2-Chloro-1,3,2-diazaphospholenes
5
3
to the procedure reported in ref.[1] All other chemicals were pur-
chased from commercial suppliers. NMR Spectra: Bruker Avance
400 (1H: 400.13 MHz; 31P: 161.9 MHz; 13C: 100.4 MHz) at 30 °C;
chemical shifts referred to ext. TMS (1H, 13C) or 85% H3PO4 (Ξ
= 40.480747 MHz, 31P); positive signs of chemical shifts denote
shifts to lower frequencies; coupling constants are given as absolute
values; prefixes i-, o-, m-, p- denote atoms of aryl substituents. MS:
Varian MAT 711, EI, 70 eV. Elemental analysis: Perkin–Elmer
2400CHSN/O analyser. Melting points were determined in sealed
capillaries.
(s, i-C), 137.0 (d, JP,C = 5.5 Hz, p-C), 131.8 (d, JP,C = 10.0 Hz, o-
4
C), 129.7 (d, JP,C = 1.0 Hz, m-CH), 125.8 (m, N-CH), 21.0 (d,
6JP,C = 0.8 Hz, p-CH3), 19.1 (d, JP,C = 1.3 Hz, o-CH3), 11.1 (d,
4
3JP,C = 2.0 Hz, CH3) ppm. 31P{1H} NMR (CDCl3): δ = 165.0 (s)
ppm. MS (EI): m/z (%) 386.2 (21.9) [M]+, 351.2 (100.0) [M – Cl]+,
363.0 (19.2) [M – CH3Cl]+, 305.2 (2.7) [M – C3 H1 0Cl]+.
C22H28ClN2P (386.90): calcd. C 68.30, H 7.29, N 7.24; found C
68.24, H 7.35, N 7.13.
2-Chloro-1,3-bis(diisopropylphenyl)-4,5-dimethyl-1,3,2-diazaphos-
pholene (3e): Crystallisation from dichloromethane at –20 °C;
1-[(2,6-Dimethylphenyl)imino]-2-[(2,6-dimethylphenyl)amino]ethane colourless crystals; yield 8.7 g (93 %); m.p. 204 °C. 1H NMR
3
(2b): Compound 1b (18.5 g, 70 mmol) was dissolved in thf
(200 mL), and lithium turnings (1.1 g, 150 mmol) were added. Af-
ter stirring for 24 h the unreacted lithium was filtered off and the
solution cooled to –78 °C. Triethylamine hydrochloride (15.1 g,
150 mmol) was added and the reaction mixture slowly warmed to
room temperature. After the solution had become colourless all
volatiles were removed in vacuo. The residue was dissolved in n-
hexane (150 mL) and the precipitate filtered off. The solution was
concentrated and the product crystallised at –20 °C. The yellow
needles obtained were filtered off and dried in vacuo. Yield 12.0 g
(CDCl3): δ = 7.45–7.13 (m, 6 H, m/p-CH), 3.14 (sept, JH,H
=
4
6.7 Hz, 4 H, CH), 1.84 (d, JP,H = 0.9 Hz, 6 H, NC-CH3), 1.31 (d,
3JH,H = 6.7 Hz, 12 H, CH3), 1.21 (d, JH,H = 6.7 Hz, 12 H, CH3)
3
ppm. 13C{1H} NMR (CDCl3): δ = 148.9 (d, 4JP,C = 5.0 Hz, m-CH),
2
5
131.0 (d, JP,C = 12.1 Hz, i-C), 129.8 (d, JP,C = 1.5 Hz, p-CH),
129.4 (s, o-C), 128.6 (s, o-C), 125.7 (s; N-C), 125.0 (d, JP, C
1.0 Hz, m-CH), 28.9 (d, JP, C = 1.0 Hz, CH3), 26.1 (d, JP, C
4
=
=
5
5
3
1.3 Hz, CH3), 25.0 (s, CH), 11.9 (d, JP,C = 3.4 Hz, NC-CH3) ppm.
31P{1H} NMR (CDCl3): δ = 157.0 (s) ppm. MS (EI): m/z (%) 470.3
(15.1) [M]+, 435.3 (100.0) [M – Cl]+. C28H40ClN2P (471.07): calcd.
(65%), m.p. 136 °C. 1H NMR (CDCl3): δ = 7.83 (t, 3JH,H = 2.1 Hz, C 71.39, H 8.56, N 5.95; found C 71.30, H 8.64, N 6.14.
1 H, CH=N), 7.25–6.80 (m, 6 H, CH), 5.42 (s, 1 H, NH), 4.15 (d,
1,3-Bis(2-tert-butylphenyl)-2-chloro-4,5-dimethyl-1,3,2-diazaphos-
3JH,H = 2.1 Hz, 2 H, CH2-N), 2.42 (s, 6 H, o-CH3), 2.14 (s, 6 H, o-
pholene (3f): Crystallisation from a mixture of dichloromethane/
CH3) ppm. 13C{1H} NMR (CDCl3): δ = 163.7 (s, CH=N), 150.2
diethyl ether (2:1) at –20 °C; colourless crystals; yield 8.7 g (74%);
(s, i-C), 146.4 (s, i-C), 128.9 (s, m-C), 128.2 (s, o-C), 128.0 (s, m-C),
3
4
m.p. 196 °C. 1H NMR (CDCl3): δ = 7.72 (dd, JH,H = 7.0, JH,H
=
126.8 (s, p-C), 123.8 (s, o-C), 121.3 (s, p-C), 52.9 (s, CH2-N), 19.0
(s, o-CH3), 18.2 (s, o-CH3) ppm.
2.0 Hz, 2 H, CH), 7.53 (dd, 3JH,H = 7.0, 4JH,H = 2.0 Hz, 2 H, CH),
7.35 (dt, JH,H = 7.0, JH,H = 2.4 Hz, 2 H, CH), 7.31 (dt, JH,H
1,4-Bis(2-tert-butylphenyl)-2,3-dimethyl-1,4-diazabuta-2-ene (2f): 7.0, JH,H = 2.4 Hz, 2 H, CH), 1.81 (d, JP,H = 0.5 Hz, 6 H, CH3),
Compound 1f (10.4 g, 30 mmol) was dissolved in thf (300 mL), and
1.37 (s, 18 H, CH3) ppm. 13C{1H} NMR (CDCl3): δ = 147.8 (d,
lithium (0.5 g, 60 mmol) was added. The mixture was stirred for 3JP,C = 6.9 Hz, o-C), 135.0 (d, JP,C = 8.4 Hz, i-C), 134.0 (d, JP,C
3
4
3
=
4
4
2
3
4
5
24 h. The remaining lithium was filtered off, the solution cooled to
–78 °C, and triethylamine hydrochloride (6.1 g, 60 mmol) was
added. The reaction mixture was slowly warmed to room tempera-
ture, and all volatiles were removed in vacuo. The residue was dis-
solved in n-hexane (100 mL) and the insoluble portion filtered off.
The filtrate was concentrated to 30 mL and stored at –20 °C. The
yellow powder formed was filtered off and dried in vacuo. Yield
= 7.9 Hz, o-C), 129.0 (d, JP,C = 1.8 Hz, m-C), 127.8 (d, JP,C
0.8 Hz, p-C), 126.8 (d, JP,C = 1.3 Hz, m-C), 125.8 (d, JP, C
6.6 Hz, N-C), 36.0 [d, JP,C = 1.0 Hz, C(CH3)3], 32.1 (d, JP,C
=
=
=
4
2
4
5
4.1 Hz, CH3), 12.0 (d, JP,C = 3.1 Hz, CH3) ppm. 31P{1H} NMR
(CDCl3): δ = 161.9 (s) ppm. MS (EI): m/z (%) 414.2 (17.2) [M]+,
379.2 (86.2) [M – Cl]+, 174.1 (19.3) [M – C12H16NPCl]+.
C24H32ClN2P (414.96): calcd. C 69.47, H 7.77, N 6.75; found C
68.91, H 7.86, N 6.77.
3
1
3
4
9.4 g (89%). H NMR (CDCl3): δ = 7.27 (dt, JH,H = 7.8, JH,H
=
1.7 Hz, 2 H, CH), 7.12 (dd, 3JH,H = 7.8, 4JH,H = 1.7 Hz, 2 H, CH),
6.83 (dt, JH,H = 7.8, JH,H = 1.7 Hz, 2 H, CH), 6.82 (dd, JH,H
7.8, JH,H = 1.7 Hz, 2 H, CH), 5.29 (s, 2 H, NH), 1.91 (s, 6 H,
CH3), 1.37 (s, 18 H, CH3) ppm. 13C{1H} NMR (CDCl3): δ = 143.2
(s, i-C), 138.0 (s, o-C), 126.7 (s, o-CH), 126.3 (s, m-CH), 122.2 (s,
N-CCH3), 119.9 (s, m-CH), 119.2 (s, p-CH), 34.4 (s, C), 30.0 [s,
C(CH3)3], 15.7 (s, CH3) ppm.
2-Chloro-1,3-dicyclohexyl-1,3,2-diazaphospholene (3h): Crystallisa-
tion from a mixture of n-hexane and thf at –28 °C, colourless crys-
tals; yield 2.46 g (43%), m.p. 148 °C. H NMR (CDCl3): δ = 6.91
3
4
3
=
4
1
(s, 2 H, N-CH), 3.98–3.77 (m, 2 H, CH), 2.40–2.25 (m, 8 H, CH2),
1.97–1.60 (m, 8 H, CH2), 1.51–1.21 (m, 4 H, CH2) ppm. 13C{1H}
2
3
NMR (CDCl3): δ = 116.7 (d, JP,C = 8.0 Hz, N-CH), 53.5 (d, JP,C
4
5
= 11.1 Hz, CH), 29.0 (d, JP,C = 9.3 Hz, CH2), 28.1 (d, JP,C
=
2-Chloro-1,3-bis(2,6-dimethylphenyl)-1,3,2-diazaphospholene (3b):
Crystallisation from acetonitrile at –30 °C; colourless crystals; yield
1.2 Hz, CH2), 19.9 (s, CH2) ppm. 31P{1H} NMR (CDCl3): δ =
176.5 ppm. MS (EI): m/z (%) 286.1 (14.4) [M]+, 251.1 (100.0) [M –
21.2 g (92%); m.p. 184 °C. 1H NMR (CDCl3): δ = 7.18 (m, 6 H, Cl]+, 169.1 (7.7) [M – C6H10Cl]+, 87.0 (44.5) [M – C12H20Cl]+.
m/p-CH), 6.46 (s, 2 H, N-CH), 2.46 (s, 12 H, o-CH3) ppm. 13C{1H}
C14H24ClN2P (286.78): calcd. C 58.71, H 8.45, N 9.79; found C
NMR (CDCl3): δ = 136.9 (d, JP,C = 4.5 Hz, i-C), 129.5 (d, 4JP,C
=
58.55, H 8.62, N 9.65. IR: ν = 1566 (m) cm–1.
2
˜
1.3 Hz, m-C), 128.7 (s, p-C), 128.2 (s, o-C), 120.8 (d, 2JP,C = 8.4 Hz,
1,3-Bis(2,6-dimethylphenyl)-1,3,2-diazaphospholenium Trifluoro-
methanesulfonate (4b): Compound 3b (1.32 g, 4 mmol) was dis-
solved in toluene (50 mL) and cooled to –78 °C. Trimethylsilyl tri-
fluoromethanesulfonate (1.78 g, 8 mmol) was added and the solu-
tion stirred for 2 h. All volatiles were then evaporated in vacuo and
the residue dissolved twice in diethyl ether (15 mL) followed by
N-C), 19.4 (d, JP,C = 2.9 Hz, o-CH3) ppm. 31P{1H} NMR
4
(CDCl3): δ = 149.2 (s) ppm. MS (EI): m/z (%) 330.1 (23.9) [M]+,
295.2 (100.0) [M – Cl]+, 190.1 (27.5) [M – C8H9Cl]+. C18H20ClN2P
(330.80): calcd. C 65.36, H 6.09, N 8.47; found C 64.55, H 6.80, N
7.84.
2-Chloro-1,3-dimesityl-4,5-dimethyl-1,3,2-diazaphospholene (3d): removal of the solvent. The product was dissolved in diethyl ether/
Crystallisation from dichloromethane at –20 °C, colourless crystals;
yield 22.6 g (90%); m.p. 219 °C. H NMR (CDCl3): δ = 6.96 (s, 4
dichloromethane (5 mL/10 mL) and crystallised at –20 °C. The
1
colourless crystals were filtered off and dried in vacuo. Yield 1.26 g
1
H, m-CH), 2.30 (s, 6 H, p-CH3), 2.28 (s, 12 H, o-CH3), 1.82 (d,
(95%); m.p. 236 °C. H NMR (CD3CN): δ = 8.14 (s, 2 H, N-CH),
4JP,H = 1.3 Hz, 6 H, CH3) ppm. 13C{1H} NMR (CDCl3): δ = 138.7 7.53–7.35 (m, 6 H, CH), 2.23 (d, 4JP,H = 0.6 Hz, 12 H, o-CH3) ppm.
Eur. J. Inorg. Chem. 2007, 5112–5119
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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