2114 J . Org. Chem., Vol. 66, No. 6, 2001
Percec et al.
CDCl3): δ 8.2-8.1 (d, 2H, J ) 1.77 Hz), 8.0-7.9 (t, 1H, J )
1.81 Hz), 7.6-7.4 (d, 4H, J ) 10.45 Hz), 7.4-7.3 (d, 4H, J )
8.5 Hz), 3.0-2.8 (q, 2H, J ) 8.71 Hz), 2.6 (s, 3H), 1.4-1.2 (t,
3H, J ) 7.30 Hz). 13C NMR (90 MHz, CDCl3): δ 197.12, 140.77,
139.66, 137.49, 135.91, 131.95, 130.10, 127.95, 128.97, 126.94,
125.15, 31.55, 26.91, 16.80. Rf: 0.63 (hexanes/EtOAc ) 4/1).
3,5-Bis[4-(ch lor osu lfon yl)p h en yl]-1-a cetop h en on e (16).
A 100 mL Schlenk tube equipped with magnetic stirring bar
was charged with 6 (0.5 g, 0.93 mmol) and 50 mL of CH2Cl2.
To this flask was added 25 mL of HCOOH and 25 mL of H2O.
After cooling to 0 °C, Cl2 gas was bubbled through the
heterogeneous reaction mixture with vigorous stirring. The
reaction mixture turned yellowish-green and then became
colorless, indicating complete conversion after 1.5 min of
bubbling Cl2 gas. Cl2 gas bubbling was continued for another
10 s to ensure complete conversion. The organic phase was
separated and diluted with 100 mL of CH2Cl2. The aqueous
phase was washed with 50 mL of CH2Cl2, and the organic
phases were combined and washed with 0.5 M NaOH followed
by brine (three times). The CH2Cl2 solution was dried over Na2-
SO4 and concentrated by rotary evaporation. The resulting
material was recrystallized from CH2Cl2/hexane to yield 0.35
g (82%) of 16 as white crystals. mp 167-170 °C. 1H NMR (200
MHz, CDCl3): δ 8.1 (d, 2 H, J ) 2 Hz), 8.0 (d, 4H, J ) 6.0 Hz),
7.9 (t, 1H, J ) 0.8 Hz), 7.8 (d, 4H, J ) 12.0 Hz), 2.65 (s, 3H).
13C NMR (90 MHz, CDCl3): δ 197.01, 146.73, 143.98, 140.57,
139.07, 130.94, 128.75, 128.05, 127.93, 27.08.
3,5-Bis(ch lor osu lfon yl)-1-a cetop h en on e (17). This com-
pound was synthesized from 8 using a similar procedure as
the one used for 16. Starting from 0.5 g of 8 (1.3 mmol), 0.3 g
(77%) of 17 was obtained. mp 100-101 °C. 1H NMR (200 MHz,
CDCl3): δ 8.9 (s, 2H), 8.8 (s, 1H), 2.8 (s, 3H). 13C NMR (90 MHz,
CDCl3): δ 192.94, 146.59, 140.27, 132.12, 128.8, 26.98.
3,5-Bis(4-ch lor osu lfon ylp h en yloxy)-1-a cet op h en on e
(18). This compound was synthesized from 10 using a similar
procedure as the one used for 16 except that Cl2 was bubbled
for 5 min. The yellowish green color of the reaction mixture
did not disappear during chlorination. Starting from 0.5 g (1.0
mmol) of 10, 0.36 g (72%) of 18 was obtained. mp 128-130
°C. 1H NMR (200 MHz, CDCl3): δ 8.1-8.0 (d, 4H, J ) 9.06
Hz), 7.58 (d, 2H, J ) 2.11 Hz), 7.22-7.12 (d, 4H, J ) 10.0
Hz), 7.1 (t, 1H, J ) 2.2 Hz), 2.59 (s, 3H). 13C NMR (90 MHz,
CDCl3): δ 193.73, 162.33, 156.66, 139.18, 130.112, 118.49,
116.92, 116.74, 27.00.
3,5-Bis(4-N,N′-d ieth ylsu lfon a m id ep h en yl)-1-a cetop h e-
n on e (19). A two-necked flask fitted with magnetic stirring
bar, septum, and a nitrogen inlet was charged with 16 (100
mg, 0.021 mmol) and 10 mL of dry THF. After cooling to 0 °C,
diethylamine (124 mg, 0.17 mmol) was added dropwise through
a syringe under N2. The solution was allowed to warm to 20
°C, and stirring was continued for 6 h. The reaction mixture
was poured into H2O (100 mL), and the aqueous phase was
extracted with EtOAc (3 × 50 mL). The combined organic
phase was washed with 10% HCl, two times with H2O, and
finally with brine. The EtOAc solution was dried over MgSO4
and concentrated by rotary evaporation. The crude solid was
recrystallized from CH2Cl2/MeOH to yield 90 mg (80%) of 19
as white crystals. mp 191-193 °C. Purity: 99.99% (HPLC). 1H
NMR (200 MHz, CDCl3): δ 8.2 (d,2H, J ) 1.68 Hz), 8.0-7.9
(m, 5H), 7.7-7.8 (d, 4H, J ) 6.83 Hz), 3.4-3.2 (q, 8H, J ) 7.2
Hz), 2.8 (s, 3H), 1.3-1.1 (t, 12H, J ) 7.11 Hz). 13C NMR (90
MHz, CDCl3): δ 197.55, 143.81, 141.1, 140.19, 138.71, 130.76,
128.05, 127.9, 127.1, 42.26, 27.07,24.36. Rf: 0.78 (hexanes/
EtOAc ) 5/5). Anal. Calcd for C28H34O5S2N2: C, 61.97; H, 6.3;
N, 5.16. Found: C, 61.65; H, 6.46; N, 5.01.
3,5-Bis(4-N,N′-d iet h ylsu lfon a m id ep h en yloxy)-1-a ce-
t op h en on e (21). This compound was synthesized from 18
using a similar procedure as the one used for 19. Starting from
100 mg (0.33 mmol) of 18, 110 mg (82%) of 21 was obtained.
mp 83-85 °C. Purity: 99% (HPLC). 1H NMR (200 MHz,
CDCl3): δ 7.9-7.8 (d, 4H, J ) 9.7 Hz), 7.4 (d, 2H, J ) 2.2 Hz),
7.1-7.0 (d, 4H, J ) 8.82 Hz),6.9 (t, 1H, J ) 2.24 Hz), 3.4-3.2
(q, 8H, J ) 7.2 Hz), 2.6 (s, 3H), 1.3-1.1 (t, 12H, J ) 7.11 Hz);
13C NMR (90 MHz, CDCl3): δ 196.3, 159.77, 157.73, 140.45,
135.64, 129.52, 118.57, 115.23, 115.04, 42.23, 26.92, 14.34.
Rf: 0.78 (hexanes/EtOAc ) 5/5). Anal. Calcd for C28H34O7S2N2:
C, 58.52; H, 5.95; N, 4.87. Found: C, 58.43; H, 6.18; N, 4.67.
1,1,1-Tr is(O-ph en yl 4-N,N′-dieth ylth iocar bam ate)eth an e
(22). A two-necked 100 mL flask fitted with N2 inlet and
magnetic stirring bar was charged with KOH (1.09 g, 19.6
mmol) and 10 mL of MeOH. When all KOH dissolved in
MeOH, 1,1,1-tris(4-hydroxyphenyl)ethane (1.0 g, 3.3 mmol)
was added portionwise under N2. The reaction was continued
for 4 h at 20 °C with stirring whereupon 50 mL of additional
MeOH was added to the reaction mixture. Solid N,N′-dieth-
ylthiocarbamoyl chloride (3.01 g, 19.9 mmol) was added in one
portion. After the reaction was stirred for 10 h, the precipitate
was collected by filtration and washed with MeOH-H2O (2 ×
100 mL) to produce white crystals (1.53 g, 72%) after recrys-
tallization from CH2Cl2/MeOH. mp 209-211 °C. Purity: 99.99%
(HPLC). 1H NMR (200 MHz, CDCl3): δ 7.1-7.0 (d, 6H, J )
8.0 Hz), 7.0-6.9 (d, 6H, J ) 10.0 Hz), 3.9-3.8 (q, 6H, J ) 8.0
Hz), 3.8-3.5 (q, 6H, J ) 6.0 Hz), 2.1 (s, 3H), 1.3-1.2 (t, 18H,
J ) 6.0 Hz). 13C NMR (90 MHz, CDCl3): δ 186.66, 152.15,
146.09, 129.62, 129.47, 122.08, 122.0, 51.75, 48.42, 44.33,
30.89, 13.62, 11.91. Rf: 0.21 (hexanes/EtOAc ) 8/2)
1,1,1-Tr is(S-ph en yl 4-N,N′-dieth ylth iocar bam ate)eth an e
(23). This compound was synthesized from 22 using a similar
procedure as the one used for 6. Starting from 1.0 g (1.5 mmol)
of 22, 0.89 g (89%) of 23 was obtained. mp 157-159 °C. Purity:
99.99% (HPLC). 1H NMR (200 MHz, CDCl3): δ 7.5-7.3 (d, 6H,
J ) 8.32 Hz), 7.2-7.08 (d, 8H, J ) 8.23 Hz), 3.5-3.4 (q, 12H,
J ) 7.17 Hz), 2.2 (s, 3H), 1.4-1.1 (br,18H). 13C NMR (90 MHz,
CDCl3): δ 165.79, 149.2, 135.38, 135.23, 129.45, 129.31, 126.6,
52.49, 42.43, 30.52, 13.91, 13.30. Rf: 0.24 (hexanes/EtOAc )
7/3).
1,1,1-Tr is(4-ch lor osu lfon ylph en yl)eth an e (24). This com-
pound was synthesized from 23 using a similar procedure as
the one used for 16 except that the product was recrystallized
from benzene. Starting from 0.5 g (0.77 mmol) of 23, 0.41 g
1
(97%) of 24 was obtained. mp 270 °C (decomp), H NMR (200
MHz, CDCl3): δ 8.1-7.9 (d, 6H, J ) 11.0 Hz), 7.4-7.3 (d, 6H,
J ) 10.6 Hz) 2.3 (s, 3H). 13C NMR (90 MHz, CD3COCD3): δ
155.67, 143.65, 131.46, 128.28, 61.44, 55.03.
1,1,1-Tr is(4-N,N′-dieth ylsu lfon am ideph en yl)eth an e (25).
This compound was synthesized from 24 using a similar
procedure as the one used for 19. Starting from 0.15 g (0.27
mmol) of 24, 0.147 g (82%) of 25 was obtained. mp 193-195
°C. Purity: 99.99% (HPLC). 1H NMR (200 MHz, CDCl3): δ 7.8-
7.7 (d, 6H, J ) 8.46 Hz), 7.2-7.0 (d, 6H, J ) 9.51 Hz), 3.5-3.2
(q, 12H, J ) 7.23 Hz), 2.2 (s, 3H), 1.2-1.0 (t, 18H, J ) 7.12
Hz). 13C NMR (90 MHz, CDCl3): δ 151.65, 139.29, 129.25,
127.25, 53.10, 42.35, 30.36, 14.46. Rf: 0.72 (hexanes/EtOAc )
5/5). Anal. Calcd for C32H45O6S3N3: C, 57.88; H, 6.82; N, 6.32.
Found: C, 57.76; H, 6.9; N, 6.29.
P h en oxya cetic Acid , 2,2-bis[(p h en oxya cetyl)oxy]m -
eth yl]-1,3-p r op a n ed iyl Ester (26).25 To a mixture of NEt3
(12.64 g, 125 mmol) and pentaerythritol (3.4 g, 25 mmol) in
CH2Cl2 (100 mmol) was added phenoxyacetyl chloride (21.32
g, 125 mmol) at 0 °C under N2. The mixture was stirred for
24 h at 20 °C. The reaction mixture was poured into a mixture
of H2O, and the organic layer was separated, washed with H2O
(2 × 200 mL), and dried over MgSO4. Evaporation of the
organic solvent and crystallization of the solid product from
EtOAc two times yielded white crystals of 26 (14.9 g, 89%).
mp 126-128 °C (lit.9 127-128 °C). Purity: 99.99% (HPLC).
1H NMR (200 MHz, CDCl3): δ 7.32-7.24 (m, 8H), 7.0-6.8 (m,
12H), 4.6 (s, 8H), 3.9 (s, 8H). 13C NMR (50 MHz,CDCl3): δ
168.26, 157.43, 129.63, 121.86, 114.34, 64.78, 62. 42.
3,5-Bis(N,N′-d ieth ylsu lfon a m id e)-1-a cetop h en on e (20).
This compound was synthesized from 17 using a similar
procedure as the one used for 19. Starting from 100 mg of 17
(0.33 mmol), 110 mg (77.5%) of 20 was obtained. mp 83-85
1
°C. Purity: 99.99% (HPLC). H NMR (200 MHz, CDCl3): δ 8.6
(s, 2H), 8.4 (s, 1H), 3.4-3.3 (q, 4H, J ) 7.17 Hz), 2.7 (s, 3H),
1.4-1.1 (t, 12H, J ) 7.14 Hz). 13C NMR (90 MHz, CDCl3):
195.01, 143.23, 138.82, 129.59, 128.93, 42.43, 26.98, 14.33.
Rf: 0.76 (hexanes/EtOAc ) 5/5). Anal. Calcd for C16H26O5S2N2:
C, 49.21; H, 6.76; N, 7.17. Found: C, 49.42; H, 6.81; N, 7.08.