Preparation of bicyclic phosphonic and phosphinic amides via N→C migration of phosphorus

Article abstract of DOI:10.1055/s-2000-6368

New phosphonic diamides and phosphinic amides of the 4,7,10-triaza- 1λ⁵-phosphabicyclo[5.3.0]decane and 4,7,10-triaza-1λ⁵- phosphabicyclo[5.5.0]dodecane structures were prepared from bicyclic phosphoric triamides via the lithiation-induced N→C migration of phosphorus, followed by proton or haloalkane quenching.

Full text of DOI:10.1055/s-2000-6368

PAPER
565
Preparation of Bicyclic Phosphonic and Phosphinic Amides via NÆC
Migration of Phosphorus
Zhengjie He, Tom A. Modro*
Center for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa
Fax +27(12)3625297; E-mail: tamodro@scientia.up.ac.za
Received 4 October 1999; revised 19 November 1999
An unsymmetrical, mono-N-alkylated phosphinic diam-
ide 3f could be obtained by quenching the product of the
first migration with haloalkane, and of the second migra-
tion with MeOH, respectively (Scheme 3).
Abstract: New phosphonic diamides and phosphinic amides of the
4,7,10-triaza-1l5-phosphabicyclo[5.3.0]decane and 4,7,10-triaza-
1l5-phosphabicyclo[5.5.0]dodecane structures were prepared from
bicyclic phosphoric triamides via the lithiation-induced NÆC mi-
gration of phosphorus, followed by proton or haloalkane quenching.
The N(4)-alkylated phosphonic amides 2d-2i could also
be prepared (in better yields and higher purity) by direct
alkylation of their corresponding N(4)-H precursors
2a-2c.
Key words: metallation induced rearrangement, bicyclic structures,
phosphonic diamides, phosphinic amides, N-alkylation
Products 2 and 3 represent interesting objects for further
studies. Solvolytic cleavage of the P–N bond in 3 leads to
a new, twelve-membered cyclic phosphinic ester system
with three amine nitrogen atoms in the ring.9 The P–N
bond cleavage in 2 can lead, depending on the conditions,
to new monocyclic, seven-membered phosphonic ami-
doesters, or to the noncyclic phosphonic diesters with a
side chain of the bis-(2-aminoethyl)amine functionality.10
All those compounds can be considered as polydentate
ligand structures, and their chemistry and application are
currently under investigation.
Preparation of (2-hydroxyaryl)phosphonic and phosphin-
ic derivatives from the corresponding aryl phosphate es-
ters via the OÆC migration of the phosphoryl function,
induced by ortho-lithiation was first observed by Melvin1
and developed by Dhawan and Redmore.2 The reaction
was extended to the metallation of (2-haloaryl)phos-
phates,3 and to the aromatic heterocyclic substrates,4 and
has become an accepted method for the formation of the
C(aromatic)–P bond. The work of Masson et. al. demon-
strated the applicability of the method to thiophosphates
which undergo a similar SÆC migration of phosphorus.5
We have reported previously that a similar transforma-
tion, but involving the NÆC migration of phosphorus, can
be performed using the N-phosphorylated secondary aro-
matic amines as substrates (Scheme 1).6
NMR spectra were recorded from CDCl3 solutions on a Bruker AC
300 spectrometer and the 31P chemical shifts are given relative to
85% H3PO4. Melting points are uncorrected. For column chroma-
tography, Merck Kieselgel 60 (0.063 - 0.200 mm) was used as a
stationary phase. Elemental analysis was performed at the Depart-
ment of Chemistry, University of Cape Town.
Preparation of substrates 1 was described before.7
Bicyclic Phosphonic Diamides (2a, 2b, 2c) and Phosphinic
Amides (3a, 3b) (Quenching with MeOH); General Procedure
A solution of 1 (2.0 mmol) in anhyd THF (60 - 100 mL) was cooled
to –78 °C under an atmosphere of anhyd N2. The required amount
of BuLi (1.6 M solution in hexane) was added by means of a syringe
while stirring and cooling. The solution was stirred at –78 °C for
1 h, warmed to r.t. and stirred for the required period. MeOH
(1-2 mL) was added, followed by CHCl3 (200 mL), the solution
was washed with H2O (3 x 20 mL), dried (Na2SO4) and evaporated
Scheme 1
We report now the application of such lithiation-induced
rearrangement to the recently synthesized bicyclic phos-
phoric triamide system, 2,8-diaryl-2,5,8-triaza-1l5-phos- under reduced pressure. The crude product was purified by column
phabicyclo[3.3.0]octane 1-oxide 1.7 In
a
recent
chromatography using CHCl3/acetone (1:1) as eluent. The individ-
ual products are listed in the Table.
communication we reported that the 2,8-diphenyl deriva-
tive 1a can undergo a single, or a double rearrangement
involving the NÆC migration of phosphorus, leading to
two types of new bicyclic systems.8 The reaction was now
applied to other substrates of 1, and was also modified to
give the N-alkylated rearrangement products in a one-pot
Bicyclic Phosphonic Diamides (2d, 2e, 2f,) and Phosphinic
Amides (3c, 3d, 3e) (Quenching with Haloalkane); General Pro-
cedure
A solution of 1 (2.0 mmol) was lithiated in the same manner as de-
scribed above. After warming to r.t., the solution was stirred for ad-
procedure using haloalkanes rather than MeOH in the fi- ditional 10 h, and the haloalkane (MeI or PhCH2Br, 5 mmol) was
injected into the solution while stirring and cooling with an ice bath.
nal quenching step (Scheme 2).
The reaction mixture was stirred overnight at r.t., the excess of BuLi
was destroyed by addition of MeOH (1 - 2 mL), and further workup
Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York

566
Z. He, T. A. Modro
PAPER
Scheme 2
was carried out as described above. The crude products were puri-
fied by column chromatography using gradient elution with CHCl3/
acetone (4:1 to 2:1). The individual products obtained are listed in
the Table.
Bicyclic Phosphonic Diamides (2g, 2h, 2i) (Alkylation of 2b, 2c);
General Procedure
A solution of 2 (0.3 mmol) in THF (20 mL) was treated with BuLi
(0.6 mmol) in the same manner as described above. After the addi-
tion of a haloalkane (0.6 mmol) the solution was stirred at r.t.
for 20 h. MeOH (1 mL) was then added, volatile components were
Scheme 3
Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Preparation of Bicyclic Phosphonic and Phosphinic Amides
567
Table Phosphonic Diamides 2 and Phosphinic Amides 3
Com- BuLi (equiv) Yield
pounda and reaction (g, %)
time at r.t. (h)
Mp (°C)
solvent
31P NMR 1H NMR (CDCl3)
13C NMR (CDCl3)
d, J (Hz)
d
δ, J (Hz)
2a
2b
2c
5, 2
5, 5
5, 5
0.51, 85
0.45, 63
0.39, 59
236.4–237.7
THF
23.7
3.05–3.25 (m, 2 H, NCH2),
44.9 (NCH2), 45.5 (d, JCP = 8.9, NCH2),
3.40–3.68 (m, 4 H, 2 NCH2), 46.6 (d, JCP = 10.7, NCH2), 49.8 (d, JCP
3.70–3.82 (m,1 H, NCH), 6.2, NCH2), 117.8 (d, JCP = 3.6, Carom),
3.96 (m, 1 H, NCH), 4.32 (br 118.1 (d, JCP = 11.6, Carom), 119.0 (d, JCP
=
s, 1 H, NH), 6.55–6.64 (m,
2 Harom), 7.00 (t, 1 H, JHH
= 13.4, Carom), 119.7 (d, JCP = 154.3, C2),
121.8 (s, Carom), 129.2 (s, Carom), 130.4 (d,
=
6.8, p-Harom), 7.09 (t, 1 H, JHH JCP = 7.1, Carom), 131.1 (d, JCP = 2.7,
= 6.7, p’-Harom), 7.29 (m,
3Harom), 7.43 (d, 2 H, JHH
Carom), 143.7 (d, JCP = 6.2, Carom), 149.9
(d, JCP = 6.2, Carom
=
)
6.4, 2 o-Harom
)
201.8–203.0
CHCl3/acetone
(1:1)
23.3
3.00–3.27 (m, 2 H, NCH2),
3.34 (s, 3 H, OMe), 3.39–
45.5 (d, JCP = 8.0, NCH2), 45.8 (s, NCH2),
47.3 (d, JCP = 10.7, NCH2), 49.0 (d, JCP
=
3.82 (m, 6 H, 3 NCH2), 3.75 6.2, NCH2), 55.1 (s, 3H, OCH3), 55.6 (s,
(s, 3 H, OMe’), 6.58 (dd, 1 H, OCH3’), 113.7 (d, JCP = 8.9, Carom), 114.7
J = 7.0, 8.8, Harom), 6.70 (m, (s, Carom), 119.4 (d, JCP = 2.7, Carom),
1 H, Harom), 6.76 (dd, 1 H, J = 120.2 (d, JCP = 13.4, Carom), 120.4 (d, JCP
15.3, 2.9, Harom), 6.85 (d, 2 H, = 3.6, Carom), 120.9 (d, JCP = 153.4, C2),
J = 8.8, 2 Harom), 7.34 (d, 2 H, 136.6 (d, JCP = 6.2, Carom), 143.8 (d, JCP
J = 8.6, 2 Harom 6.2, Carom), 152.8 (d, JCP = 16.0, Carom),
155.4 (s, Carom
=
)
)
208.4–209.0
CHCl3/ace-
tone (1:1)
24.0
3.01–3.27 (m, 2 H, NCH2),
3.32 (s, 3 H, OMe), 3.38–
3.45 (m, 1 H, NCH), 3.49–
45.2 (d, JCP = 8.9, NCH2), 45.7 (s, NCH2),
46.6 (d, JCP = 10.7, NCH2), 48.8 (d, JCP
6.2, NCH2), 55.1 (s, OCH3), 113.7 (d, JCP
=
3.71 (m, 4 H, 2 NCH2), 3.74– = 8.9, Carom), 117.9 (d, JCP = 3.6, Carom),
3.83 (m, 1 H, NCH), 6.59 (dd, 119.6 (d, JCP = 2.7, Carom), 120.5 (d, JCP
1 H, J = 8.8, 7.2, Harom), 6,70 13.4, Carom), 121.0 (d, JCP = 149.0, C2),
(dd, 1 H, J = 8.8, 2,8, Harom), 122.0 (s, Carom), 129.2 (s, Carom), 143.5 (d,
6.88 (dd, 1 H, J = 15.5, 2.8, JCP = 6.2, Carom), 143.7 (d, JCP = 6.2,
=
Harom), 6.97 (t, 1 H, JHH = 7.5, Carom), 153.0 (d, JCP = 15.2, Carom
)
p-Harom), 7.27 (t, 2 H, J = 7.5,
2 Harom), 7.41 (d, 2 H, J = 8.0,
Harom
)
2d
10, 10
0.25, 39
(separa-
ted from
57% of
3c)b
187.6–188.7
THF/hexane
(2:1)
28.8
2.91 (s, 3 H, NCH3), 3.11–
41.3 (s, NCH3), 44.0 (d, JCP = 8.0, NCH2),
3.50 (m, 5 H, 5 NCH), 3.60– 46.1 (d, JCP = 6.2, NCH2), 47.8 (d, JCP
3.90 (m, 3 H, 3 NCH), 6.90 11.6, NCH2), 53.8 (s, NCH2), 116.9 (d,
(m, 3 H, 3 Harom), 7.25 (m, JCP = 3.6, Carom), 117.7 (d, JCP = 9.8,
4 H, 4 Harom), 7.35 (m, 1 H, Carom), 121.2 (s, Carom), 121.3 (d, JCP
=
=
Harom), 7.80 (ddd, 1 H, JHP
14.2, JHH = 7.5, 1.5, Harom
ortho to P)
=
13.4, Carom), 123.3 (d, JCP = 149.0, C2),
129.0 (s, Carom), 132.7 (d, JCP = 2.7,
Carom), 134.4 (d, JCP = 7.1, Carom), 143.1
(d, JCP = 7.1, Carom), 151.8 (d, JCP 7.1,
Carom
)
2e
10, 10
0.22, 29
(separa-
ted from
39% of
3d)c
199.2–201.6
THF/hexane
(2:1)
27.2
2.98–3.15 (m, 2 H, 2 NCH), 44.1 (d, JCP = 8.0, NCH2), 46.0 (d, JCP =
3.42 (m, 3 H, 3 NCH), 3.50– 6.2, NCH2), 46.7 (d, JCP = 10.7, NCH2),
3.81 (m, 3 H, 3 NCH), 4.38 51.3 (s, NCH2), 57.2 (s, CH2Ph), 117.2
(d, 1 H, JHH = 15.0, NCHPh), (d, JCP = 4.5, Carom), 118.8 (d, JCP = 10.7,
4.53 (d, 1 H, JHH = 15.0,
Carom), 121.4 (d, JCP = 13.4, Carom), 121.5
NCHPh), 6.83–6.99 (m, 3 H, (s, Carom), 124.0 (d, JCP = 150.8, C2),
3 Harom), 7.16–7.33 (m, 10 H, 127.2 (s, Carom), 127.9 (s, Carom), 128.5 (s,
10 Harom), 7.72 (ddd, 1 H, JHP Carom), 129.2 (s, Carom), 132.4 (d, JCP
= 14.5, JHH = 7.8, 1.8, Harom 2.7, Carom), 133.6 (d, JCP = 7.1, Carom),
ortho to P) 137.8 (s, Carom), 143.2 (d, JCP = 6.2,
Carom), 151.4 (d, JCP = 6.2, Carom
=
)
Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York

568
Z. He, T. A. Modro
PAPER
Table (continued)
Com- BuLi (equiv) Yield
pounda and reaction (g, %)
time at r.t. (h)
Mp (°C)
solvent
31P NMR 1H NMR (CDCl3)
13C NMR (CDCl3)
δ, J (Hz)
d
d, J (Hz)
2f
5, 10
0.33, 44
183.3–185.0
28.8
2.85 (s, 3 H, NCH3), 2.95–
41.7 (s, NCH3), 43.7 (d, JCP = 8.9, NCH2),
(separa-
THF
3.38 (m, 4 H, 4 NCH), 3.55– 45.5 (d, JCP = 5.3, NCH2), 48.7 (d, JCP =
ted from
13% of 3e)
3.75 (m, 4 H, 4 NCH), 3.63 12.5, NCH2), 53.7 (s, NCH2), 55.5 (s,
(s, 3 H, OCH3), 3.71 (s, 3 H, OCH3), 55.6 (s, OCH3), 114.5 (s, Carom),
OCH3’), 6.76 (dt, 2 H, JHH
9.0, 2.1, 2 Harom), 6.92 (m,
2 H, 2 Harom), 7.15 (dt, 2 H, 119.9 (d, JCP = 2.7, Carom), 125.1 (d, JCP
JHH = 9.0, 2.1, 2 Harom), 7.32 148.1, C2), 136.2 (d, JCP = 7.1, Carom),
=
118.6 (d, JCP = 8.0, Carom), 118.9 (d, JCP
3.6, Carom), 119.7 (d, JCP = 12.5, Carom),
=
=
=
(dd, 1 H, JHP = 14.7, JHH
3.1, 1 Harom
=
145.3 (d, JCP = 6.2, Carom), 154.6 (d, JCP
16.0, Carom), 154.7 (s, Carom
)
)
2g
d
0.10, 75
153.4–155.9
27.4
2.95–3.17 (m, 3 H, 3 NCH), 43.6 (d, JCP = 8.0, NCH2), 45.1 (d, JCP =
(decomp.)
3.34 (m,2 H, 2 NCH), 3.52
(m, 1 H, NCH), 3.63–3.83
(m, 2 H, 2 NCH), 3.58 (s,
3 H, OCH3), 3.74 (s, 3 H,
6.2, NCH2), 47.2 (d, JCP = 11.6, NCH2),
54.1 (s, NCH2), 55.5 (s, OCH3), 55.6 (s,
OCH3), 57.7 (s, NCH2Ph), 114.6 (s, Car-
om), 117.8 (d, JCP = 8.9, Carom), 119.2 (d,
JCP = 3.6, Carom) 119.7 (d, JCP = 2.7, Carom),
OCH3’), 4.26 (d, 1 H, JHH
=
14.7, NCHPh), 4.45 (d, 1 H, 120.9 (d, JCP = 12.5, Carom), 125.9 (d, JCP
JHH= 14.7, NCHPh), 6.80– 149.8, C2), 126.9 (s, Carom), 128.1 (s, Car-
6.93 (m, 4 H, 4 Harom), 7.10– om), 128.3 (s, Carom), 136.3 (d, JCP = 6.2,
7.27 (m, 7 H, 7 Harom), 7.29 Carom), 138.0 (s, Carom), 144.6 (d, JCP = 5.4,
=
(dd, 1 H, JHP = 15.0, JHH
2.8, Harom ortho to P)
=
Carom), 154.6 (d, JCP = 16.0, Carom), 154.9
(s, Carom
)
2h
d
0.080, 78 161.4–162.9
THF/hexane
29.6
2.80 (s, 3 H, NCH3), 3.20–
3.40 (m, 4 H, 4 NCH), 3.59– 45.4 (d, JCP = 5.4, NCH2), 48.1 (d, JCP
41.8 (s, NCH3), 43.4 (d, JCP = 8.9, NCH2),
=
(1:1)
3.79 (m, 3 H, 3 NCH), 3.65 12.5, NCH2), 53.7 (s, NCH2), 55.6 (s,
(s, 3 H, OCH3), 3.88 (m, 1 H, OCH3), 116.6 (d, JCP = 4.5, Carom), 119.0
NCH), 6.80–6.93 (m, 3 H,
3 Harom), 7.20 (m, 4 H, 4
Harom), 7.46 (m, 1 H, Harom
(d, JCP = 8.9, Carom), 120.0 (d, JCP = 10.7,
Carom), 120.1 (d, JCP = 1.8, Carom), 121.1 (s,
Carom), 125.3 (d, JCP = 149.2, C2), 129.0 (s,
Carom), 142.8 (d, JCP = 6.2, Carom), 145.2 (d,
JCP = 5.3, Carom), 154.9 (d, JCP = 15.2, Car-
)
)
om
2i
d
0.104, 83 174.2–175.3
THF/hexane
27.9
2.92–3.16 (m, 3 H, 3 NCH), 43.4 (d, JCP = 8.0, NCH2), 45.2 (d, JCP =
3.34 (m, 2 H, 2 NCH), 3.50– 5.3, NCH2), 46.8 (d, JCP = 11.6, NCH2),
3.85 (m, 3 H, 3 NCH), 3.58 51.5 (s, NCH2), 55.5 (s, OCH3), 57.9 (s,
(s, 3 H, OCH3), 4.22 (d, 1H, NCH2Ph), 117.0 (d, JCP = 4.5, Carom),
(1:1)
JHH = 14.5, NCHPh), 4.40 (d, 118.3 (d, JCP = 8.9, Carom), 120.0 (d, JCP
1 H, JHH = 14.5, NCHPh), 1.8, Carom), 121.2 (d, JCP = 10.7, Carom),
=
6.81–6.94 (m, 3 H, 3 Harom), 121.3 (s, Carom), 125.9 (d, JCP = 149.0, C2),
7.04–7.26 (m, 9 H, 9 Harom), 127.1 (s, Carom), 128.2 (s, Carom), 128.3 (s,
7.39 (dd, 1 H, JHP = 15.2, JHH Carom), 129.2 (s, Carom), 137.9 (s, Carom),
= 2.8, Harom ortho to P)
142.9 (d, JCP = 6.2, Carom), 144.7 (d, JCP
6.2, Carom), 154.9 (d, JCP = 16.0, Carom
=
)
3a
20, 10
0.30, 50
253.6–254.3
CHCl3
(decomp)
33.1
3.12 (m, 2 H, 2 NCH), 3.41 47.7 (s, NCH2), 53.1 (d, JCP = 2.7, NCH2),
(m, 2 H, 2 NCH), 3.63 (m, 4 119.2 (d, JCP = 8.9, Carom), 120.1 (d, JCP
H 4 NCH), 4,06 (br s, 2 H, 2 12.5, Carom), 120.8 (d, JCP = 121.3, C2,
=
NH), 6.67 (dd, 2 H, JHH = 7.8, C12), 132.2 (d, JCP = 1.8, Carom), 133.9 (d,
5.4, 2 Harom meta to P), 6.83 JCP = 8.9, Carom), 153.3 (d, JCP = 4.5, Carom
(dd, 2 H, JHH = 7.5, 1.3, 2
)
Harom meta’ to P), 7.73 (m,
2 H, 2 Harom para to P), 7.41
(ddd, 2 H, JHP = 14.3, JHH
=
7.8, 1.6, 2 Harom ortho to P)
Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Preparation of Bicyclic Phosphonic and Phosphinic Amides
569
Table (continued)
Com- BuLi (equiv) Yield
pounda and reaction (g, %)
time at r.t. (h)
Mp (°C)
solvent
31P NMR 1H NMR (CDCl3)
13C NMR (CDCl3)
δ, J (Hz)
d
d, J (Hz)
3b
5, 5
0.11 15
(separa-
ted from
63% of
2b)
ca 80
(softening)
32.4
3.04 (m, 2 H, 2 NCH), 3.33 48.4 (s, NCH2), 51.4 (d, JCP = 3.6, NCH2),
(m, 4 H, 4 NCH), 3.57–3.68 55.7 (s, OCH3), 117.6 (d, JCP = 10.6, Car-
(m, 2 H, 2 NCH), 3.66 (s, 6 H, om), 119.4 (d, JCP = 1.8, Carom), 122.7 (d,
2 OCH3), 6.72 (dd, 2 H, JHH
=
JCP = 11.6, Carom), 124.3 (d, JCP = 126.7,
C2, C12), 143.1 (d, JCP = 4.5, Carom), 154.5
8.6, 6.0, 2 Harom), 6.82 (dd,
2 H, JHH = 8.6, 2.8, 2 Harom), (d, JCP = 15.2, Carom
7.07 (dd, 2 H, JHP = 14.7, JHH
)
= 2.8, 2 Harom ortho to P)
3c
10, 10
0.37, 57
144.4–146.3
(not recry-
stallized)
32.1
2.70 (s, 6 H, 2 NCH3), 3.02 39.8 (s, NCH3), 50,9 (d, JCP = 4.5, NCH2),
(m, 2 H, 2 NCH), 3.19 (m, 56.3 (s, NCH2), 116.4 (d, JCP = 8.0 Carom),
2 H, 2 NCH), 3.33 (m, 2 H, 120.3 (d, JCP = 13.4, Carom), 125.3 (d, JCP
2 NCH), 3.50 (m, 2H,
2 NCH), 6.80 (m, 4 H, 4
= 130.2, C2, C12), 131.8 (d, JCP = 1.8, Car-
om), 132.9 (d, JCP = 9.8, Carom), 151.9 (d,
Harom), 7.28 (m, 2 H, 2 Harom), JCP = 4.5, Carom
7.38 (ddd, 2 H, JHP = 14.5,
JHH = 7.5, 1.6, 2 Harom ortho to
P)
)
3d
10,10
0.38, 39
70.0–74.5
(not recry-
stallized)
32.6
2.70–2.89 (m, 2 H, 2 NCH), 50.4 (d, JCP = 4.5, NCH2), 53.2 (s, NCH-
3.21–3.49 (m, 6 H, 6 NCH), Ph), 56.7 (s, NCH2), 117.8 (d, JCP = 8.0,
4.16 (d, 1 H, JHH = 14.5,
NCHPh), 4.34 (d, 1 H, JHH
Carom), 120.7 (d, JCP = 12.5, Carom), 124.3
(d, JCP = 130.2, C2, C12), 127.1 (s, Carom),
=
14.5, NCHPh), 6.84 (m, 4 H, 128.0 (s, Carom), 128.4 (s, Carom), 132.1 (d,
4 Harom), 6.90–6.98 (m, 4 H, JCP = 0.9, Carom), 133.5 (d, JCP = 9.8, Car-
4 Harom), 7.18 (m, 6 H, 6
Harom), 7.36 (m, 2 H, 2 Harom), Carom
7.57 (m, 2 H, 2 Harom
om), 137.9 (s, Carom), 151.8 (d, JCP = 4.5,
)
)
3e
3f
5, 10
0.10, 13
0.15, 48
viscous
oil
33.6
31.8
2.67 (s, 6 H, 2 NCH3), 2.90– 40.4 (s, NCH3), 50.1 (br s, NCH2), 55.6 (s,
3.18 (m, 4 H, 4 NCH), 3.36 NCH2), 56.4 (s, OCH3), 117.3 (d, JCP
=
(m, 2 H, 2 NCH), 3.54–3.70 10.7, Carom), 118.5 (d, JCP = 1.8, Carom),
(m, 2 H, 2 NCH), 3.62 (s, 6 H, 118.6 (d, JCP = 9.8, Carom), 127.2 (d, JCP
=
2 OCH3), 6.79–6.95 (m, 6 H, 128.4, C2, C12), 145.4 (s, Carom), 154.3 (d,
6 Harom JCP = 15.2, Carom
)
)
2.5, 5
252.2–254.4
CHCl3
(decomp)
2.48 (s, 3 H, NCH3), 2.63 (dt, 40.1 (s, NCH3), 46.6 (s, NCH), 50.6 (d,
1 H, JHH = 11.2, 2.9, NCH), JCP = 4.8, NCH), 54.2 (d, JCP = 2.9, NCH),
2.90 (m, 1 H, NCH), 3.07 (m, 56.7 (s, NCH), 116.9 (d, JCP = 9.5, Carom),
1 H, NCH), 3.24 (dt, 1 H, JHH 118.1 (d, JCP = 13.4, Carom), 118.7 (d, JCP
= 11.3, 4.1, NCH), 3.42 (m, = 7.6, Carom), 120.7 (d, JCP = 128.8, C2),
2 H, 2 NCH), 3.72 (m, 1 H, 122.0 (d, JCP = 12.4, Carom), 125.6 (d, JCP
NCH), 4.04 (m, 1 H, NCH), = 128.8, C12), 130.4 (d, JCP = 1.9, Carom),
4.57 (br s, 1 H, NH), 6.47 (m, 131.5 (d, JCP = 11.4, Carom), 133.3 (d, JCP
1 H, Harom), 6.59 (dd, 1 H, JHH = 1.0, Carom), 134.3 (d, JCP = 7.6, Carom),
= 7.5, 5.6, Harom), 6.70 (ddd, 151.0 (d, JCP = 4.8, Carom), 151.5 (d, JCP
=
1 H, JHP = 15.6, JHH = 7.6, 1.2, 2.9, Carom
)
Harom ortho to P), 6.87 (dd,
1 H, JHH = 7.5, 5.4, Harom),
7.00 (m, 1 H, Harom), 7.13 (m,
1 H, Harom), 7.46 (m, 1 H,
Harom), 8.01 (ddd, 1 H, JCP
13.0, JHH = 7.5, 1.2, Harom
ortho to P)
=
a Satisfactory elemental analyses were obtained for each compound.
b Prepared also in 87% by direct methylation of 2a.
c Prepared also in 86% by direct benzylation of 2a.
d Prepared by direct alkylation of the corresponding 2 (see General Procedure).
Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York

570
Z. He, T. A. Modro
PAPER
Dhawan, B.; Redmore, D. Phosphorus, Sulfur, Silicon Rel.
removed under reduced pressure, CHCl3 (40 mL) was added and the
solution was washed with H2O (2 x 5 mL). After drying (Na2SO4)
and evaporation of the solvent, the products were purified by col-
umn chromatography (CHCl3/acetone, 4:1) and/or crystallization.
The individual products obtained are listed in the Table.
Elem. 1989, 42, 177.
(3) Heinicke, J.; Böhle, I.; Tzschach, A. J. Organomet. Chem.
1986, 317, 11.
Heinicke, J.; Kadyrov, R.; Kellner, K.; Nietzschmann, E.;
Tzschach, A. Phosphorus, Sulfur, Silicon Rel. Elem. 1989, 44,
209.
2,3,11,12-Dibenzo-4-methyl-4,7,10-triaza-1l5-phosphabicyc-
lo[5.5.0]dodecane 1-Oxide (3f)
(4) Paladino, J.; Guyard, C.; Thurieau, C.; Fauchere, J.L. Helv.
Chim. Acta 1993, 76, 2465.
A solution of 2d (0.313 g, 1.0 mmol) in THF (40 mL) was cooled to
–78 °C under the atmosphere of anhyd N2. BuLi (1.6 mL of 1.6 M
solution in hexane, 2.5 mmol) was added with stirring and cooling.
The solution was stirred at –78 °C for 1 h, warmed up to r.t. and
stirred for additional 5 h. MeOH (1 mL) was added, followed by
CHCl3 (50 mL), the solution was washed with H2O (2 x 10 mL),
dried (Na2SO4) and evaporated under reduced pressure. The product
was purified by column chromatography using CHCl3/acetone (2:1)
as eluent. The data for the pure product are given in the Table.
Onys’ko, P. P.; Suvalova, E. A.; Chudakova, T. I.; Sinitsa, A.
D. Heteroat. Chem.1993, 4, 361.
Onys’ko, P. P.; Suvalova, E. A.; Chudakova, T. I.; Sinitsa, A.
D. Russ. J. Gen. Chem. 1994, 64, 554.
(5) Masson, S.; Saint-Clair, J.-F.; Saquet, M. Tetrahedron Lett.
1994, 35, 3083.
Masson, S.; Saint-Clair, J.-F.; Dore, A.; Saquet, M. Bull. Soc.
Chim. Fr. 1996, 133, 951
(6) Jardine, M. A.; Vather, S. M.; Modro, T. A. J. Org. Chem.
1988, 53, 3983.
Acknowledgement
(7) Wan, H.; Modro, T. A. Synthesis 1996, 1227.
(8) Bourne, S. A.; He, Z.; Modro, T. A.; Van Rooyen, P. H. Chem.
Commun. 1999, 853.
(9) Bourne, S. A.; He, Z.; Modro, T. A. J. Mol. Str. 1999, 475,
161.
We gratefully acknowledge financial support of this work by the
University of Pretoria and the National Research Foundation.
(10) He, Z.; Modro, T. A. J. Chem. Res. (S) 1999, 656.
References
(1) Melvin, N. S. Tetrahedron Lett. 1981, 22, 3375.
(2) Dhawan, B.; Redmore, D. J. Org. Chem. 1984, 49, 4018.
Dhawan, B.; Redmore, D. J. Org. Chem. 1986, 51, 179.
Article Identifier:
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Synthesis 2000, No. 4, 565–570 ISSN 0039-7881 © Thieme Stuttgart · New York