3
570
D.V. Moiseev et al. / Inorganica Chimica Acta 363 (2010) 3569–3574
145.8 (d, 3JPC = 15.5, m-C–OH), 125.8 (s, p-C), 121.6 (d, 2JPC = 9.8),
O
3
1
PC = 87.9, Cipso), 61.2 (d, 3
1
CH
17.6 (d,
J
PC = 9.2), 100.4 (d,
J
J
PC = 16.7,
O
O
O
P(OR)2
O
P(OR)2
2
1
2
OH), 24.0 (d, JPC = 2.9, PCH
2
CH
2
), 15.3 (d, JPC = 54.0, PCH
2
CH ).
2
+
Low-resolution ESI-MS: m/z = 316.7 [M+H] ; calcd. 317.2.
+
(RO)3P
+
ꢀ
2
2 3 3 6 2
.2. Preparation of [HO(CH ) ] P C H (O )(OH)(MeO) (2b)
O
OR
ð2Þ
The compound, a grey solid, was prepared by the procedure gi-
ven for 2a, but using methoxy-p-benzoquinone (66 mg,
.48 mmol); recrystallization from 1:1 MeOH/EtOH gave a color-
less solid, yield 135 mg (81%). Anal. Calc. for C16 P: C, 55.48;
0
27 6
H O
2
. Experimental section
p-Benzoquinone, obtained from Aldrich, was recrystallized from
benzene, while 2,5-di-tert-butyl- and 2,3,5,6-tetramethyl-p-benzo-
quinone (duroquinone) and methoxy-p-hydroquinone, also Aldrich
products, were used as received; methoxy-p-benzoquinone was
prepared from methoxy-p-hydroquinone according to the litera-
ture [19]. Tris(3-hydroxypropyl)phosphine (THPP, an oil, >80%),
3
1
1
3
H, 7.86. Found: C, 55.10; H, 7.92%. P{ H} NMR (CD OD): d 27.0
1
OD): d 6.56 (d, 3JPH = 12.1, 1H, o-H), 6.20 (d,
s. H NMR (CD
J
3
4
3
PH = 5.8, 1H, m-H), 3.80 (s, 3H, OCH
3
), 3.61 (t,
J
HH = 6.0, 6H,
CH
2
OH), 2.53–2.38 (m, 6H, PCH
2
CH
2
), 1.76–1.61 (m, 6H, PCH
2
CH
2
).
1
3
1
2
ꢀ
C{ H} NMR (D
2
O): d 168.3 (d,
JPC = 4.0, o-C–O ), 155.9 (s, p-C),
3
2
1
J
35.5 (d,
J
PC = 16.1, m-C–OH), 116.9 (d,
J
PC = 10.3, o-C), 103.6 (d,
3
1
3
PC = 9.8, m-C), 89.5 (d,
CH OH), 55.5 (s, OCH ), 24.0 (d,
PC = 54.6, PCH CH ). Low-resolution ESI-MS: m/z = 347.0
M+H] ; calcd. 347.2.
JPC = 95.4, Cipso), 61.3 (d,
J
PC = 16.7,
2
2
3
JPC = 2.9, PCH CH ), 15.6 (d,
2 2
Et
ene) and Ph
Regular distilled water and D
der stirring. CD OD (Cambridge Isotope Laboratories) was used as
received. Organic solvents were dried over the appropriate agents,
3
P, Ph
2
MeP (Strem products), and Me
P (Aldrich products) were used without purification.
O were saturated with Ar for 3 h un-
3
P (1.0 M solution in tolu-
1
J
2
2
3
+
[
2
3
+
ꢀ
1
31
1
13
1
3 6 3
2.3. Preparation of Ph P C H (O )(OH) (2c)
and distilled under Ar. H, P{ H} and C{ H} NMR spectra were
recorded at 300 K on a Bruker AV300 instrument (300, 121, and
5 MHz, respectively), or (when stated) on an AV400 spectrometer
400, 161, and 100 MHz, respectively). A residual, deuterated sol-
vent proton (relative to external SiMe ) and external 85% aq
PO were used as references (s = singlet, d = doublet, t = triplet,
and m = multiplet; J values are given in Hertz); in 2a and 2c–f,
the o-, m-, and p-protons are defined relative to the phosphonium
substituent (cf. Scheme 1), while the structure of 2b correspond-
ingly reveals a p-OMe group. When necessary, assignments were
A solution of Ph
108 mg, 1.0 mmol) in benzene (5 mL) was stirred for 24 h at room
temperature under Ar. A yellow solid product was filtered off,
washed once with benzene and then Et O, and dried at 80 °C in va-
3
P (262 mg, 1.0 mmol) and p-benzoquinone
7
(
(
4
2
H
3
4
cuo for 1 h and then at room temperature overnight; yield 345 mg
3
1
1
1
(
7
93%). P{ H} NMR (CD
3
OD): d 21.8 s. H NMR (CD
3
OD): d 7.80–
3
PH = 9.0, 4
HH = 3.0, 5JPH = 0.4, 1H,
.59 (m, 15H, Ph), 7.03 (ddd,
p-H), 6.63 (dd, JPH = 7.2, JHH = 9.0, 1H, m-H), 6.16 (dd, JPH = 15.1,
HH = 3.0, 1H, o-H). Low-resolution ESI MS: m/z = 371.3 [M + H] ;
J
J
4
3
3
4
+
1
1
1
13
1
J
made by use of H– H, H– C{ H} (HSQC and HMBC), and
H– P{ H} NMR correlation spectroscopies. Elemental analyses
1
31
1
calcd. 371.1.
were performed on a Carlo Erba 1108 analyzer. Mass spectrometry
was performed on a Bruker Esquire electrospray (ESI) ion-trap
spectrometer with samples dissolved in MeOH, with positive ion
polarity scanning from 60–1000 m/z.
+
ꢀ
2
3 6 3
.4. Preparation of Me P C H (O )(OH) (2d)
This compound was prepared by the procedure given above for
c except that Me P was added dropwise as a 1.0 M solution in tol-
2
3
+
ꢀ
2
.1. Preparation of [HO(CH
) ]
2 3 3
P C
6
H
3
(O )(OH) (2a)
uene (1 mL, 1.0 mmol). An immediately formed, deep green sus-
pension was stirred for 12 h, prior to being collected and dried;
3
1
1
1
A solution of p-benzoquinone (52 mg, 0.48 mmol) in acetone
1 mL) was added dropwise to a solution of THPP (100 mg,
.48 mmol, assuming 100% purity) in acetone (3 mL) at room tem-
3
yield, 174 mg (95%). P{ H} NMR (CD OD): d 16.1 s. H NMR
3
4
5
(
0
3
(CD OD): d 6.90 (ddd, JPH = 9.0, JHH = 3.0, JPH = 0.5, 1H, p-H),
6.63 (dd, JPH = 14.7, 4JHH = 3.0, 1H, o-H), 6.56 (dd, JPH = 6.9,
3
4
3
2
perature under Ar. A precipitated, pale yellow solid was filtered off,
washed with acetone and dried overnight under vacuum; the
material was recrystallized from MeOH, yield 130 mg (86%). Anal.
PH
JHH = 9.0, 1H, m-H), 2.03 (d, J = 14.5, 9H, CH3).
Calc. for C15
H
25
O
5
P: C, 56.95; H, 7.97. Found: C, 56.77; H, 8.26%.
3
2.5. Reaction of p-benzoquinone and Et P
3
1
1
1
2 2
P{ H} NMR (D O): d 28.9 s. H NMR (D O): d 7.04 (dd,
3JHH = 8.9,
o-H), 6.55 (dd,
H, CH OH), 2.53–2.33 (m, 6H, PCH
PCH CH
4
J
HH = 3.0, 1H, p-H), 6.64 (dd,
3
J
PH = 13.0,
HH = 8.9, 1H, m-H), 3.57 (t,
CH ), 1.72–1.53 (m, 6H,
4
J
HH = 3.0, 1H,
The reaction was performed as described for 2c/2d except that
4
PH = 6.6, 3
3
J
J
J
HH = 6.1,
3
Et P was added dropwise. The initially formed red suspension was
6
2
2
2
collected to give a pale brown solid that was a mixture of two
products (2e: 2e–I ꢁ9); yield ꢁ200 mg, >90%.
1
3
1
2
ꢀ
2
2
). C{ H} NMR (D
2
O): d 165.3 (d,
J
PC = 3.4, o-C–O ),
31
1
P{ H}
H
A
H
M
H
X
O
2
c, R = R’ = Ph
d, R = R’ = Me
e, R = R’ = Et
21.8
6.63 7.03
6.56 6.90
6.54 6.90
6.59 6.99
6.16
6.63
6.57
6.05
JPA = 7.2, JPX = 15.1
JPA = 6.9, JPX = 14.7
JPA = 6.6, JPX = 12.7
JPA = 7.3, JPX = 15.3
HA
HM
PR R'
2
2
2
2
16.1
31.9
HX
f, R = Ph; R’ = Me
19.9
OH
3
Scheme 1. Some NMR data (d and J values) for 2c–f in CD OD.