The Journal of Organic Chemistry
Article
(s, C5), 137.6 (s, C7), 135.5 (s, C4/6), 135.1 (s, C10), 132.4 (s, C1/3),
129.6 (s, C8/12), 129.4 (s, C2), 127.4 (s, C9/11).
min the mixture was allowed to warm to room temperature and
stirred for a further 12 h, whereupon the precipitate was collected by
filtration, washed with diethyl ether, and dried in vacuo, resulting in
Cyanobiphenyl Diacyl Chloride (2e). 5-Cyanophenylisoph-
thalic acid (0.6 g, 2.2 mmol) in thionyl chloride (20 cm3) was
refluxed for 6 h in a bead bath. After cooling, the volatiles were
removed under reduced pressure to afford an off-white/pale-orange
1
77 mg of a yellow solid in 26% yield. H NMR (CD2Cl2): δH = 9.46
(s, ArH2, 1H), 7.71 (s, ArH4/6, 2H), 7.34 (t, Ph, 5H), 1.66 (d, P−
CH3, 2JHP = 2.3 Hz, 3H). 1H NMR (C6D6): δH = 9.21 (br, ArH2, 1H),
1
solid. Yield: 0.43 g, 64%. H NMR (CDCl3): δH = 8.90 (br t, ArH2,
2
1
7.57 (d, ArH4/6, JHH = 1.1 Hz, 2H), 6.94 (t, ArH10, JHH = 7.5 Hz,
2
1
1H), 8.59 (d, ArH4/6, JHH = 1.5 Hz, 2H), 7.85 (d, ArH8/12, JHH
=
1H), 6.87 (t, ArH9/11, 1JHH = 7.5 Hz, 2H), 6.72 (d, aromatic ArH8/12
,
8.32 Hz, 2H), 7.77 (d, ArH9/11, 1JHH = 8.32 Hz, 2H). 13C{1H} NMR
(CDCl3): δC = 167.1 (s, C = O), 141.9 (s, CN), 141.7 (s, C5), 135.6
(s, C1/3), 135.3 (s, C4/6), 133.4 (s, C2), 133.3 (s, C8/12), 128.1 (s,
1JHH = 7.53 Hz, 2H), 1.67 (d, CH3, JHP = 2.9 Hz, 3H). 13C{1H}
2
1
NMR (CD2Cl2): δC = 207.4 (d, C(O), JCP = 45.8 Hz), 144.3 (s,
C10), 138.83 (d, C1/3, JCP = 37.2 Hz), 138.8 (s, C7), 132.6 (t, C2,
2
9/11), 118.2 (s, C7), 113.4 (s, C10).
3JCP = 12.6 Hz), 129.5 (s, C8/12), 129.4 (s, C4/6), 129.1 (s, C5), 127.6
C
(s, C9/11), 1.9 (d, P−CH3, JCP = 4.7 Hz). 31P{1H} NMR (CD2Cl2):
Synthesis of m-{-C(O)-C6H3I-(C(O)PMe)}2 (3a). A diethyl ether
1
solution of 5-iodoisophthaloyl chloride (1 g, 3 mmol) was cooled via
dry ice/IMS (−78 °C) and MeP(SiMe3)2 (0.7 cm3, 3 mmol) was
added. During addition the solution assumes a purple coloration, after
stirring at −78 °C for 30 min the mixture was allowed to warm to
ambient temperature and stirred for a further 16 h, whereupon the
precipitate was collected by filtration, washed with diethyl ether, and
concentrated in vacuo. The product was extracted into toluene and
dried in vacuo, resulting in 0.169 g of an orange-yellow solid in 18.5%
yield. 1H NMR (CD2Cl2): δH = 9.43 (br t, ArH2, 1H), 7.87 (d,
δP = 36.16 (s). 31P{1H} NMR (C6D6): δP = 35.7 (s). IR νCO 1658,
1639 cm−1. HRMS (m/z): Calcd for C30H22O4P2 508.0993 ([M]+).
Found 508.0996 ([M]+).
Synthesis of m-{-C(O)-C13H7N-(C(O)PMe)}2 (3e). To a cooled
(dry ice/IMS; −78 °C) solution of 5-(4-cyanophenyl)isophthaloyl
chloride (0.316 g, 1.04 mmol) in Et2O (5 cm3) was added
MeP(SiMe3)2 (1.04 g, 1.04 mmol) resulting in an orange coloration.
After stirring for 30 min at this temperature, the mixture was allowed
to warm to ambient temperature and stir for a further 16 h. At this
point the reaction had only proceeded halfway warranting the
addition of another equivalent of MeP(SiMe3)2 (1.04 g, 1.04 mmol)
and stirred for a further 16 h, whereupon the orange precipitate was
collected by filtration, washed with Et2O (3 × 10 cm3), and dried in
2
2
ArH4/6, JHH = 1.41 Hz, 2H), 1.61 (d, P−CH3, JHP = 3 Hz, 3H).
29
13C{1H} NMR (CD2Cl2): δC = 205.4 (d, C(O), JCP = 46.5 Hz),
1
139.9 (m, Ar4/6), 139.1 (d, C1/3, JCP = 38 Hz), 132.8 (t, C2, JCP
=
2
3
13.5 Hz), 1.88 (d, CH3, 1JCP = 4.5 Hz). 31P{1H} NMR (CD2Cl2): δP
= 36.3 (s). 31P{1H} NMR (C6D6): δP = 36.1 (s). IR νCO 1640 (br)
cm−1. HRMS (m/z): Calcd for C18H12O4P2I2 607.8300 ([M]+).
Found 607.8306 ([M]+).
1
vacuo. Yield: 69 mg, 24%. H NMR (C6D6): δH = 9.29 (br, ArH2,
1H), 7.43 (d, ArH4/6, 2JHH = 1.5 Hz, 2H), 6.82 (d, ArH8/12, 1JHH = 8.5
1
2
Hz, 2H), 6.33 (d, ArH9/11, JHH = 8.5 Hz, 2H), 1.66 (d, CH3, JHP
=
=
Synthesis of m-{-C(O)-C7H6-(C(O)PMe)}2 (3b). A diethyl ether
solution of 5-methylisophthaloyl chloride (0.487 g, 2.25 mmol) was
added, slowly, to a precooled (dry ice/IMS; −78 °C) ethereal
solution of MeP(SiMe3)2 (0.432 g, 2.25 mmol). During addition, the
solution assumes a yellow coloration. After stirring at −78 °C for 30
min, the mixture was allowed to warm to ambient temperature and
stir for a further 16 h, whereupon the precipitate was collected by
filtration, washed with diethyl ether (3 × 5 cm3), hexanes (3 × 5
cm3), Et2O again (3 × 5 cm3), and dried in vacuo, resulting in 94 mg
of yellow solid in 22% yield. 1H NMR (CD2Cl2): δH = 9.34 (br, ArH2,
1H), 7.33 (br, ArH4/6, 2H), 2.23 (s, Ar−CH3, 3H), 1.58 (d, P−CH3,
2JHP = 2.7 Hz, 3H). 13C{1H} NMR (CDCl3): δC = 207.3 (d, C(O),
1JCP = 45.8 Hz), 141.5 (br t, C2) 138.0 (d, C1/3, 2JCP = 37.3 Hz), 131.8
(s, C5), 131.6 (dd, C4/6, 3JCP = 1.7 Hz), 21.3 (s, Ar−CH3), 1.9 (d, P−
CH3, 1JCP = 4.2 Hz). 31P{1H} NMR (CD2Cl2): δP = 34.2 (s). 31P{1H}
NMR (C6D6): δP = 32.3 (s). IR νCO 1653 cm−1, 1640 cm−1. HRMS
(m/z): Calcd for C20H18O4P2 384.0680 ([M]+). Found 384.0691
([M]+).
3.1 Hz, 3H). 13C{1H} NMR (C6D6): δC = 205.9 (d, C(O), JCP
1
46.4 Hz), 141.8 (s, CN), 141.4 (s, C7), 138.5 (d, C1/3, JCP = 37.8
2
Hz), 133.4 (t, C2, JCP = 13.3 Hz), 132.5 (s, C8/12), 129.1 (dd, C4/6
,
3
3JCP = 1.9 Hz), 127.3 (s, C9/11), 118.2 (s, C5), 112.9 (s, C10), 1.8 (d,
CH3, 1JCP = 4.63 Hz). 31P{1H} NMR (C6D6): δP = 35.2 (s). IR νCO
1648 (br) cm−1 νCN 2227 cm−1. HRMS (m/z): Calcd for
C32H20N2O4P2 558.0898 ([M]+). Found 558.0906 ([M]+).
Synthesis of m-{-C(O)-C5NH4(C(O)PMe)}2 (4). A diethyl ether
solution of 2,6-pyridinedicarbonyl dichloride (0.312 g, 1.5 mmol) was
added, slowly, to a precooled (dry ice/IMS; −78 °C) ethereal
solution of MeP(SiMe3)2 (0.294 g, 1.5 mmol). During addition, the
solution assumes a green-yellow coloration. After stirring at −78 °C
for 30 min the mixture was allowed to warm to ambient temperature
and stirred for a further 16 h, whereupon the precipitate was collected
by filtration, washed with diethyl ether, and dried in vacuo, resulting
in 0.161 g of a green-yellow solid in 60% yield. 1H NMR (C6D6): δH =
7.2 (d, ArH4/6, 2JHH = 7.8 Hz, 4H), 6.58 (t, ArH5, 2JHH = 7.8 Hz, 2H),
1.63 (d, CH3, 2JPH = 6.2 Hz, 6H). 13C{1H} NMR (C6D6): δC = 209.1
(d, C(O), 1JCP = 50.86 Hz), 152.9 (d, C1/3, 2JCP = 33.1 Hz), 138.4 (s,
Synthesis of m-{-C(O)-C10H12(C(O)PMe)}2 (3c). To a precooled
(dry ice/IMS; −78 °C) ethereal solution (5 cm3) of MeP(SiMe3)2
(0.254 g, 1.32 mmol) was added 5-tertbutyl isophthaloyl chloride
(0.342 g, 1.32 mmol) dropwise over 5 min in ether (5 cm3), resulting
in yellow coloration of solution. After stirring for 30 min at −78 °C,
the mixture was allowed to warm to ambient temperature and stir for
a further 16 h, whereupon the precipitate was collected by filtration,
washed with diethyl ether (2 × 5 cm3), and dried in vacuo, affording
65 mg of an intense yellow solid in 21% yield. 1H NMR (CDCl3): δH
= 9.27 (br m, ArH2, 2H), 7.50 (d, ArH4/6, JHH = 1.4 Hz, 4H), 1.65 (d,
C
4/6), 124.7 (br t, C5, 3JCP = 1.7 Hz), 3.65 (dd, CH3, 1JCP = 7.2 Hz).
31P{1H} NMR (C6D6): δP = 30.1 (s). IR νCO 1656, 1640 cm−1. Anal.
Calcd for C16H12N2O4P2: C, 53.63; H, 3.38; N, 7.82. Found: C,
52.89; H, 3.34; N, 7.80.30
Synthesis of m-{-C(O)-C6H4(C(O)PPh)}2 (5). Isophthaloyl
chloride (0.5 g, 2.46 mmol) was dissolved in diethyl ether (6 cm3)
and slowly added dropwise to a precooled (dry ice/IMS; −78 °C)
ethereal solution (10 cm3) of PhP(SiMe3)2 (0.627 g, 2.46 mmol) over
5 min yielding a yellow color change. The yellow solution was stirred
for 30 min at −78 °C, then allowed to warm to room temperature and
stir for 16 h leading to a yellow precipitate which was filtered, washed
with diethyl ether (3 × 5 cm3), and dried in vacuo, initially yielding
0.181 g of yellow powder. The solid was dissolved in the minimum
amount of DCM and layered with pentane resulting in 0.102 g of matt
yellow solid isolated in 17% yield.23 1H NMR (CD2Cl2): δH = 8.50
(br, ArH2, 1H), 8.21 (br, ArH5, 1H), 8.03 (br, ArH4/6, 2H), 7.33 (br,
PhHp + PhHm, 3H),31 7.48 (br, PhHo, 2H).31 13C{1H} NMR
2
CH3, JPH = 2.7 Hz, 6H), 1.1 (s, tBu (CH3)3, 18H). 13C{1H} NMR
1
(CDCl3): δC = 207.2 (d, C(O), JCP = 46 Hz), 154.1 (br t, C5, JCP
=
1.7 Hz), 137.5 (d, C1/3, 2JCP = 37.6 Hz), 131.2 (t, C2, 3JCP = 13.5 Hz),
127.5 (dd, C4/6 3JCP = 1.7 Hz), 35.2 (s, C(CH3)3), 30.9 (s,
,
C(CH3)3), 1.6 (d, CH3, 1JCP = 3.9 Hz). 31P{1H} NMR (CDCl3): δP =
36.1 (s). 31P{1H} NMR (C6D6): δP = 34.5 (s). IR νCO 1657, 1641
cm−1. Anal. Calcd for C26H30O4P2: C, 66.64; H, 6.46. Found: C,
66.54; H, 6.52.
Synthesis of m-{-C(O)-C12H8-(C(O)PMe)}2 (3d). A diethyl ether
solution of 5-phenylisophthaloyl chloride (0.32 g, 1.1 mmol) was
added, slowly, to a precooled (dry ice/IMS; −78 °C) ethereal
solution of MeP(SiMe3)2 (0.22 g, 1.1 mmol). During addition, the
solution assumes a yellow coloration. After stirring at −78 °C for 30
(CD2Cl2):32 δC = 208.5 (d, C(O), JCP = 35.1 Hz), 140.3 (d, JCP
=
1
1
34 Hz, P−Phi), 137.9 (d, JCP = 19.5 Hz, P−Pho), 133.4 (s, Ar4/6),
2
2
129.7 (d, JCP = 6.8 Hz, P−Phm), 129.3 (m, Ar2). 31P{1H} NMR
(C6D6): δP = 30.5 (s). 31P{1H} NMR (CD2Cl2): δP = 32.2 (s). IR
H
J. Org. Chem. XXXX, XXX, XXX−XXX