Phosphonoketene Dithioacetals
J . Org. Chem., Vol. 61, No. 23, 1996 8139
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78.9 (d, J P-C ) 8.3 Hz), 139.4 (d, J P-C ) 167.6 Hz), 150.5 (d,
2J P-C ) 9.3 Hz); MS m/z 379 (M+ - H2O). Anal. Calcd for
C17H33O4PS2: C, 51.49; H, 8.38%. Found: C, 51.31; H, 8.26%.
Dieth yl [1-[bis(eth ylth io)m eth ylen e]-2-h ydr oxy-2-ph en -
yleth yl]p h osp h on a te (18): colorless oil; IR (neat) 3350, 1510,
1200 cm-1; 1H NMR (500.00 MHz) δ 1.10 (3 H, t, J ) 7.2 Hz),
1.32 (6 H, t, J ) 7.1 Hz), 1.34 (3 H, t, J ) 7.2 Hz), 2.78-2.88
(2 H, m), 3.04 (1 H, dq, J ) 13.1, 7.2 Hz), 3.08 (1 H, dq, J )
13.1, 7.2 Hz), 3.60 (1 H, dq, 3J P-H ) 10.2 Hz, J ) 7.1 Hz), 3.61
56.4, 69.0, 122.4, 138.6 140.6, 142.1; HRMS calcd for C20H32S4,
400.1390 (M+), found 400.1376. Anal. Calcd for C20H32S4: C,
59.95; H, 8.05%. Found: C, 60.14; H, 7.89%.
(1 3 Z ,1 4 Z )-1 3 ,1 4 -D i i s o b u t y l i d e n e -1 ,5 ,8 ,1 2 -t e t r a -
t h iod isp ir o[5.0.5.2]t et r a d eca n e (24a ) a n d (Z)-2-(1,3-
D it h ia n -2-y lid e n e )-1-is o b u t y lid e n e -3-is o p r o p y l-5,9-
d ith iosp ir o[3.5]n on a n e (24b): colorless crystal; 1H NMR [for
a mixture of 24a and 24b](500.00 MHz) δ 0.93 (3 H × 0.23, d,
J ) 6.7 Hz), 1.03 (12 H × 0.77, d, J ) 6.7 Hz), 1.04 (3 H ×
0.23, d, J ) 6.7 Hz), 1.07 (3 H × 0.23, d, J ) 6.7 Hz,), 1.28 (3
H × 0.23, d, J ) 6.7 Hz), 1.90-2.30 (4 H × 0.77, m, and 5 H
× 0.23, m), 2.65-3.16 (10 H × 0.77, m, and 10 H × 0.23, m),
5.48 (2 H × 0.77, d, J ) 10.7 Hz), 5.81 (1 H × 0.23, d, J ) 10.7
Hz); 13C NMR [for a mixture of 24a and 24b](125.65 MHz) δ
19.5, 23.1, 23.5, 23.6, 23.7, 24.2, 24.3, 24.7, 28.0, 28.4, 29.2,
29.2, 29.6, 29.9, 30.4, 56.4, 64.3, 69.4, 122.9, 131.9, 136.3, 137.3,
138.1, 138.7; MS m/z 372 (M+). Anal. Calcd for C18H28S4: C,
58.01; H, 7.57%. Found [for a mixture of 24a and 24b]: C,
57.93; H, 7.44%.
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3
(1 H, dq, J P-H ) 10.1 Hz, J ) 7.1 Hz), 3.71 (2 H, dq, J P-H
)
3
10.2 Hz, J ) 7.1 Hz), 4.05 (1 H, dq, J P-H ) 10.2 Hz, J ) 7.1
3
Hz), 4.07 (1 H, dq, J P-H ) 10.2 Hz, J ) 7.1 Hz), 4.10-4.18 (2
3
H, m), 5.45 (1 H, d, J ) 11.7 Hz), 6.43 (1 H, dd, J P-H ) 27.8
Hz, J ) 11.7 Hz), 7.20-7.42 (5 H, m); 13C NMR (125.65 MHz)
3
δ 15.0, 15.0, 16.1, 16.2 (d, J P-C ) 6.2 Hz), 28.9, 29.4, 62.1 (d,
2J P-C ) 5.2 Hz), 62.1 (d, J P-C ) 5.2 Hz), 74.7 (d, J P-C ) 8.3
2
2
1
Hz), 125.5, 126.9, 128.1, 139.0 (d, J P-C ) 168.6 Hz), 142.8,
151.2 (d, J P-C ) 8.3 Hz); MS m/z 390 (M+). Anal. Calcd for
2
C17H27O4PS2: C, 52.02; H, 7.45%. Found: C, 52.26; H, 7.08%.
Th e Hor n er -Em m on s-Wittig Rea ction of Allylic Al-
coh ols 4-6, a n d 11-13. Gen er a l P r oced u r e. To a suspen-
sion of t-BuOK (0.123 g, 1.10 mmol) in THF (8 mL) was added
a solution of 4, 5, 6, 11, 12, or 13 (1.00 mmol) in THF (6 mL)
at room temperature. After the solution was stirred for 4-12
h, the reaction was quenched by the addition of saturated
aqueous NH4Cl, extracted with AcOEt, washed with brine,
dried over Na2SO4, and concentrated in vacuo. The residue
was chromatographed on silica gel (Et2O:hexane ) 1:20) to
give corresponding symmetrical dimers 20-22 or mixtures of
symmetrical and unsymmetrical dimers 23a ,b, 24a ,b, or
25a ,b. Each of pure compounds 23a ,b and 25a ,b was sepa-
rated by fractional recrystallization of the mixtures from
heptane. Attempts to obtain pure 24a and 24b from the
mixture were unsuccessful. The reaction conditions, yields,
and ratios of symmetrical dimers to unsymmetrical dimers
were summarized in Table 4. The compounds 20-22, 23a ,b,
24a ,b, and 25a ,b had the following properties.
(13Z,14Z)-13,14-Bis(cycloh e xylm e t h yle n e )-1,5,8,12-
tetr a th iod isp ir o[5.0.5.2]tetr a d eca n e (25a ): colorless crys-
tal; mp 177-178 °C; IR (KBr) 1450, 1275 cm-1 1H NMR
;
(500.00 MHz) δ 1.01-1.09 (4 H, m), 1.13-1.21 (2 H, m), 1.27-
1.37 (4 H, m), 1.64-1.77 (10 H, m), 1.99-2.13 (4 H, m), 2.81
(4 H, dt, J ) 14.3, 4.9 Hz), 2.85-2.93 (2 H, m), 2.99 (4 H, ddd,
J ) 14.3, 9.8, 4.6 Hz), 5.51 (2 H, d, J ) 10.7 Hz); 13C NMR
(125.65 MHz) δ 23.5, 25.8, 26.0, 29.1, 33.1, 37.4, 69.3, 130.3,
138.9; MS m/z 452 (M+). Anal. Calcd for C24H36S4: C, 63.66;
H, 8.01%. Found [for a mixture of 25a and 25b]: C, 63.50; H,
7.80%.
(Z)-3-C y c lo h e x y l-1-(c y c lo h e x y lm e t h y le n e )-2-(1,3-
d ith ia n -2-ylid en e)-5,9-d ith iosp ir o[3.5]n on a n e (25b): col-
1
orless crystal; mp 146-148 °C; IR (KBr) 1450, 1275 cm-1; H
NMR (500.00 MHz) δ 0.98-1.42 (10 H, m), 1.64-2.01 (13 H,
m), 2.07-2.10 (1 H, m), 2.16 (2 H, dt, J ) 11.6, 6.7 Hz), 2.69-
2.75 (2 H, m), 2.79-2.92 (4 H, m), 2.98 (1 H, dt, J ) 13.7, 6.7
Hz), 3.01 (1 H, dt, J ) 13.7, 6.7 Hz), 3.14 (1 H, d, J ) 1.5 Hz),
5.81 (1 H, d, J ) 10.7 Hz); 13C NMR (125.65 MHz) δ 24.4, 24.8,
25.6, 25.7, 26.1, 26.4, 26.5, 27.8, 29.2, 29.6, 30.0, 30.3, 37.7,
40.9, 56.6, 64.1, 122.0, 135.8, 137.0, 139.4; MS m/z 452 (M+).
Syn th esis of 3-ter t-Bu tyl-1,1-bis(eth ylth io)-1,2-p r op a -
d ien e (26). The reaction was carried out using 15 (0.446 g,
1.20 mmol) and t-BuOK (0.149 g, 1.32 mmol) in THF (40 mL)
at room temperature for 0.5 h. After similar workup as
described above, the product 26 was obtained in a almost pure
form in 0.255 g (1.18 mmol, 98%) yield. Further purification
of 26 on silica gel or by distillation was unsuccessful due to
the ease of decomposition. 26: colorless oil; IR (neat) 1930
(11Z,12Z)-11,12-D in e o p e n t y lid e n e -1,4,7,10-t e t r a -
th iod isp ir o[4.0.4.2]d od eca n e (20): colorless crystal; mp
155-156 °C; IR (KBr) 1480, 1280 cm-1; 1H NMR (500.00 MHz)
δ 1.24 (18 H, s), 3.14-3.26 (8 H, m), 5.63 (2 H, s); 13C NMR
(125.65 MHz) δ 30.9, 33.6, 40.1, 82.5, 131.8, 138.6; MS m/z
372 (M+). Anal. Calcd for C18H28S4: C, 58.01; H, 7.57%.
Found: C, 57.88; H, 7.67%.
(1 1 Z ,1 2 Z )-1 1 ,1 2 -D i i s o b u t y l i d e n e -1 ,4 ,7 ,1 0 -t e t r a -
th iod isp ir o[4.0.4.2]d od eca n e (21): colorless crystal; mp
128-129 °C; IR (KBr) 1470, 1275 cm-1; H NMR (59.8 MHz)
1
δ 1.02 (12 H, d, J ) 6.7 Hz), 2.68-3.52 (10 H, m), 5.46 (2 H,
d, J ) 10.4 Hz); 13C NMR (15.0 MHz) δ 22.8, 27.0, 40.4, 81.2,
131.1, 137.3; MS m/z 344 (M+). Anal. Calcd for C16H24S4: C,
55.77; H, 7.02%. Found: C, 56.03; H, 7.11%.
1
cm-1; H NMR (500.00 MHz) δ 1.08 (9 H, s), 1.29 (6 H, t, J )
7.3 Hz), 2.71 (4 H, q, J ) 7.3 Hz), 5.46 (1 H, s); 13C NMR
(125.65 MHz) δ 14.5, 27.9, 29.9, 33.0, 98.8, 108.4, 198.1; MS
m/z 216 (M+).
(11Z,12Z)-11,12-Bis(cycloh e xylm e t h yle n e )-1,4,7,10-
tetr a th iod isp ir o[4.0.4.2]d od eca n e (22): colorless crystal;
Syn th esis of 3,3-Bis(eth ylth io)-2-n eop en tylid en e-4,4-
d ip h en ylcyclobu ta n on e (27). To a solution of the dithio-
allene 26 (0.273 g, 1.26 mmol) and triethylamine (1.00 mL,
4.91 mmol) in benzene (6 mL) was added dropwise a solution
of diphenylacetyl chloride (1.16 g, 5.04 mmol) in benzene (4
mL) at room temperature, and the mixture was stirred for 14
h. After the reaction was quenched by the addition of H2O
and extracted with AcOEt. The extract was washed with
brine, dried over Na2SO4, and then concentrated in vacuo. The
residue was chromatographed on silica gel (CHCl3:hexane )
1:1) and then recrystallized from hexane to afford a [2 + 2]
cycloadduct 27: yield 0.339 g (0.826 mmol, 66%); pale yellow
mp 130-131 °C; IR (KBr) 1450, 1270 cm-1; H NMR (500.00
1
MHz) δ 1.00-1.08 (4 H, m), 1.16 (2 H, m), 1.28 (4 H, m), 1.63-
1.66 (2 H, m), 1.70-1.74 (4 H, m), 1.76-1.79 (4 H, m), 2.69-
2.77 (2 H, m), 3.07-3.13 (4 H, m), 3.25-3.31 (4 H, m), 5.51 (2
H, d, J ) 10.4 Hz); 13C NMR (125.65 MHz) δ 25.9, 26.0, 32.6,
36.6, 40.5, 81.0, 129.6, 138.1; HRMS calcd for C22H32S4,
424.1386 (M+), found 424.1355. Anal. Calcd for C22H32S4: C,
62.21; H, 7.59%. Found: C, 61.67; H, 7.55%.
(13Z,14Z)-13,14-D in e o p e n t y lid e n e -1,5,8,12-t e t r a -
th iod isp ir o[5.0.5.2]tetr a d eca n e (23a ): colorless crystal; mp
180.5-181.5 °C; IR (KBr) 1435, 1410, 1275 cm-1 1H NMR
;
(500.00 MHz) δ 1.31 (18 H, s), 2.01-2.10 (2 H, m), 2.16-2.22
(2 H, m), 2.77-2.81 (4 H, m), 3.10 (4 H, ddd, J ) 14.3, 11.6,
3.4 Hz), 5.73 (2 H, s); 13C NMR (125.65 MHz) δ 23.7, 29.7, 31.7,
33.1, 69.7, 133.4, 138.3; MS m/z 400 (M+). Anal. Calcd for
C20H32S4: C, 59.94; H, 8.05%. Found: C, 59.86; H, 8.17%.
(Z)-3-ter t-Bu tyl-2-(1,3-d ith ia n -2-ylid en e)-1-n eop en tyl-
id en e-5,9-d ith iosp ir o[3.5]n on a n e (23b): colorless crystal;
crystal; mp 128.5-131 °C; IR (KBr) 1750, 1635, 1500 cm-1
;
1H NMR (500.00 MHz) δ 0.80 (6 H, t, J ) 7.5 Hz), 1.34 (9 H,
s), 2.01 (2 H, dq, J ) 10.7, 7.5 Hz), 2.14 (2 H, dq, J ) 10.7, 7.5
Hz), 6.84 (1 H, s), 7.23-7.54 (10 H, m); 13C NMR (125.65 MHz)
δ 12.8, 25.9, 29.9, 34.2, 68.6, 84.0, 127.1, 127.4, 129.3, 138.9,
142.7, 148.2, 201.5; MS m/z 410 (M+). Anal. Calcd for C25H30
-
OS2: C, 73.12; H, 7.36%. Found: C, 72.99; H, 7.25%.
mp 130.5-131.0 °C; IR (KBr) 1415, 1280 cm-1
;
1H NMR
Acid -Ca ta lyzed Decom p osition of a Allylic Alcoh ol 15.
To a solution of 15 (0.100 g, 0.270 mmol) in CH2Cl2 (15 mL)
was added trifluoromethanesulfonic acid (40.5 mg, 0.270 mmol)
at room temperature. After the mixture was stirred at this
temperature for 24 h, the reaction was quenched by the
(500.00 MHz) δ 1.12 (9 H, s), 1.32 (9 H, s), 1.92-2.01 (1 H,
m), 2.06-2.18 (3 H, m), 2.71-2.98 (7 H, m), 3.04 (1 H, ddd, J
) 13.5, 8.5, 5.2 Hz), 3.05 (1 H, s), 5.91 (1 H, s); 13C NMR (125.65
MHz) δ 24.4, 24.7, 29.1 29.3, 29.9, 30.3, 30.4, 31.8, 32.9, 37.8,