ꢀDiphenylphosphorylated alkanones(alkenones)
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
789
7.16—7.27 (m, 4 H, C(2,6)6H4 + mꢀС6H5P); 7.44 (d, 1 H,
pꢀС6H5P, 3JH,H = 7.2 Hz); 7.47—7.57 (m, 3 H, mꢀ + pꢀС6H5P);
residue was dissolved in the minimum amount of boiling acetoꢀ
nitrile and cooled to 0 C, the precipitate that formed was sepaꢀ
rated and recrystallized once more from acetonitrile. The yield
was 3.5 g (58.8%), m.p. 165.0—165.5 C. Found (%): C, 67.78;
H, 5.41; P, 8.75; S, 9.04. C20H19O2PS. Calculated (%): C, 67.78;
H, 5.40; P, 8.74; S, 9.05. IR (KBr), /cm–1: 1197, 1185 (P=O);
1709 (C=O). 31P{1H} NMR (CDCl3), : 32.65 (s). 1H NMR
(400 MHz, CDCl3), 1.98 (s, 3 H, CH3); 2.91 (ddd, 1 H,
3
4
7.90 (dd, 2 H, oꢀС6H5P, JH,H = 7.7 Hz, JH,H = 1.4 Hz).
13C{1H} NMR (150 MHz, CDCl3), 30.72 (s, CH3C(O)), 40.19
1
(d, CH, JC,P = 69.7 Hz); 43.68 (s, CH2); 55.14 (d, CH3O,
4
7JC,P = 1.7 Hz); 113.81 (d, C(3,5)6H4, JC,P = 1.7 Hz); 127.63
(d, C(1)6H4, 2JC,P = 5.5 Hz); 128.12 (d, mꢀС6H5P, 3JC,P = 11.6 Hz);
3
128.87 (d, mꢀС6H5P, JC,P = 11.6 Hz); 130.74 (d, C(2,6)6H4,
2
3
3
2
3JC,P = 5.5 Hz); 131.00 (d, oꢀС6H5P, JC,P = 8.8 Hz); 131.29
CHaHb, JH ,H = 2.5 Hz, JH ,P = 10.2 Hz, JH ,H = 17.9 Hz);
a
a
a
b
(d, oꢀС6H5P, 2JC,P = 8.8 Hz); 131.42 (d, pꢀC6H5P, 4JC,P = 2.8 Hz);
131.57 (d, ipsoꢀC6H5P, 1JC,P = 93.4 Hz); 131.62 (d, ipsoꢀC6H5P,
1JC,P = 100.1 Hz); 131.97 (d, pꢀC6H5P, 4JC,P = 2.8 Hz); 158.61
(d, C(4)6H4, 5JC,P = 2.2 Hz); 205.58 (d, C=O, 3JC,P = 12.7 Hz).
4ꢀ(Diphenylphosphoryl)ꢀ4ꢀ(pꢀchlorophenyl)butanꢀ2ꢀone (7b).
To a solution of 4ꢀ(pꢀchlorophenyl)butꢀ3ꢀenꢀ2ꢀone (6b) (2.07 g,
11.46 mmol) in benzene (10 mL), a solution of DPCP (2.46 g,
11.15 mmol) in benzene (5 mL) and a solution of glacial acetic
acid (0.73 g, 12.16 mmol) in benzene (5 mL) were added dropꢀ
wise in succession. The reaction mixture was kept for 48 h at
~20 C, the solvent and other volatile substances were removed
in vacuo, and the residue was dissolved in the minimum amount
of ethanol and filtered through basic Al2O3 (5 g). Al2O3 was
washed with ethanol (2×10 mL), the combined filtrates were
evaporated until beginning of crystallization, and the precipitate
that formed was separated and dried in vacuo (~10 Torr) for 1 h at
140 C. The yield was 3.4 g (80.0%), m.p. 217—218 С. Found (%):
C, 68.79; H, 5.11; Cl, 9.15; P, 8.12. C22H20ClO2P. Calcuꢀ
3.25 (ddd, 1 H, CHaHb, JH ,H = 10.3 Hz, JH ,P = 5.0 Hz,
3
3
b
b
2JH ,H = 17.7 Hz); 4.52—4.60 (m, 1 H, CHP); 6.79 (dd, 1 H,
b
a
3
H(4)thiophen
(m, 1 H, H(3)thiophen); 7.04 (d, 1 H, H(5)thiophen, 3JH,H = 5.0 Hz);
,
3JH,H = 4.2 Hz, JH,H = 4.4 Hz); 6.87—6.93
3
4
7.29 (dt, 2 H, mꢀС6H5, JH,H = 7.4 Hz, JH,P = 2.6 Hz); 7.38
(t, 1 H, pꢀС6H5, 3JH,H = 7.2 Hz); 7.46—7.58 (m, 5 H, oꢀ + mꢀ +
+ pꢀС6H5); 7.84—7.93 (m, 2 H, oꢀС6H5). 1H{31P} NMR
(400 MHz, CDCl3), 1.98 (s, 3 H, CH3); 2.91 (dd, 1 H, CHaHb,
3JH ,H = 2.1 Hz, JH ,H = 17.7 Hz); 3.25 (dd, 1 H, СHaHb,
2
a
a
a
3JH ,H = 10.3 Hz, 2JH ,H = 17.7 Hz); 4.56 (dd, 1 H, CHP, 3JH,H
=
=
=
= 2b.6 Hz, 3JH,H = 10.3aHz); 6.79 (dd, 1 H, H(4)thiophen, 3JH,H
b
a
b
3
= 3.8 Hz, JH,H = 4.8 Hz); 6.90 (d, 1 H, H(3)thiophen
= 2.9 Hz); 7.04 (d, 1 H, H(5)thiophen
(t, 2 H, mꢀС6H5, 3JH,H = 7.5 Hz); 7.38 (t, 1 H, pꢀС6H5, 3JH,H
,
3JH,H
,
3JH,H = 4.9 Hz); 7.29
=
= 7.3 Hz); 7.46—7.58 (m, 5 H, oꢀ + mꢀ + pꢀС6H5); 7.88 (d, 2 H,
3
oꢀС6H5, JH,H = 6.9 Hz). 13C{1H} NMR (100 MHz, CDCl3),
30.47 (s, CH3); 36.44 (d, CH, 1JC,P = 70.4 Hz); 44.21 (s, CH2);
124.78 (d, СHthiophen, JC,P = 2.9 Hz); 126.62 (d, СHthiophen
,
lated (%): C, 69.02; H, 5.27; Cl, 9.26; P, 8.09. IR (KBr), /cm–1
:
JC,P = 2.6 Hz); 127.18 (d, СHthiophen, JC,P = 6.6 Hz); 128.06
(d, mꢀС6H5, 3JC,P = 11.7 Hz); 128.79 (d, mꢀС6H5, 3JC,P = 11.4 Hz);
1185, 1175 (P=O); 1715 (C=O). 31P{1H} NMR (400 MHz,
1
1
CDCl3), : 33.20 (s). H NMR (CDCl3), 1.94 (s, 3 H, CH3);
130.79 (d, ipsoꢀC6H5, JC,P = 101.2 Hz); 130.85 (d, ipsoꢀC6H5,
3
3
2
2.90 (ddd, 1 H, CHaHb, JH ,H = 2.2 Hz, JH ,P = 11.0 Hz,
1JC,P = 95.0 Hz); 130.95 (d, oꢀС6H5, JC,P = 8.8 Hz); 131.16
a
a
2JH ,H = 17.9 Hz); 3.25 (ddd, 1 H, CHaHb, JH ,H = 10.2 Hz,
3JH ,P = 5.1 Hz, 2JH ,H = 18.0 Hz); 4.11—4.25 (m, 1 H, CHP);
7.12 (d, 2 H, C(3,5)6H4, JH,H = 8.1 Hz); 7.18—7.30 (m, 4 H,
C(2,6)6H4 + mꢀC6H5P); 7.34 (t, 1 H, pꢀС6H5P, 3JH,H = 7.1 Hz);
7.39—7.60 (m, 5 H, oꢀ + mꢀ + pꢀС6H5P); 7.84—7.95 (m, 2 H,
oꢀС6H5P). 1H{31P} NMR (400 MHz, CDCl3), 1.94 (s, 3 H,
CH3); 2.90 (dd, 1 H, CHaHb, 3JH ,H = 2.9 Hz, 2JH ,H = 18.2 Hz);
(d, oꢀС6H5, 2JC,P = 8.8 Hz); 131.56 (d, pꢀC6H5, 4JC,P = 2.9 Hz);
3
a
b
b
4
132.02 (d, pꢀC6H5, JC,P = 2.9 Hz); 137.34 (d, C(2)thiophen
2JC,P = 6.2 Hz); 204.86 (d, C=O, 3JC,P = 12.1 Hz).
,
b
b
a
3
4ꢀ(Diphenylphosphoryl)ꢀ4ꢀ(furꢀ2ꢀyl)butanꢀ2ꢀone (7d). To
a solution of 4ꢀ(furꢀ2ꢀyl)butꢀ3ꢀenꢀ2ꢀone (6d) (2.4 g, 0.0176 mol)
in benzene (10 mL), a solution of DPCP (3.7 g, 0.0168 mol) in
benzene (10 mL) and a solution of glacial acetic acid (1.1 g,
0.0183 mol) in benzene (20 mL) were added dropwise in succesꢀ
sion. The reaction mixture was kept for 48 h at ~20 C, the
solvent and other volatile substances were removed in vacuo,
and the residue was dissolved in ethyl acetate (20 mL) and filꢀ
tered through basic Al2O3 (6 g). Al2O3 was washed with ethyl
acetate (2×10 mL), the combined filtrates were concentrated
until the volume of 10 mL and kept for 12 h at ~20 C, and the
precipitate that formed was separated, recrystallized from ethyl
acetate, and dried in vacuo (~1 Torr) for 1 h at 100 C. The yield
was 4.2 g (74.0%), m.p. 125.0—125.5 C. Found (%): C, 71.07;
H, 5.67; P, 9.08. C20H19O3P. Calculated (%): C, 71.00; H, 5.66;
P, 9.15. IR (KBr), /cm–1: 1203, 1190 (P=O); 1714 (C=O).
31P{1H} NMR (CDCl3), : 32.13 (s). 1H NMR (400 MHz,
a
a
b
3
2
3.25 (dd, 1 H, CHaHb, JH ,H = 10.4 Hz, JH ,H = 18.1 Hz);
4.18 (dd, 1 H, CHP, 3JH,H = 2.5 Hz, 3JH,H = 10.2 bHz); 7.12 (d, 2 H,
b
a
a
b
3
C(3,5)6H4, JH,H = 8.4 Hz); 7.19—7.29 (m, 4 H, C(2,6)6H4
+ mꢀС6H5P); 7.34 (t, 1 H, pꢀС6H5P, JH,H = 7.1 Hz); 7.45
(d, 2 H, oꢀС6H5P, JH,H = 7.3 Hz); 7.48—7.58 (m, 3 H, mꢀ +
+ pꢀС6H5P); 7.90 (d, 2 H, oꢀС6H5P, JH,H = 7.1 Hz). 13C{1H}
+
3
3
3
NMR (150 MHz, CDCl3), 30.59 (s, CH3); 40.40 (d, CH,
3
1JC,P = 68.6 Hz); 43.57 (s, CH2); 128.27 (d, mꢀС6H5P, JC,P
=
4
= 11.6 Hz); 128.53 (d, C(3,5)6H4, JC,P = 1.1 Hz); 128.99
3
2
(d, mꢀС6H5P, JC,P = 11.6 Hz); 130.86 (d, oꢀС6H5P, JC,P
=
= 8.8 Hz); 131.01 (d, C(2,6)6H4, 3JC,P = 6.1 Hz); 131.13 (d, ipsoꢀ
C6H5P, JC,P = 96.0 Hz); 131.21 (d, oꢀС6H5P, 2JC,P = 8.3 Hz);
1
1
131.22 (d, ipsoꢀC6H5P, JC,P = 99.0 Hz); 131.66 (d, pꢀC6H5P,
4JC,P = 2.8 Hz); 132.17 (d, pꢀC6H5P, JC,P = 2.8 Hz); 133.06
CDCl3), 2.04 (s, 3 H, CH3); 2.97 (ddd, 1 H, CHaHb, 3JH ,H
=
4
(d, С(4)6H4, 5JC,P = 2.8 Hz); 134.55 (d, С(1)6H4, 2JC,P = 5.5 Hz);
205.09 (d, C=O, 3JC,P = 13.3 Hz).
= 3.1 Hz, 3JH ,P = 10.0 Hz, JH ,H = 18.0 Hz); 3.23 (ddd,a1 H,
2
a
a
b
3
3
2
СHaHb, JH ,H = 10.6 Hz, JH ,P = 5.5 Hz, JH ,H = 18.0 Hz);
b
4ꢀ(Diphenylphosphoryl)ꢀ4ꢀ(thienꢀ2ꢀyl)butanꢀ2ꢀone (7c). To
a solution of 4ꢀ(thienꢀ2ꢀyl)butꢀ3ꢀenꢀ2ꢀone (6с) (2.64 g, 0.0173 mol)
in benzene (10 mL), a solution of DPCP (3.7 g, 0.0168 mol) in
benzene (10 mL) and a solution of glacial acetic acid (1.1 g,
0.0183 mol) in benzene (20 mL) were added dropwise in succesꢀ
sion. The reaction mixture was kept for 48 h at ~20 C, the
solvent and other volatile substances were removed in vacuo, the
4.47 (ddd, 1bH, CHP, 3JH,H = b3.0 Hz, 3JH,H = 10.a7 Hz, 2JH,P
=
a
b
= 10.7 Hz); 5.97 (dd, 1 H, H(3)furan, 3JH,H = 3.1 Hz, 4JH,P = 3.1 Hz);
3
6.16 (dd, 1 H, H(4)furan
,
3JH,H = 2.8 Hz, JH,H = 2.1 Hz);
7.16 (br.s, 1 H, H(5)furan); 7.34 (dt, 2 H, mꢀС6H5, 3JH,H = 7.6 Hz,
4JH,P = 3.0 Hz); 7.40—7.58 (m, 6 H, oꢀ + mꢀ + pꢀС6H5);
7.77—7.86 (m, 2 H, oꢀС6H5). 1H{31P} NMR (400 MHz CDCl3),
3
2.04 (s, 3 H, CH3); 2.97 (dd, 1 H, CHaHb, JH ,H = 3.0 Hz,
a