Benzoylhydrazones in catalytic hydrophosphorylation

Article abstract of DOI:10.1007/s11172-010-0094-3

Reactions of benzoylhydrazones derived from heterocyclic and aromatic aldehydes and aliphatic, heterocyclic, and aliphatic-aromatic ketones with diethyl phosphite in the presence of [tetra(tert-butyl)phthalocyanine]aluminum chloride afford α-benzoylhydraz

Full text of DOI:10.1007/s11172-010-0094-3

Russian Chemical Bulletin, International Edition, Vol. 59, No. 2, pp. 411—417, February, 2010
411
Benzoylhydrazones in catalytic hydrophosphorylation
E. D. Matveeva, T. A. Podrugina, I. N. Kolesnikova, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 939 0290. Eꢀmail: matveeva@org.chem.msu.ru
Reactions of benzoylhydrazones derived from heterocyclic and aromatic aldehydes and
aliphatic, heterocyclic, and aliphaticꢀaromatic ketones with diethyl phosphite in the presence
of [tetra(tertꢀbutyl)phthalocyanine]aluminum chloride afford αꢀbenzoylhydrazino phosphoꢀ
nates in high yields.
Key words: catalysis, hydrazones, benzohydrazide, αꢀhydrazino phosphonates, the Pudovik
reaction, [tetra(tertꢀbutyl)phthalocyanine]aluminum chloride.
αꢀHydrazino phosphonic acids are structural analogs
of αꢀamino phosphonic acids. The biological activity of
αꢀhydrazino phosphonic acids1 and the existence of natuꢀ
ral phosphonates2—4 stimulate scientists to search for new
methods of synthesis of this class of compounds.
Benzoylhydrazones were obtained in 85—97% yields
according to a standard procedure by reactions of benzoꢀ
hydrazide or substituted benzohydrazides with carbonyl
compounds in ethanol or without solvent.
Threeꢀcomponent reactions of any carbonyl comꢀ
pounds with benzohydrazide and diethyl phosphite in
αꢀHydrazino phosphonates are mainly obtained by hyꢀ
drophosphorylation of compounds containing the C=N
bond (the Pudovik reaction5). To the best of our knowꢀ
ledge, there are few examples of addition of dialkyl phosꢀ
phites to hydrazones.6—9 Thus formaldehyde benzylꢀ
oxycarbonylhydrazone6 and oꢀnitrobenzaldehyde phenylꢀ
hydrazone7 were hydrophosphorylated under conditions
of basic catalysis. Acidꢀcatalyzed hydrophosphorylaꢀ
tion of hydrazones of unsaturated aldehydes was also
described.8 Recently, the synthesis of αꢀhydrazino phosꢀ
phonates from acetone and cyclopentanone benzoylꢀ
hydrazones in the presence of BF3•Et2O has been docuꢀ
mented; however, the yields of the target products are low
(13—44%).9
Alternative routes (such as the LiClO4ꢀcatalyzed Kaꢀ
bachnik—Fields reaction,10,11 nucleophilic substitution of
modified αꢀhydroxy phosphonates with hydrazine,12 and
reduction of αꢀhydrazono phosphonates13) afford αꢀhydrꢀ
azino phosphonates only from aldehydes.
Thus, according to the literature data, the search for
a general method of synthesis of phosphonates from hydrꢀ
azones of aliphatic and especially aromatic ketones still
remains of current interest.
t
CH2Cl2, toluene, or xylene in the presence of PcAlCl
resulted in very rapid precipitation of the corresponding
hydrazones, which did not undergo hydrophosphorylation
under heterogeneous conditions. That is why the preformed
benzoylhydrazones were used in subsequent experiments
and their tPcAlClꢀcatalyzed hydrophosphorylation (a verꢀ
sion of the Pudovik reaction) was carried out in the excess
of diethyl phosphite as a solvent (Scheme 1).
This catalytic twoꢀcomponent process was used to obꢀ
tain αꢀbenzoylhydrazino phosphonates from benzoylhyꢀ
drazones of the following aliphatic, carbocyclic, and hetꢀ
erocyclic ketones: acetone (1a), cyclohexanone (1e), cyꢀ
clopentanone (1i), NꢀBocꢀpiperidone (1m), and cycloꢀ
propyl methyl ketone (1n) (see Scheme 1). The yields of
the corresponding αꢀbenzoylhydrazino phosphonates 2e,
2i, 2m, and 2n were 50—85%.
The presence of an electronꢀdonating or ꢀwithdrawing
substituent in the paraꢀposition of the phenyl ring of aceꢀ
tone and cyclohexanone benzoylhydrazones virtually does
not affect the reactivities of hydrazones 1b—d and 1f—h.
Thus, the corresponding αꢀbenzoylhydrazino phosphoꢀ
nates 2b—d and 2f—h were obtained in 75—85% yields
(reaction times 4—6 h).
However, variation of substituents in the phenyl ring
of cyclopentanone benzoylhydrazone, which is less reacꢀ
tive than acetone and cyclohexanone benzoylhydrazones,
revealed that the corresponding hydrazones (1f—e) signifꢀ
icantly differ in their reactivity. Thus, electronꢀdonating
substituents inhibit, while electronꢀwithdrawing ones proꢀ
mote, the hydrophosphorylation reaction.
Recently, we have developed a catalytic method
of synthesis of αꢀamino phosphonates in the presence
of [tetra(tertꢀbutyl)phthalocyanine]aluminum chloride
(tPcAlCl), affording the target compounds not only from
amines but also from amino acids and not only from aldeꢀ
hydes but also from various ketones.14—16 In the present
t
work, we used PcAlCl for the synthesis of αꢀhydrazino
phosphonates from benzoylhydrazones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 403—408, February, 2010.
1066ꢀ5285/10/5902ꢀ0411 © 2010 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Matveeva et al.
Scheme 1
Table 1. Synthesis of benzoylhydrazones 1a—s and the corresponding 2ꢀbenzoylhydrazino phosphonates 2a—s
R1C(O)R2
X
1
Yield of 1
Ratio of
t/h*
Product
Yield of 2
(%)
1 : HP(O)(OEt)2
2
(%)
MeC(O)Me
MeC(O)Me
MeC(O)Me
MeC(O)Me
(CH2)5CO
(CH2)5CO
(CH2)5CO
(CH2)5CO
(CH2)4CO
(CH2)4CO
(CH2)4CO
(CH2)4CO
(CH2)2NBoc(CH2)2CO
(CH2)3C(O)Me
PhC(O)H
H
NO2
Br
OMe
H
NO2
Br
OMe
H
NO2
Br
OMe
H
H
H
а
b
c
d
e
f
g
h
i
j
k
l
m
n
o
90
90
95
85
90
95
90
90
95
97
95
95
95
85
92
1 : 3
1 : 5
1 : 5
1 : 5
1 : 3
1 : 5
1 : 5
1 : 5
1 : 3
1 : 5
1 : 5
1 : 5
1 : 5
1 : 3
1 : 3
2
4
6
6
0.5
4
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
75
75
80
85
80
80
85
85
50
90
70
65
65
50
75
6
4
24
8
24
32
8
32
24
H
H
p
q
90
85
1 : 5
1 : 5
20
40
p
q
65
75
PhC(O)Me
H
H
r
s
95
95
1 : 5
1 : 7
40
50
r
s
50
55
* The reaction time.
To extend the scope of this method, we carried out
When the reaction time was doubled (48 and 80 h, respecꢀ
tively), the yields of these products increased only to 40 and
30%. This process was accompanied by considerable degꢀ
radation of the starting diethyl phosphite and the reaction
products, which is evident from numerous signals in the
31P NMR spectrum. At the same time, tPcAlClꢀcatalyzed
hydrophosphorylation of these hydrazones gives αꢀhydrꢀ
azino phosphonates 2i and 2r in 50% yields over 24 and
40 h, respectively.
The synthesis of phosphonates 2m and 2s is of principal
importance since, on the one hand, the compounds obꢀ
tained are bioisosters of the ligands to GABA17 and glutaꢀ
mate receptors18 and, on the other hand, it has been shown
for the first time that αꢀhydrazino phosphonates can be
synthesized from heterocyclic and aromatic ketones.
reactions of diethyl phosphite with benzoylhydrazones of
aromatic and heterocyclic aldehydes (1o and 1p) and benꢀ
zoylhydrazones of aliphaticꢀaromatic ketones (acetopheꢀ
none (1q), indanꢀ1ꢀone (1r), and methyl 1ꢀoxoindaneꢀ5ꢀ
carboxylate (1s)). The yields of the corresponding αꢀbenꢀ
zoylhydrazino phosphonates 2o—s were 55—75%.
By an example of acetone benzoylhydrazone (1a), it
was shown that noncatalytic hydrophosphorylation for 2 h
also leads to αꢀbenzoylhydrazino phosphonate 2a in 55%
yield. Under the same conditions in the presence of
tPcAlCl, the yield of this product increased to 75%. Nonꢀ
catalytic hydrophosphorylation of cyclopentanone (1i) and
indanone hydrazones (1r) affords hydrazino phosphonates
2i and 2r in 20% yields over 24 and 40 h, respectively.

αꢀBenzoylhydrazino phosphonates
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
413
163.42 (s, C=O); 164.05 (s, C=N). IR (CCl4), ν/cm–1: 1650
(C=N); 1670 (C=O); 3230 (N—H). Found (%): C, 53.10;
H, 5.25; N, 9.44. C13H15BrN2O. Calculated (%): C, 52.90;
H, 5.12; N, 9.49.
NꢀCyclohexylideneꢀ4ꢀmethoxybenzohydrazide (1h), m.p.
149—150 °C. 1H NMR (CD3CN), δ: 1.62—1.75 (m, 6 H, ring);
2.33—2.36 (m, 2 H, ring); 2.38—2.41 (m, 2 H, ring); 3.84 (s, 3 H,
Me); 6.98 (d, 2 H, arom., 3JH,H = 8.7 Hz); 7.80 (d, 2 H, arom.,
3JH,H = 9.0 Hz); 9.19 (br.s, 1 H, NH). 13C NMR (CDCl3), δ:
25.54, 25.92, 26.88, 27.06, 35.52 (Cring); 55.57 (s, OMe); 113.70,
125.97, 129.09, 162.22 (Carom); 162.52 (s, C=O); 163.83
(s, C=N). IR (CCl4), ν/cm–1: 1650 (C=N); 1660 (C=O); 3250
(N—H). Found (%): C, 68.26; H, 7.41; N, 11.15. C14H18N2O2.
Calculated (%): C, 68.27; H, 7.37; N, 11.37.
NꢀCyclopentylideneꢀ4ꢀbromobenzohydrazide (1k), m.p.
205—206 °C. 1H NMR (CD3CN), δ: 1.74—1.81 (m, 2 H, ring);
1.83—1.90 (m, 2 H, ring); 2.36—2.39 (m, 2 H, ring); 2.40—2.47
(br.m, 2 H, ring); 7.64 (d, 2 H, arom., 3JH,H = 8.4 Hz); 7.72 (d, 2 H,
arom., 3JH,H = 8.4 Hz); 8.94 (br.s, 1 H, NH). 13C NMR (CDCl3),
δ: 24.66, 24.85, 27.57, 33.60 (Cring); 126.45, 128.87, 131.91,
132.47 (Carom); 162.97 (s, C=O); 168.49 (s, C=N). IR (CCl4),
ν/cm–1: 1635 (C=N); 1650 (C=O); 3210 (N—H). Found (%):
C, 51.28; H, 4.62; N, 9.89. C12H13BrN2O. Calculated (%):
C, 51.26; H, 4.66; N, 9.96.
The structures of αꢀhydrazino phosphonates 2p—s were
determined from their 1H, 13C, and 31P NMR (see Ref. 15),
IR, and mass spectra; their compositions were confirmed
by elemental analysis data. The signals in the 31P NMR
spectra of αꢀhydrazino phosphonates 2a—n obtained from
aliphatic ketones appear at δ 26—30; analogous signals for
aromatic derivatives 2o—s appear at δ 21—25.
Experimental
NMR spectra were recorded on a Bruker Avance 400 instruꢀ
ment (400.13 (1H), 100.61 (13C), and 161.98 MHz (31P)) in
CDCl3, CD3CN, CD3OD, and DMSOꢀd6 with SiMe4 as the
internal standard (1H and 13C) and with 85% H3PO4 as the
external standard (31P). IR spectra were recorded on a URꢀ20
instrument in CCl4. Elemental analysis was carried out on
a VarioꢀII CHNꢀanalyzer. Mass spectra were measured on
a Finnigan Mat Incos 50 quadrupole mass spectrometer (EI,
70 eV, direct inlet probe).
Diethyl phosphite (Aldrich) was used as purchased. [Tetraꢀ
(tertꢀbutyl)phthalocyanine]aluminum chloride was prepared acꢀ
cording to a known procedure.19 The course of the reaction was
monitored, and the purity of the products was checked, by TLC
on ALUGRAM SIL G/UV254 plates. The products were sepaꢀ
rated by column chromatography on Merck 60 silica gel (70—230
mesh ASTM).
Synthesis of benzoylhydrazones 1a—l,n,o,q (general proceꢀ
dure). A mixture of a carbonyl compound (9 mmol) and benzoꢀ
hydrazide (3 mmol) was refluxed for 1—3 h. The mixture was
cooled to room temperature and the crystals that formed were
filtered off, washed with ether, and dried in vacuo.
Nꢀ(1ꢀMethylethylidene)benzohydrazide (1a), m.p. 142—143 °C
(cf. Ref. 20: m.p. 142—143 °C).
NꢀCyclopentylideneꢀ4ꢀmethoxybenzohydrazide (1l). Yield
95%, m.p. 177—180 °C. 1H NMR (CD3CN), δ: 1.73—1.80
(m, 2 H, ring); 1.83—1.90 (m, 2 H, ring); 2.36—2.40 (m, 2 H,
ring); 2.41—2.45 (m, 2 H, ring); 3.84 (s, 3 H, Me); 6.98 (d, 2 H,
3
3
arom., JH,H = 9.0 Hz); 7.79 (d, 2 H, arom., JH,H = 8.7 Hz);
8.83 (br.s, 1 H, NH). 13C NMR (CDCl3), δ: 24.65, 24.82, 27.36,
33.53 (Cring); 55.40 (s, OMe); 113.79, 125.69, 129.07, 162.35
(Carom); 163.48 (s, C=O); 167.17 (s, C=N). IR (CCl4), ν/cm–1
:
1650 (C=N); 1670 (C=O); 3270 (N—H). Found (%): C, 67.30;
H, 7.02; N, 11.99. C13H16N2O2. Calculated (%): C, 67.22;
H, 6.94; N, 12.06.
Nꢀ(1ꢀMethylethylidene)ꢀ4ꢀnitrobenzohydrazide (1b). Yield
90%, m.p. 158—159 °C (cf. Ref. 20: m.p. 158—159 °C).
Nꢀ(1ꢀMethylethylidene)ꢀ4ꢀbromobenzohydrazide (1c), m.p.
195—197 °C (cf. Ref. 21: m.p. 97—198 °C).
Nꢀ(1ꢀMethylethylidene)ꢀ4ꢀmethoxybenzohydrazide (1d), m.p.
127—129 °C (cf. Ref. 20: m.p. 128—129 °C).
NꢀCyclohexylidenebenzohydrazide (1e), m.p. 163—165 °C (cf.
Ref. 22: m.p. 164—165 °C).
NꢀCyclohexylideneꢀ4ꢀnitrobenzohydrazide (1f). Yield 95%,
m.p. 149—150 °C (cf. Ref. 23: m.p. 150 °C).
NꢀCyclopentylidenebenzohydrazide (1i). Yield 95%, m.p.
150—152 °C (cf. Ref. 22: m.p. 149—151 °C).
NꢀCyclopentylideneꢀ4ꢀnitrobenzohydrazide (1j), m.p.
150—152 °C (cf. Ref. 9: m.p. 150—152 °C).
Nꢀ(1ꢀCyclopropylethylidene)benzohydrazide (1n), m.p.
122—123 °C (cf. Ref. 24: m.p. 121—124 °C).
NꢀBenzylidenebenzohydrazide (1o), m.p. 209—210 °C (cf.
Ref. 25: m.p. 209—210 °C).
Nꢀ(1ꢀPhenylethylidene)benzohydrazide (1q), m.p. 155—157 °C
(cf. Ref. 26: m.p. 155—157 °C).
NꢀCyclohexylideneꢀ4ꢀbromobenzohydrazide (1g), m.p.
180—182 °C. 1H NMR (CD3CN), δ: 1.65—1.66 (m, 4 H, ring);
1.70—1.76 (m, 2 H, ring); 2.32—2.40 (m, 4 H, ring); 7.64 (d, 2 H,
tertꢀButyl 4ꢀ(benzoylhydrazono)piperidineꢀ1ꢀcarboxylate (1m).
A melt of NꢀBocꢀpiperidone (2 mmol) and benzohydrazide
(2 mmol) was heated at 80 °C for 40 min. The mixture was cooled
to room temperature and the crystals that formed were washed
with diethyl ether and dried in vacuo. The yield was 95%, m.p.
155—156 °C. 1H NMR (CDCl3), δ: 1.44 (s, 9 H, But); 2.46—2.49
(m, 4 H, ring); 3.51—3.54 (m, 4 H, ring); 7.35 (m, 1 H, arom.);
7.43—7.47 (m, 2 H, arom.); 7.74 (d, 2 H, arom., 3JH,H = 7.1 Hz);
9.34 (br.s, 1 H, NH). 13C NMR (CDCl3), δ: 27.53 (s, Cring);
28.36 (s, Me, But); 33.97 (s, Cring); 41.09 (s, Cring); 43.78
(s, Cring); 80.18 (s, C, But); 127.36, 128.35, 131.82, 133.39
(Carom); 154.55 (s, C=O, C(O)OBut); 158.93 (s, C=O, C(O)Ph);
164.54 (s, C=N). IR (CCl4), ν/cm–1: 1650 (C=N); 1670 (C=O);
1690 (C(O)(OBut)); 3200 (N—H). Found (%): C, 64.67; H, 7.33;
N, 13.12. C17H23N2O3. Calculated (%): C, 64.33; H, 7.30;
N, 13.24.
Nꢀ(1HꢀIndolꢀ3ꢀylmethylidene)benzohydrazide (1p). Indoleꢀ
3ꢀcarbaldehyde (3 mmol) and benzohydrazide (3 mmol) were
refluxed in anhydrous ethanol (2 mL) for 2 h. The mixture was
cooled to room temperature and the crystals that formed were
filtered off, washed with diethyl ether, and dried in vacuo. The
yield was 90%, m.p. 231—232 °C (cf. Ref. 27: m.p. 231—232 °C).
Nꢀ(2,3ꢀDihydroꢀ1Hꢀindenꢀ1ꢀylidene)benzohydrazide (1r).
Indanꢀ1ꢀone (2 mmol) and benzohydrazide (2 mmol) were heatꢀ
ed at 100 °C for 1 h. The mixture was cooled to room temperaꢀ
ture and the crystals that formed were washed with diethyl ether
3
3
arom., JH,H = 8.4 Hz); 7.72 (d, 2 H, arom., JH,H = 8.4 Hz);
9.28 (br.s, 1 H, NH). 13C NMR (CDCl3), δ: 25.52, 25.96, 26.91,
27.31, 35.53 (Cring); 126.26, 128.91, 131.80, 132.69 (Carom);

414
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
Matveeva et al.
and dried in vacuo. The yield was 95%, m.p. 159—161 °C (cf.
Ref. 28: m.p. 155 °C).
δ: 28.63. 13C NMR (CDCl3), δ: 16.51 (d, Me, POEt, 3JC,P = 5.1 Hz);
21.18 (s, Me); 56.87 (d, C, 1JC,P = 161.0 Hz); 62.93 (d, OCH2,
2JC,P = 7.4 Hz); 126.26, 128.48, 131.44, 131.81 (Carom);
164.51 (s, C=O). IR (CCl4), ν/cm–1: 1035, 1065 (P—O—C);
1260 (P=O); 1360, 1540 (N=O); 1630 (C=O); 3280 (N—H).
Found (%): C, 42.99; H, 5.54; N, 7.21. C14H22BrN2O4P. Calcuꢀ
lated (%): C, 42.76; H, 5.64; N, 7.12.
Methyl 1ꢀ(2ꢀbenzoylhydrazono)ꢀ2,3ꢀdihydroꢀ1Hꢀindeneꢀ5ꢀ
carboxylate (1s). Methyl 1ꢀoxoindaneꢀ5ꢀcarboxylate (2 mmol)
and benzohydrazide (2 mmol) were heated at 120 °C for 2 h. The
mixture was cooled to room temperature and the crystals that
formed were washed with diethyl ether and dried in vacuo. The
yield was 95%, m.p. 265—266 °C. 1H NMR (DMSOꢀd6), δ:
2.98—3.07 (br.m, 2 H, C(2)H2, ring); 3.09—3.20 (br.m, 2 H,
C(3)H2, ring); 3.87 (s, 3 H, Me); 7.50—7.54 (m, 2 H, arom.);
7.57—7.61 (m, 1 H, arom.); 7.73—7.82 (m, 2 H, arom.); 7.87
Diethyl {1ꢀ[2ꢀ(4ꢀmethoxybenzoyl)hydrazino]ꢀ1ꢀmethylethyl}ꢀ
phosphonate (2d), m.p. 63—64 °C. 1H NMR (CDCl3), δ: 1.29
3
(t, 6 H, 2 Me, POEt, JH,H = 7.0 Hz); 1.31 (d, 6 H, 2 Me,
3JH,P = 15.6 Hz); 3.76 (s, 3 H, OMe); 4.09—4.18 (m, 4 H,
3
3
3
(d, 2 H, arom., JH,H = 7.4 Hz); 7.91 (d, 1 H, arom., JH,H
=
2 OCH2); 4.96 (br.d, 1 H, NH, JH,P = 24.3 Hz); 6.84, 7.70
= 7.7 Hz); 7.97 (s, 1 H, arom.); 10.72 (s, 1 H, NH). 13C NMR
(DMSOꢀd6), δ: 28.12 (s, C(3)H2, ring); 28.49 (s, C(2)H2, ring);
52.73 (s, OMe); 121.52, 126.50, 127.94, 128.07, 128.19, 131.22,
131.42; 133.93, 142.41, 148.94 (Carom); 162.14 (s, C=O, C(O)Ph);
(both d, 2 H each, arom., JH,H = 8.7 Hz); 8.46 (s, 1 H,
3
NHC(O)Ph). 31P NMR (CDCl3), δ: 28.94. 13C NMR (CDCl3),
3
δ: 16.58 (d, Me, POEt, JC,P = 4.8 Hz); 21.24 (s, Me); 55.43
1
(s, OMe); 57.04 (d, C, JC,P = 161.5 Hz); 62.92 (d, OCH2,
164.38 (s, C=O, COOMe); 166.50 (s, C=N). IR (CCl4), ν/cm–1
:
2JC,P = 8.0 Hz); 113.92, 125.04, 128.68, 162.39 (Carom); 165.32
(s, C=O). IR (CCl4), ν/cm–1: 1040, 1065 (P—O—C); 1260
(P=O); 1650 (C=O); 3280 (N—H). Found (%): C, 52.25;
H, 7.37; N, 8.00. C15H25N2O5P. Calculated (%): C, 52.32;
H, 7.32; N, 8.14.
1630 (C=N); 1670 (C=O, C(O)Ph), 1720 (C=O, COOMe); 3220
(N—H). Found (%): C, 70.10; H, 5.24; N, 9.15. C18H16N2O3.
Calculated (%): C, 70.12; H, 5.23; N, 9.09.
Synthesis of αꢀhydrazino phosphonates 2a—s (general proceꢀ
dure). Diethyl phosphite (3—7 mmol) and tPcAlCl (0.05 mmol)
were added to an appropriate hydrazone (1 mmol). The reaction
mixture was stirred under argon at 80 °C until the reaction was comꢀ
pleted (monitoring by TLC). Then the reaction mixture was
dissolved in a minimum amount of CH2Cl2—MeOH (70 : 1) and
chromatographed on silica gel (column height 15 cm, column
diameter 1.5—2.0 cm). The ratios of the reagents, the reaction
times, and the yields of the compounds obtained are given in Table 1.
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)ꢀ1ꢀmethylethyl]phosphonate
(2a), m.p. 79—80 °C. 1H NMR (CDCl3), δ: 1.30 (t, 6 H, 2 Me,
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)cyclohexyl]phosphonate (2e),
m.p. 65—67 °C. 1H NMR (CDCl3), δ: 1.16—1.21 (m, 1 H, ring);
1.34 (t, 6 H, 2 Me, POEt, 3JH,H = 7.1 Hz); 1.48—1.59 (m, 2 H,
ring); 1.60—1.72 (m, 5 H, ring); 1.88—1.95 (m, 2 H, ring);
4.15—4.23 (m, 4 H, 2 OCH2); 5.46 (br.s, 1 H, NH); 7.38—7.42
(m, 2 H, arom.); 7.44—7.48 (m, 1 H, arom.); 7.79 (d, 2 H,
3
arom., JH,H = 8.1 Hz); 8.98 (s, 1 H, NHC(O)Ph). 31P NMR
(CDCl3), δ: 28.16. 13C NMR (CDCl3), δ: 16.53 (d, Me,
3
3
POEt, JC,P = 5.8 Hz); 19.87 (d, JC,P = 11.0 Hz); 25.12,
1
27.50 (Cring); 58.91 (d, C, JC,P = 163.2 Hz); 62.94 (d, OCH2,
3
3
POEt, JH,H = 7.0 Hz); 1.33 (d, 6 H, 2 Me, JH,P = 15.7 Hz);
2JC,P = 7.3 Hz); 126.69, 128.58, 131.47, 132.63 (Carom); 163.94
(s, C=O). IR (CCl4), ν/cm–1: 1035, 1070 (P—O—C); 1230
(P=O); 1660 (C=O); 3280 (N—H). Found (%): C, 57.53;
H, 7.83; N, 7.81. C17H27N2O4P. Calculated (%): C, 57.62;
H, 7.68; N, 7.90.
4.12—4.19 (m, 4 H, 2 OCH2); 4.97 (br.s, 1 H, NH); 7.35—7.38
3
3
(m, 2 H, arom., JH,H = 7.1 Hz); 7.44 (t, 1 H, arom., JH,H
=
3
= 7.3 Hz); 7.77 (d, 2 H, arom., JH,H = 7.1 Hz); 8.73 (s, 1 H,
NHC(O)Ph). 31P NMR (CDCl3), δ: 28.73. 13C NMR (CDCl3),
δ: 16.50 (d, Me, POEt, JC,P = 5.1 Hz); 21.13 (s, Me); 56.90
3
Diethyl {1ꢀ[2ꢀ(4ꢀnitrobenzoyl)hydrazino]cyclohexyl}phosꢀ
phonate (2f), m.p. 112—113 °C. 1H NMR (CDCl3), δ: 1.11—1.24
(m, 1 H, CH2, ring); 1.29 (t, 6 H, 2 Me, POEt, 3JH,H = 7.2 Hz);
1.43—1.71 (m, 7 H, ring); 1.81—1.90 (m, 2 H, ring); 4.11—4.18
(m, 4 H, 2 OCH2); 5.32 (br.s, 1 H, NH); 7.90 (d, 2 H, arom.,
3JH,H = 8.7 Hz); 8.18 (d, 2 H, arom., 3JH,H = 9.0 Hz); 9.30 (s, 1 H,
NHC(O)Ph). 31P NMR (CDCl3), δ: 27.93. 13C NMR (CDCl3),
(d, C, 1JC,P = 161.0 Hz); 62.85 (d, OCH2, 2JC,P = 7.3 Hz); 126.83,
128.56, 131.58, 132.58 (Carom); 165.63 (s, C=O). IR (CCl4),
ν/cm–1: 1040, 1070 (P—O—C); 1260 (P=O); 1630 (C=O); 3280
(N—H). Found (%): C, 53.38; H, 7.25; N, 8.99. C14H23N2O4P.
Calculated (%): C, 53.50; H, 7.38; N, 8.91.
Diethyl {1ꢀmethylꢀ1ꢀ[2ꢀ(4ꢀnitrobenzoyl)hydrazino]ethyl}ꢀ
phosphonate (2b), m.p. 122—123 °C. 1H NMR (CDCl3), δ: 1.28
δ: 16.44 (d, Me, POEt, JC,P = 4.0 Hz); 19.79 (d, JC,P
=
3
3
3
(t, 6 H, 2 Me, POEt, JH,H = 7.0 Hz); 1.31 (d, 6 H, 2 Me,
= 10.4 Hz); 25.01, 27.55 (Cring); 58.86 (d, C, 1JC,P = 162.3 Hz);
63.04 (d, OCH2, 2JC,P = 7.2 Hz); 123.73, 127.87, 138.21, 149.54
(Carom); 161.59 (s, C=O). IR (CCl4), ν/cm–1: 1040, 1060
(P—O—C); 1240 (P=O); 1350, 1525 (N=O); 1650 (C=O); 3290
(N—H). Found (%): C, 51.19; H, 6.67; N, 10.35. C17H26N3O6P.
Calculated (%): C, 51.12; H, 6.56; N, 10.52.
3JH,P = 15.1 Hz); 4.10—4.17 (m, 4 H, 2 OCH2); 5.00 (br.s, 1 H,
NH); 7.93, 8.19 (both d, 2 H each, arom., 3JH,H = 8.6 Hz); 9.17
(s, 1 H, NHC(O)Ph). 31P NMR (CDCl3), δ: 28.39. 13C NMR
(CDCl3), δ: 16.46 (d, Me, POEt, 3JC,P = 5.9 Hz); 21.19 (s, Me);
56.82 (d, C, 1JC,P = 159.5 Hz); 62.99 (d, OCH2, 2JC,P = 7.3 Hz);
123.72, 128.10, 138.21, 149.56 (Carom); 163.26 (s, C=O). IR
(CCl4), ν/cm–1: 1035, 1065 (P—O—C); 1260 (P=O); 1360, 1540
(N=O); 1630 (C=O); 3280 (N—H). Found (%): C, 46.80;
H, 6.16; N, 11.74 C14H22N3O6P. Calculated (%): C, 46.80;
H, 6.17; N, 11.69.
Diethyl {1ꢀ[2ꢀ(4ꢀbromobenzoyl)hydrazino]cyclohexyl}phosꢀ
1
phonate (2g), m.p. 84—85 °C. H NMR (CDCl3), δ: 1.08—1.21
(m, 1 H, CH2, ring); 1.29 (t, 6 H, 2 Me, POEt, 3JH,H = 7.1 Hz);
1.43—1.66 (m, 7 H, ring); 1.80—1.89 (m, 2 H, ring); 4.09—4.18
(m, 4 H, 2 OCH2); 5.36 (br.s, 1 H, NH); 7.48 (d, 2 H, arom.,
3JH,H = 8.7 Hz); 7.60 (d, 2 H, arom., 3JH,H = 8.7 Hz); 8.98 (s, 1 H,
NHC(O)Ph). 31P NMR (CDCl3), δ: 28.15. 13C NMR (CDCl3),
δ: 16.56 (d, Me, POEt, 3JC,P = 4.9 Hz); 19.93 (d, 3JC,P = 10.5 Hz);
Diethyl {1ꢀ[2ꢀ(4ꢀbromobenzoyl)hydrazino]ꢀ1ꢀmethylethyl}ꢀ
phosphonate (2c), m.p. 110—112 °C. 1H NMR (CDCl3), δ: 1.31
3
(t, 6 H, 2 Me, POEt, JH,H = 7.1 Hz); 1.33 (d, 6 H, 2 Me,
3JH,P = 15.4 Hz); 4.12—4.20 (m, 4 H, 2 OCH2); 4.98 (br.s, 1 H,
NH); 7.51 (d, 2 H, arom., 3JH,H = 8.6 Hz); 7.65 (d, 2 H, arom.,
3JH,H = 8.5 Hz); 8.83 (s, 1 H, NHC(O)Ph). 31P NMR (CDCl3),
25.16, 27.61 (Cring); 58.97 (d, C, JC,P = 162.2 Hz); 63.03
1
(d, OCH2, 2JC,P = 7.2 Hz); 126.15, 128.36, 131.58, 131.85 (Carom);
163.00 (s, C=O). IR (CCl4), ν/cm–1: 1035, 1080 (P—O—C);

αꢀBenzoylhydrazino phosphonates
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 2, February, 2010
415
1230 (P=O); 1650 (C=O); 3290 (N—H). Found (%): C, 47.04;
H, 6.22; N, 6.72. C17H26BrN2O4P. Calculated (%): C, 47.13;
H, 6.05; N, 6.74.
4.91 (br.s, 1 H, NH); 6.83 (d, 2 H, arom., 3JH,H = 8.7 Hz); 7.69
3
(d, 2 H, arom., JH,H = 8.4 Hz); 8.66 (s, 1 H, NHC(O)Ph).
31P NMR (CDCl3), δ: 29.07. 13C NMR (CDCl3), δ: 16.49
(d, Me, POEt, 3JC,P = 4.8 Hz); 24.58 (d, 3JC,P = 10.5 Hz); 32.27
Diethyl {1ꢀ[2ꢀ(4ꢀmethoxybenzoyl)hydrazino]cyclohexyl}ꢀ
phosphonate (2h). 1H NMR (CDCl3), δ: 1.06—1.21 (m, 1 H,
CH2, ring); 1.28 (t, 6 H, 2 Me, POEt, 3JH,H = 7.0 Hz); 1.40—1.52
(m, 2 H, ring); 1.53—1.66 (m, 5 H, ring); 1.77—1.90 (m, 2 H,
ring); 3.75 (s, 3 H, OMe); 4.09—4.18 (m, 4 H, 2 OCH2); 5.36
(br.s, 1 H, NH); 6.84 (d, 2 H, arom., 3JH,H = 8.8 Hz); 7.69 (d, 2 H,
2
(d, JC,P = 3.2 Hz) (Cring); 55.31 (s, OMe); 62.75 (d, OCH2,
2JC,P = 7.3 Hz); 66.99 (d, C, 1JC,P = 166.2 Hz); 113.79, 124.95,
128.55, 162.25 (Carom); 164.92 (s, C=O). IR (CCl4), ν/cm–1
:
1040, 1070 (P—O—C); 1260 (P=O); 1650 (C=O); 3280 (N—H).
Found (%): C, 55.14; H, 7.38; N, 7.63. C17H27N2O5P. Calcuꢀ
lated (%): C, 55.13; H, 7.35; N, 7.56.
3
arom., JH,H = 9.0 Hz); 8.76 (s, 1 H, NHC(O)Ph). 31P NMR
(CDCl3), δ: 28.31. 13C NMR (CDCl3), δ: 16.52 (d, Me, POEt,
3JC,P = 4.9 Hz); 19.93 (d, 3JC,P = 10.5 Hz); 25.16, 27.55 (Cring);
55.35 (s, OMe); 58.97 (d, C, 1JC,P = 163.0 Hz); 62.88 (d, OCH2,
2JC,P = 7.2 Hz); 113.81, 125.08, 128.46, 162.20 (Carom); 163.77
(s, C=O). IR (CCl4), ν/cm–1: 1045, 1075 (P—O—C); 1260
(P=O); 1660 (C=O); 3280 (N—H). Found (%): C, 56.10;
H, 7.81; N, 7.35. C18H29N2O5P. Calculated (%): C, 56.24;
H, 7.60; N, 7.29.
tertꢀButyl 4ꢀ(2ꢀbenzoylhydrazino)ꢀ4ꢀdiethoxyphosphorylpiꢀ
peridineꢀ1ꢀcarboxylate (2m), m.p. 103—104 °C. 1H NMR
3
(CDCl3), δ: 1.34 (t, 6 H, 2 Me, POEt, JH,H = 7.1 Hz); 1.42
(s, 9 H, But); 1.77—1.88 (br.m, 4 H, ring); 3.17—3.39 (br.m,
2 H, ring); 3.67—3.97 (br.m, 2 H, ring); 4.14—4.25 (m, 4 H,
2 OCH2); 5.01 (br.s, 1 H, NH); 7.39—7.43 (m, 2 H, arom.);
7.46—7.50 (m, 1 H, arom.); 7.78 (d, 2 H, arom., 3JH,H = 7.3 Hz);
8.90 (s, 1 H, NHC(O)Ph). 31P NMR (CDCl3), δ: 26.35.
3
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)cyclopentyl]phosphonate (2i),
13C NMR (CDCl3), δ: 16.55 (d, Me, POEt, JC,P = 5.8 Hz);
m.p. 55—58 °C. 1H NMR (CD3OD), δ: 1.34 (t, 6 H, 2 Me,
27.37 (s, Cring); 28.38 (s, Me, But); 37.50 (br.s, Cring); 38.55
3
1
POEt, JH,H = 7.1 Hz); 1.65—1.75 (m, 2 H, ring); 1.85—1.96
(br.s, Cring); 57.27 (d, C, JC,P = 161.8 Hz); 63.02—63.28
(m, 4 H, ring); 1.98—2.11 (m, 2 H, ring); 4.17—4.24 (m, 4 H,
2 OCH2); 7.46—7.50 (m, 2 H, arom.) 7.52—7.61 (m, 3 H, arom.);
(m, OCH2); 79.60 (s, C, But); 126.82, 128.68, 131.77, 132.47
(Carom); 154.66 (s, C=O, C(O)OBut); 165.11 (s, C=O, C(O)Ph).
IR (CCl4), ν/cm–1: 1030, 1060 (P—O—C); 1260 (P=O);
1650 (C=O, C(O)Ph); 1670 (C=O, C(O)(OBut); 3280 (N—H).
Found (%): C, 55.30; H, 7.65; N, 9.10. C21H34N3O6P. Calꢀ
culated (%): C, 55.37; H, 7.52; N, 9.23. MS (EI, 70 eV),
m/z: 455 [M]+, 399 [M + H – But]+, 318 [M – P(O)(OEt)2]+,
262 [M + H – P(O)(OEt)2 – But]+, 105 [C(O)Ph]+, 77 [Ph]+,
57 [But]+.
3
7.82 (d, 2 H, arom., JH,H = 7.3 Hz). 31P NMR (CD3OD), δ:
29.59. 13C NMR (CD3OD), δ: 15.53 (d, Me, POEt, 3JC,P = 5.9 Hz);
3
2
24.82 (d, JC,P = 10.2 Hz); 32.40 (d, JC,P = 4.4 Hz) (Cring);
2
1
62.86 (d, OCH2, JC,P = 7.3 Hz); 66.66 (d, CH, JC,P = 157.3
Hz); 126.96, 128.32, 131.62, 132.72 (Carom); 167.71 (s, C=O).
IR (CCl4), ν/cm–1: 1035, 1050 (P—O—C); 1230 (P=O); 1660
(C=O); 3280 (N—H). Found (%): C, 56.51; H, 7.72; N, 8.39.
C16H25N2O4P. Calculated (%): C, 56.46; H, 7.40; N, 8.23.
Diethyl {1ꢀ[2ꢀ(4ꢀnitrobenzoyl)hydrazino]cyclopentyl}phosꢀ
phonate (2j), m.p. 86—87 °C. 1H NMR (CDCl3), δ: 1.31 (t, 6 H,
2 Me, POEt, 3JH,H = 6.8 Hz); 1.66—1.95 (m, 8 H, ring); 4.14—4.19
(m, 4 H, 2 OCH2); 4.99 (br.s, 1 H, NH); 7.95 (d, 2 H, arom.,
3JH,H = 7.8 Hz); 8.22 (d, 2 H, arom., 3JH,H = 7.1 Hz); 9.30 (s, 1 H,
NHC(O)Ph). 31P NMR (CDCl3), δ: 28.65. 13C NMR (CDCl3),
δ: 16.50 (d, Me, POEt, 3JC,P = 5.1 Hz); 24.54 (d, 3JC,P = 10.2 Hz);
32.35 (d, 2JC,P = 2.9 Hz) (Cring); 63.03 (d, OCH2, 2JC,P = 7.3 Hz);
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)ꢀ1ꢀcyclopropylethyl]phosꢀ
phonate (2n). 1H NMR (CD3OD), δ: 0.43—0.63 (m, 4 H, CH2,
3
ring); 1.05 (d, 3 H, Me, JH,P = 16.4 Hz); 1.27—1.34 (m, 1 H,
CH, ring); 1.37 (t, 6 H, 2 Me, POEt, 3JH,H = 7.1 Hz); 4.20—4.28
(m, 4 H, 2 OCH2); 7.46—7.50 (m, 2 H, arom.); 7.54—7.60 (m, 1 H,
3
arom.); 7.81 (d, 2 H, arom., JH,H = 7.4 Hz). 31P NMR
3
(CD3OD), δ: 27.86. 13C NMR (CD3OD), δ: –0.40 (d, JC,P
=
= 9.5 Hz); 0.61, 12.47 (Cring); 13.41 (s, Me); 15.55, 15.59 (both d,
3
1
Me, POEt, JC,P = 4.3 Hz); 59.47 (d, CH, JC,P = 158.1 Hz);
1
2
66.85 (d, C, JC,P = 166.1 Hz); 123.76, 128.08, 138.17, 149.61
62.01, 63.09 (both d, OCH2, JC,P = 8.0 Hz); 126.96, 128.30,
131.56, 132.70 (Carom); 167.86 (s, C=O). IR (CCl4), ν/cm–1
:
(Carom); 162.90 (s, C=O). IR (CCl4), ν/cm–1: 1040, 1065
(P—O—C); 1230 (P=O); 1350, 1530 (N=O); 1650 (C=O); 3280
(N—H). Found (%): C, 49.95; H, 6.45; N, 10.71. C16H24N3O6P.
Calculated (%): C, 49.87; H, 6.28; N, 10.90.
1025, 1050 (P—O—C); 1230 (P=O); 1650 (C=O); 3265 (N—H).
Found (%): C, 56.21; H, 7.20; N, 8.36. C16H25N2O4P. Calcuꢀ
lated (%): C, 56.46; H, 7.40; N, 8.23.
Diethyl {1ꢀ[2ꢀ(4ꢀbromobenzoyl)hydrazino]cyclopentyl}phosꢀ
phonate (2k), m.p. 98—99 °C. 1H NMR (CDCl3), δ: 1.28 (t, 6 H,
2 Me, POEt, 3JH,H = 7.1 Hz); 1.55—1.66 (m, 2 H, ring); 1.67—1.96
(m, 6 H, ring); 4.10—4.17 (m, 4 H, 2 OCH2); 4.93 (br.s, 1 H,
NH); 7.47 (d, 2 H, arom., 3JH,H = 8.4 Hz); 7.60 (d, 2 H, arom.,
3JH,H = 8.5 Hz); 8.89 (s, 1 H, NHC(O)Ph). 31P NMR (CDCl3),
δ: 28.84. 13C NMR (CDCl3), δ: 16.49 (d, Me, POEt, 3JC,P = 4.8 Hz);
Diethyl [(2ꢀbenzoylhydrazino)(phenyl)methyl]phosphonate
(2o), m.p. 105—106 °C. 1H NMR (CDCl3), δ: 1.23, 1.25 (both t,
6 H, 2 Me, POEt, 3JH,H = 7.0 Hz); 3.98—4.11 (m, 4 H, 2 OCH2);
4.62 (d, 1 H, 2JH,P = 13.4 Hz); 5.53 (br.s, 1 H, NH); 7.30—7.37
(m, 5 H, arom.); 7.44—7.51 (m, 3 H, arom.); 7.65 (d, 2 H,
3
arom., JH,H = 8.4 Hz); 8.37 (s, 1 H, NHC(O)Ph). 31P NMR
(CDCl3), δ: 21.18. 13C NMR (CDCl3), δ: 16.37 (d, Me, POEt,
3
2
1
24.54 (d, JC,P = 10.5 Hz); 32.31 (d, JC,P = 4.1 Hz) (Cring);
62.84 (d, OCH2, 2JC,P = 7.2 Hz); 66.91 (d, C, 1JC,P = 166.3 Hz);
126.18, 128.40, 131.49, 131.76 (Carom); 164.09 (s, C=O). IR
(CCl4), ν/cm–1: 1040, 1075 (P—O—C); 1240 (P=O); 1650
(C=O); 3280 (N—H). Found (%): C, 45.89; H, 5.91; N, 6.62.
C16H24BrN2O4P. Calculated (%): C, 45.84; H, 5.77; N, 6.48.
Diethyl {1ꢀ[2ꢀ(4ꢀmethoxybenzoyl)hydrazino]cyclopentyl}ꢀ
phosphonate (2l). 1H NMR (CDCl3), δ: 1.28 (t, 6 H, 2 Me,
3JC,P = 5.8 Hz); 62.74 (d, CH, JC,P = 154.4 Hz); 62.80, 63.41
(both d, OCH2, 2JC,P = 7.3 Hz, 2JC,P = 7.4 Hz); 126.96, 128.42,
128.45, 128.56, 128.95 (d, 3JC,P = 6.6 Hz); 131.81, 132.53, 133.75
(d, 2JC,P = 6.5 Hz) (Carom); 165.79 (s, C=O). IR (CCl4), ν/cm–1
:
1025, 1055 (P—O—C); 1250 (P=O); 1655 (C=O), 3275 (N—H).
Found (%): C, 59.58; H, 6.48; N, 7.64. C18H23N2O4P. Calcuꢀ
lated (%): C, 59.66; H, 6.40; N, 7.73. MS (EI, 70 eV), m/z: 362
[M]+, 227 [M – NHNHC(O)Ph]+, 225 [M – P(O)(OEt)2]+,
119 [M – P(O)(OEt)2 – C(O)Ph – H]+, 138 [P(OH)(OEt)2]+
105 [C(O)Ph]+, 77 [Ph]+.
3
POEt, JH,H = 7.1 Hz); 1.58—1.65 (m, 2 H, ring); 1.69—1.95
(m, 6 H, ring); 3.75 (s, 3 H, OMe); 4.10—4.17 (m, 4 H, 2 OCH2);

416
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Matveeva et al.
3
3
Diethyl [(2ꢀbenzoylhydrazino)(1Hꢀindolꢀ3ꢀyl)methyl]phosꢀ
arom., JH,H = 7.5 Hz); 7.79 (d, 1 H, arom., JH,H = 8.1 Hz);
8.81 (s, 1 H, arom.); 8.59 (s, 1 H, NHC(O)Ph). 31P NMR
(CDCl3), δ: 23.70. 13C NMR (CDCl3), δ: 16.38 (d, Me, POEt,
phonate (2p). 1H NMR, δ: 1.14, 1.24 (both t, 6 H, 2 Me, POEt,
3JH,H = 7.0 Hz); 3.87—3.97 (m, 1 H, 2 OCH2); 3.99—4.13 (m, 3 H,
2 OCH2); 4.98 (d, 1 H, 2JH,P = 11.9 Hz); 5.50 (br.s, 1 H, NH);
7.06—7.15 (m, 2 H, arom.); 7.27—7.35 (m, 4 H, arom.); 7.43
3JC,P = 4.1 Hz); 29.98 (d, C(3)H2, ring, JC,P = 2.4 Hz); 32.82
(s, C(2)H2, ring); 52.02 (s, OMe); 63.10, 63.73 (both d, OCH2,
2JC,P = 7.2 Hz, 2JC,P = 7.3 Hz); 71.54 (d, C, 1JC,P = 167.0 Hz);
125.62, 126.11, 126.75, 127.94, 128.56, 130.08, 131.67, 132.28,
143.90, 145.37 (d, Carom
C(O)Ph); 166.87 (s, C=O, COOMe). IR (CCl4), ν/cm–1
1040, 1060 (P—O—C); 1230 (P=O); 1660 (C=O, C(O)Ph);
1730 (C=O, COOMe); 3230 (N—H). Found (%): C, 59.11;
H, 6.09; N, 6.19. C22H27N2O6P. Calculated (%): C, 59.16;
H, 6.10; N, 6.27.
3
3
3
(t, 1 H, arom., JH,H = 7.5 Hz); 7.64 (d, 2 H, arom., JH,H
=
3
= 7.1 Hz); 7.80 (d, 1 H, arom., JH,H = 7.8 Hz); 9.54 (s, 1 H,
NHC(O)Ph). 31P NMR, δ: 22.84. 13C NMR, δ: 16.37, 16.43
(both d, Me, POEt, JC,P = 5.1 Hz); 55.30 (d, CH, JC,P
= 163.2 Hz); 62.75, 63.42 (both d, OCH2, JC,P = 7.4 Hz,
2JC,P = 7.3 Hz); 106.81, 111.62, 119.49, 119.73, 122.10, 125.25
,
2JC,P = 7.0 Hz); 165.56 (s, C=O,
3
1
=
:
2
3
3
(d, JC,P = 5.9 Hz); 126.79 (d, JC,P = 6.6 Hz); 126.97, 128.55,
131.76, 132.62, 136.22 (Carom); 166.87 (s, C=O). IR (CCl4),
ν/cm–1: 1035, 1060 (P—O—C); 1240 (P=O); 1640 (C=O), 3230
(N—H). Found (%): C, 60.01; H, 5.89; N, 10.37. C18H23N2O4P.
Calculated (%): C, 59.84; H, 6.03; N, 10.47. MS (EI, 70 eV), m/z:
401 [M]+, 266 [M – NHNHC(O)Ph]+, 264 [M – P(O)(OEt)2]+,
138 [P(OH)(OEt)2]+, 130 [M + H – NHNHC(O)Ph –
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 08ꢀ03ꢀ00611)
and the Russian Academy of Sciences (Basic Research
Programs 1ꢀOKhNM and 9ꢀOKhNM, Grant of the Preꢀ
sidium of the Russian Academy of Sciences (9P)).
– P(O)(OEt)2]+, 116 [M – NHNHC(O)Ph – P(O)(OEt)2
– CH]+, 105 [C(O)Ph]+, 77 [Ph]+.
–
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)ꢀ1ꢀphenylethyl]phosphonate
(2q). 1H NMR, δ: 1.26, 1.28 (both t, 6 H, 2 Me, POEt, 3JH,H
References
=
= 7.1 Hz); 1.82 (d, 3 H, Me, 3JH,P = 15.7 Hz); 3.95—4.04 (m, 2 H,
2 OCH2); 4.06—4.17 (m, 2 H, 2 OCH2); 5.53 (br.d, 1 H, NH,
3JH,P = 15.7 Hz); 7.31—7.34 (m, 1 H, arom.); 7.38—7.42 (t, 4 H,
arom., 3JH,H = 7.8 Hz); 7.46—7.50 (m, 1 H, arom.); 7.69—7.71
(m, 4 H, arom.); 8.28 (s, 1 H, NHC(O)Ph). 31P NMR, δ: 24.60.
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3
13C NMR, δ: 16.37, 16.42 (both d, Me, POEt, JC,P = 5.1 Hz,
3JC,P = 5.2 Hz); 63.23, 63.63 (both d, 2JC,P = 8.0 Hz, 2JC,P = 7.3 Hz,
OCH2); 63.44 (d, CH, 1JC,P = 155.8 Hz); 126.78, 127.38 (d, 3JC,P
=
= 4.4 Hz); 127.94, 128.38, 128.65, 131.71, 132.51, 138.11
(d, 2JC,P = 3.7 Hz) (Carom); 165.70 (s, C=O). IR (CCl4), ν/cm–1
:
1035, 1060 (P—O—C); 1240 (P=O); 1660 (C=O); 3280 (N—H).
Found (%): C, 60.86; H, 6.71; N, 7.33. C19H25N2O4P. Calcuꢀ
lated (%): C, 60.63; H, 6.69; N, 7.44.
Diethyl [1ꢀ(2ꢀbenzoylhydrazino)ꢀ2,3ꢀdihydroꢀ1Hꢀindenꢀ1ꢀ
yl]phosphonate (2r), m.p. 85—86 °C. 1H NMR (CDCl3), δ: 1.14,
1.21 (both t, 6 H, 2 Me, POEt, 3JH,H = 7.0 Hz); 2.15—2.28 (m, 1 H,
C(2)H2, ring); 2.50—2.61 (m, 1 H, C(2)H2, ring); 2.86—3.03
(m, 2 H, C(3)H2, ring); 3.89—4.11 (m, 4 H, 2 OCH2); 5.56 (br.s,
1 H, NH); 7.09—7.21 (m, 3 H, arom.); 7.27—7.33 (m, 2 H,
arom.); 7.35—7.42 (m, 1 H, arom.); 7.45—7.50 (m, 1 H, arom.);
7.57—7.60 (m, 2 H, arom.); 8.83 (s, 1 H, NHC(O)Ph). 31P NMR
(CDCl3), δ: 24.56. 13C NMR (CDCl3), δ: 16.16, 16.21 (both d,
3
3
Me, POEt, JC,P = 4.4 Hz, JC,P = 5.1 Hz); 30.12 (d, C(3)H2,
13. C. Yuan, S. Chen, R. Xie, H. Feng, L. Maier, Phosphorus,
Sulfur, Silicon Relat. Elem., 1995, 106, 115.
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Zefirov, Synlett., 2003, 2321.
3
2
ring, JC,P = 3.7 Hz); 32.32 (d, C(2)H2, ring, JC,P = 2.9 Hz);
2
2
63.16, 63.84 (both d, OCH2, JC,P = 8.0 Hz, JC,P = 7.3 Hz);
1
71.54 (d, C, JC,P = 166.1 Hz); 124.93, 125.70, 126.32, 126.77,
128.48, 129.11, 131.72, 132.16, 138.05, 145.11 (d, 2JC,P = 8.8 Hz)
(Carom); 166.66 (s, C=O). IR (CCl4), ν/cm–1: 1040, 1060
(P—O—C); 1235 (P=O); 1660 (C=O); 3280 (N—H). Found (%):
C, 61.70; H, 6.35; N, 7.32. C20H25N2O4P. Calculated (%):
C, 61.85; H, 6.49; N, 7.21.
Methyl 1ꢀ(2ꢀbenzoylhydrazino)ꢀ1ꢀdiethoxyphosphorylꢀ2,3ꢀ
dihydroꢀ1Hꢀindeneꢀ5ꢀcarboxylate (2s), m.p. 235—237 °C.
1H NMR (CDCl3), δ: 1.18, 1.20 (both t, 6 H, 2 Me, POEt,
3JH,H = 7.1 Hz); 2.18—2.29 (m, 1 H, C(2)H2, ring); 2.58—2.68
(m, 1 H, C(2)H2, ring); 2.90—3.06 (m, 2 H, C(3)H2, ring); 3.80
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43, 1427.aa
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USSR (Engl. Transl.), 1971, 41].
(s, 3 H, OMe); 3.97—4.13 (m, 4 H, 2 OCH2); 5.58 (br.s, 1 H,
3
NH); 7.28—7.31 (m, 2 H, arom.); 7.38 (t, 1 H, arom., JH,H
=
20. T. V. Troepol´skaya, R. A. Sitdikov, Z. S. Titova, A. P. Stolꢀ
yarov, Yu. P. Kitaev, Izv. Akad. Nauk SSSR, Ser. Khim.,
3
= 7.2 Hz); 7.54 (d, 1 H, arom., JH,H = 7.7 Hz); 7.61 (d, 1 H,

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Received June 11, 2009;
in revised form October 30, 2009