BENZOCYCLOALKANONE OXIMES WITH LAWESSON’S REAGENTS
63
2H, JHH = 8.7 Hz, Ar), 7.93 (d, 2H, JHH = 8.7 Hz, Ar), 8.26 (d, 2H, JHH = 8.1 Hz, Ar),
and 10.7 (bs, 1H, SH, exchangeable with D2O) ppm; 13C NMR (DMSO): δ = 203.8 (d,
1
2
2JCP = 20.8 Hz, C S), 135.1 (d, JCP = 123.7 Hz, C C P), 134.0 (d, JCP = 22.4 Hz,
C C P), 135.5 (d, 2JCP = 25.1 Hz, C-Ph), 132.5 (d, 3JCP = 13.0 Hz,C-Ph), 127.2, 132.3,
126.2, 143.0 (C6H4) ppm; MS, m/z (%): 350 (100) [M+], 109 (S-Ph).
The Reaction of 1-Tetraloneoxime 3b with Lawesson’s Reagent 1a
To a suspension of 3b (0.16 g, 0.001 mol) in acetonitrile (30 mL), 1a (0.4 g, 0.001
mol) was added. The reaction mixture was stirred at rt for 8–10 h, and the solvent was
removed under pressure. The residue was placed on a column of silica-gel using eluent
solution to give adduct 10.
(4-Methoxyphenyl)(1-thioxo-1,4-dihydronaphthalen-2-yl) phosphinodi-
thioic acid (10). Eluent: petroleum ether:ethyl acetate (85:15, v/v). Product 10 was
separated as white crystals, mp 183–184◦C, yield (76%). Anal. Calcd. For C17H15OPS3
(362.47): C, 56.33; H, 4.17; P, 8.55; S, 26.54. Found; C, 56.20; H, 4.30; P, 8.43; S,
26.40%. IR (KBr): 2930 (SH) cm−1, 1232 (C S) cm−1, 720 (P S) cm−1, 1178 (P-C,
1
Aryl) cm−1; H- NMR(DMSO): δ = 3.60 (s, 2H, CH2), 3.79 (s, 3H, OCH3), 6.80 (d,1H,
2JHP = 8.9 Hz, CH C P), 6.84–6.92 (m, 4H, Ar), 7.49–7.61 (m, 4H, Ar), 9.26 (b,1H, SH,
exchangeable D2O) ppm;13C NMR (DMSO): δ = 203.1 (d, 2JCP = 18.8 Hz, S C C P),
160.2 (OCH3–4), 145.1(d,1JCP = 123.1 Hz, C C P), 140.0 (d, 2JCP = 20.8 Hz, C C P),
32.4 (CH2),125.0 (d, 1JCP = 120.0 Hz, P-C-Ph), 132.1 (d,2JCP = 18.6 Hz, P-C-Ph), 113.0
3
(d, JCP = 12.5Hz, P-C-Ph), 130.4, 128.4, 139.2, 127.6, 124.2, 146.2 ppm; MS; m/z(%):
362 (30) [M+].
The same reaction was carried out in acetonitrile (30 mL) and refluxed for 2 h.
The reaction mixture was evaporated under reduced pressure, the residue was placed on a
column of silica-gel, and eluent solution was used to yield adduct 11.
2-(3,4-Dihydronaphthalen-1(2H)-ylideneamino)naphthalene-1(4H)-one
thioxime (11). Eluent: petroleum ether:acetone (40:60, v/v). Product 11 was separated
as violet crystals, mp 217–220◦C, yield (60%). Anal. Calcd. For C20H18 N2S (318.43):
C, 75.44; H, 5.70; N, 8.80; S, 10.07. Found; C, 75.60; H, 5.52; N, 8.68; S, 10.16%. IR
1
(KBr):2925 (SH) cm−1,1589 (N C) cm −1, 1660 (C C) cm−1; H- NMR(CDCl3): δ =
1.68 (s, 1H, SH exchangeable with D2O), 2.15 (2t, 4H, 2CH2), 2.20 (m, 2H, CH2), 6.84 (t,
1H, JHH = 7.5 Hz, CH C-), 7.37–7.34 (d, 1H, JHH = 9Hz, Ar), 7.74–7.72 (m, 4H, Ar),
7.79–7.76 (d, 1H, JHH = 9 Hz, Ar), 9.10–9.07 (2d, 2H, JHH = 9 Hz, Ar) ppm; MS; m/z
(%): 318 (20) [M+],
Reaction of 2,4-Bis(thiophenoxy)-1,3,2,4-dithiaphosphetane-2,4-di-
sulfide (1b) with Tetralonoxime (3b)
To a suspension of oxime 3b (0.16 g; 0.001 mol) in dry toluene (30mL), reagent
1b (0.4 g, 0.001 mol) was added. The reaction mixture was refluxed for 0.5 h. After
cooling, the solvent was evaporated under reduced pressure. The residue was separated to
its components by column chromatography on silica gel using petroleum ether/ethyl acetate
as an eluent to give adducts 12, 13, and 14.
3,4-Dihydro-N-mercaptonaphthalen-1(2H)-imine (12). Eluent: petroleum
ether:ethyl acetate (98:2, v/v). Product 12 was separated as colorless crystals, mp
130–132◦C, yield (40%). Anal.Calcd. For C10 H11NS (177.27): C, 67.76; H, 6.25; N, 7.90;