Reaction with tosylates

Deuterio-3-iiitro-l,6-iiaphthyridiiie (168) was prepared from 4-chloro-3-iiitro-l,6-iiaphthyridiiie (166) by a reaction with tosyl hydrazide and subsequent hydrolysis of the 4-tosylhydrazino derivative (167) with Na2C03/ D2O solution (83RTC359). 7-Deuterio-l,8-naphthyridin-2(lH)-one was prepared by heating l,8-naphthyridin-2(lH)-one with deuterium oxide at 230°C for 35 h (85JHC761). Tliis deuterio compound could be converted into 2-chloro-(or 2-ethoxy-) 7-deuterio-3,6-dinitro-l,8-naphthyridine. 

In order to activate the 1,2-diacylhydrazines towards cychzation, they were reacted with tosyl chloride (Scheme 8). While the reaction with tosyl chloride alone did not afford any of the desired product, and the cychzation in the presence of strong bases, although successful, posed the same problems of removal, excellent results were obtained in the presence of both tosyl chloride and a supported strong base, with polymer-bound BEMP giving better results than polymer-supported l,3,4,6,7,8-hexahydro-l-methyl-2H-... 

Thiophene-fused benzoquinones, such as 23, can be easily alkylated to produce dialkoxybenzodithiophene compounds 111 on reaction with tosyl esters (Equation 28) <2002SM(130)139>. 

Primary alkyl halides (chlorides, bromides, and iodides) can be oxidized to aldehydes easily and in good yields with dimethyl sulfoxide.311 Tosyl esters of primary alcohols can be similarly converted to aldehydes,312 and epoxides313 give a-hydroxy ketones or aldehydes.314 The reaction with tosyl esters is an indirect way of oxidizing primary alcohols to aldehydes (9-3). This type of oxidation can also be carried out without isolation of an intermediate ester The alcohol is treated with dimethyl sulfoxide, dicyclohexylcarbodiimide (DCC),315 and anhydrous phosphoric acid.316 In this way a primary alcohol can be converted to the aldehyde with no carboxylic acid being produced. 

We have previously reported on the synthesis of a series of mono- and bifunctional poly(DMS) having a variety of reactive end groups, such as silan (Si-H), vinyl, hydroxyalkyl, dimethylamino and carboxyllic acid groups.7 We have also described already on telechelic poly(DMS) having tosylate end group, lb and l b, where the hydrosilation reaction of poly(DMS) having silan end group was performed with allyl alcohol in the presence of Pt/C catalyst, followed by the tosylation reaction with tosyl chloride in the presence of dimethylaminopyridine.9... 

Few preparations of nitriles have been performed on insoluble supports (Table 13.19). Aromatic and heteroaromatic nitriles have been prepared on solid phase from the corresponding iodoarenes by metallation followed by reaction with tosyl cyanide (Entry 1, Table 13.19). Moreover, the reaction of chloromethyl polystyrene with NaCN has been used to prepare support-bound benzyl cyanide (Entry 2, Table 13.19). Cleavage with simultaneous formation of nitriles can be achieved by treating polystyrene-bound sulfonylhydrazones with KCN (Entry 3, Table 13.19) or by cleaving amides from a Rink or Sieber linker with TFA anhydride (Entry 10, Table 3.38 [262]). Support-bound benzaldehydes have been converted into 3-aryl-2-propenenitriles by means of a Horner-Emmons reaction with (Et0)2P(0)CH2CN [263]. 

Another method of preparing azobisindolizines is by reaction with tosyl or picryl azide.191-193 2-Methylindolizine is converted into the 3,3 -bisazo compound after 2 minutes. The product yields the radical ion 130 (detected by EPR) when treated with 1 mole of silver perchlorate.194,195 The redox characteristics of such compounds have been studied by Hiinig and co-workers.196,197 In view of the instability of aminoindolizines, they have not been used to prepare diazonium salts. 1-Nitrosoindolizines, however, yield diazonium nitrates in good yield when treated with dry nitric oxide.182,198 The products are stable both in... 

Isopropylidine adenosine was converted to the p-toluene sulphonyl (tosyl) ester by reaction with tosyl chlorine solution, following the method of Clark et al. (1951) [J. Chem. Soc. 2952]. Because of its tendency to cyclization, the reagent was used directly it was ready. A reaction flask with separating funnels was set up in such a way that the whole system could be evacuated and filled with pure nitrogen two or three times, to eliminate all oxygen, and reagents could then be added when desired, in the closed system. 

Color Reaction with Tosyl Chloride I Pyridine, p-Nitrosodimethylanilinel Potassium Cyanide... 

Which of the following reactions of a chiral alcohol occurs with inversion of configuration (a) reaction with NaH (b) reaction with PBr3 (c) reaction with tosyl chloride (d) reaction with (CH3)3SiCl... 

Hydrazinopyridazine was transformed into pyridazine by the aza-transfer reaction with tosyl azide (78TL3059). Hydrazinopyridazines react with ethoxycarbonylisothiocyanate to give the corresponding thio-semicarbazides (88M83). They react with 2-chlorosulfonyl acetate to also... 

Reaction with tosyl chloride to form tosylates (9.13A)... 

Reaction with tosylates (cf. 1, 1088). Conversion of methyl 2,3,6-tribenzoyl-4-tosyl-x-D-glucoside (1) into the iodide (2) ... 

If a C-substituted derivative of TOSMIC is used in the reaction, the product is a 1,4,5-trisubstitutcd imidazole. Such substituted isocyanidcs can be made either by dehydration of the iV-(a-tosylalkyl)formamide, or by alkylation of an appropriate isocyanide followed by reaction with tosyl fluoride. It is also possible to alkylate TOSMIC directly using phase transfer conditions 13], Such alkylations work best with primary alkyl halides (75-95%), with the isopropyl (40%), allyl (75%) and benzyl (80%) derivatives proving quite accessible. 

Reaction with tosylates. The tosylates of primary alcohols react readily with a 10% solution of sodium iodide in acetone to give the corresponding iodides. Thus, as measured by the rate of separation of sodium p-toluenesulfonate, the reactions... 

Dehydration. Wintersteiner and Moore " effected dehydration of 3/3-acetoxy-cholestane-7a-ol by reaction with tosyl chloride in refluxing pyridine and obtained a mixture of stenyl acetates rich in the A -isomer and convertible into pure A "" )-cholestenyl acetate on catalytic rearrangement. 

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