Alkyl- and Arylthiodediazoniations of Dry Arenediazoniumo-Benzenedisulfonimides. Efficient and Safe Modifications of the Stadler and Ziegler Reactions to Prepare Alkyl Aryl and Diaryl Sulfides

Abstract

The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5 degrees C for the alkylthiodediazoniations and at room temperature (20-25 degrees C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.

Highly Efficient and Functional‐Group‐Tolerant Catalysts for the Palladium‐Catalyzed Coupling of Aryl Chlorides with Thiols

“…(Table 3, entry 1): [33] 100 mL of stock solution A were used; column chromatography: hexane/ethyl acetate 50:1; colorless liquid (98 % yield). Octyl phenyl sulfide (Table 3, entry 2): [44] 100 mL of stock solution A were used; column chromatography: hexane; colorless liquid (91 % yield). Octyl phenyl sulfide (Table 3, entry 3): 50 mL of stock solution A were used; colorless liquid (91 % yield).…”

“…(Table 3, entry 8): A solution of PdA C H T U N G T R E N N U N G (OAc) 2 (4.4 mg) and CyPF-tBu (11 mg) in DME (1 mL) was used as catalyst; the reaction was conducted at 70 8C; 97 % yield. (Table 3, entry 9): [45] (Table 3, entry 10): [44] 50 mL of stock solution A were used; column chromatography: hexane; colorless liquid (91 % yield). 4 mg) and CyPF-tBu (11 mg) in DME (1 mL) was used as catalyst; the reaction was conducted at 70 8C; 89 % yield.…”

Convenient preparation of aryl methyl and aryl phenyl sulfides from arenediazonium tetrafluoroborates and trimethyl(methylthio)- and trimethyl(phenylthio)silanes

“…A recent comprehensive report, in a modified Ziegler reaction, has employed stable and safe arenediazonium o-benzenesulfonimides for the preparation of a large number of alkyl aryl and diaryl sulfides using a number of aliphatic and aromatic thiolates under basic conditions. 7 The stability of arenediazonium tetrafluoroborates makes them attractive arylating agents, they are also easily prepared and stored. 8 Keumi et al 9 have reported that arenediazonium tetrafluoroborates could be readily dediazoniated with trimethylsilyl derivatives such as TMSCl, TMSBr, TMSI and TMSN 3 in dimethylformamide upon warming or at room temperature.…”

Reaction of [18F]4‐fluorobenzenediazonium cations with cysteine or the cysteinyl group: preparation of 18F‐labeled S‐aryl‐cysteine and a radiolabeled peptide

“…3 In this procedure [ 18 F]4-fluorophenylalanine (3) was obtained and diazotized in high yield, as shown by monitor reactions. Although diazothio-compounds are note suitable for a direct introduction of 18 F into an aromatic ring, the high reactivity of the sulfhydryl-group of cysteine with diazonium ions to form diazothio-compounds 4,5 and arylthioethers by thiodediazonation [6][7][8] may provide a possible reaction pathway for the synthesis of radiopharmaceuticals containing the 18 Faryl thioether moiety. In this paper, we describe an adaptation of the synthesis of the diazonium ion 4 and its application to the synthesis of 18 F-labeled 7 ( Figure 2).…”