The reaction of dithiols with epoxides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1529
were recorded on a Specord 75ꢀIR and Nicolet FTIR NEXUS
spectrophotometers in Nujol and for neat samples. Individuality
and purity of compounds obtained were monitored by TLC on
Silufol UVꢀ254 plates, iodine vapors were used for visualization.
Nꢀ(Oxiranꢀ2ꢀylmethyl)morpholine was obtained according to
the procedure described earlier.5
Synthesis of compounds 4 and 5 (general procedure). A mixꢀ
ture of corresponding dithiol (0.02 mol), EtOH (15 mL) (20 mL
in the case of epoxide 2), pyridine (0.01 mL), and corresponding
epoxide (0.044 mol) was refluxed for 2—3 h.
CH2Ar); 3.95 (dt, 4 H, CH2CH=CH2, J = 5.4 Hz, J = 1.5 Hz);
4.53 (d, 2 H, OH, J = 5.2 Hz); 5.13 (dq, 2 H, CH=CH2,
J = 10.4 Hz, J = 1.5 Hz); 5.23 (dq, 2 H, CH=CH2, J = 17.2 Hz,
J = 1.5 Hz); 5.85 (ddt, 2 H, CH=CH2, J = 17.2 Hz, J = 10.4 Hz,
J = 5.4 Hz); 7.30—7.55 (m, 8 H, Ar).
4,4´ꢀBis(3ꢀallyloxyꢀ2ꢀhydroxypropylthiomethyl)diphenylꢀ
methane (4d). The mixture was refluxed for 1 h and filtered, the
solvent was evaporated from the filtrate in vacuo, the residue was
dissolved in xylene (25 mL) and hexane (200 mL) was added
with cooling. Then a mass formed was separated, dissolved in
ethanol (20 mL), the solvent was evaporated, the residue was
dried in vacuo to dryness. The yield was 4.8 g (49%), nD20 1.5927.
Found (%): C, 66.52; H, 7.23; S, 13.36. C27H36O4S2. Calculatꢀ
ed (%): C, 66.36; H, 7.42; S, 13.12. Rf 0.41 (EtOH—dichloroꢀ
ethane—nꢀC6H14 (0.2 : 1.0 : 0.1)). IR, ν/cm–1: 3460 (OH); 1650
4,4´ꢀBis(3ꢀallyloxyꢀ2ꢀhydroxypropylthio)biphenyl (4a). The
mixture was refluxed for 3 h, followed by addition of EtOH
(20 mL) and water (10 mL) to the reaction mixture and heating
until complete dissolution, the mixture obtained was filtered.
The filtrate was cooled and a precipitate formed was filtered off,
washed with diethyl ether, and recrystallized. The yield was 6.5 g
(73%), m.p. 90—92 °C (from EtOH—H2O). Found (%): C, 64.48;
H, 6.55; S, 14.48. C24H30O4S2. Calculated (%): C, 64.54;
H, 6.77; S, 14.36. Rf 0.45 (EtOH—dichloroethane—nꢀC6H14
(0.2 : 1.0 : 0.1)). IR, ν/cm–1: 3330 (OH); 1650 (C=C, All); 1600
1
(C=C, All); 1605 (C=C, Ar). H NMR, δ: 2.38—2.59 (m, 4 H,
CH2S); 3.35 (dd, 2 H, CH2OAll, J = 14.3 Hz, J = 6.9 Hz); 3.40
(dd, 2 H, CH2OAll, J = 14.3 Hz, J = 3.6 Hz); 3.62 (s, 4 H,
SCH2Ar); 3.74 (m, 2 H, CHOH); 3.82 (m, 2 H, ArCH2Ar);
3.95 (dt, 4 H, CH2CH=CH2, J = 5.4 Hz, J = 1.5 Hz); 4.55 (d, 2 H,
OH, J = 5.2 Hz); 5.13 (dq, 2 H, CH=CH2, J = 10.4 Hz, J = 1.5 Hz);
5.23 (dq, 2 H, CH=CH2, J = 17.2 Hz, J = 1.5 Hz); 5.85 (ddt,
2 H, CH=CH2, J = 17.2 Hz, J = 10.4 Hz, J = 5.4 Hz); 6.89—7.22
(m, 8 H, Ar).
1
(C=C, Ar). H NMR, δ: 2.95 (dd, 2 H, CH2S, J = 13.8 Hz,
J = 7.5 Hz); 3.15 (dd, 2 H, CH2S, J = 13.8 Hz, J = 4.2 Hz); 3.41
(dd, 2 H, CH2OAll, J = 14.3 Hz, J = 6.9 Hz); 3.48 (dd, 2 H,
CH2OAll, J = 14.3 Hz, J = 3.6 Hz); 3.79 (m, 2 H, CHOH); 3.95
(dt, 4 H, CH2CH=CH2, J = 5.4 Hz, J = 1.5 Hz); 4.75 (d, 2 H,
OH, J = 5.2 Hz); 5.13 (dq, 2 H, CH=CH2, J = 10.4 Hz, J = 1.5 Hz);
5.23 (dq, 2 H, CH=CH2, J = 17.2 Hz, J = 1.5 Hz); 5.85 (ddt,
2 H, CH=CH2, J = 17.2 Hz, J =10.4 Hz, J = 5.4 Hz); 7.30—7.55
(m, 8 H, Ar). 13C NMR, δ: 36.6; 68.2; 71.2; 72.5; 115.7; 126.4;
128.2; 134.6; 135.9; 136.8.
4,4´ꢀBis(2ꢀhydroxyꢀ3ꢀmorpholinopropylthio)biphenyl (5a).
The mixture was refluxed for 3 h, followed by addition of EtOH
(250 mL) to the reaction mixture and heating until complete
dissolution, the mixture formed was filtered. The filtrate was
cooled, a precipitate formed was filtered off and recrystallized.
The yield was 4.65 g (92%), m.p. 143 °C (from EtOH). Found
(%): C, 61.63; H, 7.32; N, 5.83; S, 12.86. C26H36N2O4S2. Calꢀ
culated (%): C, 61.87; H, 7.19; N, 5.55; S, 12.71. Rf 0.59
4,4´ꢀBis(3ꢀallyloxyꢀ2ꢀhydroxypropylthio)diphenyl ether (4b).
The mixture was refluxed for 2 h and filtered, the solvent was
evaporated from the filtrate in vacuo, the residue was dissolved
in diethyl ether (10 mL) and dried in vacuo to dryness. The yield
(EtOH—dichloroethane—nꢀC6H14 (0.5 : 1.0 : 0.3)). IR, ν/cm–1
:
3495 (OH); 3030 (C=C, Ar). 1H NMR, δ: 2.25—2.65 (m, 12 H,
CH2N,); 2.95 (dd, 2 H, CH2S, J = 13.8 Hz, J = 7.5 Hz); 3.15
(dd, 2 H, CH2S, J = 13.8 Hz, J = 4.2 Hz); 3.60 (t, 8 H, CH2O);
3.83 (m, 2 H, CHOH); 4.75 (br.s, 2 H, OH); 7.30—7.55
(m, 8 H, Ar). 13C NMR, δ: 38.2; 53.5; 53.6; 62.9; 63.0; 66.0;
126.4; 128.3.
20
was 7.7 g (83%), nD 1.5972. Found (%): C, 62.22; H, 6.71;
S, 13.99. C24H30O5S2. Calculated (%): C, 62.31; H, 6.54; S, 13.86.
Rf 0.47 (EtOH—dichloroethane—nꢀC6H14 (0.2 : 1.0 : 0.1)). IR,
ν/cm–1: 3350 (OH); 1650 (C=C, All); 1600 (C=C, Ar). 1H NMR,
δ: 2.95 (dd, 2 H, CH2S, J = 13.8 Hz, J = 7.5 Hz); 3.15 (dd, 2 H,
CH2S, J = 13.8 Hz, J = 4.2 Hz); 3.41 (dd, 2 H, CH2OAll, J =
= 14.3 Hz, J = 6.9 Hz); 3.48 (dd, 2 H, CH2OAll, J = 14.3 Hz,
J = 3.6 Hz); 3.79 (m, 2 H, CHOH); 3.95 (dt, 4 H, CH2CH=CH2,
J = 5.4 Hz, J = 1.5 Hz); 4.65 (d, 2 H, OH, J = 5.2 Hz); 5.13 (dq,
2 H, CH=CH2, J =10.4 Hz, J = 1.5 Hz); 5.23 (dq, 2 H,
CH=CH2, J = 17.2 Hz, J = 1.5 Hz); 5.85 (ddt, 2 H, CH=CH2, J
= 17.2 Hz, J = 10.4 Hz, J = 5.4 Hz); 6.89, 7.34 (both m, 4 H,
4 H, Ar).
4,4´ꢀBis(2ꢀhydroxyꢀ3ꢀmorpholinopropylthio)diphenyl ether
(5b). The mixture was stirred for 3 h at room temperature and for
another 0.5 h at 50—55 °C, then H2O (200 mL), NaCl (20 g),
and toluene (50 mL) were added, the organic layer was separatꢀ
ed and washed with water. The aqueous layer was extracted with
toluene (2×10 mL), the combined extracts were dried with
Na2SO4, the solvent was evaporated in vacuo to dryness. The
20
yield was 3.9 g (75%), nD 1.5900. Found (%): C, 60.13; H,
4,4´ꢀBis(3ꢀallyloxyꢀ2ꢀhydroxypropylthiomethyl)biphenyl (4c).
The mixture was refluxed for 4 h, followed by addition of EtOH
(15 mL) to the reaction mixture and heating until complete disꢀ
solution, the mixture obtained was filtered. The solvent was evapꢀ
orated from the filtrate in vacuo, the residue was dissolved in
toluene (20 mL) and hexane (200 mL) was added with cooling.
Then a precipitate formed was filtered off and washed with hexꢀ
ane. The yield was 6.85 g (72%), m.p. 48—50 °C. Found (%):
C, 65.88; H, 7.39; S, 13.31. C26H34O4S2. Calculated (%): C, 65.79;
H, 7.22; S, 13.51. Rf 0.43 (EtOH—dichloroethane—nꢀC6H14
(0.2 : 1.0 : 0.1)). IR, ν/cm–1: 3410 (OH); 1650 (C=C, All); 1600
(C=C, Ar). 1H NMR, δ: 2.38—2.59 (m, 4 H, CH2S); 3.36 (dd, 2 H,
CH2OAll, J = 14.3 Hz, J = 6.9 Hz); 3.39 (dd, 2 H, CH2OAll,
J = 14.3 Hz, J = 3.6 Hz); 3.74 (m, 2 H, CHOH); 3.78 (s, 4 H,
7.20; N, 5.09; S, 12.40. C26H36N2O5S2. Calculated (%): C, 59.97;
H, 6.97; N, 5.38; S, 12.32. Rf 0.43 (EtOH—dichloroetꢀ
hane—nꢀC6H14 (0.2 : 1.0 : 0.2)). IR, ν/cm–1: 3330 (OH); 1605
(C=C, Ar). 1H NMR, δ: 2.25—2.65 (m, 12 H, CH2N); 2.95 (dd,
2 H, CH2S, J = 13.8 Hz, J = 7.5 Hz); 3.15 (dd, 2 H, CH2S,
J = 13.8 Hz, J = 4.2 Hz); 3.60 (t, 8 H, CH2O); 3.79 (m, 2 H,
CHOH); 4.66 (d, 2 H, OH, J = 5.2 Hz); 6.89 (m, 4 H, Ar), 7.34
(m, 4 H, Ar).
4,4´ꢀBis(2ꢀhydroxyꢀ3ꢀmorpholinopropylthiomethyl)biphenyl
(5c). The mixture was refluxed for 3 h and filtered, followed by
addition of H2O (250 mL) to the reaction mixture, a precipitate
formed was filtered off and washed with water. The yield was 4.5 g
(84%), m.p. 85 °C. Found (%): C, 63.33; H, 7.29; N, 5.55;
S, 12.16. C26H36N2O4S2. Calculated (%): C, 63.13; H, 7.53;