The synthesis of the title compounds I by 1:1 condensation of Ar-N = S = N
= SiMe3 2 with SCl2 followed by intramolecular ortho-cyclization of each [A
r-N = S = N-S-Cl] intermediate is complicated by further reaction of 1 with
SCl2 to give Herz salts 3. With the 2:SCl2 ratio of 2:1, the formation of
by-products 3 is reduced and novel compounds 1 are accessible. With ortho-I
containing starting material 2j, the parent compound Is is obtained as the
result of an unexpected 1, not H, substitution. The rate of the I + SCl2 r
eaction depends upon a substituent position, and the minor 8-R isomers 1l,p
(R = Br, I) are isolated for the first time from mixtures with the major 6
-R isomers due to reduced reactivity toward SCl2. The Synthesized compounds
1-3 are characterized by multi. nuclear (including nitrogen) NMR and X-ray
crystallography. According to the X-ray diffraction data, 1j (6-Br) and 1k
(7-Br) derivatives are planar, whereas 1i (5-Br) and 1l (8-Br) are bent al
ong the S1 . . . N4 line by similar to5 degrees and similar to4 degrees, re
spectively, and the Ir (7-OCH3) derivative is planar in contrast to the kno
wn 5-OCH3 isomer, which possesses a significantly folded heterocycle. The d
istortion of the planar geometry of some compounds I is interpreted in term
s of a pseudo-Jahn-Teller effect as the result of pi -highest occupied mole
cular orbital (HOMO) - sigma*-(LUMO) lowest unoccupied molecular orbital I mixing in a planar conformation. The 2p compound is the first structurall
y defined Ar-N = S = N-SiMe3 azathiene. The compound Ar-N = S = N-S-NH-Ar 6
modeling the aforementioned intermediate has been isolated and structurall
y characterized. We describe the attempts to synthesize compounds I from 2-
aminobenzenethiols and (SN)(4) and from salts 3 and Me3SiN3, and we discuss
the reaction pathways. (C) 2001 John Wiley & Sons, Inc.