Pseudosaccharin chloride

Pseudosaccharin chloride (Expt 6.42) reacts with alcohols to give ethers (O-alkyl derivatives of saccharin) ... 

Heat a little pseudosaccharin chloride with excess of the anhydrous alcohol in a test tube until hydrogen chloride is no longer evolved. Recrystallise from ethanol or other organic solvent. 

When pseudosaccharin chloride is heated with an excess of a phenol, O-aryl derivatives of saccharin are produced (compare Section 9.6.4, p. 1244). 

Heat 0.5 g of pseudosaccharin chloride with an excess of the phenol to 125— 140 °C for 15-20 minutes hydrogen chloride is evolved. Wash the product with dilute sodium hydroxide solution and then with water. Recrystallise the derivative from ethanol. 

N-Acylsaccharins (13) possess a certain potential as acylating agents. They will acylate amines, but will react with water or alcohols only when acid or base is present.167 The method was used to acylate a-amino-penicillanic acid.170 Micheel162-165 has based a peptide (38) synthesis on the acyl transfer from 31 [Z = carbobenzoxy, obtained through reaction with DCC or with pseudosaccharin chloride (6) or with thionyl chloride and imidazole] to amino acids. Pseudosaccharin anhydride 323, lee js thg product of a condensation between 6 and 1, mostly from hydrolysis of 6. Formation of 32 tends to occur in nonprotic solvents with base catalysis, even when practical precautions are taken to exclude moisture. Water and protic solvents seem to shield the anion 19 and prevent attack on 6. 

Chlorobenz[d]isothiazole-l, 1-dioxide ( pseudosaccharin chloride ) (6)3,24.25, lee, 25i, 26i, 262 displays the reactivity of a cyclic imidoyl chloride263 resembling very much carboxylic acid halides. In previous sections preparation of 3, 4, 5, 13, 68, 86, 89 from 6 has been mentioned. Derivatives of 6 substituted in the phenyl ring have been described.250 Interestingly, Meadow observed231 that crude 6 and material that contained phosphorus pentachloride reacted with thiols more readily than the pure compound. In the reaction of 6 with aromatic sulfonamides, aluminum chloride had been added for activation.252... 

From the alcohol with pseudosaccharin chloride without solvent. 

From the alcohol with pseudosaccharin chloride and a catalytic amount of pyridine in chloroform. 

For the identification of glycols, their monoalkyl ethers, and esters of glycolic acid, alkyl pseudosaccharin ethers are suitable, which can be prepared by reacting the hydroxy compound with pseudosaccharin chloride in chloroform in the presence of pyridine, or also without any solvent (30, 31). 

Thieno[2, 3 4,5]pyrimido[l,2-6][l,2]benzisotliiazoles.—Compounds of this ring system, e.g. (91), are obtainable by the condensation of pseudosaccharin chloride and 2-aminothiophen-3-amide, followed by cyclization of the resulting intermediate in boiling glacial acetic acid. The corresponding 13 T[l]benzothieno-(five membered) ring system is similarly accessible. ... 

A soln. of tetradecylamine and pseudosaccharin ethyl ether in acetonitrile stored 30 hrs. at room temp. 3-tetradecylaminopseudosaccharin. Y ca. 100%. - The reaction can also he performed in a shorter time at higher temp. F. e., also from pseudosaccharin chloride, s. H. Hettler, Z. Anal. Chem. 220, 9 (1966). 

---