3
1H NMR δ: 8.09 (1H, dd, J8,7=7.9, J8,6=1.1, H-8); 8.04 (2H, d, J=7.3, Ar(o) Bz); 7.56-7.51
3
(2H, m, H-6, Ar(p) Bz); 7.39 (2H, t, J=7.9, Ar(m) Bz); 7.35 (1H, t, J7,6=J7,8=7.5, H-7); 7.29 (1H, d,
2
J5,6=7.7, H-5); 5.26 (1H, dd, J2,3=12.3, J2,3=4.6, H-2); 3.28 (1H, ddd, J=16.9, J4,3=11.5, J4,3=4.4, H-
2
2
4); 3.10 (1H, dt, J=16.9, J4,3=4.2, H-4); 2.67 (1H, dq, J=13.0, J3,4=J3,2=4.4, H-3); 2.35 (1H, qd,
2J=J3,4=J3,2=12.3, J3,4=4.3, H-3). 13C NMR δ: 226.0 (C=S dithioester), 193.1 (C-1); 144.8 (Ar Cq Bz);
143.7 (C-4a); 134.1 (C-6); 132.7 (Ar(p) Bz); 132.1 (C-8a); 128.9 (C-5); 128.4 (Ar(m) Bz); 128.0 (C-
8); 127.1 (Ar(o) Bz); 127.0 (C-7); 58.3 (C-2); 29.7 (C-3); 29.4 (C-4). FTIR (neat): 1680 (C=O st.);
1215; 1041; 759, 739, 683 (Ar C-H bend. o.o.p.). M.p.=109°C. Anal. Calcd for C17H14OS2: C
68.42; H 4.73; S 21.49. Found: C 68.10; H 4.94; S 21.40.
4.2.21. 1-Oxo-1,2,3,4-tetrahydronaphthalen-2-yl pentanedithioate 1w
To a stirred solution of K2CO3 (1.2 eq., 370 mg) in dry acetone (5 mL) at 0°C under
argon atmosphere was added dithiopentanoic acid (1.2 eq., 360 mg) dropwise. After 15 min 2-
bromo-1-tetralone (500 mg, 2.2mmol) was added and stirring was continued at r.t. for 30min.
Afterward H2O (5 mL) was added and extracted with DCM (3x5mL). The combined organic
layers were dried with MgSO4 and evaporated to dryness. After purification by flash column
chromatography (eluted with 2:1 Hex:DCM), 483 mg (78%) of pure product were obtained as a
yellow greenish solid.
1H NMR δ: 8.06 (1H, d, J8,7=7.9, H-8); 7.52 (1H, td, J6,5=J6,7=7.5, J6,8=1.3, H-6); 7.33 (1H, t,
J7,6=J7,8=7.6, H-7); 7.27 (1H, d, J5,6=7.7, H-5); 5.10 (1H, dd, J2,3=12.4, J2,3=4.6, H-2); 3.24 (1H, ddd,
3
2
2J=16.9, J4,3=11.6, J4,3=4.4, H-4); 3.08 (2H, t, J=7.6, H-2’); 3.06 (1H, dt, J=17.0, J4,3=4.1, H-4);
2.57 (1H, dq, 2J=13.0, J3,4=J3,2=4.4, H-3); 2.26 (1H, qd, 2J=J3,4=J3,2=12.3, J3,4=4.3, H-3); 1.86 (2H, p,
3J=7.6, H-3’); 1.42 (2H, sex, J=7.4, H-4’); 0.94 (3H, t, J=7.4, H-5’). 13C NMR δ: 236.9 (C-1’);
193.1 (C-1); 143.6 (C-4a); 134.1 (C-6); 132.0 (C-8a); 128.8 (C-5); 127.9 (C-8); 126.9 (C-7); 57.5
(C-2); 51.7 (C-2’); 33.5 (C-3’); 29.5 (C-3); 29.4 (C-4); 22.0 (C-4’); 13.8 (C-5’). FTIR (neat): 1684
(C=O st.); 1304; 1218 (C=S st.); 893; 740 (Ar C-H bend. o.o.p.). M.p.=85°C. Anal. Calcd for
C15H18OS2: C 64.71; H 6.52; S 23.03. Found: C 65.00; H 6.22; S 23.08.
3
3
4.2.22. O,O-Diethyl
yl)sulfanyl]phosphonothioate 1x
[(1-oxo-1,2,3,4-tetrahydronaphthalen-2-
To a stirred solution of K2CO3 (1.2 eq., 660 mg) in dry DMF (10 mL) at 0°C under argon
atmosphere was added O,O-diethyl dithiophosphate (1.2 eq., 1.1mL) dropwise. After 15 min 2-
bromo-1-tetralone (1.07g, 4.75mmol) was added and stirring was continued at r.t. for 2h.
Afterward NH4Cl aqueous saturated solution (20 mL) was added and extracted with DCM
(3x10mL). The combined organic layers were dried with MgSO4 and evaporated to dryness.
After purification by flash column chromatography (eluted with 1:1 Hex:DCM), 1.13g (72%) of
pure product were obtained as a colorless oil.
1H NMR δ: 8.04 (1H, d, J8,7=7.9, H-8); 7.50 (1H, td, J6,5=J6,7=7.5, J6,8=1.2, H-6); 7.33 (1H, t,
J7,6=J7,8=7.6, H-7); 7.25 (1H, d, J5,6=7.7, H-5); 4.36-4.14 (5H, m, H-2, 2xCH2 Et); 3.19-3.05 (2H, m,
2
2
H-4); 2.64 (1H, ddt, J=13.5, J=6.3, J=4.6, H-3); 2.37 (1H, tdd, J=13.5, J=8.9, J=4.9, H-3); 1.40
(3H, t, 3J=6.8, CH3 Et); 1.39 (3H, t, 3J=7.0, CH3 Et). 13C NMR δ: 192.9 (d, 3JC,P=7, C-1); 143.3 (C-4a);
2
134.0 (C-6); 131.5 (C-8a); 128.8 (C-5); 128.1 (C-8); 127.0 (C-7); 64.6 (d, JC,P=6, CH2 Et); 64.3 (d,
2
3
3
2JC,P=6, CH2 Et); 55.0 (d, JC,P=3, C-2); 31.7 (d, JC,P=4, C-3); 28.1 (C-4); 15.9 (d, JC,P=8, CH3 Et);
15.8 (d, 3JC,P=8, CH3 Et). 31P NMR δ: 93.0. FTIR (neat): 1684 (C=O st.); 1008, 957 (P-O-C st.); 652
(P=S st.). HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C14H20O3PS2 331.0586; Found 331.0588.
15