References
1
Couret C.
Escudié J.
Satgé J.
Anh NT.
Soussan G.
J. Organomet.
Chem.
1975,
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11
2
Märkl G.
Olbrich H.
Tetrahedron Lett.
1968,
35:
3813
3a
Fuchs EPO.
Heydt H.
Regitz M.
Schoeller WW.
Busch T.
Tetrahedron Lett.
1989,
30:
5111
3b
Fuchs EPO.
Breit B.
Bergsträsser U.
Hoffmann J.
Heydt H.
Regitz M.
Synthesis
1991,
1099
4a
Haber S.
Boese R.
Regitz M.
Angew. Chem., Int. Ed. Engl.
1990,
29:
1436 ; Angew. Chem. 1990, 102, 1523
4b
Haber S.
Schmitz M.
Bergsträsser U.
Hoffmann J.
Regitz M.
Chem.-Eur.
J.
1999,
5:
1581
5
Kochetkov AN.
Efimova IV.
Trostyanskaya IG.
Kazankova MA.
Beletskaya IP.
Russ. Chem. Bull.
1998,
47:
1744
6a
1a: Appel R.
Geisler K.
J. Organomet. Chem.
1976,
112:
61
6b
1b: Fritz G.
Poppenburg G.
Angew.
Chem.
1960,
72:
208
6c
Fritz G.
Poppenburg G.
Rocholl MG.
Naturwissenschaften
1962,
74:
255
6d
1c Was
obtained analogously form 1-phenyl- or 1H-phospholane.
7 (Z)-3-(Diphenylphosphanyl)-1,3-diphenyl-2-(trimethyl-silyl)prop-2-en-1-one(3a); general procedure: A solution of 1,3-diphenylprop-2-yn-1-one
(2a, 3.1 g, 15.0 mmol) in THF (100 mL)
was cooled at 0 °C and diphenyl(trimethyl-silyl)phosphane
(1a, 3.87 g, 15.0 mmol) was added. The reaction
mixture was kept with stirring at 0 °C for 2 h, then at
20 °C for 12 h. The solvent was evaporated at 15 mbar and the
solid residue was recrystallized from CH3CN to furnish 3a as colorless crystals (5.22 g, 75%),
mp 127-128 °C. IR (KBr): 1663 s, 1243 s, 1233
s, 858 s, 842 s cm-1. 1H
NMR (CDCl3, 500.14 MHz): δ = 0.51 (d, 5
J
H,P = 1.2 Hz, 9
H, SiMe3), 6.3-7.8 (20 HPh). MS (EI,
70 eV): m/z (%) = 466
(9), 465 (33), 464 (100) [all M+].
3b: From 1b and 2a; large pale-yellow crystals, 69% yield, mp
100 °C. IR (KBr): 1655 s, 1237 s, 844 s, 703 m cm-1.
1H
NMR (CDCl3, 500.14 MHz, 233 K): δ = 0.35
(d, 5
J
H,P = 1.6
Hz, 9 H, SiMe3), 1.0-1.4 (m, 10 Hethyl),
6.6-7.6 (10 HPh). 29Si NMR
(CDCl3, 99.37 MHz): δ = -8.5
(d, 3
J
Si,P = 11.4
Hz). MS (EI, 70 eV): m/z (%) = 370
(5), 369 (10), 368 (39) [all M+],
279 (100). C22H29OSiP (368.53): calcd C 71.70,
H 7.93; found C 71.38, H 8.12.
3c:
From 1c and 2a;
pale-yellow crystals, 69% yield, mp 99 °C. IR
(KBr): 1667/1650 vs, 1230 vs, 1174 vs, 702 vs
cm-1. 1H
NMR (CDCl3, 500.14 MHz): δ = 0.35 (d, 5
J
H,P = 1.5 Hz, 9
H, SiMe3), 1.08-1.25 (m, coalescing, 2 H), 1.35-1.45 (m,
2 H), 1.65-1.90 (m, 4 H), 6.7-7.7 (10 HPh).
MS (EI, 70 eV): m/z (%) = 368
(2), 367 (7), 366 (25) [all M+],
279 (100). C22H27OPSi (366.51): calcd C 72.10,
H 7.42; found C 71.80, H 7.55.
3d:
From 1a and 2b;
70% yield, amorphous solid, mp 149 °C. IR (KBr):
1629 vs, 1413 s, 1261 s, 1246 s, 846 vs, 743 vs, 725 s, 702 vs cm-1. 1H
NMR (CDCl3, 500.14 MHz):
δ = 0.44
(s, 9 H, SiMe3), 6.4-7.5 (18 Harom).
MS (EI, 70 eV): m/z (%) = 472
(13), 471 (36), 470 (100) [all M+], 469
(39). C28H27OPSSi (470.64): calcd C 71.46,
H 5.78; found C 71.52, H 5.62.
3e:
From 1b and 2c,
malodorous colorless oil, isolated by bulb-to-bulb distillation
at 80-100 °C/0.0001 mbar; 76% yield.
IR (KBr): 1687 s, 1245 s, 1187 s, 841 s cm-1. 1H
NMR (CDCl3, 500.14 MHz): δ = 0.49 (d, 5
J
H,P = 1.5 Hz, 9
H, SiMe3), 1.19 (dt, 6 H, CH2CH
3), 1.35 (m, 4 H, PCH2),
1.86 (d, 5
J
H,P = 1.4
Hz, COCH3), 6.90-7.00 (m, 2 HPh),
7.32-7.43 (m, 3 HPh). MS (EI, 70 eV): m/z (%) = 308
(2), 307 (9), 306 (43) [all M+],
217 (100). C17H27OPSi (306.46): calcd C 66.63,
H 8.88; found C 67.31, H 8.25.
8
Duncan M.
Callagher MJ.
Org. Magn. Reson.
1981,
15:
37
9 Crystal data for 3b:
Triclinic, space group P1, a = 9.432 (3), b = 9.611
(2), c = 12.548 (3) Å, α = 98.82 (3), β = 102.21 (3), γ = 101.69 (3); Z = 2, D
calc = 1.149
g·cm-3. Crystallographic data
have been deposited at the Cambridge Crystallographic Data Centre
as supplementary publication no. CCDC-187712. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Data Centre, 12, Union Road,
Cambridge CB2 1EZ, UK; fax: +44(1223)336033).
10 Yield of crude 4a,b: ˜90%; since both compounds
are extremely malodorous oils, we refrained from further purification.
Data for 4a: 1H NMR
(CDCl3, 500.14 MHz): δ = 0.17 (s, SiMe3),
5.33 (d, 2
J
H,P = 1.2
Hz, HCC≡C), 7.23-7.70 (m, 5 HPh). 13C{1H} NMR
(CDCl3, 50.32 MHz): δ = 0.2 (s, SiMe3),
64.4 (s, HCC≡C), 88.21 (d, J
C,P = 10.6 Hz) and 88.63
(d, J
C,P = 5.0 Hz)
(C≡C).
This product was isolated as a 6.2:1 mixture (31P
NMR) with 5a [δ(1H) = 0.43
(d, 5
J
H,P = 1.5,
SiMe3); δ(13C) = 1.8
(d, 4
J
C,P = 9.1,
SiMe3), 198.0 (3
J
C,P = 17.4,
CHO); δ(31P) = 3.4].
Data
for 4b: IR (film): 1679 m, 1599 m, 1251
vs, 1065 vs, 868 vs, 844 vs, 754 m cm-1. 1H
NMR (CDCl3, 200.13 MHz): δ = 0.16 (s,
9 H, SiMe3), 0.90-1.15 (dt, 6 H, CH2CH
3), 1.30-1.70 (m,
4 H, PCH2), 4.78 (d, J
H,P = 5.0
Hz, HCC≡C), 7.15-7.40 (m, 5 HPh). 13C{1H} NMR
(CDCl3, 50.32 MHz): δ = 0.09 (s, SiMe3),
9.85 and 9.95 (each d, J
C,P = 15.1
Hz, CH2CH3), 16.4 (d, J
C,P = 15.1
Hz, PCH2), 16.7 (d, J
C,P = 14.1 Hz,
PCH2), 61.9 (d, J
C,P = 11.6
Hz, HCC≡C), 87.2 (s) and 87.9
(d, J
C,P = 4.0 Hz)
(C≡C).
This product was isolated as a 94:6 mixture (31P
NMR) with 5b [δ(1H) = 0.32
(d, 5
J
H,P = 1.6 Hz,
SiMe3); δ(13C) = 2.3
(d, 4
J
C,P = 10.7
Hz, SiMe3)].
11 Allene 6 was
obtained as an oil (˜97% purity by 31P
NMR) which could not be purified further by chromatography or vacuum
distillation without decomposition. 1H NMR (CDCl3,
500.14 MHz): δ = 0.21 (s, 9 H, SiMe3),
1.04 and 1.42 (each dt, 3 H, PCH2CH3), 1.58-1.74
(m, 4 H, PCH2), 7.24-7.38 (m, 6 HPh),
7.61 (dd, 2 HPh), 7.64 (dd, 2HPh).
12
7: colorless
crystals, mp 89 °C. IR (KBr): 1688 (s, C=O), 1266
m, 1158 (s, P=O) cm-1. 1H
NMR (CDCl3, 400.13 MHz): δ = 1.01 (dt, 3
J
P,H = 17.0 Hz, 3
J
H,H = 7.7 Hz, 3
H, CH2CH
3), 1.23
(dt, 3
J
P,H = 17.2
Hz, 3
J
H,H = 7.7
Hz, 3 H, CH2CH
3),
1.49-1.74 (m, 2 H, PCH2), 1.84-2.05
(m, 2 H, PCH2), 3.80 (mc, 2 H, COCH2),
3.95 (mc, 1 H, PCH), 7.26-7.55 (m, 8 Harom),
7.96 (dd, 2 Harom). 13C{1H} NMR
(CDCl3, 100.61 MHz): δ = 5.88/5.92
(2 d, J
P,C = 44.3/44.3
Hz, PCH2
CH3), 18.51/19.25
(2 overlapping d, PCH2), 38.6 (s, COCH2),
39.1 (d, J
P,C = 61.4
Hz, CHPOEt2), 127.2-137.5 (CPh),
196.9 (d, J
P,C = 10.2
Hz, CO). 31P (CDCl3): δ = 54.8. C19H23O2P
(314.36): calcd C 72.59, H 7.37; found C 72.82, H 7.51.
For other methods to prepare γ-ketophosphinates
and -phosphanoxides, see:
14a
Bell A.
Davidson AH.
Earnshaw C.
Norrish HK.
Torr RS.
Trowbridge DB.
Warren S.
J. Chem. Soc., Perkin Trans. 1
1983,
2879
14b
Pudovik AN.
Sovanov AA.
Bakhtiyarova IV.
Zimin MG.
Zh.
Obshch. Khim.
1983,
53:
2456
14 (Z)-8: Colorless oil. IR(film): 1669 (s, C=O),
1225 (s), 1174 (s, P=O) cm-1. 1H
NMR (CDCl3, 400.13 MHz): δ = 1.14 (dt, 3
J
P,H = 17.4 Hz, 3
J
H,H = 7.7 Hz, 6
H, PCH2CH
3), 1.80-1.97 (m,
4 H, POCH2), 7.24 (d, 3
J
P,H = 30.5 Hz, 1
H, COCH=), 7.35-7.60 (3 m, 8 Harom),
7.97-8.00 (dd, 2 Harom). 13C{1H} NMR
(CDCl3, 100.61 MHz): δ = 5.67 (d, J
P,C = 5.3 Hz, PCH2
CH3), 21.9 (d, J
P,C = 69.1 Hz, PCH2),
128.1-128.8 (several C), 133.8 (CH), 137.0, 138.8 (d, J
P,C = 9.1 Hz), 142.3
(J
P,C = 5.4 Hz, COCH=), 145.8, 146.5, 192.9 (d, J
P,C = 4.9 Hz, C=O). 31P: δ = 46.4.
C19H21O2P (312.35): calcd C 73.06,
H 6.78; found C 72.68, H 6.94. (E)-8: Colorless crystals, mp 80 °C.
IR (solid, ATR): 1659 (s, C=O), 1254 (s), 1188 (s, P=O)
cm-1. 1H NMR (CDCl3,
400.13 MHz): δ = 1.25 (dt, 3
J
P,H = 16.9 Hz, 3
J
H,H = 7.6 Hz, 6
H, PCH2CH
3), 1.67-1.86
(m, 4 H, POCH2), 7.09-7.52 (4 m, 8 Harom),
7.82 (d, 3
J
P,H = 17.8
Hz, 1 H, COCH=), 7.87 (dd, 2 Harom). 13C{1H} NMR
(CDCl3, 100.61 MHz): δ = 5.42 (d, J
P,C = 5.7 Hz, PCH2
CH3), 19.6 (d, J
P,C = 69.8 Hz, PCH2),
127.6-128.9 (several C), 133.5 (CH), 134.9 (d, J
P,C = 9.1 Hz), 136.6, 140.3
(J
P,C = 5.7 Hz, COCH=), 145.8, 146.5, 191.9 (d, J
P,C = 14.8 Hz, C=O). 31P: δ = 44.2.
C19H21O2P (312.35): calcd C 73.06,
H 6.78; found C 73.11, H 6.83.
