660
M. K. Bromley et al.
2,2-diphenoxy-1,3-dithian (9b) as ne white crystals (0 51 g,
39%), m.p. 93–95 (Found: C, 64 5; H, 5 0. C17H16O2S2
24 h. The mixture was treated in the standard manner
to yield an orange viscous oil. This material was sub-
limed (50 /0 05 mmHg) a ording a white crystalline prod-
uct. Following recrystallization from ethyl acetate/hexane,
3-methylidene-1,5-dioxa-7,11-dithiaspiro[5.5]undecane (12) was
isolated as white crystals (1 26 g, 36%), m.p. 48–49 (Found:
C, 47 2; H, 5 9. C8H12O2S2 requires C, 47 0; H, 5 9%). 1H
n.m.r. 4 93, s, 2H, C=CH2; 4 51, s, 4H, OCH2; 3 03–3 00,
m, 4H, SCH2; 2 09–2 04, m, 2H, SCH2CH2. 13C n.m.r.
(CDCl3) 139 0, C 3; 111 9, C 6; 109 3, C=CH2; 65 3, C 2/4;
29 6, C 8/10; 25 3, C 9. Mass spectrum (c.i., NH4+) m/z 207
(21%), 206 (14), 205 (100), 204 (8), 106 (20).
requires C, 64 5; H, 5 1%). I.r.
1489, 1205, 1191, 1169, 1030, 947, 850, 753 cm
(KBr) 3072, 1641, 1587,
1
max
.
1H n.m.r.
7 37–7 31, m, 8H, ArH; 7 19–7 16, m, 2H, ArH; 5 08, s, 2H,
C=CH2; 3 53, s, 4H, SCH2. 13C n.m.r. 153 2; 137 9, C 5;
129 2; 124 7; 121 2; 114 5, C=CH2; 113 8, C 2; 35 3, C 4/6.
Mass spectrum (c.i., NH4+) m/z 317 (4 8%), 231 (77), 223
(100), 94 (60).
1,5-Dioxa-7,11-dithiaspiro[5.5]undecane (10)
Method A. A solution of 2,2-diphenoxy-1,3-dioxan (8a)
(10 0 g, 36 8 mmol), propane-1,3-dithiol (4 38 g, 40 5 mmol)
and pyridine (8 93 ml, 110 4 mmol) was stirred at 60 for 36 h.
The mixture underwent normal workup to yield an amorphous
yellow material. This material was extracted with hot hexane
(3 50 ml) and the solvent removed in vacuum to a ord an
o -white solid. This material was sublimed (50 /0 05 mmHg)
to yield 1,5-dioxa-7,11-dithiaspiro[5.5]undecane (10) as small
white crystals (4 362 g, 62%), m.p. 60–62 (Found: C, 43 7;
H, 6 1; S, 33 4. C7H12O2S2 requires C, 43 7; H, 6 3; S,
2,2-Diphenoxy-1,3-oxathiolan (13)/1,6-Dioxa-4,9-
dithiaspiro[4.4]nonane (14)
A
solution of dichlorodiphenoxymethane (6) (1 72 g,
6 4 mmol) in dichloromethane (10 ml) was added dropwise
over 0 5 h to a stirred solution of 2-mercaptoethanol (1 00
g, 12 8 mmol) and triethylamine (1 78 ml, 12 8 mmol) in
dichloromethane (10 ml). After the addition was complete, the
reaction mixture was re uxed overnight. The organic extract
underwent a typical workup to a ord a waxy solid (0 580 g).
A portion (0 29 g) of this material was recrystallized from
ethyl acetate and yielded 2,2-diphenoxy-1,3-oxathiolan (13) as
a crystalline white powder (0 08 g), m.p. 114–114 5 (Found:
C, 65 7; H, 5 1; S, 11 8. C15H14O2S2 requires C, 65 7; H,
33 4%). I.r.
1089, 1022, 921, 862, 800 cm
(KBr) 2930, 2886, 1424, 1378, 1282, 1245,
1H n.m.r. 4 15, t, 4H, J
max
1
.
5 6 Hz, OCH2; 3 00–2 97, m, 4H, SCH2; 2 08–2 03, m, 2H,
SCH2CH2; 1 85, quin, 2H, J 5 6 Hz, OCH2CH2. 13C n.m.r.
110 5, C 6; 61 8, C 2/4; 29 5, C 8/10; 25 8, C 9; 24 6, C 3.
Mass spectrum (c.i., NH4+) m/z 195 (9 5%), 194 (11), 193
(100), 192 (16), 119 (28), 118 (25), 106 (21).
5 2; S, 11 7%). I.r.
1736, 1586, 1484, 1230, 1198, 1108, 1034, 984, 752 cm
(KBr) 3114, 3069, 2996, 2943, 2891,
1
max
.
1H
Method B. A solution of 2,2-diphenoxy-1,3-dithian (8b)
(0 50 g, 1 64 mmol), propane-1,3-diol (0 125 g, 1 64 mmol)
and pyridine (0 266 ml, 3 28 mmol) was stirred at 60 for 20
h. The mixture was treated by the standard method producing
a yellow solid. This material was recrystallized from ethyl
acetate/hexane to yield 1,5-dioxa-7,11-dithiaspiro[5.5]undecane
(10) as small white crystals (0 117 g, 37%), m.p. 60–62 . The
spectroscopic data were identical to those of the authentic
material obtained in method A.
n.m.r. 7 31–7 22, m, 8H, ArH; 7 12–7 08, m, 2H, ArH; 4 36,
t, 2H, J 6 0 Hz, OCH2; 3 11, t, 2H, J 6 0 Hz, SCH2. 13C
n.m.r.
153 2; 132 4, C 2; 129 1; 124 1; 120 8; 70 7, C 5;
33 9, C 4. Mass spectrum (c.i., NH4+) m/z 292 (1%), 275 (1),
232 (19), 182 (12 5), 181 (100).
The other portion of this material (0 290 g) was sub-
limed (50 /0 1 mmHg) and the liquid collected allowed
to solidify in the freezer overnight providing 1,6-dioxa-4,9-
dithiaspiro[4.4]nonane (14) as white crystals (0 122 g). 1H
n.m.r. 4 52, t, 4H, J 6 95 Hz, OCH2; 3 57, t, 4H, SCH2.
13C n.m.r. 173 4, C 5; 68 4, C 2/7; 32 0, C 3/8.
9-Methylidene-1,5-dioxa-7,11-dithiaspiro[5.5]undecane (11)
Method A. A solution of 2,2-diphenoxy-1,3-dioxan (8a)
(9 068 g, 33 3 mmol), 2-methylidenepropane-1,3-dithiol (4 00 g,
33 3 mmol)and pyridine(5 38 ml, 66 5 mmol)wasstirredat 60
for 24 h. The mixture was treated in the standard manner yield-
ing a yellow solid. Recrystallization from ethyl acetate/hexane
a orded 9-methylidene-1,5-dioxa-7,11-dithiaspiro[5.5]undecane
(11) as white crystals (3 87 g, 57%), m.p. 81–83 (Found:
C, 47 4; H, 6 0; S, 31 8. C8H12O2S2 requires C, 47 0; H,
1,7-Dioxa-5,11-dithiaspiro[5.5]undecane (16)/2,2-
Diphenoxy-1,3-oxathian (15)
A
solution of dichlorodiphenoxymethane (6) (1 460 g,
5 43 mmol) in dichloromethane (10 ml) was added dropwise
over 0 5 h to a stirred solution of 3-mercaptopropan-1-ol (1 0
g, 10 85 mmol) and triethylamine (1 098 g, 10 85 mmol) in
dichloromethane (10 ml). The mixture was stirred at re ux for
24 h, and the organic extract underwent typical treatment to
yield a creamy solid. The solid was extracted with hot hexane
(4 50 ml) and solvent removed in vacuum a ording a white
solid. This material, when sublimed (50 /0 2 mmHg), yielded
1,7-dioxa-5,11-dithiaspiro[5.5]undecane (16) as ne white crys-
tals (0 195 g, 19%), m.p. 44–45 (Found C, 43 8; H, 6 2.
5 9; S, 31 4%). I.r.
1638, 1458, 1413, 1242, 1088, 1030, 912, 869, 835, 750 cm
1H n.m.r. (CDCl3)
5 03, s, 2H, C=CH2; 4 17, t, 4H, J
5 6 Hz, OCH2; 3 50, s, 4H, SCH2; 1 88, quin, 2H, J 5 6
Hz, OCH2CH2. 13C n.m.r. (CDCl3)
139 0, C 9; 113 0,
(KBr) 2964, 2920, 2876, 1866, 1747,
max
1
.
C=CH2; 111 9, C 6; 62 2, C 2/4; 34 4, C 8/10; 24 5, C 3.
Mass spectrum (c.i., NH4+) m/z 207 (10%), 206 (12), 205
(100), 204 (6 8), 140 (29), 119 (44), 118 (15).
C7H12O2S2 requires C, 43 7 H, 6 3%). I.r.
(KBr) 2960,
max
2913, 2831, 1452, 1424, 1279, 1198, 1182, 1087, 1056, 1016,
1
975, 955, 905, 847, 813 cm
.
1H n.m.r. 4 16, ddd, 2H, J
Method B. A solution of 2,2-diphenoxy-5-methylidene-1,3-
dithian (9b) (0 200 g, 0 63 mmol), propane-1,3-diol (0 04 g,
0 63 mmol) and pyridine (0 12 ml, 1 26 mmol) was stirred at
60 for 24 h. The mixture underwent a typical workup yielding
a yellow solid. Recrystallization from ethyl acetate/hexane
provided 9-methylidene-1,5-dioxa-7,11-dithiaspiro[5.5]undecane
(11) as white crystals (0 056 g, 43%). The spectroscopic data
were identical to those of the authentic material obtained in
method A.
11 8, 9 1, 3 3 Hz, OCHa; 4 07, ddd, 2H, J 11 7, 5 1, 4 9 Hz,
OCHb; 3 07, ddd, 2H, J 13 2, 9 7, 3 4, SCHa; 2 79, ddd, 2H,
J 13 1, 6 6, 3 6 Hz, SCHb; 2 07–1 97, m, 2H; 1 87–1 79, m,
2H. 13C n.m.r. 108 4, C 6; 63 7, C 2/8; 26 2, C 4/10; 24 2,
C 3/9. Mass spectrum (c.i., NH4+) m/z 195 (11%), 194 (10),
193 (100), 192 (10), 74 (30).
The residual material from the sublimation was recrystallized
from hexane to yield 2,2-diphenoxy-1,3-oxathian (15) as white
crystals (0 100 g), m.p. 101–102 . I.r.
(KBr) 3062, 2966,
max
3-Methylidene-1,5-dioxa-7,11-dithiaspiro[5.5]undecane (12)
2923, 1591, 1488, 1202, 1105, 1077, 1047, 1006, 955, 899, 847,
1
A
solution of 2,2-diphenoxy-1,3-dithian (8b) (5 22 g,
813 cm
.
1H n.m.r.
7 33–7 28, m, 8H, ArH; 7 14–7 10,
17 1 mmol), 2-methylidenepropane-1,3-diol (1 51 g, 17 1 mmol)
and pyridine (2 77 ml, 34 3 mmol) was stirred at 60 for
m, 2H, ArH; 4 82, dd, J 5 2, 5 6 Hz, OCH2; 2 95, dd, 2H,
J 5 6, 6 0 Hz, SCH2; 1 97, m, 2H, OCH2CH2. 13C n.m.r.