11436 J. Am. Chem. Soc., Vol. 119, No. 47, 1997
Chandrasekaran et al.
methyl-6-tert-butylphenol) (6),17 and N-chlorodiisopropylamine20 were
was added to the filtrate, and the solution was left under a nitrogen
flow to give a mixture of crystals and brown oil. The oil was washed
off with Skelly-F, and the crystals were dried under vacuum: yield
4.7 g (87.5%), mp 225-230 °C. 1H NMR: 1.30 (s, 18 H, t-Bu), 2.30
synthesized according to literature methods. Solvents were purified
21
according to the standard procedures. All of the reactions were carried
out in a dry nitrogen atmosphere. Proton NMR spectra were recorded
on a Bruker AC200 FT-NMR spectrometer. Phosphorus-31 NMR
spectra were recorded on a Bruker MSL300 FT-NMR spectrometer.
Fluorine-19 spectra were recorded on a Bruker DPX-300 spectrometer
3
1
(s, 6 H, aryl-Me), 6.92-7.35 (br m, 17 H, aryl), 7.67 (s, 2 H, aryl).
NMR: -80.54. 31P NMR (solid): -76.8 (relative to CaHPO
at -1.5).
PS: C, 68.75; H, 6.20. Found: C, 68.41;
P
4
Anal. Calcd for C40
H, 6.14.
43 7
H O
using CFCl
in CDCl unless otherwise mentioned. Chemical shifts are reported in
ppm, downfield positive, relative to tetramethylsilane for H NMR or
3
as an internal reference. All of the spectra were recorded
3
[Dioxythiobis(4-methyl-6-tert-butylphenoxy)](phenoxy)(1,2-ben-
zendioxy)phosphorane, O S[(t-Bu)MeC H O] P(OPh)(C H O ) (3).
1
2
6
2
2
6
4
2
31
85% H PO
3 4
for P NMR, and coupling constants (J) are given in hertz
A solution of phosphorane 2 (1.49 g, 2.13 mmol) and catechol (0.240
All NMR spectra were recorded at 23 °C unless otherwise mentioned.
Elemental analyses were performed by the University of Massachusetts
Microanalysis Laboratory.
g, 2.18 mmol) in toluene (40 mL) was heated under reflux for 1 h.
31
Since the reaction was not complete ( P NMR evidence), it was further
refluxed for 11 h. The solvent was removed under vacuum, and the
residue was extracted with ether (150 mL). The residue had about
(A) Syntheses. Dioxythiobis(4,6-di-tert-butylphenol) (7). A solu-
2
1% of the required phosphorane, and the rest consisted of two
tion of hydrogen peroxide (30%, 10.0 mL, 88 mmol) in glacial acetic
2
2
phosphates (11.46 and -7.29 ppm; corresponding to 27 and 52%,
respectively). The ether extract had 50% of the required phosphorane,
and the rest consisted of phosphates (-18.3 and -19.38 ppm;
corresponding to 20 and 30%, respectively). Solvent was removed from
the extract, and the residue was dissolved in a dichloromethane/hexane
acid (35 mL) was added with thiobis(di-tert-butylphenol) (6.5 g, 15
mmol), and the suspension was heated for 3 h at about 100 °C. The
resulting mixture was filtered, and the solid residue was thoroughly
1
washed with water and dried: yield 6.4 g (92%), mp 172-174 °C. H
NMR: 1.24 (s, 18 H, t-Bu), 1.40 (s, 18 H, t-Bu), 7.51 (s, 4 H, aryl),
(1:1) mixture. The solution was left under a nitrogen flow which
9
.41 (s, 2H, OH). Anal. Calcd for C28
Found: C, 71.04; H, 9.16.
Dioxythiobis(4-methyl-6-tert-butylphenoxy)]tris(2,2,2-trifluoro-
ethoxy)phosphorane, O S[(t-Bu)MeC O] P(OCH CF (1). To
a solution of diol 6 (1.82 g, 4.61 mmol) and P(OCH CF
.53 mmol) in ether (150 mL) was added an excess of i-Pr
42 4
H O S: C, 70.85; H, 8.92.
resulted in a mixture of crystals and oil. The oil was washed off with
Skelly-F, and the crystals were separated by picking manually and dried
[
1
under vacuum: yield 0.20 g (15%), mp >250 °C. H NMR: 1.56 (s,
2
6
H
2
2
2
3 3
)
1
(
8 H, t-Bu), 2.35 (s, 6 H, aryl-Me), 6.67-7.16 (br m, 9 H, aryl), 7.43
2
3
)
3
(1.00 mL,
2
NCl (1.50
s, 2 H, aryl), 7.61 (s, 2 H, aryl). 31P NMR: -53.7. Anal. Calcd for
PS: C, 65.79; H, 6.01. Found: C, 65.38; H, 5.94.
Dioxythiobis(4,6-di-tert-butylphenoxy)]tris(2,2,2-trifluoro-
4
34 37 7
C H O
mL, 10.20 mmol) with constant stirring at about 23 °C for 1 min. The
resultant mixture was stirred for an additional period of 44 h. The
solvent was removed under vacuum, and the residue was extracted with
ether (100 mL) and filtered. Hexane (50 mL) was added to the filtrate,
and the solution was left under a nitrogen flow to give a mixture of
crystals and oil. The oil was washed off with Skelly-F, and the crystals
were dried under vacuum: yield 1.6 g (48.5%), mp 200-205 °C. It
[
ethoxy)phosphorane, O
solution of diol 7 (2.15 g, 4.53 mmol) and P(OCH
.53 mmol) in ether (200 mL) was added an excess of (i-Pr)
2
S[(t-Bu)
2
C
6
H
2
O]
2
P(OCH
2
CF
3
)
3
(4). To a
(1.00 mL,
2
CF
3
)
3
4
2
NCl (1.00
mL, 6.80 mmol) with constant stirring at about 23 °C for 1 min. The
resultant mixture was stirred for an additional period of 44 h. The
solvent was removed under vacuum, and the residue was extracted with
ether (100 mL) and filtered. Hexane (50 mL) was added to the filtrate,
and the solution left was under a nitrogen flow to give a mixture of
crystals and brown oil. The oil was washed off with Skelly-F, and the
crystals were dried under vacuum: yield 2.1 g (58%), mp >250 °C. It
was found to have two isomers (1A and 1B) in solution. In CDCl
3
,
the isomer ratio 1A/1B was 2:1. In C
in a 1:1 mixture of CDCl and C CD
6
5 3
D CD , the ratio was 2:3, and
31
3
D
6 5
3
1
(only P), the ratio was 2:1.5.
3
1
The isomer ratio was obtained from P and H NMR signals except
as noted for the mixture of CDCl and C CD . The isomer ratio
3
6
D
5
3
was found to have two isomers (4A and 4B) in solution. In CDCl
3
,
3
1
1
was the same in the P NMR spectra as that observed in the H NMR
spectra. The chemical shifts were independent of temperature as
3
1
the isomer ratio 4A/4B was 3.2:1. In C
was 0.87:1, and in a 1:1 mixture of CDCl
the ratio was 1.8:1. The isomer ratio from the P NMR spectrum was
6
H
3
5
CH
3
(only P), the ratio
H CH (only P),
6 5 3
3
1
and C
3
1
1
determined by P NMR spectral measurements. H NMR (CDCl
3
):
31
(1A) 1.43 (s, 18 H, t-Bu), 2.37 (s, 6 H, aryl-Me), 3.21 (qd, 2 H, 8.3,
1
the same as observed in the H NMR spectrum for CDCl
two solvent systems, only the 31P NMR spectra were recorded.
NMR (CDCl ): (4A) 1.32 (s, 18 H, t-Bu), 1.45 (s, 18 H, t-Bu), 3.19
qd, 2 H, 8.4, 3.0 Hz), 4.53 (qd, 2 H, 8.3, 2.5 Hz), 4.70 (qd, 2 H, 8.9,
3
. In the other
4
.0 Hz), 4.53 (qd, 2 H, 8.3, 2.5 Hz), 4.68 (qd, 2 H, 8.7, 5.1 Hz), 7.39
1
H
(s, 2 H, aryl), 7.75 (s, 2 H, aryl); (1B) 1.36 (s, 18 H, t-Bu), 2.32 (s, 6
3
H, aryl-Me), 4.29 (m, 4 H), 4.43 (qd, 2 H, 6.5, 2.0 Hz), 7.39 (s, 2 H,
(
1
6 5 3
aryl), 7.56 (s, 2 H, aryl). H NMR (C D CD ): (1A) 1.28 (s, 18 H,
5
1
.4 Hz), 7.60 (d, 2 H, 2.5 Hz, aryl), 7.94 (s, 2 H, 2.5 Hz, aryl); (4B)
.32 (s, 18 H, t-Bu), 1.39 (s, 18 H, t-Bu), 4.28 (qd, 4 H, 8, 6 Hz,
t-Bu), 1.95 (s, 6 H, aryl-Me), 3.38 (qd, 2 H, 8.5, 3.6 Hz), 4.52 (qd, 2
H, 8.1, 2.5 Hz), 4.97 (qd, 2 H, 8.9, 5.2 Hz), 7.13 (s, 2 H, aryl), 7.96 (s,
poorly resolved), 4.46 (qd, 2 H, 8.3 Hz, JPH not resolved), 7.64 (s, 2
2
4
H, aryl); (1B) 1.32 (s, 18 H, t-Bu), 1.87 (s, 6 H, aryl-Me), 4.21 (m,
1
H, aryl), 7.76 (s, 2 H, aryl). H NMR (C
(
(
6
D
5
CD
s, 18 H, t-Bu), 1.32 (s, 18 H, t-Bu), 3.36 (m, 2 H), 4.50 (m, 2 H), 5.00
m, 2H), 7.64 (s, 2 H, aryl), 8.29 (s, 2 H, aryl); (4B) 1.17 (s, 18 H,
3
, 298 K): (4A) 1.07
H), 4.39 (qd, 2 H, 8.5, 6.5 Hz), 7.18 (s, 2 H, aryl), 7.70 (s, 2 H,
1
aryl). H NMR (C
6
D
5
CD
3
at 90 °C): 1.34 (s, 18 H, t-Bu), 1.97 (s, 6
CF ), 7.21 (s, 2 H, aryl-CH), 7.76 (s, br,
H, aryl-CH). P NMR (CDCl
CD ): (1A) -85.5; (1B) -74.2. P NMR (C
1A) -85.2; (1B) -74.7. P NMR: (CDCl
H, Me), 4.33 (br, 6 H, OCH
2
2
3
t-Bu), 1.38 (s, 18 H, t-Bu), 4.20 (m, 4 H), 4.38 (m, 2 H), 7.55 (s, 2 H,
3
1
31
3
): (1A) -85.5; (1B) -73.1. P NMR
aryl), 8.14 (s, 2 H, aryl). 1H NMR (C
(
6
D
5
CD at 90 °C (363 K)): 1.16
s, 18 H, t-Bu), 1.38 (s, 18 H, t-Bu), 4.39 (br, 6 H, OCH CF ), 7.61 (s,
H, aryl-CH), 8.15 (s, br, 2 H, aryl-CH). P NMR (CDCl ): (4A)
): (4A) -85.3; (4B) -73.6.
3
3
1
(C
6
D
5
3
6
D
5
CD
3
at 92 °C):
1:1): (1A)
at
2
3
3
1
(
3
/C
6
D
5
CD
3
31
2
3
3
1
-
-
3
85.3; (1B) -73.3. P NMR (solid): -82.6 (relative to CaHPO
1.5). F NMR: (1A) -75.30 (s, 3 F), -75.49 (s, 3 F), -76.89 (s,
F); (1B) -74.95 (s, 3 F), -75.41 (s, 6 F). Anal. Calcd for
4
31
-
85.7; (4B) -73.3. P NMR (C
6
H
5
CH
3
1
9
31
19
P NMR: (CDCl
3
)/C
6
H
5
CH
3
1:1): (4A) -84.7; (4B) -72.6.
F
NMR: (4A) -75.31 (s, 3 F), -75.47 (s, 3 F), -77.10 (s, 3 F); (4B)
74.96 (s, 3 F), -75.47 (s, 6 F). Anal. Calcd for C34 PS: C,
50.99; H, 5.79. Found: C, 51.14; H, 5.93.
Dioxythiobis(4,6-di-tert-butylphenoxy)](triphenoxy)phospho-
rane, O S[(t-Bu) O] P(OPh) (5). To a solution of diol 7 (3.65
g, 7.69 mmol) and P(OPh) (2.00 mL, 7.63 mmol) in ether (250 mL)
C
28
H
34
F
9
O
7
PS: C, 46.93; H, 4.78. Found: C, 46.83; H, 4.67.
Dioxythiobis(4-methyl-6-tert-butylphenoxy)](triphenoxy)phos-
phorane, O S[(t-Bu)MeC O] P(OPh) (2). To a solution of diol 6
3.00 g, 7.68 mmol) and P(OPh) (2.00 mL, 7.63 mmol) in ether (250
mL) was added an excess of (i-Pr) NCl (1.60 mL, 10.88 mmol) with
-
46 9 7
H F O
[
2
6
H
2
2
3
[
(
3
2
2 6
C H
2
2
3
2
3
constant stirring at about 23 °C for 1 min. The resultant mixture was
stirred for an additional period of 22 h and filtered. Hexane (50 mL)
was added an excess of (i-Pr) NCl (1.60 mL, 10.88 mmol) with constant
2
stirring at about 23 °C for 1 min. The resultant mixture was stirred
for an additional period of 22 h and filtered. Hexane (50 mL) was
added to the filtrate, and the solution was left under a nitrogen flow to
give a mixture of crystals and brown oil. The oil was washed off with
Skelly-F, and the crystals were dried under vacuum: yield 5.1 g (87%),
mp 213-216 °C. 1H NMR: 1.31 (s, 18 H, t-Bu), 1.33 (s, 18 H, t-Bu),
(
(
20) Bock, H.; Kompa, K. L. Chem. Ber. 1996, 99, 1347.
21) (a) Riddick, J. A.; Bunger, W. B., Organic SolVents: Physical
Properties and Methods of Purification, 3rd ed.; Techniques of Chemistry
Series; Wiley Interscience: New York, 1970; Vol. II. (b) Vogel, A. I.
Textbook of Practical Organic Chemistry; Longman: London, 1978.
31
(
22) Pastor, S. D.; Spivak, J. D.; Steinhuebel, L. P. J. Heterocycl. Chem.
6.86-7.86 (br m, 19 H, aryl). P NMR: -80.6. Anal. Calcd for
PS: C, 70.56; H, 7.08. Found: C, 70.73; H, 7.22.
1
984, 21, 1285.
46 55 7
C H O