Phthalocyanine-catalyzed hydrophosphorylation of hydrazones and azines

Article abstract of DOI:10.1007/s11172-010-0114-3

Benzaldehyde, acetone, and N-Boc-piperidone phenylhydrazones, as well as azines derived from aromatic aldehydes and ketones, react with diethyl phosphite in the presence of [tetra(tert-butyl)phthalocyanine]aluminum chloride to give α-hydrazino phosphonate

Full text of DOI:10.1007/s11172-010-0114-3

Russian Chemical Bulletin, International Edition, Vol. 59, No. 3, pp. 584—589, March, 2010
584
Phthalocyanineꢀcatalyzed hydrophosphorylation of hydrazones and azines*
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
Benzaldehyde, acetone, and NꢀBocꢀpiperidone phenylhydrazones, as well as azines deꢀ
rived from aromatic aldehydes and ketones, react with diethyl phosphite in the presence of
[tetra(tertꢀbutyl)phthalocyanine]aluminum chloride to give αꢀhydrazino phosphonates in
high yields.
Key words: αꢀhydrazino phosphonates, the Pudovik reaction, [tetra(tertꢀbutyl)phthaloꢀ
cyanine]aluminum chloride, azines, phthalocyanines, hydrazones, diethyl phosphite.
A search for new routes to αꢀhydrazino phosphonates,
which are biologically active compounds1—4 and structurꢀ
al analogs of the corresponding αꢀamino phosphonic acꢀ
ids, still attracts the attention of researchers. Known methꢀ
ods for the synthesis of these compounds include (1) seꢀ
lective reduction of αꢀhydrazono phosphonic acids with
NaBH3CN or BH3•THF,5 (2) nucleophilic substitution
in 3ꢀmethoxyꢀ1,2,3,4ꢀpyridazines using dimethyl phosꢀ
phite in the presence of Lewis acids,6 nucleophilic subꢀ
stitution in modified αꢀhydroxy phosphonates,7 (3)
a MeONaꢀcatalyzed reaction of 2ꢀnitrobenzaldehyde
phenylhydrazone with dimethyl phosphite,8 and (4) reacꢀ
tions of N,Nꢀdimethylhydrazine with aldehydes and silyꢀ
lated phosphite in the presence of LiClO4 (see Refs 9, 10).
Preparation of αꢀhydrazino phosphonates is based on
(1) baseꢀcatalyzed reactions of aliphatic aldazines with
dialkyl phosphites followed by hydrolysis (note that this
method is unsuitable with aromatic aldazines)10—12 and
(2) noncatalytic addition of dialkyl phosphites to benzalꢀ
dehyde azine and cyclohexanone azine.13—17
used separately prepared hydrazones and azines in the hyꢀ
drophosphorylation reaction (a version of the Pudovik reꢀ
action20). Recently,21 we have published our data on the
phosphorylation of some Nꢀacetylhydrazones and NꢀBocꢀ
t
Thus, a quest for an efficient general route to αꢀhydrꢀ
azino phosphonates from both aromatic aldehydes and
ketones remains of current interest.
hydrazones in the presence of PcAlCl. In the present
work, we studied methylꢀ and arylhydrazones and azines.
t
We found that both the PcAlClꢀcatalyzed and nonꢀ
Previously, we have proposed a catalytic threeꢀcomꢀ
ponent "one pot" synthesis of αꢀamino phosphonates (the
Kabachnik—Fields reaction) with [tetra(tertꢀbutyl)phthaꢀ
locyanine]aluminum chloride (tPcAlCl) as a catalyst.18,19
We attempted to obtain αꢀhydrazino phosphonates in
a similar way using hydrazine derivatives as the amine
component. However, the threeꢀcomponent "one pot" synꢀ
thesis in conventional solvents such as dichloromethane,
alcohols, toluene, etc. failed because of rapid formation of
insoluble hydrazones and azines. That is why we further
catalytic hydrophosphorylation of acetone phenylhydrꢀ
azone occurs in an excess of diethyl phosphite (DEP) servꢀ
ing as a solvent as well. However, the presence of the
catalyst increases the yield of αꢀhydrazino phosphonate 1
from 45 to 70%, the other conditions being the same
(80 °C, 8 h) (Table 1, entries 1, 2). NꢀBocꢀPiperidone
phenylhydrazone also reacts with DEP in the presence of
tPcAlCl to give the corresponding αꢀhydrazino phosphoꢀ
nate 2 in 68% yield (entry 3).
A tPcAlClꢀcatalyzed reaction of benzaldehyde phenylꢀ
hydrazone with an excess of DEP at 80 °C for 50 h affords
αꢀhydrazino phosphonate 3 in 35% yield (entry 4). At 100 °C,
this reaction gives αꢀanilino phosphonate 4 (Scheme 2).
* Dedicated to Academician V. I. Minkin on the occasion of his
75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 571—576, March, 2010.
1066ꢀ5285/10/5903ꢀ0584 © 2010 Springer Science+Business Media, Inc.

Hydrophosphorylation of hydrazones
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
585
Scheme 1
Scheme 2
i. tPcAlCl, 80 °С.
Table 1. Synthesis of αꢀhydrazino phosphonates
Entry
Hydrazone
H : DEPa t/h
Product
(yield (%))
R1
R2
Scheme 3
1
2
3
4
Me
Me
Me
Me
1 : 3
1 : 3
1 : 5
1 : 3
8
8
8
1 (45b)
1 (70)
2 (68)
3 (35c)
—(CH2)2N(Boc)(CH2)2—
Ph
H
50
a The ratio of hydrazone to HP(O)(OEt)2.
b The reaction was carried out in the absence of a catalyst.
c The yield with respect to the consumed phenylhydrazone.
Noncatalytic hydrophosphorylation of benzaldehyde
azine gives monoadduct 5 in 25% yield (Table 2, entry 1;
Scheme 3). With sodium ethoxide as a catalyst,11 the yield
of compound 5 does not exceed 10%, the reaction time
i. tPcAlCl, 80 °C.
t
being the same. In the presence of PcAlCl, the yield of
compound 5 increases to 77% (Table 2, entry 2) and its
analogs 7 and 9 can be obtained in 82—85% yields (Table 2,
entries 4—7).
When the reaction time was increased to 70 h, diethyl
phosphite added to both the imino groups of the aldazines
to give hydrazodiphosphonates 6, 8, and 10 in 40—55%
yields; monoadducts 5, 7, and 9 were also isolated in
15—35% yields (Table 2, entries 3, 5, 7).
αꢀHydrazino phosphonates were obtained by tPcAlClꢀ
catalyzed hydrophosphorylation of cyclopentanone, cycloꢀ
Table 2. Synthesis of hydrazino phosphonates and hydrazodiphosphonates
Entry
Azine
Ratio of
azine : HP(O)(OEt)2
t/h
Monophosphonate,
yield (%)
Diphosphonate,
yield (%)
R1
R2
1
2
3
4
5
6
7
8
H
H
H
H
H
H
H
Ph
Ph
Ph
1 : 3
1 : 3
1 : 5
1 : 3
1 : 5
1 : 5
1 : 5
1 : 1.2
1 : 5
1 : 1.2
1 : 3
1 : 5
1 : 5
1 : 5
1 : 5
2
2
70
5
70
2
70
8
30
0.5
8
8
8
15, 25a
15, 77
15, 23
17, 82
17, 15
19, 85
19, 35
11, 85
11, 10
13, 85
11—
16, —
16, —
16, 50
18, —
18, 55
10, —
10, 40
12, —
12, 40
11—
14, 80
16, 10a
16, 20
16, 70
11—
2ꢀMeOC6H4
2ꢀMeOC6H4
3ꢀO2NC6H4
3ꢀO2NC6H4
—(CH2)4—
—(CH2)4—
—(CH2)5—
—(CH2)5—
9
10
11
12
13
14
15
—(CH2)2N(Boc)(CH2)2—
—(CH2)2N(Boc)(CH2)2—
—(CH2)2N(Boc)(CH2)2—
15, 30a
15, 60
15, 10
17, 40b
24
50
Me
Ph
a The reaction was carried out in the absence of a catalyst.
b The yield with respect to the consumed acetophenone azine.

586
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Matveeva et al.
Diethyl phosphite (Aldrich) was used as purchased. [Tetraꢀ
(tertꢀbutyl)phthalocyanine]aluminum chloride was prepared acꢀ
cording to a known procedure.22
Thinꢀlayer chromatography was carried out on Silufol plates.
The products were separated by column chromatography on
Merck 60 silica gel (70—230 mesh ASTM).
Synthesis of αꢀhydrazino phosphonates 1—3, αꢀarylideneꢀ and
αꢀ(cyclo)alkylidenehydrazino phosphonates 5, 7, 9, 11, 13, 15,
and 17, and α,α´ꢀhydrazodiphosphonates 6, 8, 10, 12, 14, and 16
(general procedure). Diethyl phosphite (1.2—5 mmol) and
tPcAlCl (0.05 mmol) were added to a hydrazone, an azine, or
a ketazine (1 mmol). The reaction mixture was stirred under
argon at 80 °C until the reaction was completed (monitoring by
TLC). The final reaction mixture was dissolved in a minimum
amount of CH2Cl2—MeOH (70 : 1) and chromatographed on
silica gel (column length 15 cm, diameter 1.5—2.0 cm) with the
above mixed solvent as an eluent. The ratios of the reagents, the
reaction times, and the yields of the compounds obtained are
given in Tables 1 and 2.
hexanone, NꢀBocꢀpiperidone, and acetophenone azines.
Depending on the reaction time and the excess of DEP,
the major products were αꢀ(cyclo)alkylidenehydrazino
phosphonates 11, 13, 15, and 17 or bisadducts 12, 14, and
16 (for their yields, see Table 2, entries 8—11, 13—15).
The structures of the phosphonates obtained were conꢀ
1
firmed by IR and H, 13C, and 31P NMR spectroscopy;
their molecular formulas were confirmed by elemental
analysis and mass spectrometry. Diphosphonates 6, 8, and
1
10 are 1 : 1 mixtures of diastereomers (their 31P, H, and
13C NMR spectra contain double sets of all signals).
The IR spectra of all the αꢀhydrazino phosphoꢀ
nates obtained show absorption bands at 1240—1270 and
3220—3270 cm–1 characteristic of the P=O and N—H
groups, respectively.
The 31P NMR spectra of monophosphonate 3, diphosꢀ
phonates 6, 8, and 10, and αꢀarylidenehydrazino phosꢀ
phonates 5, 7, and 9 exhibit signals for the phosphonate
group at δ 19.37—22.70; in compounds 1, 2, and 11—17,
Diethyl [1ꢀmethylꢀ1ꢀ(2ꢀphenylhydrazino)ethyl]phosphonate
3
(1). 1H NMR, δ: 1.29 (d, 6 H, 2 Me, JH,P = 15.4 Hz); 1.36
3
1
(t, 6 H, 2 Me, POEt, JH,H = 7.1 Hz); 3.76 (br.s, 1 H, NH);
these groups resonate at δ 25.93—31.88. In the H NMR
4.14—4.22 (m, 4 H, 2 OCH2); 6.02 (br.s, 1 H, NH); 6.71 (t, 1 H,
spectra of αꢀhydrazino phosphonates 3, 6, 8, and 10 and
αꢀarylidenehydrazino phosphonates 5, 7, 9, and 17, the
signals for the nonequivalent ethoxy groups appear as
two triplets (δ 1.00—1.38) and two or three multiplets
(δ 3.66—4.27). For αꢀhydrazino phosphonates 1, 2, 12,
14, and 16 and αꢀcycloalkylidenehydrazino phosphonates
11, 13, and 15, the signals for the ethoxy groups appear as
a triplet at δ 1.26—1.36 and a multiplet at δ 3.97—4.22.
The signal for the αꢀCH proton is a doublet at δ 4.33—5.53
3
3
arom., JH,H = 7.3 Hz); 6.90 (d, 2 H, arom., JH,H = 8.6 Hz);
7.16 (t, 1 H, arom., JH,H = 7.7 Hz). 31P NMR, δ: 30.89.
3
13C NMR, δ: 16.63 (d, Me, POEt, 3JC,P = 5.1 Hz); 21.56 (d, Me,
2JC,P = 9.0 Hz); 56.51 (d, C, 1JC,P = 139.0 Hz); 62.25 (d, OCH2,
2JC,P = 7.3 Hz); 112.35, 118.29, 128.86, 150.62 (Carom). IR, ν/cm–1
:
1040, 1080 (P—O—C); 1260 (P=O); 3280 (N—H). MS, m/z:
286 [M]+, 148 [M – P(OH)(OEt)2 – H]+, 138 [P(OH)(OEt)2]+.
Found (%): C, 54.47; H, 8.24; N, 9.75. C13H23N2O3P. Calcuꢀ
lated (%): C, 54.54; H, 8.10; N, 9.78.
Diethyl [1ꢀtertꢀbutoxycarbonylꢀ4ꢀ(2ꢀphenylhydrazino)piperiꢀ
dinꢀ4ꢀyl]phosphonate (2). 1H NMR, δ: 1.29 (t, 6 H, 2 Me, POEt,
3JH,H = 7.2 Hz); 1.37 (s, 9 H, Me, But); 1.71—1.79 (m, 4 H,
CH2C, ring); 3.08—3.15 (m, 2 H, CH2N, ring); 3.62—3.80 (m, 2 H,
CH2N, ring); 3.90 (br.s, 1 H, NH); 4.06—4.17 (m, 4 H, 2 OCH2);
6.03 (br.s, 1 H, NH); 6.64—6.68 (m, 1 H, arom.); 6.83—6.85
(m, 2 H, arom.); 7.08—7.12 (m, 2 H, arom.). 31P NMR, δ:
28.05. 13C NMR, δ: 16.63 (d, Me, POEt, 3JC,P = 4.8 Hz); 27.65
(CH2C, ring); 28.45 (Me, But); 38.38 (CH2N, ring); 57.08 (d, C,
(2JH,P = 20.5—22.5 Hz) for compounds 3, 5, and 7,
3
a doublet of doublets at δ 5.08 (2JH,P = 22.0 Hz, JH,H
=
= 6.3 Hz) for compound 9, and two doublets at
δ 4.14—5.46 (2JH,P = 22.5—20.9 Hz) for the diastereꢀ
omers of compounds 6, 8, and 10.
The 13C NMR spectra of compounds 1—3 and 5—17
show a signal for the αꢀC atom at δ 53.34—66.17 (1JC,P
=
= 136.1—152.2 Hz) and signals for the C atoms of the
ethoxy groups at δ 16.01—16.63 (3JC,P = 4.4—6.5 Hz) and
61.52—63.63 (2JC,P = 5.9—8.1 Hz).
In the conclusion, we developed a general method of
catalytic hydrophosphorylation of aliphatic and aromatic
hydrazones and azines for the synthesis of αꢀhydrazino
phosphonates, αꢀarylideneꢀ and αꢀ(cyclo)alkylideneꢀ
hydrazino phosphonates, and α,α´ꢀhydrazodiphosphonates.
2
1JC,P = 145.3 Hz); 62.50 (d, OCH2, JC,P = 8.1 Hz); 79.46
(s, But); 112.47, 118.67, 129.07, 149.63 (Carom), 154.73 (C=O). IR,
ν/cm–1: 1030, 1060 (P—O—C); 1250 (P=O); 1680 (C=O); 3270
(N—H). Found (%): C, 56.48; H, 7.93; N, 9.75. C20H34N3O5P.
Calculated (%): C, 56.19; H, 8.02; N, 9.83.
Diethyl (phenyl)(2ꢀphenylhydrazino)methylphosphonate (3).
1H NMR, δ: 1.14, 1.38 (both t, 6 H, 2 Me, POEt, 3JH,H = 7.1 Hz,
3JH,H = 7.0 Hz); 3.78—3.88, 3.94—4.02 (both m, 1 H each,
OCH2); 4.17—4.27 (m, 2 H, OCH2); 4.33 (d, 1 H, CH, 2JH,P
=
= 20.5 Hz); 6.81—6.88 (m, 3 H, arom.); 7.19—7.23 (m, 2 H, arom.);
7.36—7.45 (m, 5 H, arom.). 31P NMR, δ: 21.60. 13C NMR, δ:
16.24, 16.53 (both d, Me, POEt, 3JC,P = 5.2 Hz, 3JC,P = 5.9 Hz);
Experimental
1
H, 13C, and 31P NMR spectra were recorded on a Bruker
1
61.16 (d, CH, JC,P = 147.1 Hz); 62.96, 63.07 (both d, OCH2,
Avance 400 instrument (400.13, 161.98, and 100.61 MHz, reꢀ
spectively) in CDCl3 with SiMe4 as the internal standard
(1H, 13C) and with 85% H3PO4 as the external standard (31P).
IR spectra were recorded on a URꢀ20 instrument in CCl4. Eleꢀ
mental analysis was carried out on a VarioꢀII CHNꢀanalyzer.
Mass spectra were measured on a Finnigan Mat Incos 50 quaꢀ
drupole mass spectrometer (EI, 70 eV, direct inlet probe).
2JC,P = 7.3 Hz); 113.74, 119.82, 128.49, 128.67, 128.74, 128.88,
128.18, 129.28, 134.29, 147.84 (Carom). IR, ν/cm–1: 1030, 1060
(P—O—C); 1240 (P=O); 3230 (N—H). Found (%): C, 60.89;
H, 6.74; N, 8.17. C15H20N3O3P. Calculated (%): C, 61.07;
H, 6.93; N, 8.38.
Diethyl (benzylidenehydrazino)(phenyl)methylphosphonate
(5), m.p. 115—116 °C (cf. Ref. 14: m.p. 115—116 °C). 1H NMR,

Hydrophosphorylation of hydrazones
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
587
3
δ: 1.14, 1.31 (both t, 6 H, 2 Me, POEt, JH,H = 7.1 Hz);
3.75—3.85, 3.94—4.04 (both m, 1 H each, OCH2); 4.11—4.19
(m, 2 H, OCH2); 4.94 (d, 1 H, CH, 2JH,P = 22.5 Hz); 6.28 (br.s,
2 H, NH); 7.23—7.31 (m, 4 H, arom.); 7.37 (t, 2 H, arom.,
3JH,H = 7.5 Hz); 7.47—7.48 (m, 4 H, arom.); 7.65 (s, 1 H,
CH=N). 31P NMR, δ: 22.08. 13C NMR, δ: 16.22, 16.45 (both d,
(s, 1 H, CH=N); 7.76 (d, 1 H, arom., 3JH,H = 5.9 Hz); 7.84 (d, 1 H,
3
3
arom., JH,H = 8.1 Hz); 8.06 (d, 1 H, arom., JH,H = 8.5 Hz);
8.17 (d, 1 H, arom., 3JH,H = 8.3 Hz); 8.26 (s, 1 H, arom.); 8.37
(d, 1 H, arom., 4JH,P = 2.0 Hz). 31P NMR, δ: 19.67. 13C NMR,
3
3
δ: 16.29, 16.43 (both d, Me, POEt, JC,P = 5.1 Hz, JC,P
=
= 5.8 Hz); 60.07 (d, CH, 1JC,P = 148.6 Hz); 63.47, 63.63 (both d,
OCH2, 2JC,P = 6.6 Hz, 2JC,P = 7.3 Hz); 120.69, 122.86, 123.04,
123.11, 129.44, 129.53, 131.55, 134.30 (d, JC,P = 5.1 Hz);
3
3
Me, POEt, JC,P = 5.1 Hz, JC,P = 5.9 Hz); 61.15 (d, CH,
1JC,P = 148.5 Hz); 63.09, 63.15 (both d, OCH2, 2JC,P = 5.9 Hz,
2JC,P = 6.5 Hz); 126.17, 127.96, 128.16, 128.21, 128.43, 128.60,
135.20, 135.52 (Carom); 140.19 (s, CH=N). IR, ν/cm–1: 1030,
1070 (P—O—C); 1250 (P=O); 1600 (CH=N); 3230 (N—H).
Tetraethyl α,α´ꢀhydrazobis(benzylphosphonate) (6), m.p.
3
136.83, 137.46, 138.06, 148.43, 148.53 (Carom); 143.60
(d, CH=N, 4JC,P = 2.9 Hz). IR, ν/cm–1: 1030, 1070 (P—O—C);
1250 (P=O); 1350, 1530 (N=O, NO2); 1600 (CH=N); 3230
(N—H). MS, m/z: 436 [M]+, 299 [M – P(O)(OEt)2]+, 138
[P(OH)(OEt)2]+. Found (%): C, 49.60; H, 5.08; N, 12.61.
C18H21N4O7P. Calculated (%): C, 49.55; H, 4.85; N, 12.84.
Tetraethyl α,α´ꢀhydrazobis(3ꢀnitrobenzylphosphonate) (10),
m.p. 105—108 °C. 1H NMR, δ: 1.04, 1.05, 1.13, 1.18 (all t, 12 H,
Me, POEt, 3JH,H = 7.1 Hz); 3.76—3.93, 3.94—4.11 (both m, 4 H
each, OCH2); 4.28 (br.s, 2 H, NHNH); 5.31, 5.46 (both d, 2 H,
1
92—95 °C. H NMR, δ: 1.01, 1.03, 1.13, 1.19 (all t, 12 H, Me,
POEt, 3JH,H = 7.1 Hz); 3.62—3.72 (m, 2 H, OCH2); 3.80—4.03
(m, 8 H, OCH2, NHNH); 4.13, 4.31 (both d, 2 H, CH, 2JH,P
=
= 20.7 Hz); 7.28—7.42 (m, 10 H, arom.). 31P NMR, δ: 21.22,
21.27. 13C NMR, δ: 16.09—16.36 (m, Me, POEt); 60.51, 63.35
(both d, CH, JC,P = 148.5 Hz, 1JC,P = 147.9 Hz); 62.64, 63.14
1
(both d, OCH2, 2JC,P = 7.3 Hz, 2JC,P = 6.6 Hz); 128.11, 128.55,
128.66, 128.72, 134.40, 135.50 (Carom). IR, ν/cm–1: 1040, 1070
(P—O—C); 1250 (P=O); 3260 (NH). Found (%): C, 54.37;
H, 7.15; N, 5.56. C22H34N2O6P2. Calculated (%): C, 54.54;
H, 7.07; N, 5.78.
CH, JH,P = 22.2 Hz, JH,P = 22.5 Hz); 7.37—7.46 (m, 2 H,
arom.); 7.50—7.54, 7.60—7.64 (both m, 2 H, arom.); 7.70—7.73,
7.79—7.83 (both m, 2 H, arom.); 7.86, 7.88 (both d, 2 H, arom.,
3JH,H = 8.1 Hz). 31P NMR, δ: 19.37, 19.64. 13C NMR, δ: 16.01,
16.19 (both d, Me, POEt, 3JC,P = 5.9 Hz, 3JC,P = 5.1 Hz); 55.89,
2
2
1
Diethyl (2ꢀmethoxyphenyl)(2ꢀmethoxybenzylidenehydrazino)ꢀ
methylphosphonate (7), m.p. 109—110 °C. 1H NMR, δ: 1.09,
1.32 (both t, 6 H, Me, POEt, 3JH,H = 7.1 Hz); 3.70—3.81, 3.84—3.97
(both m, 1 H each, OCH2); 3.78, 3.91 (both s, 3 H each, 2 OMe);
4.16—4.23 (m, 2 H, OCH2); 5.53 (d, 1 H, CH, 2JH,P = 22.0 Hz);
6.80—6.98 (m, 4 H, arom.); 7.18—7.28 (m, 2 H, arom.); 7.46
57.32 (both d, CH, 1JC2,P = 145.7 Hz, JC,P = 146.3 Hz); 62.96,
63.52 (both d, OCH2, JC,P = 7.4 Hz); 124.74, 124.82, 128.46,
3
3
129.53 (d, JC,P = 2.2 Hz); 129.79 (d, JC,P = 2.9 Hz); 130.75,
131.11, 132.90, 133.10, 149.95, 150.02 (Carom). IR, ν/cm–1: 1030,
1060 (P—O—C); 1240 (P=O); 1360, 1525 (N=O); 3270 (N—H).
Found (%): C, 46.18; H, 5.74; N, 9.58. C22H32N4O10P2. Calcuꢀ
lated (%): C, 46.00; H, 5.61; N, 9.75.
3
3
(d, 1 H, arom., JH,H = 7.5 Hz); 7.74 (dd, 1 H, arom., JH,H
=
= 7.7 Hz, 4JH,H = 1.4 Hz); 8.02 (s, 1 H, CH=N). 31P NMR, δ:
Diethyl 1ꢀ(cyclopentylidenehydrazino)cyclopentylphosphonate
22.70. 13C NMR, δ: 16.16, 16.46 (both d, Me, POEt, JC,P
=
(11). H NMR, δ: 1.27 (t, 6 H, 2 Me, POEt, JH,H = 7.0 Hz);
1.62—1.69 (m, 4 H, ring); 1.74—1.81 (m, 4 H, ring); 1.93—2.06
(m, 4 H, ring); 2.12 (t, 2 H, ring, 3JH,H = 7.3 Hz); 2.29 (t, 2 H,
ring, 3JH,H = 7.2 Hz); 4.01—4.09 (m, 4 H, 2 OCH2); 4.71 (br.s,
1 H, NH). 31P NMR, δ: 31.45. 13C NMR, δ: 16.50 (d, Me, POEt,
3
1
3
3
1
= 5.9 Hz, JC,P = 6.6 Hz); 53.74 (d, CH, JC,P = 152.2 Hz);
55.51, 55.75 (both s, 2 OMe); 62.93 (d, OCH2, 2JC,P = 7.4 Hz);
110.76, 110.92, 120.70, 120.89, 123.87, 125.62, 128.56,
128.86, 129.04, 129.28 156.81, 157.24 (d, 3JC,P = 6.5 Hz) (Carom);
135.34 (s, CH=N). IR, ν/cm–1: 1040, 1060 (P—O—C); 1250
(P=O); 1600 (CH=N); 3230 (N—H). Found (%): C, 59.38;
H, 6.68; N, 6.85. C20H27N2O5P. Calculated (%): C, 59.11;
H, 6.70; N, 6.89.
3JC,P = 5.1 Hz); 24.87, 26.27, 33.16, 33.83 (d, JC,P = 5.8 Hz)
(Cring); 61.69 (d, OCH2, JC,P = 7.3 Hz); 66.17 (d, C, JC,P
2
2
1
=
= 147.8 Hz); 158.47 (C=N). IR, ν/cm–1: 1040, 1070 (P—O—C);
1240 (P=O); 1650 (C=N); 3250 (N—H). Found (%): C, 55.73;
H, 9.22; N, 9.17. C14H27N2O3P. Calculated (%): C, 55.61;
H, 9.00; N, 9.27.
Tetraethyl 1,1´ꢀhydrazobis(cyclopentylphosphonate) (12).
1H NMR, δ: 1.26 (t, 6 H, 2 Me, POEt, 3JH,H = 7.0 Hz); 1.58—1.82
(m, 14 H, ring); 2.04—2.14 (m, 1 H, ring); 2.30—2.34 (m, 1 H,
Tetraethyl α,α´ꢀhydrazobis(2ꢀmethoxybenzylphosphonate)
(8), m.p. 44—46 °C. 1H NMR, δ: 1.00—1.05 (m, 6 H, 2 Me,
3
POEt); 1.18, 1.24 (both t, 6 H, 2 Me, POEt, JH,H = 7.1 Hz);
3.66—4.09 (m, 14 H, 4 OCH2, 2 OMe); 4.80, 4.98 (both d, 2 H,
2
2
CH, JH,P = 21.5 Hz, JH,P = 21.3 Hz); 6.82—7.32 (m, 8 H,
arom.). 31P NMR, δ: 22.20, 22.31. 13C NMR, δ: 16.05—16.42
ring); 3.73 (br.s, 2 H, NHNH); 4.03—4.11 (m, 4 H, 2 OCH2).
1
3
(m, Me, POEt); 53.34, 56.06 (both d, CH, JC,P = 150.7 Hz,
31P NMR, δ: 31.88. 13C NMR, δ: 16.53 (d, Me, POEt, JC,P
=
1JC,P = 150 Hz); 55.39, 55.75 (both s, 2 OMe); 62.93
(m, 4 OCH2); 110.53, 110.75, 120.59, 120.90, 123.84, 128.88,
126.99 (Carom); 157.61, 158.00 (both d, COMe, 3JC,P = 7.3 Hz,
3JC,P = 8.1 Hz). IR, ν/cm–1: 1040, 1080 (P—O—C); 1270 (P=O);
3270 (N—H). MS, m/z: 544 [M]+, 407 [M – P(O)(OEt)2]+, 269
[M – 2 P(O)(OEt)2 – H]+, 137 [P(O)(OEt)2]+. Found (%):
C, 53.16; H, 7.20; N, 4.99. C24H38N2O8P2. Calculated (%):
C, 52.94; H, 7.03; N, 5.14.
= 5.0 Hz); 24.46 (d, 2JC,P = 8.1 Hz), 32.72 (d, 3JC,P = 11.7 Hz)
2
1
(Cring); 61.63 (d, OCH2, JC,P = 7.4 Hz); 65.75 (d, C, JC,P
=
= 143.5 Hz). IR, ν/cm–1: 1040, 1060 (P—O—C); 1250 (P=O);
3280 (N—H). MS, m/z: 440 [M]+, 303 [M – P(O)(OEt)2]+,
165 [M – 2P(O)(OEt)2 – H]+, 138 [P(OH)(OEt)2]+. Found (%):
C, 49.22; H, 8.70; N, 6.38. C18H38N2O6P2. Calculated (%):
C, 49.08; H, 8.70; N, 6.36.
Diethyl 1ꢀ(cyclohexylidenehydrazino)cyclohexylphosphonate
(13), m.p. 90—91 °C (cf. Ref. 17: m.p. 87 °C). 1H NMR, δ:
1.15—1.34 (m, 2 H, ring); 1.29 (t, 6 H, 2 Me, POEt, 3JH,H = 7.0 Hz);
1.42—2.07 (m, 16 H, ring); 2.20—2.25 (m, 2 H, ring), 3.98—4.20
(m, 4 H, 2 OCH2). 31P NMR, δ: 31.35. 13C NMR, δ: 16.51
Diethyl (3ꢀnitrobenzylidenehydrazino)(3ꢀnitrophenyl)methylꢀ
phosphonate (9), m.p. 155—156 °C. 1H NMR, δ: 1.23, 1.34 (both t,
6 H, Me, POEt, 3JH,H = 7.1 Hz); 3.94—4.05, 4.05—4.13 (both m,
1 H each, OCH2); 4.15—4.23 (m, 2 H, OCH2); 5.08 (dd, 1 H,
CH, JH,P = 22.0 Hz, JH,H = 6.3 Hz); 7.44 (t, 1 H, arom.,
3JH,H = 8.0 Hz); 7.56 (t, 1 H, arom., JH,H = 8.0 Hz); 7.75
2
3
3
(d, Me, POEt, JC,P = 5.9 Hz); 20.15, 20.26, 24.98, 25.61
3
3
(d, JC,P = 5.8 Hz), 25.89, 26.98, 29.05, 35.42 (Cring); 58.59

588
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Matveeva et al.
1
2
(CH, JC,P = 142.0 Hz); 61.52 (d, OCH2, JC,P = 7.3 Hz). IR,
ν/cm–1: 1040, 1080 (P—O—C); 1270 (P=O); 1630 (CH=N);
3270 (N—H). MS, m/z: 330 [M]+, 192 [M – P(O)(OEt)2 – H]+,
138 [P(OH)(OEt)2]+.
Diethyl (anilino)(phenyl)methylphosphonate (4).23 Diethyl
phosphite (3 mmol) and PcAlCl (0.05 mmol) were added to
t
benzaldehyde phenylhydrazone (1 mmol). The reaction mixture
was stirred under argon at 100 °C for 30 h. Further workup of the
reaction mixture followed the general procedure for the syntheꢀ
sis of αꢀhydrazino phosphonates. The yield of αꢀanilino phosꢀ
phonate 4 was 35% (with respect to the consumed phenylhydraꢀ
Tetraethyl 1,1´ꢀhydrazobis(cyclohexylphosphonate) (14).
1H NMR, δ: 1.17—1.34 (m, 2 H, ring); 1.31 (t, 12 H, 2 Me,
3
POEt, JH,H = 7.1 Hz); 1.38—1.48 (m, 4 H, ring); 1.53—1.75
(m, 10 H, ring); 1.78—1.92 (m, 4 H, ring); 4.08—4.18 (m, 8 H,
4 OCH2). 31P NMR, δ: 31.18. 13C NMR, δ: 16.67 (d, Me, POEt,
3JC,P = 5.9 Hz); 20.34 (d, 3JC,P = 11.0 Hz), 25.73, 28.56 (Cring);
58.67 (CH, 1JC,P = 136.1 Hz); 61.63 (d, OCH2, 2JC,P = 8.1 Hz).
IR, ν/cm–1: 1040, 1070 (P—O—C); 1270 (P=O); 3260 (N—H).
MS, m/z: 468 [M]+, 330 [M – P(O)(OEt)2 – H]+, 192 [M –
– 2 P(O)(OEt)2 – 2 H]+, 138 [P(OH)(OEt)2]+. Found (%):
C, 51.06; H, 9.10; N, 6.07. C20H42N2O6P2. Calculated (%):
C, 51.27; H, 9.04; N, 5.97.
zone). 1H NMR, δ: 1.13, 1.30 (both t, 6 H, 2 Me, POEt, 3JH,H
=
= 7.1 Hz); 3.92—4.14 (m, 4 H, 2 OCH2); 4.94 (d, 1 H, CH,
2JH,P = 24.3 Hz); 6.60—7.49 (m, 10 H, arom.). 31P NMR, δ:
22.80. 13C NMR, δ: 16.26, 16.41 (both d, Me, POEt, 3JC,P = 5.1 Hz,
1
3JC,P = 5.9 Hz); 61.95 (d, CH, JC,P = 150.1 Hz); 63.23, 63.44
(both d, OCH2, 2JC,P = 6.6 Hz, 2JC,P = 6.5 Hz); 126.25, 128.30,
128.84, 129.10, 129.14, 136.59, 139.48 (Carom). IR, ν/cm–1: 1030,
1070 (P—O—C); 1250 (P=O); 3230 (N—H). MS, m/z: 319 [M]+,
182 [M – P(O)(OEt)2]+, 137 [P(O)(OEt)2]+.
Diethyl {1ꢀtertꢀbutoxycarbonylꢀ4ꢀ[1ꢀ(tertꢀbutoxycarbonyl)ꢀ
piperidinꢀ4ꢀylidenehydrazino]piperidinꢀ4ꢀyl}phosphonate (15),
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 and the Program of
the Presidium of the Russian Academy of Sciences (9P)).
m.p. 64—66 °C. 1H NMR, δ: 1.26 (t, 6 H, 2 Me, POEt, 3JH,H
=
= 7.1 Hz); 1.43 (both s, 18 H, 6 Me, But); 1.83—2.02 (m, 4 H,
ring); 2.32—2.55 (m, 4 H, ring); 2.97—3.28 (br.m, 2 H, ring);
3.33—3.68 (m, 4 H, ring); 3.72—3.95 (br.m, 2 H, ring);
3.97—4.05 (m, 4 H, 2 OCH2); 4.92 (br.s, 1 H, NH). 31P NMR,
δ: 28.85. 13C NMR, δ: 16.48 (d, Me, POEt, JC,P = 5.1 Hz);
3
References
25.66 (Cring); 28.40 (s, Me, But); 28.61, 33.09 (Cring); 56.79
(d, C, 1JC,P = 146.4 Hz); 61.87 (d, OCH2, 2JC,P = 7.3 Hz); 79.34,
79.80 (both s, C, But); 147.35 (C=N); 154.91 (C=O). IR, ν/cm–1
:
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1040, 1060 (P—O—C); 1260 (P=O); 1690 (C=O); 3280 (N—H).
MS, m/z: 532 [M]+, 395 [M – P(O)(OEt)2]+, 337 [M –
– P(OH)(OEt)2 — But]+, 138 [P(OH)(OEt)2]+, 57 [But]+.
Found (%): C, 54.20; H, 8.47; N, 10.34. C24H45N4O7P. Calcuꢀ
lated (%): C, 54.12; H, 8.52; N, 10.52.
Tetraethyl 4,4´ꢀhydrazobis{[1ꢀ(tertꢀbutoxycarbonyl)pipeꢀ
ridinꢀ4ꢀyl]phosphonate} (16). 1H NMR, δ: 1.32 (t, 6 H, 2 Me,
3
POEt, JH,H = 7.1 Hz); 1.44 (s, 18 H, 6 Me, But); 1.81—1.95
(br.m, 8 H, ring); 2.99—3.21 (br.m, 4 H, ring); 3.66—3.87 (br.m,
4 H, ring); 3.66—3.87 (br.s, 2 H, NHNH); 4.09—4.17 (m, 4 H,
2 OCH2). 31P NMR, δ: 28.32. 13C NMR, δ: 16.61 (d, Me, POEt,
3JC,P = 5.2 Hz); 28.08, 28.10 (Cring); 28.42 (s, Me, But); 56.64
(d, C, 1JC,P = 142.7 Hz); 62.11 (d, OCH2, 2JC,P = 7.3 Hz); 79.47
(s, C, But); 154.66 (C=O). IR, ν/cm–1: 1030, 1050 (P—O—C);
1260 (P=O); 1690 (C=O); 3280 (N—H). MS, m/z: 670 [M]+,
533 [M – P(O)(OEt)2]+, 395 [M – 2 P(O)(OEt)2 – H]+, 339
[M – 2 P(O)(OEt)2 – But]+, 57 [But]+. Found (%): C, 49.93;
H, 8.48; N, 8.23. C28H56N4O10P2. Calculated (%): C, 50.14;
H, 8.42; N, 8.35.
Diethyl 1ꢀphenylꢀ1ꢀ(1ꢀphenylethylidene)hydrazinoethylꢀ
phosphonate (17). 1H NMR, δ: 1.17, 1.25 (both t, 6 H, 2 Me,
10. A. Heydari, M. Mehrdad, M. Schaffie, M. Abdolrezaie,
R. Hajinassirei, Chem. Lett., 2002, 31, 1146.
3
POEt, 3JH,H = 7.1 Hz); 2.02 (d, 3 H, Me,, JH,P = 15.9 Hz); 2.22
11. J. Racon, C. Wasielevski, Rocz. Chem., 1976, 50, 447.
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Vandyukova, A. V. Chernova, A. M. Kibardin, M. A. Pudoꢀ
vik, Izv. Akad. Nauk, Ser. Khim., 1996, 2063 [Russ. Chem.
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Mukhamadeeva, I. Kh. Shakirov, A. N. Pudovik, Zh. Obꢀ
shch. Khim., 1994, 64, 613 [J. Gen. Chem. (Engl. Transl.),
1994, 64].
(s, 3 H, Me); 3.80—3.87, 3.93—4.01 (both m, 1 H each, OCH2);
4.03—4.12 (m, 2 H, OCH2); 7.24—7.30 (m, 3 H, arom.);
7.34—7.39 (m, 5 H, arom.); 7.45—7.50 (m, 2 H, arom.).
31P NMR, δ: 25.93. 13C NMR, δ: 12.23 (s, Me); 16.34 (both d,
1
Me, POEt, 3JC,P = 6.5 Hz); 22.22 (s, Me); 62.72 (d, C, JC,P
=
2
= 140.0 Hz); 63.01, 63.15 (both d, OCH2, JC,P = 7.3 Hz);
125.51, 127.63, 128.00, 128.07, 128.32, 128.58, 133.13, 139.34,
140.35 (Carom), 144.96 (s, C=N). IR, ν/cm–1: 1040, 1060
(P—O—C); 1250 (P=O); 1600 (C=N); 3220 (N—H). MS, m/z:
374 [M]+, 237 [M – P(O)(OEt)2]+, 138 [P(OH)(OEt)2]+.
Found (%): C, 64.05; H, 7.13; N, 7.28. C20H27N2O3P. Calcuꢀ
lated (%): C, 64.16; H, 7.27; N, 7.48.
15. E. E. Nifant´ev, N. V. Zyk, M. P. Koroteev, Zh. Obshch.
Khim., 1974, 45, 1455 [J. Gen. Chem. USSR (Engl. Transl.),
1974, 45].

Hydrophosphorylation of hydrazones
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Received February 4, 2009;
in revised form December 11, 2009