The stereochemical behavior of terephthalic schiff bases in addition of dialkyl or diaryl phosphites

Article abstract of DOI:10.1080/104265090508172

Addition of dialkyl (or diaryl) phosphites to N-alkyl terephthalic Schiff bases led exclusively to a meso-form but addition to N-aryl terephthalic Schiff bases depended on the substituent of the aryl group. Semi-empirical calculations were involved to fin

Full text of DOI:10.1080/104265090508172

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The Stereochemical Behavior
of Terephthalic Schiff Bases in
Addition of Dialkyl or Diaryl
Phosphites
Jarosław Lewkowski a
a Department of Organic Chemistry, University of
Łódź, Narutowicza 68, 90-136, Łódź, Poland
Published online: 01 Feb 2007.
To cite this article: Jarosław Lewkowski (2005): The Stereochemical Behavior of
Terephthalic Schiff Bases in Addition of Dialkyl or Diaryl Phosphites, Phosphorus,
Sulfur, and Silicon and the Related Elements, 180:1, 179-195
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Phosphorus, Sulfur, and Silicon, 180:179–195, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090508172
The Stereochemical Behavior of Terephthalic Schiff
Bases in Addition of Dialkyl or Diaryl Phosphites
Jaroslꢀaw Lewkowski
Department of Organic Chemistry, University ofLꢀ o´dz´, Narutowicza 68,
90-136Lꢀ o´dz´, Poland
Addition of dialkyl (or diaryl) phosphites to N-alkyl terephthalic Schiff bases led
exclusively to a meso-form but addition to N-aryl terephthalic Schiff bases depended
on the substituent of the aryl group. Semi-empirical calculations were involved to
find the reason of this phenomenon.
Keywords Addition of phosphites; imino-ester intermediates; meso-form formation;
stereoselectivity; terephthalic Schiff bases
INTRODUCTION
About 10 years ago, Barycki et al.1 and Gancarz2 have reported
that the addition of diethyl phosphite to N,Nꢀ-terephthalylidene-
bis-benzylamine was stereoselective leading nearly exclusively to
one diastereoisomeric form. This fact was also noted by Failla and
Finocchiaro,3−5 but they neither made attempts to determine which di-
astereoisomeric form occurred, nor gave any suggestion to explain the
reason of this phenomenon. Some years ago, we reported several ex-
amples of this reaction with four N-alkyl (and alkylaryl) substituted6
and with N-1-naphthyl7 terephthallic Schiff bases. We noted that al-
though in a case of N-alkyl (and alkylaryl) substituted terephthallic
Schiff bases, the reaction led exclusively to one diastereoisomeric form
but in a case of N-1-naphthyl derivative, it depended on the kind of the
phosphite: the addition of dibenzyl and diphenyl ones led indeed to one
product and the addition of diethyl phosphite led to two diastereomeric
forms. We determined by the NMR experiments that the exclusively
occurring product is the meso one.6
Received June 1, 2004; in final form June 15, 2004.
Address correspondence to Jaroslꢀaw Lewkowski, Department of Organic Chemistry,
University of Lꢀ o´dz´, Narutowicza 68, 90-136 Lꢀ o´dz´, Poland. E-mail: JLEWKOW@uni.
lodz.pl
179

180
L. Lewkowski
RESULTS AND DISCUSSION
For this study, the author performed the addition of three model
phosphites—diethyl, dibenzyl, and diphenyl— to various N-alkyl (and
alkylaryl) terephthallic Schiff bases 1a–f, which led nearly exclusively
(in 98–100%) to the one diastereoisomeric form, which was demon-
strated to be the meso-form. (Scheme 1) The structure of diastereoiso-
mers has been determined, as previously6,7 by the NMR measurement,
i.e., the NMR spectra of salts of esters 2 with (R)-mandelic acid. As
1
salts gave one set of H and 31P NMR signals, I concluded that esters
2 had a meso configuration. The 31P NMR data of esters 2aA–2fC are
summarized in the Table I.
SCHEME 1
However, when the addition was performed to N-aryl substituted
terephthalic Schiff bases 1ꢀa–j, results varied dependently on two fac-
tors: the kind of the substituent of the aryl group and the phosphite
used. For example, the addition to N-phenyl substituted tereph-
thalic Schiff base 1ꢀa led in the case of diethyl and dibenzyl phos-
phite to the mixture of both expected diastereoisomeric forms and
in the case of diphenyl one—to the meso-form. The addition to the
N-p-methoxyphenyl terephthalic Schiff base led to exclusive products
TABLE I 31P NMR Data for Bis-N-alkyl (or Alkylaryl)-
aminophosphonates 2aA–2fC
31P NMR data
Rꢀ = CH2CH3(A)
Rꢀ = CH2Ph (B)
Rꢀ = Ph (C)
2a
2b
2c
2d
2e
2f
R = CH2Ph
24.056
23.676
20.676
23.53
23.476
22.696
19.896
23.46
15.476
15.486
15.416
15.67
R = CH2Fur
R = C(CH3)3
R = CHPh2
R = CH2CH2(2-Pyr)
R = c-C6H11
23.703
24.663
23.543
23.783
15.273
15.653

Phenylene-Bis(Aminomethanephosphonates
181
in the case of diethyl and diphenyl phosphites, but both diastereoiso-
meric forms occurred in the course of dibenzyl phosphite addition. The
addition to N-m-methoxyphenyl terephthalic Schiff base was stereose-
lective in all three cases and the addition to N-m-methylphenyl tereph-
thalic Schiff base led to both diastereoisomeric forms in all three cases.
The addition to N-m-nitrophenyl and N-p-nitrophenyl Schiff bases led
to both diastereoisomeric forms. The configuration of exclusive prod-
ucts was analysed as previously described. The 31P NMR data of esters
2ꢀaA–2ꢀfC are summarized in the Table II.
The syntheses of N-p-nitrophenyl derivatives 2ꢀfA–2ꢀfC was trou-
blesome as their conversion rates did not exceed 20%. Therefore they
were not isolated and were characterized by means of 1H and 31P NMR
spectroscopy and for all three cases signals of both diastereoisomeric
forms of products and corresponding phosphites were observed. These
data are included in Table II.
According to this author’s observations, it depends on whether the
substituent is an electron withdrawing group or an electron donat-
ing one. Previous papers,6 have proposed the hypothetical reason of
such a highly stereoselective reaction starting from completely achiral
reagents. According to this hypothesis, the reaction is controlled kinet-
ically and the key step is the formation of such an active complex 4 con-
sisting of two molecules of iminoester 3 and two molecules of phosphite
TABLE II 31P NMR Data for Bis-N-arylaminophosphonates 2ꢀaA–2ꢀjC
31P NMR data
Rꢀ = CH2CH3 (A)
Rꢀ ꢀ CH2Ph (B)
Rꢀ = Ph (C)
2ꢀa R = C6H5
22.47 and 22.42 (1:2)
23.08 and 23.00 14.95
(1:1)
24.54 and 24.46 16.42
(1:1)
2ꢀb R = p-C6H4-OCH3
23.923
2ꢀc R = m-C6H4-OCH3 23.60
22.97
16.14
2ꢀd R = p-C6H4-CH3
2ꢀe R = m-C6H4-CH3
2ꢀf R = p-C6H4-NO2
2ꢀg R = m-C6H4-NO2
22.42
23.25 and 23.14 15.13
(3:2)
24.47 and 24.37 16.36 and 16.32
23.81 and 23.75 (1:1)
21.65 and 21.09 (1:1)
20.89 and 20.79 (1:1)
(1:1)
22.15 and 21.89 13.82 and 13.32
(1:1) (5:2)
21.29 and 21.21 13.61 and 13.26
(1:1) (1:1)
(1:1)
2ꢀh R = p-C6H4-COOH 21.84 and 18.33 (5:1)4
2ꢀi R = m-C6H4-COOH 21.87
21.34 and 21.03 20.52
(3:1)
23.12
22.48
16.01
12.51
2ꢀj R = α-naphthyl
21.73 and 21.64 (1:1)

182
L. Lewkowski
linked to each other with hydrogen bonding (Scheme 2), which forced
the attack of the phosphite molecule from strictly defined side. As it
is generally known that the electron density on an azomethine nitro-
gen atom is less in a case of N-aryl derivatives and it depends on the
substituent on the aryl ring. Thus the formation of such a complex is
less probable in the case of N-aryl iminoeters 3ꢀ and strongly depends
on the kind of a substituent. Electron withdrawing substituents make
the complex 4ꢀ not to be formed, while electron-donating ones promote
the formation of the complex 4ꢀ. In a case of the N-p-nitrophenyl or
N-m-nitrophenyl derivatives, the occurrence of two diastereoisomeric
forms seems to support this theory, the same as the nearly exclu-
sive formation of the meso-form in the case of N-m-methoxyphenyl
derivative.
SCHEME 2
The formation of both diastereoisomeric forms of bis-amino-
phosphonate in the case of N,Nꢀ-terephthalylidene-bis-m-toluidine 1ꢀe
was rather unexpected, the same as the exclusive formation of the
meso-forms of 2ꢀi in the course of addition to N-m-carboxyphenyl
terephthalic Schiff base for all three phosphites. But the preliminary
semi-empirical AM18 Mulliken population analysis demonstrated that
charge distribution in iminoesters 3ꢀ on an azomethine nitrogen atom
and on an amine group nitrogen and hydrogen atoms have values
much less convenient for the hydrogen bonding (−0.14900e for =N,
+0.204500e for H for 3ꢀeA) comparing to these values of the N-m-
methoxyphenyl 3ꢀcA and carboxyphenyl derivatives 3ꢀiA (−0.15570e
for =N, +0.21260e for H and −0.15740e for =N and +0.21570e for H)
(Table III).
In the case of N-p-methylphenyl and N-p-methoxyphenyl Schiff
bases 1ꢀb and 1ꢀd gave in the course of dibenzyl phosphite addi-
tion two diastereoisomeric forms. The preliminary AM1 results of

Phenylene-Bis(Aminomethanephosphonates
183
TABLE III Charges (Mulliken) of Iminoesters 3ꢀaA–3ꢀjC
Charge distribution (Mulliken)
Rꢀ = CH2CH3 (A)
Rꢀ = CH2Ph (B)
Rꢀ = Ph (C)
HC
N
H
N
HC
N
H
N
HC
N
H N
3ꢀa R = C6H5
−0.15090 +0.20400 −0.15250 +0.20910 −0.15510 +0.21480
3ꢀb R = p-C6H4-OCH3 −0.15560 +0.20940 −0.15300 +0.20150 −0.15200 +0.20590
3ꢀc R = m-C6H4-OCH3 −0.15570 +0.21260 −0.15580 +0.21330 −0.15610 +0.20930
3ꢀd R = p-C6H4-CH3
3ꢀe R = m-C6H4-CH3
3ꢀf R = p-C6H4-NO2
3ꢀg R = m-C6H4-NO2
−0.15770 +0.20160 −0.15490 +0.20060 −0.15640 +0.20840
−0.14900 +0.20450 −0.14870 +0.18960 −0.14400 +0.20190
−0.14760 +0.20120 −0.14770 +0.19060 −0.14510 +0.20090
−0.14210 +0.19090 −0.14680 +0.18750 −0.14380 +0.18790
3ꢀh R = p-C6H4-COOH −0.15590 +0.21370 −0.16010 +0.21650 −0.16450 +0.22460
3ꢀi R = m-C6H4-COOH −0.15740 +0.21570 −0.17430 +0.22760 −0.16260 +0.22530
3ꢀj R = α-naphthyl
−0.15090 +0.19900 −0.15650 +0.20910 −0.15510 +0.21480
Mulliken population analysis suggested that in case of benzyl imi-
noesters, the formation of the complex 4ꢀb and 4ꢀd would be less proba-
ble, as the values of charge distribution demonstrates too small acidity
of hydrogen and too small basicity of an azomethine nitrogen atom
(Table III).
Analysing data from Tables II and III, it is found that when charge
distribution values suggest the lower basicity of an azomethine nitro-
gen and the lower acidity of an amine hydrogen (Table III), NMR data
demonstrate the formation of both diastereoisomeric forms. Moreover
the AM1 Mulliken population analysis of N-alkyl an N-alkylaryl imi-
noesters 3 demonstrated that, in all studied cases charge distribution
values suggest a higher basicity of an azomethine nitrogen and a higher
acidity of an amine hydrogen (Table IV). This indicates a higher pos-
sibility of the active complex 4 formation, and, in all these cases the
TABLE IV Charges (Mulliken) of Iminoesters 3aA–3fC
Charge distribution (Mulliken)
Rꢀ = CH2CH3 (A)
Rꢀ = CH2Ph (B)
Rꢀ = Ph (C)
HC
N
H
N
HC
N
H
N
HC
N
H N
2a R = CH2Ph
2b R = CH2Fur
2c R = C(CH3)3
2d R = CHPh2
−0.18300 +0.17440 −0.18380 +0.17320 −0.18360 +0.17090
−0.18040 +0.18040 −0.18100 +0.17880 −0.17940 +0.18310
−0.17060 +0.17420 −0.17000 +0.17550 −0.16850 +0.17890
−0.17010 +0.17690 −0.17050 +0.17710 −0.16940 +0.17550
2e R = CH2CH2(2-Pyr) −0.17770 +0.16900 −0.17630 +0.16940 −0.17570 +0.16890
2f R = c-C6H11
−0.17470 +0.18050 −0.17570 +0.17890 −0.17400 +0.18440

184
L. Lewkowski
exclusive formation of meso forms of 2 was observed. So, our hypothesis
concerning the formation of iminoesters first and then the formation of
their active complexes 4 and 4ꢀ seems to explain quite well the experi-
mental data. But the explicit proof would be the isolation of iminoesters
and studies on their physico-chemical properties (e.g., the IR study on
hydrogen bonding) which have only recently been isolated.
EXPERIMENTAL
All solvents were routinely dried and distilled prior to use. Terephthalic
aldehyde (Aldrich) as well as the three phosphites (Aldrich) and amines
(Aldrich) were used as received. NMR measurements were recorded on
a Varian Gemini 200 BB at 200 MHz (1H NMR) and 81 MHz (31P NMR)
apparatus. Melting points were measured on a MeltTemp II apparatus
and were not corrected. Elemental analyses were made in the Center
for Molecular and Macromolecular Studies inLꢀ o´dz´, Poland.
All computations were performed on a PC with a CeleronꢁR 1 GHz pro-
cessor and 128 MB RAM. Minima of all hypothetical intermediates 3 or
3ꢀ were searched by the use of Molecular Dynamics protocol in a MM2
packet included in the ChemOffice 7.0 Ultra pack with 10000 steps and
2 fs intervals. The generated conformational families were examined
by the use of the MM2 force field packet included in the ChemOffice 7.0
Ultra pack. Geometries of resulting models with global minima were
optimized by the use of the AM1 method and their geometries mini-
mized and their charge distributions were computed. Semi-empirical
RHF PM3 and AM1 computations were performed by the use of the
GAMESS8 for ChemOffice 7.0 pack. The tight convergence criteria have
been used.
Synthesis of Terephthalic Schiff Bases—General Procedure
In a 250-ml round-bottom flask, 1.34 g (10 mmol) of terephthalic alde-
hyde was placed in 100 ml of benzene. To this solution was added
20 mmol of amine. Then it was stirred for 24 hours at room temper-
ature. The precipitate was collected by filtration.
N,Nꢀ-Terephthalylidene-bis-diphenylmethylamine (1d)
Y = 3.22 g (70%); Mp = 197–200◦C.
1H NMR (CDCl3, 200 MHz): δ 8.44 (s, CH N, 2H); 7.87 (s, C6H4, 4H);
7.35 (m, ArH, 20H); 5.61 (s, CHPh2, 2H).
Elemental analysis:
Calcd for C34H28N2: C-87.90; H-6.07; N-6.03; Found: C-87.82; H-6.15;
N-6.11.

Phenylene-Bis(Aminomethanephosphonates
185
N,Nꢀ-Terephthalylidene-bis-aniline (1ꢀa)
Y = 1.70 g (60%); Mp = 163–165◦C.
1H NMR (CDCl3, 200 MHz): δ 8.53 (s, CH N, 2H); 8.02 (s, C6H4, 4H);
7.43 (dd, J = 7.4 and 7.5 Hz, CHm, 4H); 7.32 (m, CHp, 2H); 7.26 (d, J =
7.5 Hz, CHo, 4H).
Elemental analysis:
Calcd for C20H16N2: C-84.48-H, 5.67; N-9.85; Found: C-84.52; H-5.73;
N-9.92.
N,Nꢀ-Terephthalylidene-bis-p-anisidine (1ꢀb)
Y = 3.10 g (90%); Mp = 214–216◦C
1H NMR (CDCl3, 200 MHz): δ 8.54 (s, CH N, 2H); 7.99 (s, C6H4, 4H);
7.29 (d, J = 8.8 Hz, Hp, 4H); 6.95 (d, J = 8.8 Hz, Hp, 4H); 3.85 (s, OCH3,
6H).
Elemental analysis:
Calcd for C22H20N2O2: C-76.72; H-5.85; N-8.13; Found: C-76.68; H-
5.92; N-8.22.
N,Nꢀ-Terephthalylidene-bis-m-anisidine (1ꢀc)
Y = 2.89 g (84%); Mp = 106–108◦C
1H NMR (CDCl3, 200 MHz): δ 8.52 (s, CH N, 2H); 8.01 (s, C6H4, 4H);
7.31 (t, J = 7.9 Hz, CHm, 2H); 6.83 (m, CHarom, 6H); 3.86 (s, OCH3, 6H).
Elemental analysis:
Calcd for C22H20N2O2: C-76.72; H-5.85; N-8.13; Found: C-76.79; H-
5.91; N-8.19.
N,Nꢀ-Terephthalylidene-bis-p-toluidine (1ꢀd)
Y = 2.97 g (95%); Mp = 187–189◦C; lit9 = 195◦C.
1H NMR (CDCl3, 200 MHz): δ 8.53 (s, CH N, 2H); 8.00 (s, C6H4, 4H);
7.23 (d, J = 8.5 Hz, CHp, 4H); 7.18 (d, J = 8.5 Hz, CHp, 4H); 2.37 (s,
CH3, 6H).
N,Nꢀ-Terephthalylidene-bis-m-toluidine (1ꢀe)
Y = 2.84 g (91%); Mp = 98–101◦C; lit10 = 98◦C
1H NMR (CDCl3, 200 MHz): δ 8.52 (s, CH N, 2H); 8.01 (s, C6H4,
4H); 7.30 (t, J = 8.0 Hz, CHm, 2H); 7.08 (m, CHarom, 6H); 2.41 (s, CH3,
6H).
N,Nꢀ-Terephthalylidene-bis-p-nitroaniline (1ꢀf)
Y = 2.43 g (65%); Mp = 278–280◦C; lit11 = 276.5–278.5◦C.
1H NMR (CDCl3, 200 MHz): δ 8.58 (s, CH N, 2H); 8.09 (d, J = 8.6
Hz, CHp, 4H); 7.96 (s, C6H4, 4H); 7.78 (d, J = 8.5 Hz, CHp, 4H).

186
L. Lewkowski
N,Nꢀ-Terephthalylidene-bis-m-nitroaniline (1ꢀg)
Y = 2.43 g (65%); Mp = 287–288◦C.
1H NMR (CDCl3, 200 MHz): δ 8.59 (s, CH N, 2H); 7.87 (s, C6H4, 4H);
8.12 (m, CHarom, 2H); 7.60 (m, CHarom, 2H); 7.27 (m, CHarom, 2H); 7.17
(d, J = 6.8 Hz, CHarom, 2H).
Elemental analysis:
Calcd for C20H14N4O4: C-64.17; H-3.77; N-14.97; Found: C-64.28; H-
3.86; N-15.08.
N,Nꢀ-Terephthalylidene-bis-p-aminobenzoic acid (1ꢀh)
Y = 3.13 g (84%); Mp = 386–389◦C.
1H NMR (CDCl3, 200 MHz): δ 8.75 (s, CH N, 2H); 8.12 (s, C6H4, 4H);
8.01 (d, J = 8.5 Hz, CHp, 4H); 7.39 (d, J = 8.5 Hz, CHp, 4H).
Elemental analysis:
Calcd for C22H16N2O4: C-70.96; H-4.33; N-7.52; Found: C-70.82; H-
4.21; N-7.47.
N,Nꢀ-Terephthalylidene-bis-m-aminobenzoic acid (1ꢀi)
Y = 3.61 g (97%); Mp = 320–323◦C.
1H NMR (CDCl3, 200 MHz): δ 8.79 (s, CH N, 2H); 8.12 (s, C6H4, 4H);
8.12 (m, CHm, 2H); 7.86 (m, CHm, 4H); 7.58 (d, J = 5.1 Hz, CHp, 2H).
Elemental analysis:
Calcd for C22H16N2O4: C-70.96; H-4.33; N-7.52; Found: C-70.79; H-
4.44; N-7.66.
Synthesis of 1,4-phenylene-bis-(N-alkyl (or N-aryl)
aminomethane)-bis-phosphonates—General procedure
To a 250-ml round bottom flask equipped with a condenser was placed
10 mmol of the Schiff base and 20 mmol of dialkyl (diaryl) phosphite.
Then it was heated for 0.5 h until melting, and the whole mixture
was allowed to cool. Then 50 ml of toluene was added and stirred
for 5 h at the boiling temperature. The precipitate was filtered, the
filtrate concentrated, and the re-precipitated solid was collected by
filtration.
Tetraethyl 1,4-phenylene-bis-
(N-diphenylmethylaminomethane)-bis-phosphonate (2dA)
Y = 2.51 g (34%). Mp 181–184◦C.
1H NMR (CDCl3, 200 MHz): δ 7.34–7.20 (m, ArH, 24H); 4.66 (s,
2
CHPh2, 2H); 4.22 and 3.94 (2m, CH2CH3, 8H); 3.95 (d, JPH = 22.0
Hz, CHP, 2H); 1.38 and 1.09 (2t, J = 7.1 Hz, CH2CH3, 12H).
31P NMR (CDCl3, 81 MHz): δ 23.53.

Phenylene-Bis(Aminomethanephosphonates
187
Elemental analysis:
Calcd for C42H50N2O6P2: C-68.10; H-6.80; N-3.78; Found: C-68.14;
H-6.65; N-3.70.
Tetrabenzyl 1,4-phenylene-bis-
(N-diphenylmethylaminomethane)-bis-phosphonate (2dB)
Y = 3.45 g (35%). Mp 149–152◦C
1H NMR (CDCl3, 200 MHz): δ 7.36 (s, C6H4, 4H); 7.20 (m, ArH, 40H);
2
3
5.15 (Cze¸s´c´ uklꢀ. ABX, JHH = 11.8 Hz, JPH = 8.0 and 6.8 Hz, CH2Ph,
2
3
4H); 4.74 (Cze¸s´c´ uklꢀ. AMX, JHH = 11.8 Hz, JPH = 7.2 and 6.4 Hz,
2
CH2Ph, 4H); 4.65 (s, CHPh2, 2H); 4.05 (d, JPH = 21.9 Hz, CHP, 2H);
2.63 (s, NH, 2H).
31P NMR (CDCl3, 81 MHz): δ 23.46.
Elemental analysis:
Calcd for C62H58N2O6P2: C-75.29; H-5.91; N-2.83; Found: C-74.80;
H-5.92; N-3.01.
Tetraphenyl 1,4-phenylene-bis-
(N-diphenylmethylaminomethane)-bis-phosphonate (2dC)
Y = 2.85 g (30%). Mp 190–193◦C
1H NMR (CDCl3, 200 MHz): δ 7.46 (s, C6H4, 4H); 7.32–7.12 (m, ArH,
2
40H); 4.75 (s, CHPh2, 2H); 4.34 (d, JPH = 22.2 Hz, CHP, 2H); 2.75 (s,
NH, 2H).
31P NMR (CDCl3, 81 MHz): δ 15.67.
Elemental analysis:
Calcd for C58H50N2O6P2: C-74.67; H-5.40; N-3.00; Found: C-74.58;
H-5.38; N-2.90.
Tetraethyl 1,4-phenylene-bis-(N-anilinomethane)-bis-
phosphonate (2ꢀaA)
Y = 4.48 g (80%). Mp 162–165◦C (benzen-heksan).
1H NMR (CDCl3, 200 MHz): δ 7.44 (s, C6H4, 4H); 7.06 (dd, J = 7.8
and 7.6 Hz, CHm, 4H); 6.67 (t, J = 7.6 Hz, CHp, 2H); 6.54 (d, J = 7.8 Hz,
CHo, 4H); 4.73 (d, 2JPH = 23.3 Hz, CHP, 2H); 4.08 (m, OCH2CH3, 4H);
3.83 and 3.54 (2m, OCH2CH3, 2×2H); 2.17 (s, NH, 2H); 1.26 and 1.23
(2t, J = 6.9 Hz, OCH2CH3, 6H); 1.04, 0.93 (2t, J = 7.1 Hz, OCH2CH3,
6H).
31P NMR (CDCl3, 81 MHz): δ 22.47 and 22.42.
Elemental analysis:
Calcd for C28H38N2O6P2: C-59.99; H-6.83; N-5.00; Found: C-60.18;
H-6.98; N-4.82.

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Tetrabenzyl 1,4-phenylene-bis-(N-anilinomethane)-bis-
phosphonate (2ꢀaB)
Y = 6.46 g (80%). Mp 143–145◦C.
1H NMR (CDCl3, 200 MHz): δ 7.42 (s, C6H4, 4H); 7.26–6.94 (m, ArH,
24H); 6.65 (m, ArH, 2H); 6.51 (m, ArH, 4H); 4.95–4.73 (m, OCH2Ph,
2
6H); 4.89 and 4.82 (2d, JPH = 23.1 Hz, CHP, 2H); 4.47 and 4.31
3
2
(Part of 2 AMX system, JPH = 8.0 Hz, JHH = 11.6 Hz; OCH2Ph,
4H).
31P NMR (CDCl3, 81 MHz): δ 23.08 and 23.00.
Elemental analysis:
Calcd for C48H46N2O6P2: C-71.28; H-5.73; N-3.46; Found: C-71.42;
H-5.89; N-3.58.
Tetraphenyl 1,4-phenylene-bis-(N-anilinomethane)-bis-
phosphonate (2ꢀaC)
Y = 6.01 g (80%). Mp 181–184◦C.
1H NMR (CDCl3, 200 MHz): δ 7.56 (s, C6H4, 4H); 7.25–7.02 (m, ArH,
20H); 6.74 (m, CHp+m, 6H); 6.62 (d, J = 7.3 Hz, CHo, 4H); 5.13 (d, 2JPH
= 23.7 Hz, CHP, 2H); 5.05 (s, NH, 2H).
31P NMR (CDCl3, 81 MHz): δ 14.95.
Elemental analysis:
Calcd for C44H38N2O6P2: C-70.21; H-5.09; N-3.72; Found: C-70.43;
H-4.89; N-3.90.
Tetraethyl 1,4-phenylene-bis-(N-p-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀbA)
Y = 2.48 g (40%); mp = 188–192◦C.
1H NMR (200 MHz, CDCl3): δ 7.41 (s, C6H4, 4H); 6.64 (d, J = 9.0
Hz, p-C6H4, 4H); 6.50 (d, J = 9.0 Hz, p-C6H4, 4H); 4.64 (d, 2JPH = 22.7
Hz, CHP, 2H); 4.52 (large s, NH, 2H); 4.08 (m, OCH2CH3, 4H); 3.80 (m,
OCH2CH3, 2H); 3.67 (s, OCH3, 6H); 3.48 (m, OCH2CH3, 2H); 1.26 (t, J
= 7.0 Hz, OCH2CH3, 6H); 0.95 (t, J = 7.0 Hz, OCH2CH3, 6H). 31P NMR
(81 MHz, CDCl3): δ 23.92.
Elemental analysis:
Calcd for C30H42N2O8P2: C-58.06; H-6.82; N-4.51; Found: C-57.83;
H-7.17; N-4.45.
Tetrabenzyl 1,4-phenylene-bis-(N-p-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀbB)
Y = 7.91 g (92%); mp = 177–180◦C.
1H NMR (200 MHz, CDCl3): δ 7.42 (s, C6H4, 4H); 7.29–7.09 (m, C6H5,
20H); 6.59 and 6.58 (2d, J = 9.0 Hz, p-C6H4, 4H); 6.47 and 6.46 (2d, J
= 9.0 Hz, p-C6H4, 4H); 4.98 and 4.74 (m, OCH2Ph, 8H); 4.47 and 4.32

Phenylene-Bis(Aminomethanephosphonates
189
2
(2d, JPH = 19.7 Hz, CHP, 2H); 4.30 (large s, NH, 2H); 3.60 and 3.57
(2s, OCH3, 6H). 31P NMR (81 MHz, CDCl3): δ 24.54 and 24.46.
Elemental analysis:
Calcd for C50H50N2O8P2: C-69.12; H-5.80; N-3.22; Found: C-69.31;
H-5.95; N-3.20.
Tetraphenyl 1,4-phenylene-bis-(N-p-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀbC)
Y = 5.85 g (72%); mp = 177–179◦C.
1H NMR (200 MHz, CDCl3): δ 7.55 (s, C6H4, 4H); 7.27–7.01 (m, C6H5,
20H); 6.67 (d, J = 8.9 Hz, p-C6H4, 4H); 6.57 (d, J = 8.9 Hz, p-C6H4, 4H);
5.05 (d, 2JPH = 23.2 Hz, CHP, 2H); 4.65 (large s, NH, 2H); 3.71 (s, OCH3,
6H). 31P NMR (81 MHz, CDCl3): δ 16.42.
Elemental analysis:
Calcd for C46H42N2O8P2: C-67.98; H-5.21; N-3.45; Found: C-68.07;
H-5.32; N-3.18.
Tetraethyl 1,4-phenylene-bis-(N-m-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀcA)
Y = 3.54 g (57%); mp = 166–170◦C.
1H NMR (200 MHz, CDCl3): δ 7.43 (s, C6H4, 4H); 6.69 (dd, J = 8.2
and 10.0 Hz, m-C6H4, 2H); 6.22 (dd, J = 8.1 and 2.2 Hz, m-C6H4, 2H);
6.17 (dd, J = 8.1 and 1.7 Hz, m-C6H4, 2H); 6.08 (t, J = 2.0 Hz, m-C6H4,
2H); 4.70 (d, 2JPH = 23.4 Hz, CHP, 2H); 4.82 (large s, NH, 2H); 4.08 (m,
OCH2CH3, 4H); 3.82 (m, OCH2CH3, 2H); 3.66 (s, OCH3, 6H); 3.48 (m,
OCH2CH3, 2H); 1.26 (t, J = 7.1 Hz, OCH2 CH3, 6H); 0.96 (t, J = 7.1 Hz,
OCH2CH3, 6H). 31P NMR (81 MHz, CDCl3): δ 23.60.
Elemental analysis:
Calcd for C30H42N2O8P2: C-58.06; H-6.82; N-4.51; Found: C-57.88;
H-6.64; N-4.62.
Tetrabenzyl 1,4-phenylene-bis-(N-m-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀcB)
Y = 7.57 g (88%); mp = 117–120◦C.
1H NMR (200 MHz, CDCl3): δ 7.42 (s, C6H4, 4H); 7.39–7.07 (m, C6H5,
20H); 6.95 (m, m-C6H4, 2H); 6.17 (m, m-C6H4, 4H); 6.05 (m, m-C6H4,
2H); 4.99 (m, OCH2Ph, 4H); 4.82 (m, OCH2Ph, 2H); 4.79 (d, 2JPH = 24.9
Hz, CHP, 2H); 4.41 (m, OCH2Ph, 2H); 3.57 (s, CH3, 6H). 31P NMR (81
MHz, CDCl3): δ 22.97.
Elemental analysis:
Calcd for C50H50N2O8P2: C-69.12; H-5.80; N-3.22; Found: C-69.33;
H-5.63; N-3.34.

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Tetraphenyl 1,4-phenylene-bis-(N-m-
methoxyphenylaminomethane)-bis-phosphonate (2ꢀcC)
Y = 3.48 g (56%); mp = 160–163◦C.
1H NMR (200 MHz, CDCl3): δ 7.78 (s, C6H4, 4H); 7.48–7.24 (m,
C6H5, 20H); 6.98 (dd, J = 8.3 and 8.0 Hz, m-C6H4, 2H); 6.55 (d, J
= 8.1 Hz, m-C6H4, 2H); 6.54 (d, J = 8.0 Hz, m-C6H4, 2H); 6.45 (t,
2
J = 3.0 Hz, m-C6H4, 2H); 5.34 (d, JPH = 23.6 Hz, CHP, 2H); 5.15
(large s, NH, 2H); 3.82 (m, OCH3, 6H). 31P NMR (81 MHz, CDCl3): δ
16.14.
Elemental analysis:
Calcd for C46H42N2O8P2: C-67.98; H-5.21; N-3.45; Found: C-68.13;
H-5.35; N-3.58.
Tetraethyl 1,4-phenylene-bis-(N-p-
methylphenylaminomethane)-bis-phosphonate (2ꢀdA)
Y = 5.41 g (92%); mp = 182–185◦C.
1H NMR (200 MHz, CDCl3): δ 7.42 (s, C6H4, 4H); 6.86 (d, J = 7.8
Hz, p-C6H4, 4H); 6.45 (d, J = 7.8 Hz, p-C6H4, 4H); 4.69 (d, 2JPH = 23.4
Hz, CHP, 2H); 4.07 (m, OCH2CH3, 4H); 3.86–3.41 (m, O CH2CH3, 4H);
2.16 (s, OCH3, 6H); 1.25 and 1.23 (2t, J = 6.8 Hz, OCH2CH3, 6H); 1.04
and 0.94 (2t, J = 7.0 Hz, OCH2CH3, 6H). 31P NMR (81 MHz, CDCl3): δ
22.42.
Elemental analysis:
Calcd for C30H42N2O6P2: C-61.22; H-7.19; N-4.76; Found: C-61.41;
H-7.15; N-4.51.
Tetrabenzyl 1,4-phenylene-bis-(N-p-
methylphenylaminomethane)-bis-phosphonate (2ꢀdB)
Y = 7.45 g (90%); mp = 174–176◦C.
1H NMR (200 MHz, CDCl3): δ 7.41 and 7.40 (2s, C6H4, 4H); 7.31–7.08
(m, C6H5, 20H); 6.81 (d, J = 8.5 Hz, p-C6H4, 4H); 6.43 (d, J = 8.5 Hz,
p-C6H4, 4H); 4.99–4.68 (m, OCH2Ph, 6H); 4.81 (d, 2JPH = 22.4 Hz, CHP,
2H); 4.46 and 4.27 (2dd, 3JPH = 8.3 Hz, 2JHH = 11.8 Hz, OCH2Ph, 2H);
2.11 and 2.08 (2s, CH3, 6H). 31P NMR (81 MHz, CDCl3): δ 23.25 and
23.14 (3:2).
Elemental analysis:
Calcd for C50H50N2O6P2: C-71.76; H-6.02; N-3.35; Found: C-71.49;
H-5.82; N-3.07.
Tetraphenyl 1,4-phenylene-bis-(N-p-
methylphenylaminomethane)-bis-phosphonate (2ꢀdC)
Y = 7.18 g (92%); mp = 203–205◦C.
1H NMR (200 MHz, CDCl3): δ 7.53 (s, C6H4, 4H); 7.21–7.03 (m,
C6H5, 16H); 6.93 (d, J = 8.2 Hz, p-C6H4, 4H); 6.74 (m, C6H5, 4H); 6.52

Phenylene-Bis(Aminomethanephosphonates
191
2
(d, J = 8.2 Hz, p-C6H4, 4H); 5.09 (d, JPH = 23.8 Hz, CHP, 2H); 3.86
(large s, NH, 2H); 2.20 (2s, CH3, 6H). 31P NMR (81 MHz, CDCl3): δ
15.13.
Elemental analysis:
Calcd for C46H42N2O6P2: C-70.76; H-5.42; N-3.59; Found: C-70.49;
H-5.09; N-3.29.
Tetraethyl 1,4-phenylene-bis-(N-m-
methylphenylaminomethane)-bis-phosphonate (2ꢀeA)
Y = 5.17 g (88%); mp = 141–144◦C.
1H NMR (200 MHz, CDCl3): δ 7.44 (s, C6H4, 4H); 6.94 (ddd, 3JHH
=
5
9.1 and 7.9 Hz, JHH = 1.4 Hz, m-C6H4, 2H); 6.49 (d, J = 9.1 Hz, m-
C6H4, 2H); 6.38 (m, m-C6H4, 2H); 6.33 (d, J = 7.9 Hz, m-C6H4, 2H); 4.73
and 4.72 (2d, 2JPH = 23.2 Hz, CHP, 2H); 4.08 (m, OCH2CH3, 4H); 3.83
(m, OCH2CH3, 2H); 3.60 (m, OCH2CH3, 1H); 3.49 (m, OCH2CH3, 1H);
2.18 and 2.17 (2s, CH3, 6H); 1.25 and 1.23 (2t, J = 7.1 Hz, OCH2CH3,
6H); 1.04 and 0.95 (2t, J = 7.0 Hz, OCH2CH3, 6H). 31P NMR (81 MHz,
CDCl3): δ 23.81 and 23.75.
Elemental analysis:
Calcd for C30H42N2O6P2: C-61.22; H-7.19; N-4.76; Found: C-61.43;
H-7.28; N-4.91.
Tetrabenzyl 1,4-phenylene-bis-(N-m-
methylphenylaminomethane)-bis-phosphonate (2ꢀeB)
Y = 6.95 g (84%); mp = 123–125◦C.
1H NMR (200 MHz, CDCl3): δ 7.45 and 7.44 (2s, C6H4, 4H); 7.34–7.10
3
(m, C6H5, 20H); 6.91 (dd, JHH = 13.2 and 7.5 Hz, m-C6H4, 2H); 6.48
and 6.46 (2d, J = 7.5 Hz, m-C6H4, 2H); 6.37 and 6.36 (2m, m-C6H4,
2H); 6.33 and 6.32 (2d, J = 13.2 Hz, m-C6H4, 2H); 4.99 (m, OCH2Ph,
4H); 4.80 (Part of ABX system, 3JPH = 7.2 and 7.5 Hz, 2JHH = 12.1 Hz,
2
OCH2Ph, 2H); 4.79 (d, JPH = 24.9 Hz, CHP, 2H); 4.42 (Part of AMX
system, 3JPH = 7.8 and 8.1 Hz, 2JHH = 11.5 Hz, OCH2Ph, 2H); 2.15 and
2.13 (2s, CH3, 6H). 31P NMR (81 MHz, CDCl3): δ 24.47 and 24.37.
Elemental analysis:
Calcd for C50H50N2O6P2: C-71.76; H-6.02; N-3.35; Found: C-71.91;
H-6.22; N-3.51.
Tetraphenyl 1,4-phenylene-bis-(N-m-
methylphenylaminomethane)-bis-phosphonate (2ꢀeC)
Y = 6.72 g (86%); mp = 179–181◦C.
1H NMR (200 MHz, CDCl3): δ 7.57 and 7.56 (2s, C6H4, 4H); 7.21 (m,
3
C6H5, 4H); 7.14–7.00 (m, C6H5, 16H); 6.76 (t, JHH = 8.2 Hz, m-C6H4,
2H); 6.58 (m, m-C6H4, 2H); 6.47 and 6.46 (2m, m-C6H4, 2H); 6.41 (d, J

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L. Lewkowski
= 8.2 Hz, m-C6H4, 2H); 5.13 (d, 2JPH = 23.6 Hz, CHP, 2H); 3.86 (large
s, NH, 2H); 2.22 and 2.21 (2s, CH3, 6H). 31P NMR (81 MHz, CDCl3): δ
16.36 and 16.32.
Elemental analysis:
Calcd for C46H42N2O6P2: C-70.76; H-5.42; N-3.59; Found: C-70.91;
H-5.56; N-3.70.
Tetraethyl 1,4-phenylene-bis-(N-meta-nitroanilinemethane)-
bis-phosphonate (2ꢀgA)
Y = 2.54 g (39%). Mp 198–201◦C.
1H NMR (CDCl3, 200 MHz): δ 7.62 and 7.33 (2m, CHarom, 2H); 7.52
and 7.49 (2s, C6H4, 4H); 7.43 (d, J = 8.1 Hz, CHarom, 2H); 7.18 and
7.17 (2d, J = 8.2 Hz, CHarom, 2H); 6.88 (m, CHarom, 2H); 4.84 and
2
4.78 (2d, JPH = 23.8 Hz, CHP, 2H); 4.26 and 3.59 (2m, CH2CH3, 8H);
1.97 (s, NH, 2H); 1.31, 1.27 and 1.06, 0.98 (4t, J = 6.6 Hz, CH2 CH3,
12H).
31P NMR (CDCl3, 81 MHz): δ 20.89 and 20.79.
Elemental analysis:
Calcd for C28H36N4O10P2: C-51.70; H-5.58; N-8.61; Found: C-51.52;
H-5.30; N-8.63.
Tetrabenzyl 1,4-phenylene-bis-(N-meta-nitroanilinomethane)-
bis-phosphonate (2ꢀgB)
Y = 4,05 g (45%). Mp 158–161◦C.
1H NMR (CDCl3, 200 MHz): δ 7.57 and 7.45 (2s, C6H4, 4H); 7.30–7.05
2
(m, CHarom, 28H); 4.86 (2d, JPH = 22.6 Hz, CHP, 2H); 5.10–4.70 and
4.57–4.42 (2m, CH2Ph, 8H); 3.10 (s, NH, 2H).
31P NMR (CDCl3, 81 MHz): δ 21.29 and 21.21.
Elemental analysis:
Calcd for C48H44N4O10P2: C-64.14; H-4.93; N-6.23; Found: C-63.97;
H-4.85; N-6.02.
Tetraphenyl 1,4-phenylene-bis-(N-meta-nitroanilinomethane)-
bis-phosphonate (2ꢀgC)
Y = 2,70 g (32%). Mp 201–203◦C.
1H NMR (CDCl3, 200 MHz): δ 7.58 (2s, C6H4, 4H); 7.35 and 7.24–6.61
(2m, CHarom, 28H); 5.24 (d, 2JPH = 24.2 Hz, CHP, 2H); 1.97 (s, NH, 2H).
31P NMR (CDCl3, 81 MHz): δ 13.61 and 13.26.
Elemental analysis:
Calcd for C44H36N4O10P2: C-62.71; H-4.31; N-6.65; Found: C-62.59;
H-4.27; N-6.49.

Phenylene-Bis(Aminomethanephosphonates
193
Tetraethyl 1,4-phenylene-bis-(N-p-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀhA)
Y = 2.91 g (45%); mp = 235–237◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.13 (c, COOH, 2H); 7.58 (d, J
= 8.4 Hz, p-C6H4, 4H); 7.49 (s, C6H4, 4H); 6.81 (d, J = 8.4 Hz, p-C6H4,
2
4H); 5.15 and 5.10 (d, JPH = 23.7 Hz, CHP, 2H); 3.68 (m, OCH2CH3,
8H); 1.12 and 0.93 (2t, J = 7.0 Hz, OCH2CH3, 6H). 31P NMR (81 MHz,
CD3S(O)CD3): δ 21.84 and 18.33 (5:1).
Elemental analysis:
Calcd for C30H38N2O10P2: C-55.56; H-5.91; N-4.32; Found: C-55.72;
H-6.08; N-4.48.
Tetrabenzyl 1,4-phenylene-bis-(N-p-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀhB)
Y = 7.88 g (88%); mp = 220–224◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.16 (s, COOH, 2H); 7.61 (d, J
= 8.4 Hz, p-C6H4, 4H); 7.52 (s, C6H4, 4H); 6.86 (d, J = 8.4 Hz, p-C6H4,
4H); 4.99 (m, OCH2Ph, 4H); 4.82 (m, OCH2Ph, 2H); 4.41 (m, OCH2Ph,
2H). 31P NMR (81 MHz, CD3S(O)CD3): δ 21.34 and 21.03 (3:1).
Elemental analysis:
Calcd for C50H46N2O10P2: C-66.96; H-5.17; N-3.12; Found: C-67.12;
H-5.32; N-3.27.
Tetraphenyl 1,4-phenylene-bis-(N-p-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀhC)
Y = 6.64 g (79%); mp = 215–217◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.14 (s, COOH, 2H); 7.75 (s,
C6H4, 4H); 7.67 (d, J = 8.2 Hz, p-C6H4, 4H); 7.28–6.96 (m, C6H5, 16H);
6.72 (m, C6H5, 4H); 6.53 (d, J = 8.2 Hz, p-C6H4, 4H); 5.81 (d, 2JPH = 22.6
Hz, CHP, 2H); 3.86 (large s, NH, 2H). 31P NMR (81 MHz, CD3S(O)CD3):
δ 20.52.
Elemental analysis:
Calcd for C46H38N2O10P2: C-65.71; H-4.56; N-3.33; Found: C-65.90;
H-4.71; N-3.49.
Tetraethyl 1,4-phenylene-bis-(N-m-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀiA)
Y = 3.30 g (51%); mp = 201–206◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.18 (s, COOH, 2H); 7.83 (m, m-
C6H4, 2H); 7.76 (s, C6H4, 4H); 7.58 (m, m-C6H4, 2H); 6.71 (m, m-C6H4,
2H); 5.34 (d, 2JPH = 23.5 Hz, CHP, 2H); 4.09 (m, OCH2CH3, 4H); 3.66 (m,
OCH2CH3, 4H); 1.26 and 1.24 (2t, J = 6.8 Hz, OCH2CH3, 6H); 1.07 and

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L. Lewkowski
0.98 (2t, J = 6.9 Hz, OCH2CH3, 6H). 31P NMR (81 MHz, CD3S(O)CD3):
δ 21.87.
Elemental analysis:
Calcd for C30H38N2O10P2: C-55.56; H-5.91; N-4.32; Found: C-55.72;
H-6.21; N-4.51.
Tetrabenzyl 1,4-phenylene-bis-(N-m-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀiB)
Y = 7.97 g (89%); mp = 209–210◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.09 (s, COOH, 2H); 7.79 (m,
m-C6H4, 2H); 7.71 (s, C6H4, 4H); 7.53 (m, m-C6H4, 2H); 7.48–7.24 (m,
2
C6H5, m-C6H4, 22H); 6.70 (m, m-C6H4, 2H); 5.34 (d, JPH = 23.8 Hz,
CHP, 2H); 4.99 (m, OCH2Ph, 4H); 4.82 (m, OCH2Ph, 2H); 4.41 (m,
OCH2Ph, 2H). 31P NMR (81 MHz, CD3S(O)CD3): δ 23.12.
Elemental analysis:
Calcd for C50H46N2O10P2: C-66.96; H-5.17; N-3.12; Found: C-67.22;
H-5.34; N-3.28.
Tetraphenyl 1,4-phenylene-bis-(N-m-
carboxyphenylaminomethane)-bis-phosphonate (2ꢀiC)
Y = 6.64 (79%); mp = 220–224◦C (decomp).
1H NMR (200 MHz, CD3S(O)CD3): δ 10.17 (s, COOH, 2H); 7.83 (m,
m-C6H4, 2H); 7.74 (s, C6H4, 4H); 7.53 (m, m-C6H4, 2H); 7.48–7.24 (m,
2
C6H5, m-C6H4, 22H); 6.70 (m, m-C6H4, 2H); 5.70 (d, JPH = 23.8 Hz,
CHP, 2H); 5.15 (large s, NH, 2H). 31P NMR (81 MHz, CDCl3): δ 16.01.
Elemental analysis:
Calcd for C46H38N2O10P2: C-65.71; H-4.56; N-3.33; Found: C-65.94;
H-4.71; N-3.17.
ACKNOWLEDGMENTS
The financial support of the Polish State Committee for Scientific Re-
search (KBN) is kindly acknowledged. GAMESS for ChemOffice7.0 was
provided free of charge by the Department of Chemistry of the Iowa
State University in Ames.
REFERENCES
[1] J. Barycki, R. Gancarz, M. Milewska, and R. Tyka, Phosphorus, Sulfur and Silicon,
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