4
Tetrahedron
White solid, 84% yield. m.p.: 45-46 oC; IR (neat): 3045,
4.3.5 5-Chloro-2-ethoxy-6-ethyl-3,3-difluoro-6-methyl-3,6-
ACCEPTED MANUSCRIPT
2996, 1644, 1301, 1055, 1005, 759, 731 cm-1;1H-NMR (400
dihydro-2H-1,2-oxaphosphinine 2-oxide (2e)
MHz, CDCl3): δ 6.08-5.99 (m, 1H), 4.34-4.28 (m, 2H), 1.70
Pale yellow liquid, isolated as a mixture (52:48) 73%
yield; IR (neat): 3048, 2984, 2942, 1642, 1458, 1301, 1167,
(s, 3H), 1.62 (d,
NMR (100 MHz, CDCl3): δ 146.8 (td, JC-F = 12.6 Hz, JC-P
J
= 1.6 Hz, 3H), 1.38-1.34(m, 3H); 13C-
=
1
1122, 784, 727 cm-1; H-NMR (400 MHz, CDCl3): δ 6.18-
3.7 Hz), 120.2 (td, JC-F = 28.0 Hz, JC-P = 12.3 Hz), 111.2 (td,
JC-F = 252.4 Hz, JC-P = 201.0 Hz), 87.4 (d, JC-P = 8.3 Hz),
65.8 (d, JC-P = 6.1 Hz), 27.8, 27.7, 16.3 (d, JC-P = 5.1 Hz);
19F-NMR (376 MHz, CDCl3): δ -101.9 (ABdd, JF-F = 317.4
Hz, JP-F = 94.0 Hz, JH-F = 8.2 Hz), 104.2 (ABdd, JF-F = 317.4
Hz, JP-F = 102.6, JH-F = 9.7 Hz); 31P-NMR (162 MHz,
CDCl3): δ -2.87 (dd, JP-F= 94.8, 102.7 Hz); HRMS calcd for
C8H1235ClF2O3PNa[M+Na]+ 283.0073, Found 283.0069.
6.10 (m, 1H), 4.41-4.32 (m, 2H ), 2.00-1.93 (m, 1.18H),
1.88-1.79 (m, 1.10H), 1.77 (s, 1.58H), 1.67 (s, 1.81H), 1.44-
1.38 (m, 3H), 0.97-0.90 (m, 3H); 13C-NMR (100 MHz,
CDCl3): δ 145.7-145.3 (m), 122.3-121.3 (m), 114.7-107.4
(m), 90.6 (d, JC-P = 10.5 Hz), 90.0 (d, JC-P = 7.6 Hz), 65.8 (d,
JC-P = 6.1 Hz), 65.7 (d, JC-P = 6.4 Hz), 33.2-33.1 (m), 25.9,
25.4, 16.4 (t, JC-P = 5.3 Hz), 7.2; 19F-NMR (376 MHz,
CDCl3): δ -94.6 to -97.6 (m), -108.6 to -109.9 (m); 31P-NMR
(162 MHz, CDCl3): δ -1.23 to -3.57 (m); HRMS calcd for
C9H1435ClF2O3PNa[M+Na]+ 297.0229, Found 297.0239.
4.3.2
5-Chloro-2-ethoxy-6,6-diethyl-3,3-difluoro-3,6-
dihydro-2H-1,2-oxaphosphinine 2-oxide (2b
)
Pale yellow liquid, 63% yield; IR (neat): 3042, 2983,
1641, 1460, 1292, 1209, 1161, 1124, 860, 784, 751, 720 cm-
4.3.6 5-Chloro-2-ethoxy-3,3-difluoro-6-methyl-3,6-dihydro-
2H-1,2-oxaphosphinine 2-oxide (2g
)
1; H-NMR (400 MHz, CDCl3): δ 6.20-6.11 (m, 1H), 4.36-
1
Pale yellow liquid, isolated as a mixture (42:58) 60%
yield; IR (neat): 3045, 2984, 2942, 1647, 1458, 1306, 1167,
1122, 941, 837, 784, 727 cm-1; 1H-NMR (400 MHz, CDCl3):
δ 6.17-6.08 (m, 1H), 5.13-5.07 (m, 0.42H), 5.03-4.96 (m,
0.58H), 4.43-4.34 (m, 2H), 1.71-1.65 (m, 3H), 1.44-1.38 (m,
3H); 13C-NMR (100 MHz, CDCl3): δ 143.2-143.0 (m),
121.4-121.0 (m), 114.4-107.2 (m), 78.7 (d, JC-P = 8.2 Hz),
4.28 (m, 2H), 1.98-1.87 (m, 4H), 1.36 (t,
J = 7.2 Hz, 3H),
0.97 (t, = 7.4 Hz, 3H), 0.92 (t,
J
J
= 7.4 Hz, 3H); 13C-NMR
(100 MHz, CDCl3): δ 145.2 (td, JC-F = 12.6 Hz, JC-P = 3.8
Hz), 122.5 (td, JC-F = 27.8 Hz, JC-P = 12.2 Hz), 110.9 (td, JC-F
= 252.1 Hz, JC-P = 199.6 Hz), 93.5 (d, JC-P = 9.5 Hz), 65.7 (d,
JC-P = 6.0 Hz), 30.7, 30.3, 16.4 (d, JC-P =5.1 Hz), 7.2, 7.1;
19F-NMR (376 MHz, CDCl3): δ -100.7 (ABdd, JF-F = 317.6
77.9 (d, JC-P = 6.7 Hz), 66.2 (d, JC-P = 6.2 Hz), 65.9 (d, JC-P
=
Hz, JP-F = 93.7 Hz, JH-F = 8.2 Hz), -102.6 (ABdd, JF-F
=
6.2 Hz), 20.5-20.3(m), 16.4 (d, JC-P = 5.0 Hz); 19F-NMR
(376 MHz, CDCl3): δ -98.3 to -100.5 (m), -106.3 to -107.4
(m); 31P-NMR (162 MHz, CDCl3): δ -0.09 to -2.95 (m);
HRMS calcd for C7H1035ClF2O3PNa [M+Na]+ 268.9916,
Found 268.9916.
317.6 Hz, JP-F = 102.1, Hz, JH-F = 9.6 Hz); 31P-NMR (162
MHz, CDCl3): δ -2.63 (dd, JP-F = 102.3, 93.7 Hz); HRMS
calcd for C10H1635ClF2O3PNa [M+Na]+ 311.0386, Found
311.0392.
4.3.3
10-Chloro-7-ethoxy-8,8-difluoro-6-oxa-7-
4.3.7 5-Chloro-2-ethoxy-3,3-difluoro-6-propyl-3, 6-dihydro-
phosphaspiro [4.5]dec-9-ene-7-oxide (2c
)
2H-1, 2-oxaphosphinine 2-oxide (2h
)
Pale yellow liquid, 68% yield; IR (neat): 3042, 2962,
1640, 1438, 1335, 1300, 1194, 1134, 1053, 1005, 786, 728
Pale yellow liquid, isolated as a mixture (44:56) 57%
yield; IR (neat): 3042, 2966, 2936, 1645, 1302, 1203, 771,
738 cm-1; 1H-NMR (400 MHz, CDCl3): δ 6.21-6.11 (m, 1H),
5.05-5.00 (m, 0.45H ), 4.94-4.88 (m, 0.58H), 4.43-4.31 (m,
2H), 2.02-1.89 (m, 2H), 1.59-1.39 (m, 5H), 0.99-0.94 (m, 3
H); 13C-NMR (100 MHz, CDCl3): δ 142.4-142.0 (m), 122.5-
121.6 (m), 114.3-107.2 (m), 82.0 (d, JC-P = 8.9 Hz), 80.9 (d,
JC-P = 7.0 Hz), 66.2 (d, JC-P = 6.2 Hz), 65.8 (d, JC-P = 5.3 Hz),
35.2-35.0 (m), 16.9 (d, JC-P = 2.4 Hz), 16.3 (d, JC-P = 5.0 Hz),
13.4; 19F-NMR (376 MHz, CDCl3): δ -96.0 to -98.6(m), -
108.2 to -109.4 (m); 31P-NMR (162 MHz, CDCl3): δ -0.35 to
-2.92 (m); HRMS calcd for C9H1435ClF2O3PNa [M+Na]+
297.0229, Found 297.0235.
1
cm-1; H NMR (400 MHz, CDCl3): δ 6.18-6.10 (m, 1H),
4.40-4.32 (m, 2H), 2.31-2.24 (m, 3H), 2.10-2.06 (m, 1H),
1.94-1.80 (m, 4H), 1.41 (t,
MHz, CDCl3): δ 145.2 (td, JC-F = 12.4 Hz, JC-P = 3.2 Hz),
121.5 (td, JC-F = 27.8 Hz, JC-P = 12.5 Hz), 111.1 (td, JC-F
J
= 7.0 Hz, 3H); 13C-NMR (100
=
252.2 Hz, JC-P = 200.6 Hz), 96.8 (d, JC-P = 8.6 Hz), 65.8 (d,
JC-P = 6.1 Hz), 39.1, 24.3, 24.2, 16.3 (d, JC-P = 5.1 Hz); 19F-
NMR (376 MHz, CDCl3): δ -101.9 (Abdd, JF-F = 317.8 Hz,
JP-F = 94.0 Hz, JH-F = 8.3 Hz)
, -103.7 (Abdd, JF-F = 317.8
Hz, JP-F = 102.6 Hz, JH-F = 9.7 Hz); 31P-NMR (162 MHz,
CDCl3): δ -2.64 (dd, JP-F = 102.9, 94.3 Hz); HRMS calcd for
C10H1435ClF2O3PNa [M+Na]+ 309.0229, Found 309.0228.
4.3.8
5-Chloro-2-ethoxy-3,3-difluoro-6-isopropyl-3,6-
4.3.4 5-Chloro-2-ethoxy-3,3-difluoro-1-oxa-2-phosphaspiro
dihydro-2H-1,2-oxaphosphinine 2-oxide (2i
)
[5.5] undec-4-ene 2-oxide (2d
)
Pale yellow liquid, isolated as a mixture (35:65) 50%
yield; IR (neat): 3043, 2966, 2936, 1645, 1302, 1203, 771,
738 cm-1; 1H-NMR (400 MHz, CDCl3): δ 6.26-6.15 (m, 1H),
4.92-4.89 (m, 0.34H), 4.79-4.77 (m, 0.63H), 4.44-4.30 (m, 2
Pale yellow liquid, 85% yield; IR (neat): 3036, 2940,
2868, 1638, 1450, 1302, 1161, 809, 778, 719 cm-1; 1H-NMR
(400 MHz, CDCl3): δ 6.09-6.00 (m, 1H), 4.37-4.28 (m, 2H ),
2.07-1.86 (m, 4H), 1.75-1.60 (m, 6H), 1.37 (t,
J = 7.2 Hz, 3
H), 2.50-2.43 (m, 1H), 1.46-1.38 (m, 3H), 1.11 (t,
J = 7.0 Hz,
H); 13C-NMR (100 MHz, CDCl3): δ 147.1 (td, JC-F = 12.4 Hz,
JC-P = 3.6 Hz), 120.6 (td, JC-F = 27.9 Hz, JC-P = 12.4 Hz),
3H), 0.89 (t,
J
= 7.4 Hz, 3H); 13C-NMR (100 MHz, CDCl3):
δ 141.9-141.5 (m), 123.4-122.4 (m), 114.4-107.2 (m), 86.1
(d, JC-P = 9.3 Hz), 84.6 (d, JC-P = 5.2 Hz), 66.2 (d, JC-P = 6.2
Hz), 65.7 (d, JC-P = 5.2 Hz), 30.4-30.1 (m), 18.6, 16.3 (d, JC-P
= 4.9 Hz), 13.7, 13.6; 19F-NMR (376 MHz, CDCl3): δ -92.9
to -95.8 (m), -110.8 to -112.7 (m); 31P-NMR (162 MHz,
110.9 (td, JC-F = 252.2 Hz, JC-P = 201.3 Hz), 89.3 (d, JC-P
=
8.8 Hz), 65.7 (d, JC-P = 6.3 Hz), 34.2, 34.1, 24.1, 20.4, 20.3,
16.4 (d, JC-P = 5.0 Hz); 19F-NMR (376 MHz, CDCl3): δ -
101.9 (ABdd, JF-F = 317.5 Hz, JP-F = 94.0 Hz, JH-F = 8.4 Hz),
-103.5 (ABdd, JF-F = 317.5 Hz, JP-F = 102.7 Hz, JH-F = 9.7
Hz); 31P-NMR (162 MHz, CDCl3): δ -2.89 (dd, JP-F = 102.7,
94.1 Hz); HRMS calcd for C11H1635ClF2O3PNa [M+Na]+
323.0386, Found 323.0394.
CDCl3):
δ
1.61 to -2.26 (m); HRMS calcd for
C9H1435ClF2O3PNa [M+Na] + 297.0229, Found 297.0238.
3a-3f, 3h-3i were known compounds.14b