidene) group to the less strained alkyne. 

Chloro-2-cyano-1 -(4-methylpheny 1-sulfonyl)-3-phenyl N -(2-Benzoyl-4-chlor ophenyl)-p- toluenesulfonamide, chloroacetronitrile DMF, reflux 71 [4]... 

Cm.OROCARBONSANDCm.OROHYDROCARBONS - RDIG-Cm.ORINATED TOLUENES] (Vol 6) N,N-Dichloro-p-toluenesulfonamide [473-34-7]... 

On the other hand, elimination of the hydrazino group in 3-hydrazinopyridazines is possible with p-toluenesulfonamide under phase transfer reaction conditions (78TL3059). 

Diethylamine [109-89-7] M 73.1, b 55.5, d 0.707, n 1.38637, pK 11.38. Dried with LiAlH4 or KOH pellets. Refluxed with, and distd from, BaO or KOH. Converted to the p-toluenesulfonamide and crystd to constant melting point from dry pet ether (b 90-120 ), then hydrolysed with HCl, excess NaOH was added, and the amine passed through a tower of activated alumina, redistd and dried with activated alumina before use [Swift 7 Am Chem Soc 64 115 1942]. 

V-Methyl-7V-nitroso-p-toluenesulfonamide (diazald) [80-11-5] M 214.2, m 62 . Crystd from benzene by addition of pet ether, store in a refrigerator. 

Chloramine-T (A -chloro-p-toluenesulfonamide sodium salt) 3H2O [7080-50-4] M 281.7, m 168-170°(dec). Crystd from hot water (2mL/g). Dried in a desiccator over CaCh where it loses water. Protect from sunlight. Used for detection of bromate and halogens, and Co, Cr, Fe, Hg, Mn, Ni and Sb ions. 

Sulfonylureas are accessible by the many methods that have been developed for the preparation of simpler ureas. For example, treatment of p-toluenesulfonamide (184) with butyl isocyanate (185) affords tolbutamide (186). ... 

Treatment of piperidine with nitrous acid affords the N-nitroso derivative (190) reduction gives the corresponding hydrazine (191). Condensation of this intermediate with the carbamate (192) obtained from p-toluenesulfonamide leads to the oral hypoglycemic agent tolazemide (193). In a similar vein, reaction of the hydrazine obtained by the same sequence from azepine (194) with the carbamate, 188, gives azepinamide (195). ... 

Cyclohexanecarbonyl chloride EK Triethylamine MCB, EK N-Methyl-A -nitroso-p-toluenesulfonamide A Isophorone MCB, A d < -Octalone-2 (Chapter 9, Section III)... 

Two procedures have been developed for the aminohydroxylation of a, 3-unsat-urated amides Procedure A for products that are insoluble in the reaction mixture and Procedure B for soluble products (Scheme 12.17) [48]. These differ only in that the former requires a 10-25% excess of chloramine-T and t-BuOH as the cosolvent, while the latter uses only one equivalent of the chloramine salt and MeCN as the cosolvent. The excess of chloramine-T in Procedure A allows better turnover near the end of the reaction, and the trace amount of p-toluenesulfonamide byproduct can be removed by recrystallization. However, elimination of the necessity to remove p-toluenesulfonamide far outweighed the inconvenience of slightly longer reaction times needed in procedure B without the use of excess chloramine salt. 

Sodium dodecyl sulfate and hydrogen dodecyl sulfate have been used as catalysts in the denitrosation iV-nitroso-iV-methyl-p-toluenesulfonamide [138]. The kinetics of condensation of benzidine and p-anisidine with p-dimethylamino-benzaldehyde was studied by spectrophotometry in the presence of micelles of sodium dodecyl sulfate, with the result that the surfactant increases the rate of reaction [188]. The kinetics of reversible complexation of Ni(II) and Fe(III) with oxalatopentaaminecobalt(III) has been investigated in aqueous micellar medium of sodium dodecyl sulfate. The reaction occurs exclusively on the micellar surface [189]. Vitamin E reacts rapidly with the peroxidized linoleic acid present in linoleic acid in micellar sodium dodecyl sulfate solutions, whereas no significant reaction occurs in ethanol solution [190]. 

Various N-nitroso-AT-alkyl compounds undergo elimination to give diazoalkanes. One of the most convenient methods for the preparation of diazomethane involves base treatment of V-nitroso-V-methyl-p-toluenesulfonamide (illustrated above, with... 

C7H7CIO2S 98-59-9) see Benproperine Brinzolamide Carzenide Cefoxitin Diazepam Flurotyl Fosinopril Gusperimus trihydrochloride Idarubicin Idoxuridine Indeloxacine Levocabastine Mazindol Medazepam Mibefradil hydrochloride Nemonapride Pioglitazone Prenalterol Ropinirole Tinidazole Tolterodine p-toluenesulfonamide... 

C7H9NO2S 88-19-7) see Saccharin Zafirlukast p-toluenesulfonamide sodium salt see under p-toluenesulfamide sodium salt p-toluenesulfonic acid... 

The acid-catalyzed cyclization of p-toluenesulfonamides of A/-benzylaminoacetaldehyde usually yields 1,2-dihydroisoquinolines. However, cyclization of intermediates bearing a substitutent a to the carbonyl group affords 3-substituted 2-p-toluenesulfonyl tetrahydroisquinolin-4-ol derivatives, capable of further transformation into the related 1,2,3,4-tetrahydroisoquinolines <95CJC(73)1348>. 

A mixture of catalyst 110 and vinyl trimethylsilyl enolether 115 has been used in cycloisomerisation of (V-allyl-o-vinylanilines 114 and (V.A-diallyl-p-toluenesulfonamide 115 to afford the corresponding products 118 and 119, respectively (Scheme 5.30) [34]. It is believed that the active catalyst species is the ruthenium hydride NHC complex 117. 

Amino-Hydroxylation. A related reaction to asymmetric dihydroxylation is the asymmetric amino-hydroxylation of olefins, forming v/c-ami noalcohols. The vic-hydroxyamino group is found in many biologically important molecules, such as the (3-amino acid 3.10 (the side-chain of taxol). In the mid-1970s, Sharpless76 reported that the trihydrate of N-chloro-p-toluenesulfonamide sodium salt (chloramine-T) reacts with olefins in the presence of a catalytic amount of osmium tetroxide to produce vicinal hydroxyl p-toluenesulfonamides (Eq. 3.16). Aminohydroxylation was also promoted by palladium.77... 

If iV-sulfinyl-p-toluenesulfonamide is prepared from p-tohienesulfonamide by using SOCl2 only, the yield turns out to be low even after heating the reaction mixture (refluxing benzene) for five days. By method B, however, the yield is high after only one hour at 20 °C in dichloromethane. 

Hoemer and Neumann found that electrochemical cleavage of the sulfur-nitrogen bond of alkyl p-toluenesulfonamides proceeds in high yield, under mild conditions, and with little or no racemization 71 ) ... 

An improved procedure59,60 uses bicyclo[3.3.1]nona-2,6-diene (39) instead of dione 31. Addition of N.JV-dibromo-p-toluenesulfonamide to 39 gives 40 which is debrominated to 41 and hydrolyzed to 2. 

An entry to 2-aza-6-thiaadamantane (235) from A-tosyl-9-azabocyclo-[3.3.l]nona-2,6-diene (64) and sulfur dichloride is similar to that of 2,6-diazaadamantane, where Ai,N-dibromo-p-toluenesulfonamide is used in-... 

Sodium AT-chloro-AT-alkylsulfamates, 13 108 Sodium IV-chloro-p-toluenesulfonamide (chloramine T), 4 54 Sodium chromate... 

---