Heterocondensed 1,2,3-diazaphosphorines

Article abstract of DOI:10.1002/hc.1099

The reaction of phosphorus tribromide with phenylhydrazones of heterocyclic aldehydes leads to formation of a new phosphorus-containing heterocyclic system-heterocondensed 1,2,3-diazaphosphorines. Properties of the phosphorus-containing heterocyclic compounds that have been synthesized are described.

Full text of DOI:10.1002/hc.1099

Heteroatom Chemistry
Volume 12, Number 7, 2001
Heterocondensed 1,2,3-Diazaphosphorines
Sergey P. Ivonin,1 Andrew A. Tolmachev,2 Alexandra A.
Chaikovskaya,2 Tamara N. Kudraya,2 Andrew A. Anischenko,1
Eduard B. Rusanov,2 Alexander N. Chernega,2
and Alexandr, M. Pinchuk2
1Department of Chemistry, Dnepropetrovsk National University, per. Naychney 16,
Dnepropetrovsk-10, 49625, Ukraine
2Institute of Organic Chemistry, Ukrainian Academy of Sciences, Myrmanskaja str 5.
Kiev, 02094, Ukraine
Received 3 April 2001; revised 18 June 2001
1,2,3-diazaphosphorines. It should be noted that,
ABSTRACT: The reaction of phosphorus tribromide
up to the present, only one example of the synthe-
with phenylhydrazones of heterocyclic aldehydes leads
sis of the 1,2,3-diazaphosphorine cycle has been de-
to formation of a new phosphorus-containing hetero-
scribed [5]. Preliminary results of the investigation
cyclic system—heterocondensed 1,2,3-diazaphospho-
of this reaction have been given in a concise report
rines. Properties of the phosphorus-containing hete-
[6].
rocyclic compounds that have been synthesized are
C
described.
2001 John Wiley & Sons, Inc. Heteroatom
Chem 12:658–664, 2001
RESULTS AND DISCUSSION
As we have found, the reaction of hydrazones 1a–e
with phosphorus tribromide in pyridine at 20 C
and with use of a 1:1 ratio of reagents proceeds
at the nitrogen atom of the hydrazone group and
leads to the formation of thermally unstable di-
bromophosphinohydrazides (2a–e) ( P = 155–165
p.m.), which are converted into the corresponding
dimorpholinothiophosphonates (3a–e) when treated
consecutively with morpholine in the presence of
triethylamine and with sulfur. Compounds 2a,b,e
in a solution of pyridine at .20 C are converted
into the heterocondensed 1,2,3-diazaphosphorines
(3a,b,e) (Scheme 1).
The compound 2a is the most active in the
reaction of cyclization, and this is conditioned by
enhanced nucleophility of the carbon atom of the
pyrrole ring. However introduction of an electron-
acceptor phosphorus-containing substituent into
position 5 increases the time of cyclization of 2e by
several hours.
INTRODUCTION
As we have previously shown, tervalent phosphorus
halides in basic media are effective phosphorylat-
ing reagents with respect to ␲-excessive aromatic
heterocycles such as pyrrole, furan, thiophene, in-
dole, benzofuran, and phosphole [1–4]. The aim of
this work is a study of phosphorylation of phenyl-
hydrazones of pyrrolyl-, indolyl-, and furylcarbox-
aldehydes by tervalent phosphorus halides. These
phenylhydrazones containe two nucleophilic cen-
tres in the molecule (the nitrogen atom of the hy-
drazone group and the carbon atom of the hete-
rocycle) that influenced us to expect the formation
of new heterocyclic systems—the heterocondensed
Correspondence to: Sergey P. Ivonin, Heroev Stalingrada 133/60,
Dnepropetrovsk, 49033, Ukraine; e-mail: ivonin@dp.ukrtel.net.
c
2001 John Wiley & Sons, Inc.
658

Heterocondensed 1,2,3-Diazaphosphorines 659
SCHEME 1
Phenylhydrazone (2b), containing an indole
Peculiarities of the molecular and crystal struc-
ture of 10a have been studied by the x-ray diffrac-
tion method. The perspective view of molecule 10a
is shown in Fig. 1, the main geometrical parame-
ters being given in Table 1. The P(1)N(1)N(2)N(3)C
(1–5) central bicyclic system is approximately pla-
nar: deviations of atoms from the least-squares
plane do not exceed 0.081 A ; the dihedral angle
between the 6-membered heterocycle P(1)N(1)N(2)
C(1)C(2)C(5) and 5-membered cycle N(3)C(1–4) is
only 4.3(1) . Benzene rings C(8–13) and C(15–20)
form with the central plane dihedral angles of
61.71(6) and 78.74(7) , respectively. Both N(1) and
N(3) nitrogen atoms have trigonal planar bond con-
figurations (the sum of bond angles, 360.0(3.0)
and 359.7(6) ). The geometrical parameters of the
N(3)C(1–4) heterocycle indicate significant delocal-
ization of electron density [7]. Bond lengths and
angles around the phosporus atom are unexceptional
[8,9].
residue, is less active in the reaction of cyclization.
Thus, the time of its reaction, compared with hy-
drazone 1a, is increased to 48 h. Heterocyclization
of dibromophosphinoamides, (2c) containing much
less active heterocycles with respect to electrophilic
phosphorylation, such as furan and benzofuran, as
monitored by the 31P NMR spectroscopy, does not
occur even during a period of a month.
Cyclic bromoanhydrides are bright-yellow crys-
talline substances, which are highly soluble in ben-
zene and chloroform and are stable in the absence
of atmospheric moisture. Their structures were con-
firmed by 1H and 31P NMR spectral data.
Reaction of the most active hydrazone 1a with a
less active phosphorylating reagent—diphenylbro-
mophosphine, as monitored by 31P NMR spectros-
copy, also leads to the formation of the 1,2,3-diaz-
aphosphorine ring (Scheme 2). Amidophosphine 5
was converted into the corresponding oxide (6),
thiooxide (7), and imine (8).
3
˚
The bromine atom present in the hetero-
condensed 1,2,3-diazaphosphorines is reactive in
nucleophilic substitution, which allowed us to re-
alize, in good yields, syntheses of different deriva-
tives 9–12 with a four-coordinated phosphorus atom
(Scheme 3).
Diazaphosphorines 10–12 are bright-yellow
crystalline substances that are very soluble in
benzene and chloroform. Their structures were con-
firmed by 1H and 31P NMR spectral data.
SCHEME 2

660 Ivonin et al.
SCHEME 3
TABLE 1 Selected Bond Lengths (E) and Angles (deg) in
EXPERIMENTAL
10a
31P and 1H, NMR spectra were recorded on a
Varian- VXR 300 spectrometer TMS being used as an
internal standard for 1H and 85% H3PO4 as an exter-
nal standard for 31P signals. All manipulations were
carried out in anhydrous solvents.
Bond lengths
P(1) N(1)
P(1) N(4)
P(1) N(5)
P(1) C(1)
1.712(2)
1.542(2)
1.642(2)
1.753(2)
1.408(2)
1.279(3)
1.384(3)
1.380(3)
1.436(3)
1.392(3)
1.429(3)
1.372(3)
1.375(3)
1.428(3)
N(1) N(2)
N(2) C(5)
N(3) C(3)
N(3) C(4)
X-ray Structure Determination of 10a
Crystal data: C30H32N5OP, M = 509.6 triclinic, a =
N(3) C(8)
N(4) C(15)
˚
9.015 (1), b= 10.599 (2), c= 15.317 (2) A, = 104.73
C(1) C(2)
C(1) C(4)
C(2) C(3)
C(2) C(5)
(1) , = 100.88 (1) , = 99.76 (1) , V = 1353.1 (3)
3
1
˚
¯
A , Z = 2, dcalc = 1.25 g cm , space group P1
Bond angles
N(4) P(1) N(5)
N(1) P(1) N(4)
N(1) P(1) N(5)
N(4) P(1) C(1)
N(5) P(1) C(1)
N(1) P(1) C(1)
P(1) N(1) N(2)
N(1) N(2) C(5)
C(3) N(3) C(4)
P(1) N(4) C(15)
P(1) C(1) C(2)
C(2) C(1) C(4)
C(1) C(2) C(3)
C(1) C(2) C(5)
N(3) C(3) C(2)
N(3) C(4) C(1)
N(2) C(5) C(2)
104.77(9)
116.16(11)
106.16(10)
120.40(10)
110.41(10)
98.28(9)
130.3(1)
119.3(2)
110.5(2)
130.9(2)
122.6(2)
107.6(2)
108.2(2)
122.3(2)
106.6(2)
107.2(2)
126.5(2)
FIGURE 1

Heterocondensed 1,2,3-Diazaphosphorines 661
1
TABLE 2 Coordinates of Atoms and Equivalent Isotropic
Thermal Parameters Beq (A) in 10a
(N2), = 11.5 cm , F(000) = 540, crystal size ca.
˚
0.22 0.41 0.53 mm. All crystallographic mea-
surements were performed at 18 C on a CAD-
4-Enraf-Nonius diffractometer operating in the
Atom
x
y
z
Ueq
ω
2 scan mode (the ratio of the scanning rates
P(1)
N(1)
N(2)
N(3)
N(4)
N(5)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
O(1A)
C(21A)
C(22A)
C(23A)
C(24A)
O(1B)
C(21B)
C(22B)
C(23B)
C(24B)
C(25A)
C(26A)
C(27A)
C(28A)
C(29A)
C(30A)
C(25B)
C(26B)
C(27B)
C(28B)
C(29B)
C(30B)
4201(1)
5436(2)
5351(2)
1255(2)
4971(2)
3250(2)
3002(2)
3129(2)
2029(2)
1837(2)
4296(2)
1591(3)
1268(3)
119(2)
9750(1)
11135(2)
11823(2)
8305(2)
8711(2)
10299(2)
9302(2)
10118(2)
9490(2)
8184(2)
11328(2)
9927(2)
6991(3)
7295(2)
6710(2)
5763(2)
5371(2)
5963(2)
6925(2)
4332(3)
7825(2)
7289(1)
7241(1)
6565(1)
4826(1)
7635(1)
8067(1)
6163(1)
5556(1)
4734(1)
5694(1)
5806(1)
3895(1)
5988(2)
4081(1)
3279(1)
2551(2)
2604(1)
3422(2)
4149(1)
1812(2)
7218(2)
7793(2)
7424(3)
6493(3)
5920(2)
6274(2)
9619(5)
8013(5)
8915(4)
9688(5)
8799(4)
9495(8)
7960(7)
8687(11)
9433(9)
9595(10)
8064(8)
8498(6)
9336(10)
9740(6)
9306(8)
8468(9)
8102(9)
8699(9)
9508(8)
9719(8)
9122(9)
8313(10)
47(1)
56(1)
54(1)
46(1)
58(1)
55(1)
47(1)
44(1)
45(1)
49(1)
51(1)
58(1)
75(1)
46(1)
54(1)
58(1)
55(1)
58(1)
53(1)
79(1)
57(1)
90(1)
113(1)
97(1)
79(1)
62(1)
82(2)
55(2)
57(1)
78(2)
71(2)
141(6)
56(3)
319(18)
98(3)
160(8)
64(3)
69(2)
92(3)
104(4)
101(3)
73(3)
73(4)
95(4)
106(4)
111(5)
114(5)
85(3)
ω/2 = 1.2). Intensity data were collected within the
range 3 < < 62 (0 < h < 10, 12 < k < 11, 17 <
l < 17) using graphite monochromated Cu -K radi-
ation ( = 1.54178 A ). Intensities of 4566 reflections
˚
(4261 unique reflections, Rint = 0.014) were mea-
sured. Data were corrected for Lorentz and polar-
isation effects but not for absorption. The struc-
ture was solved by direct methods [10] and refined
by the full-matrix least-squares technique in the
anisotropic approximation [11]. In the refinement,
4041 reflections with I > 2 (I) were used. All hy-
drogen atoms were placed in calculated positions
and were included in the final refinement with fixed
positional and thermal parameters. Convergence
543(2)
555(3)
2075(3)
2461(3)
1386(2)
3262(4)
5787(3)
6917(4)
7709(5)
7429(4)
6338(4)
5512(3)
2496(10)
2212(9)
2722(6)
3516(8)
2853(11)
1872(16)
2622(12)
1770(25)
2657(19)
3595(14)
6571(16)
7590(14)
8651(14)
8694(17)
7675(20)
6614(19)
6473(21)
7454(19)
8450(18)
8465(20)
7485(23)
6488(22)
was obtained at R (F) = 0.044 and Rw(F2) = 0.128,
1
GOF = 1.065 (411 refined parameters; obs./variabl.
9.8; the largest and minimal peaks in the final dif-
7453(4)
6529(4)
5959(3)
6304(3)
3
˚
ference map, 0.21 and 0.23 e/A ). The weighting
scheme ω = 1/[ 2(Fo2) + (0.079P)2 + 0.356P)] with P
= (Fo2 + 2Fc2)/3 was used. The final atomic coordi-
nates are listed in Table 2.
7225(2)
11782(8)
11219(6)
12353(5)
10916(8)
9756(8)
Full crystallographic details have been deposited
at the Cambridge Crystallographic Data Centre
(CCDC). Any request to the CCDC for these materials
should quote the full literature citation and reference
number CCDC 156084.
11543(14)
11444(8)
11944(23)
10525(16)
10029(22)
11877(13)
11248(11)
11962(9)
13304(9)
13933(10)
13219(14)
12048(16)
11583(11)
12477(12)
13835(11)
14300(12)
13406(17)
General Procedure for Synthesis
of Thioamidophosphonates (3a–e)
To a solution of each phenylhydrazone (1a–e)
(0.03 mol) in pyridine (30 ml) a solution of phos-
phorus tribromide (0.03 mol) in pyridine (10 ml) was
added and the reaction mixture was allowed to stand
for 5 min. Then a solution of morpholine (0.06 mol)
and triethylamine (0.06 mol) in benzene was added
and, an 1 h later, sulfur (0.03 mol) was added to the
reaction mixture. The reaction mixture was heated
at 80 C for 1 h and, after cooling, was filtered. The
filtrate was evaporated in a vacuum, and the product
was crystallized from hexane.
The morpholine O(1)N(5)C(21-24) and benzene C(25)-C(30) cycles
are disordered over two positions (A and B) with multiplicity 0.53 and
0.47.
N0-[2,5-Dimethyl-1-(4-methylphenyl)-1H-pyrrol-
3-yl]methylidenedi(4-morpholinyl)-N-phenylphosphi-
nothioic hydrazide (3a). Yield 82%; m.p. 132–133 C.
3.68 (t, 8H, JHH = 4.1 Hz, O CH2), 6.21 (s, 1H, Het),
6.85–7.21 (m, 2H, m-Ar, 5H, N Ph), 7.32 (d, 2H,
JHH = 5.8 Hz, o-Ar), 7.74 (s, 1H, CH N). Anal. calcd
for C28H36N5O2PS: N, 13.03; P, 5.76. Found: N, 13.44;
P, 5.78.
1
31P NMR (CHCl3): = 65. H NMR (CDCl3, TMS):
= 1.95 (s, 1H, C5 CH3), 2.14 (s, 1H, C2 CH3),
2.43 (s, 3H, Ar CH3), 3.1–3.25 (m, 8H, N CH2),

662 Ivonin et al.
N0-(1-Methyl-1H-indol-3-yl)methylidenedi(4-mor-
pholinyl)-N-phenylphosphinothioic hydrazide (3b).
Yield 87%; m.p. 183–184 C. 31P NMR (CHCl3):
1-Bromo-9-methyl-2-phenyl-2,9-dihydro-1H-[1,2,
3]diazaphosphinino[4,5-b]indole (4b). To a solution
of phosphorus tribromide (0.01 mol) in pyridine
(30 ml) a solution of phenylhydrazone (1b) (0.01
mol) and methylene chloride (20 ml) was added. The
reaction mixture was heated at 60 C for 12 h, then,
cooled and evaporated. The product was purified
by reprecipitation with hexane from benzene. Yield
=
67. 1H NMR (CDCl3, TMS): = 3.1–3.3 (m, 8H,
N CH2), 3.6–3.7 (m, 8H, O CH2), 3.9 (s, 3H,
N CH3), 6.2 (s, 5H, Ph), 7.2–7.6 (m, 5H, Het), 8.25
(s, 1H, CH=N). Anal. calcd for C24H30N5O2PS: N,
14.33; P, 6.24. Found: N, 14.48; P, 6.41.
1
68%; m.p. 179–180 C. 31P NMR (CHCl3): = 82. H
N0 -(5-Methyl-2-furyl)methylidenedi(4-morpholi-
NMR (CDCl3, TMS): = 4.06 (s, 3H, N CH3), 7.08–
7.43 (m, 7H, 5H Ph, 2H Ind), 7.72 (d, 1H, JHH = 7.8
Hz, H Ind), 7.87 (d, 1H, JHH = 7.8 Hz, H Ind), 8.01 (s,
1H, CH N). Anal. calcd for C16H13N3BrP: N, 11.73;
P, 8.65. Found: N, 11.86; P, 8.60.
nyl)-N-phenylphosphinothioic hydrazide (3c). Yield
1
81%; m.p. 211–212 C. 31P NMR (CHCl3): = 67. H
NMR (CDCl3, TMS): = 2.32 (s, 3H, Het-Me), 3.06–
3.11 (m, 8H, N CH2), 3.66–3.71 (m, 8H, O CH2),
5.87 (d, 1H, JHH = 1.7 Hz, H4), 5.95 (d, 1H, JHH = 1.7
Hz, H3), 7.41–8.04 (m, 6H, Ph, CH N). Anal. calcd
for C20H27N4O3PS: N, 12.31; P, 7.01. Found: N, 12.38;
P, 7.19.
1-Bromo-6-(diphenylphosphoryl)-7-methyl-2-ph-
enyl-2,7-dihydro-1H-pyrrolo [2,3-d][1,2,3]diazaphos-
phinine (4e). This compound was obtained from
phenylhydrazone (1e) analogously to 4a. Yield 62%;
1
N0 -1-Benzofuran-2-ylmethylidenedi(4-morpholi-
m.p. 164–165 C. 31P NMR (CHCl3): = 86. H NMR
nyl)-N-phenylphosphinothioic hydrazide (3d). Yield
(CDCl3, TMS): = 4.06 (s, 3H, N CH3), 6.87 (br
s, 1H, Het), 7.03–8.01 (m, 10H, Ph), 8.80 (s, 1H,
CH N). Anal. calcd for C24H20N3BrP2: N, 8.27; P,
12.19. Found: N, 8.73; P, 12.11.
1
78%; m.p. 239–240 C. 31P NMR (CHCl3): = 68. H
NMR (CDCl3, TMS): = 3.30–3.41 (m, 8H, N CH2),
3.70–3.81 (m, 8H, O CH2), 6.74 (s, 1H, H3 Het), 7.07
(s, 1H, CH N), 7.11–7.50 (m, 9H, H2,3,4,5 Ph). Anal.
calcd for C23H27N4O3PS: N, 12.07; P, 6.34. Found: N,
12.11; P, 6.20.
5,7-Dimethyl-6-(4-methylphenyl)-1,2-diphenyl-2,
6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,3]diazaphosphi-
nine-1-one (6). To a solution of diphenylbromo-
phosphine (0.01 mol) in pyridine (20 ml), a solution
of hydrazone (1a) (0.01 mol) and triethylamine
(0.02 mol) in pyridine (20 ml) was added; 48 h
later, the reaction mixture was filtered and the
filtrate evaporated to dryness. The oil obtained
was dissolved in benzene and, then, Br2 (0.01 mol)
was added; 2 h later, a benzene solution was de-
canted. The obtained oil was dissolved in methylene
chloride (30 ml) and washed with a 3% solution
of NaOH. Then, the organic layer was separated,
dried over Na2SO4 and evaporated to dryness. The
product was crystallized from acetone. Yield 25%;
m.p. 250–251 C. 31P NMR (CHCl3): = 8.1. 1H NMR
(CDCl3, TMS): = 1.97 (s, 3H, C7 CH3), 2.20 (s,
3H, C5 CH3), 2.44 (s, 3H, Ph CH3), 7.04 (d, 2H,
JHH = 5.4 Hz, m-H T1), 7.17–7.36 (m, 10H, Ph), 7.55
(d, 2H, JHH = 5.4 Hz, o-H T1), 7.81 (s, 1H, CH N).
Anal. calcd for C26H24N3OP: N, 9.88; P, 7.28. Found:
N, 7.64; P, 7.33.
N0 -[5-(Diphenylphosphoryl)-1-methyl-1H-pyrrol-
2-yl]methylidenedi(4-morpholinyl)-N-phenylphosphi-
nothioic hydrazide (3e). Yield 65%; m.p. 173–174 C.
1
31P NMR (CHCl3): = 65. H NMR (CDCl3, TMS):
= 2.60–2.81 (m, 8H, O CH2), 3.30–3.50 (m, 8H,
O CH2), 3.84 (s, 3H, N CH3), 5.31 (dd, 1H, JHP = 4.2
Hz, JHH = 3.4 Hz, H4, Het), 6.24 (dd, 1H, JHP = 1.8
Hz, JHH = 3.4 Hz, H4, Het), 7.50–7.88 (m, 15H, Ph).
Anal. calcd for C23H27N4O3PS: N, 11.05; P, 9.78.
Found: N, 10.81; P, 9.86.
1-Bromo-5,7-dimethyl-6-(4-methylphenyl)-2-phe-
nyl-2,6-dihydro-1H-pyrrolo[3,4-d][1,2,3]diazaphosp-
hinine (4a). To a solution of phosphorus tribro-
mide (0.01 mol) in pyridine (10 ml) with cooling
and stirring, a solution of phenylhydrazone (1a)
(0.01 mol) in pyridine (10 ml) was added dropwise.
The reaction mixture was allowed to stand for 24
h and, after that, was evaporated in a vacuum.
Then, it was purified by reprecipitation with hexane
from benzene. Yield 62%; m.p. 176–177 C. 31P NMR
5,7-Dimethyl-6-(4-methylphenyl)-1,2-diphenyl-2,
6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,3]diazaphosphi-
nine-1-thione (7). To a solution of diphenylbro-
mophosphine (0.01 mol) in pyridine (20 ml) a
solution of hydrazone (1a) (0.01 mol) and triethy-
lamine (0.02 mol) in pyridine (20 ml) was added;
48 h later sulfur (0.01 mol) was added and the
1
(CHCl3): = 96.4. H NMR (CDCl3, TMS): = 2.13
(s, 3H, C7 CH3), 2.23 (d, 3H, JHP = 1.2 Hz, C5 CH3),
2.46 (s, 3H, Ph CH3), 7.51 (m, 7H, m-H Tl, Ph),
7.64 (s, 1H, CH N), 7.71 (d, 2H, JHH = 8.0 Hz, o-H
Tl). Anal. calcd for C20H19N3BrP: N, 10.19; P, 7.51.
Found: N, 10.22; P, 7.56.

Heterocondensed 1,2,3-Diazaphosphorines 663
(CHCl3): = 41.01. 1H NMR (CDCl3, TMS):
=
mixture was boiled for 1 h. A residue was filtered
off, and the filtrate was evaporated in a vacuum. The
product was crystallized from acetone. Yield 30%;
m.p. 210–212 C. 31P NMR (CHCl3): = 40, 30. 1H
NMR (CDCl3, TMS): = 2,00 (s, 3H, C7 CH3), 2.18
(s, 3H, C5 CH3), 2.43 (s, 3H, Ph CH3), 7.00–7.50 (m,
12H, m-H Tl, Ph), 7.77 (s, 1H, CH = N), 7.85 (d, 2H,
sJHH = 8.1 Hz, o-H T1). Anal. calcd for C26H24N3PS:
N, 9.52; P, 7.03. Found: N, 9.28; P, 6.63.
2.70–3.10, 3.20–3.40 (m, 4H, N CH2), 3.41 (t, 4H,
JHH = 4.0 Hz, O CH2), 4.06 (s, 3H, N CH3), 7.10–
7.55 (m, 7H, 5H Ph, 2H Ind), 7.75 (d, 1H, JHH = 7,8
Hz, H Ind), 7.89 (d, 1H, JHH = 7.8 Hz, H Ind), 8.05 (s,
1H, CH N). Anal. calcd for C20H21N4OPS: N, 14.11;
P, 7.81. Found: N, 14.03; P, 7.85.
6-(Diphenylphosphoryl)-7-methyl-1-(4-morpholi-
nyl)-2-phenyl-2,7-dihydro-1H-1 5-pyrrolo[2,3-d][1,2,
3]diazaphosphinine-1-thione (9e). Yield 51%; m.p.
N-[5,7-Dimethyl-6-(4-methylphenyl)-1,2-diphen-
yl-2,6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,3]diazapho-
sphinine-1-ylidene]-4-methylaniline(8). To a solu-
tion of diphenylbromophosphine (0.01 mol) in pyri-
dine (20 ml) a solution of hydrazone (1a) (0.01 mol)
and triethylamine (0.02 mol) in pyridine (20 ml)
was added. After 48 h the mixture was filtered and,
then, to the filtrate a solution of p-tolyl azide (0.01
mol) in toluene (30 ml) was added. The mixture
was boiled for 3 h and evaporated. The product
was crystallized from methanol. Yield 28%; m.p.
1
176–178 C. 31P NMR (CHCl3): = 43, 62. H NMR
(CDCl3, TMS): = 2.82–3.15, 3.22–3.45 (m, 4H,
N CH2), 3.43 (t, 4H, JHH = 4.2 Hz, O CH2), 4.12
(s, 3H, N CH3), 6.91 (d, 1H, JHP = 1.2 Hz, Het),
7.05–8.10 (m, 10H, Ph), 8.82 (s, 1H, CH N). Anal.
calcd for C28H28N4O2P2S: N, 10.25; P, 11.33. Found:
N, 8.73; P, 12.11.
N-[5,7-Dimethyl-6-(4-methylphenyl)-1-(4-morph-
olinyl)-2-phenyl-2,6-dihydro-1H-1 5-pyrrolo[3,4-d][1,
2,3]diazaphosphinin-1-ylidene]aniline (10a). To a
solution of bromophosphine 4a (0.01 mol) in ben-
zene (20 ml), with cooling and stirring, a solution of
morpholine (0.01 mol) and triethylamine (0.03 mol)
in benzene (30 ml) was added; 2 h later, phenylhy-
drazide (0.01 mol) in benzene (20 ml) was added.
The reaction mixture was heated at 60 C for 1 h,
cooled and, then, treated with a mixture of diethyl
ether and acetone (1:1). The precipitated product
1
221–223 C. 31P NMR (CHCl3): ␦= 9.21. H NMR
(CDCl3, TMS): ␦= 1.98 (s, 3H, C7 CH3), 2.18 (s, 3H,
C5 CH3), 2.24 (s, 3H, P N Ph CH3), 2.39 (s, 3H,
N Ph CH3), 6.97–7.63 (m, 14H, m-H T1, Ph), 7.82
(s, H, CH N), 7.85 (m, 4H, o-H T1). Anal. calcd for
C33H31N4P: N,10.89; P, 6.03. Found: N, 10.67; P, 6.24.
General Procedure for Synthesis
of Thioamides (9a,b,e)
was recrystallized from ethanol. Yield 72%; m.p.
1
To a solution of bromophosphine 4a–e (0.01 mol)
in benzene (20 ml), with cooling and stirring, a so-
lution of morpholine (0.01 mol) and triethylamine
(0.03 mol) in benzene (30 ml) was added; 2 h later,
sulfur (0.01 mol) was added and the mixture was
boiled for 1 h. After that, the mixture was filtered and
the filtrate was evaporated. The product was crystal-
lized from ethanol.
208–210 C. 31P NMR (CHCl3):
=
3, 13. H NMR
(CDCl3, TMS): = 2.35 (s, 3H, C7 CH3), 2.39 (s, 3H,
C5 CH3), 2.65 (s, 3H, Ph CH3), 3.08–3.20 (m, 4H,
N CH2), 3.42 (m, 4H, O CH2), 6.89–7.56 (m, 2H,
m-Tol, 5H, N Ph, 5H, N Ph), 7.82 (d, 2H, JHH = 6
Hz, o-H, T1), 7.93 (s, 1H, CH N). Anal. calcd for
C30H32N5OP: N, 13.74; P, 6.08. Found: N, 13.89; P,
6.06.
5,7-Dimethyl-6-(4-methylphenyl)-1-(4-morpholi-
nyl)-2-phenyl-2,6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,
3]diazaphosphinine-1-thione (9a). Yield 55%; m.p.
191–195 C. 31P NMR (CHCl3): = 47.10. 1H NMR
(CDCl3, TMS): = 2.15 (s, 3H, C7 CH3), 2.46 (d,
3H, JHP = 1.0 Hz, C5 CH3), 2.46 (s, 3H, Ph CH3),
2.90–3.10, 3.20–3.40 (m, 4H, N CH2), 3.48 (t, 4H,
JHH = 4,8 Hz, O CH2), 7.00–7.50 (m, 7H, m-H T1,
Ph), 7.64 (s, 1H, CH N), 7.70 (d,2H, JHH = 8.1 Hz,
o-H T1). Anal. calcd for C24H27N4OPS: N, 12.44; P,
6.88. Found: N, 12.03; P, 6.84.
General Procedure for Synthesis
of Thiophosphonates 11a,b
To a solution 4a (0.01 mol), with cooling and stir-
ring, a solution of methanol (0.01 mol) and triethy-
lamine (0.01 mol) in benzene (20 ml) was added; 0.5
h later, sulfur (0.01 mol) was added and, then, the
mixture was boiled for 0.5 h. The reaction mixture
was cooled, filtered and evaporated to dryness. The
product was crystallized from ethanol.
1-Methoxy-5,7-dimethyl-6-(4-methylphenyl)-2-ph-
enyl-2,6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,3]diazaph-
osphinine-1-thione(11a). Yield 43%; m.p. 163–
164 C. 31P NMR (CHCl3): = 55,87. 1H NMR (CDCl3,
9-Methyl-1-(4-morpholinyl)-2-phenyl-2,9-dihyd-
ro-1H-1 5 -[1,2,3]diazaphosphinino[4,5-b]indole-1-
thione (9b). Yield 57%; m.p. 192–193 C. 31P NMR

664 Ivonin et al.
TMS): = 2.17 (s, 3H, C7 CH3), 2.38 (s, 3H, C5 CH3),
2.46 (s, 3H, Ph CH3), 6.61 (d, 3H, JHP = 1.5 Hz,
O CH3), 7.10–7.43 (m, 7H, m-H T1, Ph), 7.57 (d, 2H,
JHH = 9.0 Hz, o-H T1), 7.76 (s, 1H, CH N). Anal.
calcd for C21H22N3OPS: N, 10.63; P, 7.83. Found: N,
10.21; P, 7.94.
NH Ph), 7.45 (d, 2H, JHH = 6.0 Hz, o-H T1), 7.76
(s, 1H, CH N). Anal. calcd for C26H25N4PS: N,
12.28; P, 6.80. Found: N, 11.83; P, 7.01.
REFERENCES
5
1-Methoxy-9-methyl-2-phenyl-2,9-dihydro-1H-1
[1] Tolmachev, A. A.; Ivonin, S. P.; Pinchuk, A. M. Het-
eroat Chem 1995, 6, 407.
[1,2,3]-diazaphosphinino[4,5-b]indole-1-thione(11b).
[2] Ivonin, S. P.; Terikovska, T. E.; Chaikovskaya, A. A.;
Marchenko, A. P.; Koydan, G. N.; Pinchuk, A. M.;
Tolmachev, A. A. Heteroat Chem 1999, 10, 213.
[3] Tolmachev, A. A.; Chaikovskaya, A. A.; Terikovska, T.
E.; Ivonin, S. P.; Pinchuk, A. M. Heteroat Chem 1996,
525.
[4] Keglevich, G.; Chuluunbaatar, T.; Dobo, A.; Toke, L. J
Chem Soc Perkin Trans 1 2000, 1495.
[5] Morrison, G. C.; Waite, R. O.; Shawel, J. Jr. J Hetero-
cycl Chem 3, 4, 1966, 540.
Yield 51%; m.p. 174–173 C. 31P NMR (CHCl3):
1
= 78.23. H NMR (CDCl3, TMS): = 4.09 (s, 3H,
N CH3), 6.58 (d, 3H, JHP = 1.1 Hz, O CH3), 7.11–
7.54 (m, 7H, 5H Ph, 2H Ind), 7.71 (d, 1H, JHH
=
7.0 Hz, H Ind), 7.89 (d, 1H, JHH = 7.0 Hz, H Ind),
8.05 (s, 1H, CH N). Anal. calcd for C17H16N3OPS:
N, 12.31; P, 9.07. Found: N, 12.74; P, 9.43.
1-Anilino-5,7-dimethyl-6-(4-methylphenyl)-2-phe-
nyl-2,6-dihydro-1H-1 5-pyrrolo[3,4-d][1,2,3]diazaph-
osphinin-1-one(12a). To a solution of 4a (0.01 mol),
with cooling and stirring, a solution of aniline (0.01
mol) and triethylamine (0.03 mol) in benzene (30
ml) was added; 1 h later, sulfur (0.01 mol) was added
and the mixture was boiled for 1 h. After cooling
the reaction mixture was filtered. The filtrate was
evaporated to dryness. When treating the residue
with ethanol, the product was precipitated. It
was recrystallized from ethanol. Yield 72%; m.p.
195–196 C. 31P NMR (CHCl3): = 32.88. 1H NMR
(CDCl3, TMS): = 2.17 (s, 3H, C7 CH3), 2.19 (s, 3H,
[6] (a) Ivonin, S. P.; Chaikovskaya, A. A.; Kudrya,
T. N.; Terikovskaya, T. E.; Tolmachev, A. A. Chem
Heterocycl Comp 1999, 34, 986; (b) Ivonin, S. P.;
Chaikovskaya, A. A.; Kudrya, T. N.; Terikovskaya,
T. E.; Tolmachev, A. A. Chem Abstr 1999, 130, 325196.
[7] Burke-Laing, M.; Laing, M. Acta Crystallogr (B) 1976,
32, 3216.
[8] Naumov, V. A.; Vilkov, L. V. Moleculular Structures of
Organo-phosphorus Compounds (Russian); Nauka:
Moskow, 1986.
[9] Allen, F. H.; Kennard, O.; Watson, D. G.;
Brammer, L.; Orpen, A. G.; Tailor, R. J Chem Soc
Perkin Trans 2 1987, P1.
[10] Sheldric, G. M. SHELXS-86, Program for the solu-
tion of crystal structures; University of Gottingen:
Gottingen, Germany, 1986.
C5 CH3), 2.23 (s, 3H, Ph CH3), 5.59 (d, 1H, JHP
=
[11] Sheldric, G. M. SHELXL-93, Program for the refine-
ment of crystal structures; University of Gottingen,
Gottingen: Germany, 1993.
9 Hz, NH), 6.61 (d, 2H, JHH = 9 Hz, o-H, Ph NH),
6.92–7.34 (m, 10H, 2H, m-H T1, 5H N Ph, 3H,