The dimer, trimer and 1,2,4-trithiolane of adamantanethione

Abstract

The molecules of dispiro[1,3-dithietane-2,2':4,2"-diadamantane], C(20)H(28)S(2), have crystallographic C(i) symmetry, as well as local D(2h) symmetry, and a planar 1,3-dithietane ring. The molecules of trispiro[1,3,5-trithiane-2,2':4,2":6,2"'-triadamantane], C(30)H(42)S(3), have approximate C(2) symmetry and the 1,3,5-trithiane ring has a twist-boat conformation. The C-S-C bond angles within the ring are about 8 degrees larger than observed in most related 1,3,5-trithiane structures. In dispiro[1,2,4-trithiolane-3,2':5,2"-diadamantane], C(20)H(28)S(3), the molecules have local C(2) symmetry and the 1,2,4-trithiolane ring has a half-chair conformation.

Sulfur addition to aldimines: thioamides, not thiaziridines, as products; revision of an old report

“…On the other hand, heating of 1 in CDCl 3 in the presence of adamantanethione (4) led to the known 1,2,4-trithiolane 5. [14,15] In accordance with the proposed sulfur-transfer reactions, [12] thiaziridine 2 is believed to act as the S-donor, which transfers 4 into the corresponding thiocarbonyl S-sulfide. The latter undergoes a [3+2] cycloaddition with 4 to give 5.…”

Adamantanethione

“…17 Reaction of 1 with PCl 5 in boiling tetrachloromethane leads to the dimer 3. 18 The same product is formed by direct irradiation ( = 254 nm or > 420 nm) as well as when sensitized with benzophenon. 19 eq 2The trimer 4 is obtained from 1 upon treatment with methane sulfonic acid diluted in diethyl ether at rt (eq 2).…”

“…2 Its formation is also reported when a solution of 1 in dichloromethane is stirred in the presence of silica gel. 18 The main product of this reaction is dispiro [1,2,4-trithiolane-3,2':5,2"-diadamantane].…”

Studies on Reactions of Thioketones with Trimethyl(trifluoromethyl)silane Catalyzed by Fluoride Ions

“…After 4 h at room temperature, the reaction mixture was separated chromatographically and colorless crystals of 1,2,4-trithiolane 18 were isolated as the sole product (Scheme 10). Its structure was confirmed by comparison with an authentic sample [22] [38]. 13 ) The information given in [21] concerning the dimer of thiobenzophenone is wrong; the indicated paper relates to dimers of aliphatic thioketones exclusively (see [36b]).…”

“…) The formation of 18 from 3 has been observed under different conditions, e.g., on treatment with nitrile sulfides or S 8[40], with organic azides[38] [41], sodium thiophenolate[42], P 4 S 10[43], or with SiO 2[22].…”