Phosphorylation of αꢀamino ketones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 2, February, 2006
299
3JP,H = 11.14 Hz). 31P NMR (C6D6), δ: 35.9. Found (%):
N, 6.06; P, 13.23. C11H24NO2P. Calculated (%): N, 6.00;
P, 13.28.
tetrachloride (200 mL). Stirring was continued without cooling
for an additional 2 h. The reaction mixture was treated as deꢀ
scribed in general procedure A and the product was purified by
distillation. The yield was 63%, b.p. 102—104 °C (0.09 Torr).
IR (thin film), ν/cm–1: 1030 (POC), 1260 (P=O), 1725 (C=O).
1H NMR (C6D6), δ: 1.05 (d, 6 H, Me2CHN, 3JH,H = 6.70 Hz);
1ꢀ[Diphenylphosphanyl(isopropyl)amino]ꢀ3,3ꢀdimethylbutanꢀ
2ꢀone (5c) was obtained according to procedure A. The yield
was 64%, m.p. 55—56 °C (pentane, –10 °C). IR (KBr pellets),
ν/cm–1: 990 (P—N), 1440 (P—Ph), 1720 (C=O). 1H NMR
1.20 (s, 9 H, But); 3.56 (dsept, 1 H, Me2CH, JP,H = 10.00 Hz,
3
3
(C6D6), δ: 1.17 (s, 9 H, But); 1.56 (d, 6 H, Me2CHN, JH,H
=
=
3JH,H = 6.70 Hz); 3.76 (d, 6 H, (MeO)2P, 3JP,H = 8.00 Hz); 3.98
3
3
3
6.50 Hz); 2.76 (dsept, 1 H, Me2CH, JP,H = 6.50 Hz, JH,H
(d, 2 H, NCH2CO, JP,H = 12.10 Hz). 31P NMR (C6D6), δ:
3
6.50 Hz); 3.17 (d, 2 H, NCH2CO, JP,H = 6.50 Hz); 7.44, 7.84
(both m, 10 H, Ph2P). 31P NMR (C6D6), δ: 47.8. Found (%):
N, 4.04; P, 9.15. C21H28NOP. Calculated (%): N, 4.10; P, 9.07.
1ꢀ[Phenyleneꢀ1,2ꢀdioxyphosphanyl(isopropyl)amino]ꢀ3,3ꢀ
dimethylbutanꢀ2ꢀone (5d) was obtained according to procedure A.
The yield was 87%. In benzene, compound 5d exists in equilibꢀ
rium with compound 9a (the content of 5d was 80%). IR (thin
11.9. Found (%): N, 5.67; P, 11.68. C11H24NO4P. Calcuꢀ
lated (%): N, 5.28; P, 11.68.
1ꢀ[Diethoxyphosphoryl(isopropyl)amino]ꢀ3,3ꢀdimethylbutanꢀ
2ꢀone (5i) was obtained analogously from amino ketone 4b
(0.11 mol), triethylamine (0.12 mol), and diethyl phosphite
(0.1 mol) in diethyl ether. The yield was 91%, b.p. 109—110 °C
(0.09 Torr). IR (thin film), ν/cm–1: 1030 (POC), 1260 (P=O),
1725 (C=O). 1H NMR (C6D6), δ: 1.06 (d, 6 H, Me2CHN,
3JH,H = 6.70 Hz); 1.20 (s, 9 H, But); 1.32 (t, 6 H, CH3CH2O,
film), ν/cm–1: 1720 (C=O). H NMR (C6D6), δ: 0.76 (s, 9 H,
1
But); 0.86 (d, 6 H, Me2CHN, JH,H = 7.00 Hz); 3.47 (dsept,
3
3
3
3
1 H, Me2CH, JP,H = 7.40 Hz, JH,H = 7.00 Hz); 3.56 (d, 2 H,
NCH2CO, JP,H = 10.60 Hz); 6.6—7.0 (m, 4 H, Ar). 31P NMR
3JH,H = 6.70 Hz); 3.64 (dsept, 1 H, Me2CH, JP,H = 10.00 Hz,
3
3
3JH,H = 6.70 Hz); 3.98 (d, 2 H, NCH2CO, JP,H = 12.10 Hz);
3
3
(C6D6), δ: 150.3. Found (%): N, 4.79; P, 10.40. C15H22NO3P.
4.14 (dq, 4 H, CH3CH2O, JP,H = 11.00 Hz, JH,H = 6.70 Hz).
31P NMR (C6D6), δ: 9.3. Found (%): N, 4.71; P, 10.62.
C13H28NO4P. Calculated (%): N, 4.78; P, 10.56.
Calculated (%): N, 4.74; P, 10.49.
4
4ꢀtertꢀButylꢀ2ꢀhydridoꢀ1ꢀisopropylꢀ∆ ꢀ1,3,2ꢀoxazaphosphoꢀ
lineꢀ2ꢀspiroꢀ2´,4´,5´ꢀbenzoꢀ1´,3´,2´ꢀdioxaphospholane (9a).
NꢀIsopropyl(2ꢀdimethylphosphoryloxyꢀ3,3ꢀdimethylbutylꢀ
idene)imine (6b) was obtained according to procedure B. The
yield was 71%, b.p. 77—79 °C (0.05 Torr). IR (thin film),
ν/cm–1: 1020 (P—O), 1230 (P=O), 1300 (P—Me), 1670 (C=N).
1H NMR (C6D6), δ: 5.49 (d, 1 H, C=CH, 3JP,H = 30 Hz); 8.81
1
(d, 1 H, PH, JP,H = 879 Hz). 31P NMR (C6D6), δ: –35.8 (dd,
1JP,H = 879 Hz, 3JP,H = 30 Hz).
4
1ꢀ[5ꢀtertꢀButylꢀ3ꢀisopropylꢀ∆ ꢀ1,3,2ꢀoxazaphospholinꢀ2ꢀ
1H NMR (C6D6, δ: 0.96 (s, 9 H, But); 1.11 (dd, 6 H, Me2CHN,
2
yl(isopropyl)amino]ꢀ3,3ꢀdimethylbutanꢀ2ꢀone (5e) was obtained
according to procedure A. The yield was 63%, b.p. 135 °C
(0.05 Torr). In benzene, compound 5e exists in equilibrium with
compound 9b (the content of 5e was 90%). IR (thin film),
ν/cm–1: 1720 (C=O). 1H NMR (C6D6), δ: 1.01 (dd, 6 H,
3JH,H = 6.67 Hz, ∆δ 0.011); 1.19 (dd, 6 H, Me2P, JP,H
=
10.12 Hz, ∆δ 0.017); 3.16 (sept, 1 H, Me2CHN, 3JH,H = 6.67 Hz);
4.58 (dd, 1 H, OCHCH=N, 3JH,H = 5.62 Hz, 3JP,H = 7.30 Hz);
7.52 (d, 1 H, OCHCH=N, 3JH,H = 5.62 Hz). 31P NMR (C6D6),
δ: 49.1. Found (%): N, 6.20; P, 13.20. C11H24NO2P. Calcuꢀ
lated (%): N, 6.01; P, 13.28.
Me2CH lin., 3JH,H = 6.80 Hz, ∆δ 0.014); 1.13 (s, 9 H, But ring);
3
1.16 (s, 9 H, But lin.); 1.23 (dd, 6 H, Me2CH ring, JH,H
=
=
NꢀtertꢀButyl(2ꢀdiethylphosphoryloxyꢀ3,3ꢀdimethylbutylꢀ
idene)imine (6g) was obtained according to procedure A. The
yield was 70%, b.p. 98—99 °C (0.05 Torr). IR (thin film),
3
6.60 Hz, ∆δ 0.014); 3.47 (dsept, 1 H, Me2CH lin., JP,H
6.80 Hz, 3JH,H = 6.80 Hz); 3.65 (m, 1 H, Me2CH ring); 3.84 (dd,
2
3
1
2 H, CH2, JH,H = 20.00 Hz, JP,H = 10.80 Hz, ∆δ 0.154); 5.53
ν/cm–1: 1670 (C=N). H NMR (C6D6), δ: 0.96 (s, 9 H, ButC);
(d, 1 H, =CH, JP,H = 8.20 Hz). 31P NMR (C6D6), δ: 133.3.
1.08 (m, 6 H, CH3CH2P); 1.17 (s, 9 H, ButN); 1.65 (m, 4 H,
3
Found (%): N, 8.25; P, 9.15. C18H34N2O2P. Calculated (%):
CH3CH2P); 4.34 (dd, 1 H, OCHCH=N, 3JH,H = 6.5 Hz, 3JPH
=
N, 8.16; P, 9.02.
7.8 Hz); 7.62 (d, 1 H, OCHCH=N, 3JH,H = 6.5 Hz). 31P NMR
(C6D6), δ: 56.6. Found (%): N, 5.19, P, 11.14. C14H30NO2P.
Calculated (%): N, 5.09, P, 11.25.
4,4´ꢀDiꢀtertꢀbutylꢀ2ꢀhydridoꢀ1,1´ꢀdiisopropylꢀ2,2´ꢀspiroꢀ
4
1
bi(∆ ꢀ1,3,2ꢀoxazaphospholine) (9b). H NMR (C6D6), δ: 5.41
3
1
(d, 1 H, C=CH, JP,H = 30 Hz); 9.22 (d, 1 H, P—H, JP,H
=
NꢀIsopropyl(2ꢀdiethylphosphinyloxyꢀ3,3ꢀdimethylbutylꢀ
idene)imine (6j) was obtained according to procedure B. The
yield was 49%, b.p. 50—52 °C (0.05 Torr). IR (thin film),
850 Hz). 31P NMR (C6D6), δ: –50.1 (dd, JP,H = 850 Hz,
1
3JP,H = 30 Hz).
4
1
1ꢀ[5ꢀtertꢀButylꢀ4ꢀdeuterioꢀ3ꢀisopropylꢀ∆ ꢀ1,3,2ꢀoxazaphosꢀ
ν/cm–1: 1010 (P—O), 1670 (C=N). H NMR (C6D6), δ: 0.97
pholinꢀ2ꢀyl(isopropyl)amino]ꢀ3,3ꢀdimethylbutanꢀ2ꢀone (5f) was
obtained according to procedure A. Its physicochemical characꢀ
teristics are identical with those of compound 5e, except for the
absence of a doublet at δ 5.53 in the H NMR spectrum. Comꢀ
pound 5f exists in equilibrium with compound 9c (the content of
(s, 9 H, But); 1.04 (m, 6 H, CH3CH2P); 1.14 (dd, 6 H, Me2CHN,
3
3JH,H = 6.6 Hz, ∆δ = 0.05); 1.49 (dq, 4 H, CH3CH2P, JH,H
=
2
6.5 Hz, JP,H = 13.0 Hz, ∆δ 0.014); 3.18 (sept, 1 H, Me2CHN,
3JH,H = 6.6 Hz); 3.93 (dd, 1 H, OCHCH=N, JH,H = 6.3 Hz);
1
3
7.53 (d, 1 H, OCHCH=N, JH,H = 6.3 Hz). 31P NMR (C6D6),
3
5f was 90%.
δ: 139.8. Found (%): N, 5.82; P, 12.59. C13H28NOP. Calcuꢀ
lated (%): N, 5.71; P, 12.63.
4,4´ꢀDiꢀtertꢀbutylꢀ5ꢀdeuterioꢀ2ꢀhydridoꢀ1,1´ꢀdiisopropylꢀ
2,2´ꢀspirobi(∆ ꢀ1,3,2ꢀoxazaphospholine) (9c). Its spectroscopic
4
NꢀtertꢀButyl(2ꢀdimethylphosphoryloxyꢀ3,3ꢀdimethylbutylꢀ
idene)imine (6k) was obtained according to procedure B. The
yield was 74%, m.p. 67—68 °C (diethyl ether, –5 °C). IR (thin
film), ν/cm–1: 1230 (P=O), 1300 (P—Me), 1670 (C=N).
1H NMR (C6D6), δ: 0.99 (s, 9 H, ButC); 1.20 (s, 9 H, ButN);
1.49 (dd, 6 H, Me2P, 2JP,H = 10.21 Hz, ∆δ 0.014); 4.41 (dd, 1 H,
characteristics are identical with those of compound 9b, except
for the absence of a doublet at δ 5.41 in the 1H NMR spectrum.
1ꢀ[Dimethoxyphosphoryl(isopropyl)amino]ꢀ3,3ꢀdimethylꢀ
butanꢀ2ꢀone (5h). A solution of dimethyl phosphite (0.1 mol)
was added dropwise at 5—10 °C to a stirred solution of amino
ketone 4b (0.11 mol) and triethylamine (0.12 mol) in carbon
3
3
OCHCH=N, JH,H = 5.64 Hz, JP,H = 7.8 Hz); 7.59 (d, 1 H,