2
PAPER
π-Excess σ P,O Ligands
1777
ture of 50 °C, and the more volatile 7 was separated by distillation.
The residue was almost pure 6 (≥95 mol%, based on t-Bu integra-
tion), which solidified to give a colorless solid; corrected yield: 1.0
g (63%); mp 158 °C.
2-tert-Butyl-4-methoxy-1H-1,3-benzazaphosphole–(2R)-2-tert-
butyl-4-methoxy-2,3-dihydro-1H-1,3-benzazaphosphole 3-Ox-
ide–Benzene-d Cocrystallizate (3:1:2) (10)
6
A crystal of cocrystallizate 10 measuring 0.19 × 0.12 × 0.05 mm
was mounted on a glass fiber in inert oil and transferred to the cold
gas stream [100(2) K]. Data were recorded on a Bruker SMART
The distillate consisted of slightly contaminated colorless liquid 7
[
yield: ~200 mg (~12%)], which was used in the reaction with (di-
6000 CCDC diffractometer using Cu Kα radiation, λ = 1.54184 Å,
methoxymethyl)dimethylamine without further purification.
to θ = 66.9° (96.8% complete to 66.5°). The crystal was a nonmero-
hedral twin by 180° rotation about c*, associated presumably with
the closeness of α and β to 90°. Absorption corrections were applied
by using multiple scans, with transmissions 0.925–0.792. The struc-
ture was refined by using SHELXL-97 by full-matrix least-squares
6
1
4
H NMR (C D ): δ = 1.50 (d, J = 1.2 Hz, 9 H, CH ), 3.97 (s, 3 H,
6
6
3
3
4
4
OCH ), 6.51 (ddd, J = 7.5, J = 3.3, J = 0.7 Hz, 1 H, H-7), 7.17
3
PH
3
4
4
3
(dt, J = 8.2, J = 1.5, J = 0.7 Hz, 1 H, H-5), 7.24 (t, J = 8.2, 7.5
PH
2 24
on F . Hydrogen atom treatment: All hydrogen atoms at N, P3, C2
Hz, 1 H, H-6), 9.10 (br s, NH).
were clearly identified; NH und PH hydrogen atoms were freely re-
fined (although the PH bond was slightly short). Methyl groups
were refined as idealized rigid groups allowed to rotate but not to
tip; all other hydrogen atoms were included by using a riding model
starting from the calculated positions. The final R indices were [I >
2σ(I)] R1 = 0.0365, (all data) wR2 = 0.1018, for 696 parameters;
1
3
1
3
C{ H} (DEPT) NMR (C D ): δ = 31.42 (d, J = 9.0 Hz, CMe ),
6
6
3
2
3
3
5.73 (d, J = 13.0 Hz, C Me ), 55.33 (s, OCH ), 99.32 (d, J = 6.3
q 3 3
4
Hz, CH-5), 106.24 (s, CH-7), 125.59 (d, J = 2.0 Hz, CH-6), 129.86
1
2
(
d, J = 42.1 Hz, C -3a), 143.76 (d, J = 5.1 Hz, C -7a), 159.64 (d,
J = 10.8 Hz, C -4), 189.97 (d, J = 57.6 Hz, C -2).
q
q
2
1
q
q
2
−3
31
1
S(F ) = 1.05, largest diff. peak and hole 0.49 and −0.30 e A .
P{ H} NMR (C D ): δ = 56.8.
6
6
Crystal data:25 Triclinic, space group P1, a = 10.9825(4), b =
+
MS (EI, 70 eV, 140 °C): m/z (%) = 222 (11), 221 (69) [M ], 207
13), 206 (100), 182 (70), 168 (26).
1
6
4.7958(5), c = 19.2873(7) Å, α = 89.739(2), β = 89.818(2), γ =
(
3
3
−1
8.579(2)°, 2917.56(18) Å , Z = 2, D = 1.220 Mg/m , μ = 1.6 mm ,
x
HRMS (ESI in MeOH–H O, HCO H): m/z calcd for C H NOP
2
2
12 16
F(000) = 1132.
+
(
221.24): [M + H]+ 222.10423, [M + Na] 244.08617; found:
222.10434, 244.08631.
Acknowledgment
7
1
H NMR (C D ): δ = 0.85 (s, 9 H, CH ), 2.76 (s, 2 H, NCH ), 3.39
6
6
3
2
Support of this study by the Deutsche Forschungsgemeinschaft (HE
1997/12) is gratefully acknowledged. We thank Dr. M. K. Kinder-
mann, B. Witt, and M. Steinich for recording the NMR and mass
spectra, and Dr. H. Frauendorf and G. Sommer-Udvarnoki (Georg-
August-Universität Göttingen, Institut für Organische und Biomo-
lekulare Chemie) for performing the HRMS measurements.
1
(s, 3 H, OCH ), 3.64 (d, J = 205.3 Hz, PH ), 4.20 (br s, NH), 6.14
3
2
3
4
4
3
(
dd, J = 8.2, J + J = 1.8 Hz, 1 H, H-4 or H-6), 6.35 (dd, J = 8.2,
PH
4
4
3
JPH + J = 2.6 Hz, 1 H, H-4 or H-6), 7.18 (t, J = 8.2 Hz 1 H, H-5).
13
1
C{ H} and DEPT135 NMR (C D ): δ = 28.30 (s, CMe ), 32.49 (s,
6
6
3
1
C Me ), 56.02 (s, OCH ), 56.76 (s, NCH ), 99.20 (d, J = 11.6 Hz,
C -2), 100.44 (d, J = 0.7 Hz, CH-6 or 4), 105.13 (d, J = 1.5 Hz,
CH-4 or 6), 131.43 (s, CH-5), 153.50 (d, J = 8.0 Hz, C -1), 163.10
q
3
3
2
3
3
q
2
q
2
(d, J = 5.4 Hz, C -3).
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
q
m
tgioSrantnugIifoop
r
itmnatr
31
1
P{ H} NMR (C D ): δ = –178.3.
6
6
+
MS (EI, 70 eV): m/z (%) = 226 (7), 225 (44) [M ], 168 (100), 166
18), 136 (27).
(
References
(
1) Current address: Novartis Pharma AG, CH-4056 Basel,
1
-(2,2-Dimethylpropyl)-4-methoxy-1H-1,3-benzazaphosphole
8)
Phosphine 7 (150 mg, 0.67 mmol) and Me NCH(OMe) (0.09 mL,
(
Switzerland.
2
2
(2) (a) Heinicke, J. Trends Organomet. Chem. 1994, 1, 307.
(b) Bansal, R. K.; Heinicke, J. Chem. Rev. 2001, 101, 3549.
(3) Schmidpeter, A. In Comprehensive Heterocyclic Chemistry
II; Vol. 3; Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V.,
Eds.; Pergamon: Oxford, 1996, 709.
(4) (a) Multiple Bonds and Low Coordination in Phosphorus
Chemistry; Regitz, M.; Scherer, O. J., Eds.; Thieme:
Stuttgart, 1990. (b) Phosphorus-Carbon Heterocyclic
Chemistry: The Rise of a New Domain; Mathey, F., Ed.;
Elsevier Science: Amsterdam, 2001. (c) Le Floch, P. Coord.
Chem. Rev. 2006, 250, 627. (d) Müller, C.; Vogt, D. C. R.
Chim. 2010, 13, 1127.
0.73 mmol) were heated at 60 °C for 2 d. Excess Me NCH(OMe)
2 2
was removed in vacuum, and the residue was dissolved in Et O (10
mL). The soln was washed with cold degassed 10% aq H SO (2
mL). The Et O layer was washed with degassed H O (2 × 2 mL),
dried (Na SO ), and separated from the drying agent. Removal of
the solvent under vacuum gave an oily product contaminated with a
minor impurity (≤10%); yield: 135 mg (corrected yield: 80%).
2
2
4
2
2
2
4
1
H NMR (CDCl ): δ = 1.02 (s, 9 H, CMe ), 4.01 (s, 3 H, OCH ),
3
3
3
3
4
4.09 (s, 2 H, NCH ), 6.55 (dd br, J = 7.5, Hz, J = 3.4 Hz, 1 H,
2
P
H
3
3
H-5), 7.22 (d br, J = 8.6 Hz, 1 H, H-7), 7.31 (t br, J = 8.5, 7.5 Hz,
1
2
H, H-6), 8.37 (d, J = 38.4 Hz, 1 H, H-2).
PH
1
3
1
(5) (a) Nyulászi, L. Chem. Rev. 2001, 101, 1229. (b) Nyulászi,
L.; Veszprémi, T. J. Mol. Struct.: THEOCHEM 1995, 347,
57. (c) Nyulászi, L.; Csonka Réffy, J.; Veszprémi, T.;
Heinicke, J. J. Organomet. Chem. 1989, 373, 49.
(6) Schmidpeter, A.; Karaghiosoff, K. In CRC Handbook of
Phosphorus-31 Nuclear Magnetic Resonance Data; Tebby,
J. C., Ed.; CRC Press: Boca Raton, 1991, 29.
C{ H} and DEPT135 NMR (CDCl ): δ = 28.34 (s, CH ), 34.55 (d,
3
3
4
3
J = 0.8 Hz, CMe ), 55.50 (s, OCH ), 61.20 (d, J = 3.0 Hz, NCH ),
8.92 (d, J = 6.6 Hz, CH-5), 106.83 (s, CH-7), 125.61 (d, J = 2.3
3
3
2
3
4
9
1
2
Hz, H-6), 131.65 (d, J = 40.3 Hz, C -3a), 145.14 (d, J = 5.5 Hz,
C -7a), 159.81 (d, J = 10.6 Hz, C -4), 162.15 (d, J = 51.4 Hz, CH-
2
q
2
1
q
q
).
31
1
P{ H} NMR (CDCl ): δ = 61.5.
3
(
7) (a) Heinicke, J. Tetrahedron Lett. 1986, 27, 5699.
(b) Surana, A.; Singh, S.; Bansal, R. K.; Peulecke, N.;
Spannenberg, A.; Heinicke, J. J. Organomet. Chem. 2002,
+
+
MS (EI, 70 eV, 100 °C): m/z (%) = 236 (15) [M ], 236 (100) [M ],
78 (88), 136 (72).
1
6
46, 113. (c) Aluri, B. R.; Burck, S.; Gudat, D.; Niemeyer,
HRMS (ESI in MeOH, H O, HCO H): m/z calcd for C H NOP
(
2
2
13 18
235.26): [M + H]+ 236.11988, [M + Na] 258.10182; found:
+
M.; Holloczki, O.; Nyulászi, L.; Jones, P. G.; Heinicke, J.
Chem. Eur. J. 2009, 15, 12263.
236.11990, 258.10195.
©
Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 1773–1778