Toluenesulfonamide derivative

S)-Tetrahydro-l -methyl-3,3-diphenyl-1 H,3H-pyrrolo[1,2-c][1,3,2]oxazabo-role was prepared from (S)-proline in two steps according to the literature procedure4 and purified by bulb-to-bulb distillation (170°C, 0.2 mm). The enantiomeric purity of the intermediate, (S)-a,a-diphenyl-2-pyrrolidinemethanol, was determined to be 99% ee by chiral HPLC analysis of its corresponding N-p-toluenesulfonamide derivative (DIACEL Chiralcel OD column hexane/ethanol, 92/8 1.0 mLVmin Rt(S) 8.6 min Rt(R) 12.8 min). The checkers used the crystalline p-methyloxazaborolidineborane complex (1.84 g, 6.34 mmol) as the catalyst. 

The A,A -bis(p-toluenesulfonamide) derivative of diaza-18-crown-6 was prepared by treating the ditosylate ester of triethylene glycol with the N,N -bis(/7-tolucnesulfonamide) derivative of a diamino ether in base (method... 

Lehn and coworkers used a number of methods to prepare some interesting polyoxaaza macrocycles. These authors used many steps to elaborate a bis(p-toluenesulfonamide) derivative of a diamino ether to form [24]Nf,02 macrocycles (method M-7) (Lehn et al., 1977). In the process, the reaction of a... 

Richman and Atkins (1974, 1978), as well as Vogtle and coworkers, have prepared a number of polyaza-crowns by treating the appropriate per-p-toluenesulfonamide derivative of a polyamine with the ditosylate (dimesylate or dihalide) derivative of an oligoethylene glycol (method N-1) (Buhl-eier et ah, 1977 Rasshofer and Vogtle, 1977 Rasshofer et ah, 1976). They were able to prepare polyaza-crowns with different ring sizes and numbers... 

Additives used in final products Piasticizers acetyl triethyl citrate, di-(2-ethylhexyl) phthal-ate, diethyl phthalate, dimethyl phthalate, dimethyl sebacate, dioctyi sebacate, polyethylene glycol, polypropylene glycol, sulfolane, toluenesulfonamide derivatives, tri-(2-ethylhexyl) phosphate, triacetin, tributyl citrate, triethyl citrate, triphenyl phosphate Antistatics silver-doped vanadium pentoxide, vanadium pentoxide Antiblocking hydrogenated tallow amide, laponite, silica, talc Release magnesium stearate, sodium benzoate Slip silicone oil ... 

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. 

The N-oxides of isoquinolines have proved to be excellent intermediates for the preparation of many compounds. Trialkylboranes give 1-alkyl derivatives (147). With cyanogen bromide in ethanol, ethyl N-(l- and 4-isoquinolyl)carbamates are formed (148). A compHcated but potentially important reaction is the formation of 1-acetonyLisoquinoline and 1-cyanoisoquinoline [1198-30-7] when isoquinoline N-oxide reacts with metbacrylonitrile in the presence of hydroquinone (149). Isoquinoline N-oxide undergoes direct acylamination with /V-benzoylanilinoisoquinoline salts to form 1-/V-benzoylanilinoisoquinoline [53112-20-4] in 55% yield (150). A similar reaction of AJ-sulfinyl- -toluenesulfonamide leads to l-(tos5larriino)isoquinoline [25770-51-8] which is readily hydrolyzed to 1-aminoisoquinoline (151). 

It can also be prepared by the reaction of phenyUithium with tetraphenylbismuth chloride or the /V-triphenylbismuth derivative of 4-toluenesulfonamide... 

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). ... 

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>. 

Various saccharin derivatives 260 have been prepared by chromium (VI) oxide catalyzed H5IO6 oxidation of substituted ort/ro-toluenesulfonamides 259 <06T7902>. The reaction presumably proceeds through a benzylic radical intermediate 261 generated from the... 

The allene moiety of N-(3-alkoxy-4,5-dienyl)toluenesulfonamide 308 is attacked by acetyltetracarbonylcobalt to form a jt-allyl-Co intermediate 309, which may be converted to trans-pyrrolidine derivatives 310 via an intramolecular nucleophilic substitution [150,151]. 

H, Cl, Br, NO2, Me, MeO) by bromamine-B, catalysed in the presence of HCl in 30% aqueous methanol by RuCls have been smdied and a biphasic Hammett a-relationship derived. A kinetic study of the ruthenium(in)-catalysed oxidation of aliphatic primary amines by sodium A-bromo-j -toluenesulfonamide (bromamine-T, BAT) in hydrochloric acid medium has been undertaken and the mechanism of the reaction discussed. A concerted hydrogen-atom transfer one-electron transfer mechanism is proposed for the ruthenium(in)-catalysed oxidation of 2-methylpentane-2,4-diol by alkaline hexacyanoferrate(III). The kinetics of the oxidation of propane-... 

Iodine was found to be an efficient catalyst for the aziridination of alkenes (Scheme 6) utilizing chloramine-T (A-chloro-A-sodio-p-toluenesulfonamide) as the nitrogen source. For example, when 2 equiv. of styrene (45a) were added to chloramine-T in the presence of a catalytic amount of iodine (10mol%) in a 1 1 solvent mixture of acetonitrile and neutral buffer, the corresponding aziridine (46) was obtained in 91% yield. The reaction proved to work with other acyclic and cyclic alkenes, such as oct-l-ene and cyclohexene. The aziridination of para-substituted styrene derivatives (45b-e) demonstrated that, as expected for an electrophilic addition, electron-rich alkenes reacted faster than electron-poor alkenes. However, with 1 equiv. of I2, mainly iodohydrin (47) was formed. A catalytic cycle has been proposed to account for the fact that only a catalytic amount of iodine is required (Scheme 1) ... 

The most common method of radiolabeling employs Chloramine-T, the sodium salt of the N-monochloro derivative of p-toluenesulfonamide (Fig. 17). It breaks down slowly in aqueous solution to hypochlorous acid and is used as a mild oxidizing agent in radioiodination reactions. Other oxidation reagents used in radioiodination include... 

N-ethyl-p-toluenesulfonamide and derivs 6 E334 N-(2-azidoethyl)-p-toluene sulfonamide 6 E334 3,N-dinitro-N-ethyl-p-toluene sulfonamide 6E334... 

Ma and co-workers have reported the selective synthesis of pyrrolidine derivatives through a three-component reaction based on a conceptually related strategy (Scheme 8.29) [72], Beginning with the catalytic intermolecular carbopalladation of y-allenic malonate 57 in the presence of a base, they succeeded in intercepting the internal carbonucleophile 58 with an imine such as the N-benzylidene p-toluenesulfonamide 59. The attack of the newly formed heteronucleophile on the 7r-allyl palladium intermediate affords the functionalized pyrrolidine 60 with high... 

Sodium TV-chloro-/ -toluenesulfonamide (chloramine T, CAT) is a stable N—Cl derivative, which has been widely used in organic synthesis, particularly as an oxidant768. Kinetic study on the chlorination of / -aminobenzoic acid by CAT reveals simultaneous catalysis by H+ and Cl"769. 

If a C3 unit needs to be introduced bearing a carbon chain, then there are several options. A P-amino add could be used as a precursor in a parallel synthesis to those discussed above. Alternatively, a strategy based on malonate syntheses could be employed. Co-condensation of a C-substituted malonate with a primary diamine in boiling ethanol gives reasonable yields of cyclic diamide which may be reduced with borane in THF to yield the desired polyamine (Scheme 1.12 and Protocol 5).18 Another possibility is to prepare a linear bis-toluenesulfonate ester from a malonate by reduction (e.g. LiBH4) and tosylation, followed by a standard toluenesulfonamide cyclisation reaction. Yet another variant, this time giving racemic product, is to react a coumarin derivative with a linear polyamine (Scheme 1.12).1819 In this case, a... 

Furfurylamine derivatives could be prepared, via an in j tV -generated aldimine intermediate, by treatment of an aldehyde and A-sulfinyl-/)-toluenesulfonamide with furan in the presence of ZnCl2 <2003T4939>. As shown in Equation (8), enantioselective addition of 2-methoxyfuran to aldimines was achieved using the chiral C -symmetric phosphoric acid 6 as an organocatalyst <2004JA11804>. This reaction uniformly provided >94% ee irrespective of the substitution pattern on the aldimine phenyl ring. 

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