The first synthesis of ferrocenyl aminophosphonic esters

Article abstract of DOI:10.1016/S0022-328X(01)01011-7

The series of aminophosphonates bearing the ferrocenyl moiety was obtained by the addition of dialkyl phosphites to an azomethine bond of Schiff bases. Some successful attempts to perform the asymmetrical synthesis of aminophosphonates were made, but the

Full text of DOI:10.1016/S0022-328X(01)01011-7

Journal of Organometallic Chemistry 631 (2001) 105–109
www.elsevier.com/locate/jorganchem
The first synthesis of ferrocenyl aminophosphonic esters
Jarosław Lewkowski *, Monika Rzez´niczak, Romuald Skowron´ski, Janusz Zakrzewski
Department of Organic Chemistry, Uni6ersity of Ło´dz´, Narutowicza 68, 90-136 Lodz, Poland
Received 19 March 2001; accepted 30 May 2001
Abstract
The series of aminophosphonates bearing the ferrocenyl moiety was obtained by the addition of dialkyl phosphites to an
azomethine bond of Schiff bases. Some successful attempts to perform the asymmetrical synthesis of aminophosphonates were
made, but the isolation of diastereomers failed. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ferrocenecarboxaldehyde; Schiff bases; Aminophosphonates; Asymmetrical induction; Ferrocene moiety
cenylalanine. Much later, Carlstro¨m and Frejd [22,23]
and Jackson et al. [24] presented the stereoselective
synthesis of 1,1%-ferrocenyl-bis-(alanine). Brunner et al.
[25] reported the synthesis of the optically active ferro-
cenylalanine and suggested its application as a possible
substitute for phenylalanine in the commercial sweet-
ener aspartame. Kraatz et al. [26] have proposed the
synthesis and the structural study on ferrocenoyl amino
acids.
Regarding all the above, we wanted to combine
properties of mentioned groups of compounds and to
synthesize aminophosphonic acids and esters bearing a
ferrocenyl moiety. In this paper, we present the first
synthesis of variously N-substituted ferrocenyl-
aminomethane phosphonic acids and esters using the
methodology described by Tyka [4]. These compounds
may eventually show potential properties as plant-pro-
tection agents or anti-tumour drugs.
1. Introduction
The importance of aminophosphonic acids and esters
is commonly known. After the first preparation [1–3] of
various phosphono-analogues of natural amino acids,
one could notice the great development of their chem-
istry in the aspect of the synthesis [4–6], the stereo-
chemistry [7–9], biochemical properties [10,11] and
their applications in various fields of agriculture and
medicine [12–14].
Since the last decade ferrocene-derived compounds
have been widely employed in the molecular recogni-
tion, because they are characterized by their ability to
make metal-centred redox systems to generate oxidized
or reduced form of different properties, as described by
E.C. Constable [15]. For the formation of such molecu-
lar switches containing a ferrocene moiety, it was pro-
posed
ferrocenemethanol [15], derivatives of (ferrocenyl-
methyl)malonate [16] and ferrocene-containing
to
use
dihydrocholesteryl
ester
of
thioethers [17] as well as some derivatives of ferrocenyl-
methylamines [18] and ferrocenyl ligands containing the
tetrathiafulvalene molecules [19].
In late 1950s, Schlo¨gl [20] and Osgerby and Pauson
[21] reported the first synthesis of the racemic ferro-
2. Results and discussion
Ferrocenylaminophosphonates were synthesized by
the addition of dialkyl phosphites to the azomethine
bond of Schiff bases. As the model compounds, diethyl,
dibenzyl and diphenyl phosphites were chosen (Scheme
1).
* Corresponding author. Tel.: +48-42-678-4731; fax: +48-42-678-
6583.
E-mail address: jlewkow@krysia.uni.lodz.pl (J. Lewkowski).
Schiff bases of ferrocenecarboxaldehyde 2a–e were
prepared following the known methodology [6,27].
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01011-7

106
J. Lewkowski et al. / Journal of Organometallic Chemistry 631 (2001) 105–109
They were characterized by means of elemental analy-
ses and H-NMR spectroscopy.
ucts of the reaction were the starting ferrocenecarbox-
aldehyde 1 and the corresponding amine.
1
The phosphite additions were carried out in toluene
or in acetonitrile at a boiling temperature for 5–7 h.
Esters were isolated from the post-reaction mixture by
the multiple washing with ether of their aqueous acidic
solution and by subsequent extraction of the alkaline
aqueous mixture with dichloromethane. Resulting
crude esters decomposed on silica gel and on neutral
aluminium oxide. The esters 3a–k were purified by the
column chromatography on cellulose powder. In this
way, we have obtained N-substituted diethyl and diben-
zyl ferrocenyl aminomethanephosphonates 3a–j and
We are searching for a more suitable method for the
synthesis of ferrocene-derived aminophosphonic acids,
as they are of interest as the starting material for the
synthesis of their derivatives bearing such biomolecules
as steroids or nucleosides. This is why the problem is
still under study.
3. Experimental
All solvents were routinely distilled and dried prior to
use. Amines (Aldrich), phosphites (Aldrich) and fer-
rocenecarboxaldehyde (Aldrich) were used as received.
Cellulose powder was provided by Aldrich. All NMR
spectra were recorded on a Brucker Gemini 200 BB
1
diphenyl one 3k. The H- and 31P-NMR spectroscopy
and the elemental analysis confirmed their identity and
their purity.
Diphenyl aminophosphonates 3l–n decomposed in
the above-described conditions. Their isolation was
then very troublesome and their formation was confi-
rmed only by spectroscopic measurements of post-reac-
tion mixtures. Their data are quoted in Section 3.
The addition of dialkyl phosphites to the chiral N-
(R)-a-methylbenzyl ferrocenecarbimine 2e led to the
formation of two diastereoisomers of diethyl N-(R)-a-
methylbenzylamino(ferrocenyl)methanephosphonate 3i
in a 1:3 ratio or dibenzyl N-(R)-a-methylbenzylamino(-
ferrocenyl)methanephosphonate 3j in a 2:5 ratio, which
1
spectrometer operating at 200 MHz for H-NMR and
at 81 MHz for 31P-NMR. Elemental analyses were
performed in the Laboratory of Microanalysis at the
Centre of Molecular and Macromolecular Studies in
Ło´dz´.
3.1. Schiff bases of ferrocenecarboxaldehyde
To a solution of ferrocenecarboxaldehyde (1.07 g, 5
mmol) in methanol (30 ml), an amine (5 mmol) was
added. The mixture was then stirred for 20 h at a room
temperature (r.t.), then the mixture was evaporated, the
solid residue dissolved in benzene and precipitated with
hexane to give a pure product as red–brown crystals.
1
was demonstrated by means of the H- and 31P-NMR
spectroscopy. Unfortunately, diastereoisomers were not
separated due to their fragility to silica gel and cellulose
powder was found not efficient enough to provide a
good resolution of diastereoisomers.
All attempts to hydrolyse ethyl esters 3a, 3c, 3e, 3g
and 3i failed. We tried to use acidic cleavage with
aqueous hydrochloric acid as well as the known [6]
method with trimethylsilyl bromide. Both methods led
to a variety of products, among which, we identified
phosphoric acid derivatives. The rest remained
unidentified.
Attempts were made to cleave diethyl esters with
aqueous sodium hydroxide but instead of this, the
retro-addition reaction was observed. The main prod-
3.1.1. N-Ferrocenylidenebenzylamine (2a)
Y=1.46 g (96%); m.p: 99–102 °C (benzene–hexane,
1:1).
1H-NMR (200 MHz, CDCl3): l 8.24 (s, CHꢀN, 1H);
7.3–7.2 (m, ArH, 5H); 4.68 (m, Hfer, 2H); 4.67 (s,
CH2Ph, 2H); 4.38 (m, Hfer, 2H); 4.17 (s, C5H5, 5H).
Elemental analysis: Anal. Found: C, 71.27; H, 5.54;
N, 4.61. Calc. for C18H17FeN: C, 71.31; H, 5.65; N,
4.62%.
Scheme 1. Synthesis of aminophosphonates 3a–n

J. Lewkowski et al. / Journal of Organometallic Chemistry 631 (2001) 105–109
107
3.1.2. N-Ferrocenylidenefurfurylamine (2b)
Y=1.13 g (77%); m.p.: 86–91 °C (benzene–hexane,
1:1).
1H-NMR (200 MHz, CDCl3): l 8.20 (s, CHꢀN, 1H);
7.39 (m, H5fur, 1H); 6.34 (m, H3fur, 1H); 6.27 (m, H4fur
1H); 4.69 (m, Hfer, 2H); 4.61 (s, CH2Fur, 2H); 4.39 (m,
Hfer, 2H); 4.18 (s, C5H5, 5H).
Elemental analysis: Anal. Found: C, 65.63; H, 5.13;
N, 4.63. Calc. for C16H15FeNO: C, 65.55; H, ,5.16; N,
4.78%.
3.2.1. Diethyl N-benzylaminoferrocenylo-
methanephosphonate (3a)
Y=1.65 g (75%).
1H-NMR (200 MHz, CDCl3): l 7.47–7.21 (m, ArH,
,
5H); 4.67 (m, CHfer, 2H); 4.38–3.97 (m, OCH2CH3,
CHfer, CH2Ph, 8H); 4.06 (s, C5H5, 5H); 3.74 (d, JPH
2
=
10.1 Hz, CHP, 1H); 1.28 and 1.25 (2t, J=6.8 Hz, 6H,
OCH2CH6 3
). 31P-NMR (81 MHz, CDCl3): l 22.08.
EI-MS: m/z=441.1 [M+]; 303.1 [M+ꢁHOP(OEt)2];
212.0 [Fc-CHꢀN+]; 121.1 [CpFe+]; 109.3 [+P(O)-
(OH)(OEt)]; 91.1 [+CH2Ph]; 65.1 [Cp+]; 28.1
[CH2ꢀCH2].
3.1.3. N-Ferrocenylidene tert-butylamine (2c)
Y=2.45 g (91%); m.p.: 65–69 °C (benzene–hexane,
1:1).
Elemental analysis: Anal. Found: C, 60.03; H, 6.31;
N, 3.43. Calc. for C22H28FeNO3P: C, 59.88; H, 6.40; N,
3.17%.
1H-NMR (200 MHz, CDCl3): l 8.12 (s, CHꢀN, 1H);
4.80 (m, Hfer, 2H); 4.44 (m, Hfer, 2H); 4.18 (s, C5H5,
5H); 1.32 (s, CH3, 9H).
3.2.2. Dibenzyl N-benzylaminoferrocenylo-
methanephosphonate (3b)
Y=1.76 g (62%).
Elemental analysis: Anal. Found: C, 66.53; H, 7.06;
N, 4.95. Calc. for C15H19FeN: C, 66.93; H, 7.12; N,
5.20%.
1H-NMR (200 MHz, CDCl3): l 7.36–7.23 (m, ArH,
15H); 4.95 (m, OCH2Ph, 2H); 4.26 (m, CHfer, 2H); 4.22
(d, J=12.6 Hz, CH2Ph, 1H); 4.15 (m, CHfer, 2H); 4.05
(d, J=12.6 Hz, CH2Ph, 1H); 4.04 (s, C5H5, 5H); 3.95
(m, OCH2Ph, 2H); 3.81 (d, 2JPH=10.0 Hz, 1H); 1.25 (s,
NH, 1H). 31P-NMR (81 MHz, CDCl3): l 22.67.
EI-MS: m/z=565.2 [M+]; 303.1 [M+ꢁHOP-
(OCH2Ph)2]; 212.0 [Fc-CHꢀN+]; 171.0 [+P(O)(OH)-
(OCH2Ph)]; 121.1 [CpFe+]; 107.1 [+OCH2Ph]; 91.1
[+CH2Ph]; 65.1 [Cp+].
3.1.4. N-ferrocenylidenediphenylmethylamine (2d)
Y=90% (1.7 g); m.p.: 143–144 °C (benzene–hex-
ane, 1:1).
1H-NMR (200 MHz, CDCl3): l 8.26 (s, CHꢀN, 1H);
7.31 (m, ArH, 10 H); 5.49 (s, CH, 1H); 4.73 (dd, J=1.8
and 1.9 Hz, CH2, 2H); 4.37 (dd, J=1.8 and 1.9 Hz,
CH2, 2H); 4.08 (s, C5H5, 5H).
Elemental analysis: Anal. Found: C, 75.96; H, 5.54;
N, 3.68. Calc. for C24H21FeN: C, 76.00; H, 5.58; N,
3.69%.
Elemental analysis: Anal. Found: C, 68.21; H, 5.80;
N, 2.84. Calc. for C32H32FeNO3P: C, 7.95; H, 5.71; N,
2.48%.
3.1.5. N-Ferrocenylidene-(R)-h-methylbenzylamine (2e)
Y=1.70 g (90%); m.p.: 48–50 °C (benzene–hexane,
1:1).
3.2.3. Diethyl N-furfurylaminoferrocenylo-
methanephosphonate (3c)
1H-NMR (200 MHz, CDCl3): l 8.21 (s, CHꢀN, 1H);
7.37–7.25 (m, ArH, 5H); 4.73 (m, CHfer, 1H); 4.65 (m,
CHfer, 1H); 4.43 (quart, J=6.8 Hz, CHPh, 1H); 4.36
(m, CHfer, 2H); 4.12 (s, C5H5, 5H); 1.58 (d, J=6.8 Hz,
CH3, 3H).
Y=1.1 g (51%).
1H-NMR (200 MHz, CDCl3): l 7.42 (m, Hf5ur, 1H);
6.37 (m, Hf3ur, 1H); 6.32 (m, Hf4ur, 1H); 4.25 (m, CHfer,
2H); 4.18 (s, CH2Fur, 2H); 4.14 (m, CHfer, 2H); 4.10 (s,
C5H5, 5H); 4.00 (m, OCH2CH3, 4H); 3.68 (d, JPH
2
=
Elemental analysis: Anal. Found: C, 71.75; H, ,6.18;
N, 4.51. Calc. for C19H19FeN: C, 71.94; H, 6.04; N,
4.42%.
7.54 Hz, CHP, 1H); 1.26 and 1.24 (2t, J=7.0 Hz, 6H,
OCH2CH6 3
). 31P-NMR (81 MHz, CDCl3): l 22.13.
EI-MS: m/z=431.2 [M+]; 293.0 [M+ꢁHOP(OEt)2];
212.0 [Fc-CHꢀN+]; 121.1 [CpFe+]; 109.3 [+P(O)-
(OH)(OEt)]; 81.2 [+CH2Fur]; 65.1 [Cp+]; 28.1
[CH2ꢀCH2].
3.2. Dialkyl N-alkylaminoferrocenemethane-
phosphonates (3a–n)
To a solution of an imine (5 mmol) in toluene (or in
acetonitrile, in the case of 2e) (50 ml), dialkyl phosphite
(5 mmol) was added. The solution was refluxed for 7 h,
then stirred at a r.t. for 12 h. The solvent was evapo-
rated, the residue was dissolved in the 10% aqueous
HCl–ethanol (4:1), washed with ether (3×20 ml), the
aqueous layer extracted with dichloromethane (3×25
ml), the organic layers dried and evaporated to give an
appropriate product. The product was purified by
means of column chromatography on cellulose powder.
Elemental analysis: Anal. Found: C, 55.28; H, 5.79;
N, 3.28. Calc. for C20H26FeNO4P: C, 55.67; H, 6.08; N,
3.25%.
3.2.4. Dibenzyl N-furfurylaminoferrocenylomethane-
phosphonate (3d)
Y=2.44 g (88%); m.p.: 93–95 °C.
1H-NMR (200 MHz, CDCl3): l 7.40–7.16 (m, ArH,
Hf5ur, 11H); 6.34 (m, H4fur, 1H); 6.21 (m, Hf4ur, 1H); 4.92
3
2
(the AB part of ABX system, JPH=4.6 Hz, JHH
=

108
J. Lewkowski et al. / Journal of Organometallic Chemistry 631 (2001) 105–109
11.3 Hz, OCH2Ph, 2H); 4.27 (m, CH2Ph, 2H); 4.25 (m,
CHfer, 2H); 4.19 (m, CHfer, 2H); 4.15 (s, CH2Fur, 2H);
EI-MS: m/z=517.2 [M+]; 379.1 [M+ꢁHOP(OEt)2];
212.0 [Fc-CHꢀN+]; 167.1 [+CHPh2]; 121.1 [CpFe+];
109.3 [+P(O)(OH)(OEt)]; 77.2 [+Ph]; 65.1 [Cp+]; 28.1
[CH2ꢀCH2].
Elemental analysis: Anal. Found: C, 64.73; H, 6.43;
N, 2.78. Calc. for C28H32FeNO3P: C, 65.00; H, 6.23; N,
2.71%.
2
4.09 (s, C5H5, 5H); 3.74 (d, JPH=7.2 Hz, 1H). 31P-
NMR (81 MHz, CDCl3): l 22.62.
EI-MS:
m/z=555.2
212.0
121.1
[M+];
[Fc-CHꢀN+];
293.0
[M+
171.0
107.1
ꢁHOP(OCH2Ph)2];
[+P(O)(OH)(OCH2Ph)];
[CpFe+];
[+OCH2Ph]; 91.1 [+CH2Ph]; 81.2 [+CH2Fur]; 65.1
[Cp+].
3.2.8. Dibenzyl N-diphenylmethylamino( ferrocenyl)-
methane phosphonate (3h)
Elemental analysis: Anal. Found: C, 64.96; H, 5.32;
N, 2.45. Calc. for C30H30FeNO4P: C, 64.85; H, 5.45; N,
2.52.
Y=2.3 g (72%); m.p.: 103–105 °C.
1H-NMR (200 MHz, CDCl3): l 7.48–7.25 (m, ArH,
20H); 5.58 (s, CH, 1H); 4.93 (m, CH2Ph, 4H); 4.31 (m,
CHfer, 1H); 4.24 (m, CHfer, 1H); 4.16 (m, CHfer, 2H);
3.2.5. Diethyl N-tert-butylaminoferrocenylomethane-
phosphonate (3e)
2
4.03 (s, C5H5, 5H); 3.90 (d, JHH=14.1 Hz, CHP, 1H);
Y=1.2 g (59%).
2.17 (large s, NH, 1H). 31P-NMR (81 MHz, CDCl3): l
22.96.
1H-NMR (200 MHz, CDCl3): l 4.36–4.04 (m, 2Hafer,
2Hbfer, OCH2CH3, 8H); 4.21 (s, C5H5, 5H); 3.82 (d,
2JPH=17.1 Hz, CHP, 1H); 1.34 and 1.31 (2t, J=7.1
EI-MS: m/z=641.3 [M+]; 379.1 [M+ꢁHOP-
(OCH2Ph)2]; 212.0 [Fc-CHꢀN+]; 171.0 [+P(O)(OH)-
(OCH2Ph)]; 167.1 [+CHPh2]; 121.1 [CpFe+]; 107.1
[+OCH2Ph]; 91.1 [+CH2Ph]; 77.2 [+Ph]; 65.1 [Cp+].
Elemental analysis: Anal. Found: C, 71.00; H, 5.89;
N, 2.36. Calc. for C38H36FeNO3P: C, 71.15; H, .66; N,
2.18%.
Hz, 6H, OCH2CH3
MHz, CDCl3): l 23.59.
EI-MS: m/z=431.2 [M+]; 269.1 [M+ꢁHOP(OEt)2];
6 ); 1.18 (s, CH6 3
, 9H). 31P-NMR (81
213.0
[Fc-CHꢀHN+];
121.1
[CpFe+];
109.3
[+P(O)(OH)(OEt)]; 65.1 [Cp+]; 55.9 [Me2CꢀCH2]; 28.1
[CH2ꢀCH2].
Elemental analysis: Anal. Found: C, 56.07; H, 7.38;
N, 3.51. Calc. for C19H30FeNO3P: C, 56.00; H, 7.43; N,
3.44%.
3.2.9. Diethyl N-(R)-h-methylbenzylaminoferrocenylo-
methanephosphonate (3i )
Y=1.4 g (62%).
1H-NMR (200 MHz, CDCl3): l 7.47–7.27 (m, ArH,
5H); 4.41 and 4.34 (quart, J=6.4 Hz, CHN, 1H);
4.23–4.00 (m, OCH2CH3, CHfer, 8H); 3.97 (s, C5H5,
5H); 3.74 (d, 2JPH=19.0 Hz, CHP, 1H); 3.62 (d,
2JPH=10.1 Hz, CHP, 1H); 1.48 and 1.40 (d, J=6.7
Hz, CH3, 3H); 1.27 and 1.26 (2t, J=7.0 Hz, 6H,
3.2.6. Dibenzyl N-tert-butylaminoferrocenylomethane-
phosphonate (3f)
Y=1.77 g (70%); m.p.: 95–98 °C.
1H-NMR (200 MHz, CDCl3): l 7.36–7.29 (m, ArH,
10H); 5.09 (dd, 2JHH=12.3 Hz, 2JPH=7.4 Hz,
2
2
OCH2Ph, 2H); 4.94 (dd, JHH=12.3 Hz, JPH=8.7 Hz,
OCH2CH3
17.84.
EI-MS: m/z=455.2 [M+]; 317.2 [M+ꢁHOP(OEt)2];
6
). 31P-NMR (81 MHz, CDCl3): l 18.36 and
OCH2Ph, 2H); 4.27 (m, CHfer, 2H); 4.21 (m, CHfer,
2
2H); 4.15 (s, C5H5, 5H); 3.89 (d, JPH=16.6 Hz, 1H);
1.16 (s, NH, 1H). 31P-NMR (81 MHz, CDCl3): l 24.08.
EI-MS: m/z=531.3 [M+]; 269.1 [M+ꢁHOP-
(OCH2Ph)2]; 213.0 [Fc-CHꢀNH+]; 171.0 [+P(O)(OH)-
(OCH2Ph)]; 121.1 [CpFe+]; 107.1 [+OCH2Ph]; 91.1
[+CH2Ph]; 65.1 [Cp+]; 55.9 [Me2CꢀCH2].
213.0
[Fc-CHꢀNH+];
121.1
[CpFe+];
109.3
[+P(O)(OH)(OEt)]; 104.0[PhCHꢀCH2]; 77.2[+Ph];
65.1[Cp+]; 28.1[CH2ꢀCH2].
Elemental analysis: Anal. Found: C, 60.64; H, 6.66;
N, 3.40. Calc. for C23H30FeNO3P: C, 60.67; H, 6.64; N,
3.08%.
Elemental analysis: Anal. Found: C, 65.41; H, 6.40;
N, 2.35. Calc. for C29H34FeNO3P: C, 65.55; H, 6.45; N,
2.64%.
3.2.10. Dibenzyl N-(R)-h-methylbenzylaminoferro-
cenylomethanephosphonate (3j)
3.2.7. Diethyl N-diphenylmethylamino( ferrocenyl)-
methane phosphonate (3g)
Y=1.8 g (65%).
1H-NMR (200 MHz, CDCl3): l 7.35–7.24 (m, ArH,
15H); 5.01–4.84 (m, CHMe, CH2Ph, 3H); 4.41 (m,
CH2Ph, 1H); 4.28–4.19 (m, CH2Ph, CHfer, 5H); 4.11
Y=1.9 g (75%); m.p.: 138–140°C.
1H-NMR (200 MHz, CDCl3): l 7.56–7.25 (m, ArH,
10H); 5.60 (s, CH, 1H); 4.33 (m, CHfer, 1H); 4.27 (m,
CHfer, 1H); 4.24–3.97 (m, CH2CH3, 4H); 4.15 (m,
2
and 3.94 (2s, C5H5, 5H); 3.83 (d, JPH=18.4 Hz, CHP,
2
1H); 3.68 (d, JPH=9.6 Hz, CHP, 1H); 1.41 and 1.38
2
CHfer, 2H); 4.06 (s, C5H5, 5H); 3.82 (d, JHH=15.0 Hz,
(d, J=6.8 Hz, CH3, 3H). 31P-NMR (81 MHz, CDCl3):
l 23.49 and 22.94.
CHP, 1H); 2.04 (large s, NH, 1H); 1.27 and 1.26 (2t,
J=7.1 Hz, CH2CH3, 6H). 31P-NMR (81 MHz,
CDCl3): l 22.41.
EI-MS: m/z=565.3 [M+]; 317.1 [M+ꢁHOP(OCH2-
Ph)2]; 213.0 [Fc-CHꢀNH+]; 171.0 [+P(O)(OH)(OCH2-

J. Lewkowski et al. / Journal of Organometallic Chemistry 631 (2001) 105–109
109
Ph)]; 121.1 [CpFe+]; 107.1 [+OCH2Ph]; 104.0
[PhCHꢀCH2]; 91.1 [+CH2Ph]; 77.2 [+Ph]; 65.1 [Cp+].
Elemental analysis: Anal. Found: C, 68.49; H, 6.03;
N, 2.46. Calc. for C23H30FeNO3P: C, 68.40; H, 5.91; N,
2.42%.
3.2.14. Diphenyl N-tert-butylaminoferrocenylo-
methanephosphonate (3n) (identified by means of NMR
spectroscopy)
1H-NMR (200 MHz, CDCl3): l 7.24–6.62 (m, ArH,
15H); 4.52 (d, 2JPH=12.8 Hz, 1H); 4.79 (m, CHfer, 2H);
4.41 (m, CHfer, 2H); 4.17 (s, C5H5, 5H); 1.32 (s, CH3,
9H). 31P-NMR (81 MHz, CDCl3): l 15.53.
EI-MS: m/z=503.3 [M+]; 269.1 [M+ꢁHOP(OPh)2];
234.0 [+P(O)(OPh)2]; 213.0 [Fc-CHꢀNH+]; 121.1
[CpFe+]; 94.1 [+OPh]; 77.2 [+Ph]; 65.1 [Cp+]; 55.9
[Me2CꢀCH2].
3.2.11. Diphenyl N-diphenylmethylamino( ferrocenyl)-
methane phosphonate (3k)
Y=2.2 g (72%); m.p.: 128–130 °C.
1H-NMR (200 MHz, CDCl3): l 7.49–6.83 (m, ArH,
20H); 5.62 (s, CH, 1H); 4.37 (m, CHfer, 2H); 4.20 (d,
2JHH=22.0 Hz, CHP, 1H); 4.19 (m, CHfer, 2H); 4.07 (s,
2
C5H5, 5H); 3.90 (d, JHH=14.1 Hz, CHP, 1H); 2.14
References
(large s, NH, 1H). 31P-NMR (81 MHz, CDCl3): l
15.83.
[1] V. Chavane, Bull. Soc. Chim. Fr. 15 (1948) 774.
[2] M.I. Kabachnik, T.J. Medved, Izv. Akad. Nauk SSSR Otd.
Khim. Nauk (1953) 868; C.A. 49 (1955) 840.
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[7] M. Mikolajczyk, J. Drabowicz, Formation of C–P bond,
Houben-Weyl (Eds.) Chapter 8, Vol. 21e, 1995 and references
cited within.
EI-MS: m/z=613.3 [M+]; 379.1 [M+ꢁHOP(OPh)2];
234.0 [+P(O)(OPh)2]; 212.0 [Fc-CHꢀN+]; 167.1
[+CHPh2]; 121.1 [CpFe+]; 94.1 [+OPh]; 77.2 [+Ph];
65.1 [Cp+].
Elemental analysis: Anal. Found: C, 70.49; H, 5.76;
N, 2.35. Calc. for C38H36FeNO3P: C, 70.48; H, 5.26; N,
2.28%.
[8] S. Hanessian, Y.L. Bennani, Synthesis (1994) 1272.
[9] C. Maury, J. Royer, H.P. Husson, Tetrahedron Lett. 33 (1992)
6127.
[10] J.W. Goding, Monoclonal Antibodies. Principles and Practice,
Academic Press, New York, 1986.
[11] M.K. Mao, J.E. Franz, Synthesis (1991) 920.
[12] E.K. Baylis, C.D. Campbell, J.G. Dingwall, J. Chem. Soc.
Perkin Trans. I (1984) 2845 and references cited within.
[13] P. Kafarski, B. Lejczak, Phosphorus Sulfur Silicon 63 (1991)
193.
[14] L. Maier, Phosphorus Sulfur Silicon 61 (1991) 65.
[15] E.C. Constable, Angew. Chem. Int. Ed. Engl. 30 (1991) 407.
[16] G. De Santis, L. Fabrizzi, M. Licchelli, P. Pallavicini, A. Perotti,
J. Chem. Soc. Dalton Trans. (1992) 3283.
3.2.12. Diphenyl N-benzylaminoferrocenylo-
methanephosphonate (3l) (identified by means of NMR
spectroscopy)
1H-NMR (200 MHz, CDCl3): l 7.36–6.85 (m, ArH,
15H); 4.37 (d, 2JPH=12.8 Hz, 1H); 4.27 (m, CHfer, 2H);
4.15 (m, CHfer, 2H); 4.11 (s, C5H5, 5H). 31P-NMR (81
MHz, CDCl3): l 14.49.
EI-MS: m/z=537.3 [M+]; 303.1 [M+ꢁHOP(OPh)2];
234.0 [+P(O)(OPh)2]; 212.0 [Fc-CHꢀN+]; 121.1
[CpFe+]; 94.1 [+OPh]; 91.1 [+CH2Ph]; 77.2 [+Ph];
65.1 [Cp+].
[17] P.D. Beer, J.E. Nation, M.E. Harman, M.B. Hursthouse, J.
Organomet. Chem. 441 (1992) 465.
[18] P.D. Beer, D.R. Smith, J. Chem. Soc. Dalton Trans. (1998) 417.
[19] A.J. Moore, P.J. Skabara, M.R. Bryce, A.S. Batsanov, J.A.K.
Howard, S.T.A.K. Daley, J. Chem. Soc. Chem. Commun. (1993)
417.
[20] K. Schlo¨gl, Monatsh. Chem. 88 (1957) 601.
[21] J.M. Osgerby, P.L. Pauson, J. Chem. Soc. (1958) 656–660.
[22] A.-S. Carlstro¨m, T. Frejd, Synthesis (1989) 414.
[23] A.-S. Carlstro¨m, T. Frejd, J. Org. Chem. 55 (1990) 4175.
[24] R.F.W. Jackson, D. Turner, M.H. Block, Synlett (1996) 862.
[25] H. Brunner, W. Ko¨nig, B. Nuber, Tetrahedron Asym. 4 (1993)
699.
3.2.13. Diphenyl N-Furfurylaminoferrocenylo-
methanephosphonate (3m) (identified by means of NMR
spectroscopy)
1H-NMR (200 MHz, CDCl3): l 7.43–7.04 (m, ArH,
Hf5ur, 11H); 6.77 (m, H4fur, 1H); 6.37 (m, Hf4ur, 1H); 4.61
(d, 2JPH=12.1 Hz, CHP, 1H); 4.34 (m, CHfer, 2H); 4.27
(s, CH2Fur, 2H); 4.18 (m, CHfer, 2H); 4.14 (s, C5H5,
5H). 31P-NMR (81 MHz, CDCl3): l 14.41.
EI-MS: m/z=527.3 [M+]; 293.0 [M+ꢁHOP(OPh)2];
234.0 [+P(O)(OPh)2]; 212.0 [Fc-CHꢀN+]; 121.1
[CpFe+]; 94.1 [+OPh]; 81.1 [+CH2Fur]; 77.2 [+Ph];
65.1 [Cp+].
[26] H.-B. Kraatz, J. Lusztyk, G.D. Enright, Inorg. Chem. 36 (1997)
2400.
[27] L. Cottier, G. Descotes, J. Lewkowski, R. Skowron´ski, Phospho-
rus Sulfur Silicon 116 (1996) 92.
.