Studies on organophosphorus compounds: The synthesis of [1,3,2]-diazaphospholes and [1,3,2]-oxaazaphospholes

Article abstract of DOI:10.1080/10426500600754794

A number of spiro[cyclopentane (cyclohexane, and cycloheptane)-1,4′- perhydro-[1,3,2]diazaphosphole] derivatives (3a-c, 5a-c, 11a-c, and 12a-c) and spiro-[cyclopentane (cyclohexane, and cycloheptane)-1,4′-perhydro[1,3,2] oxaazaphos-phole] derivatives (7a-

Full text of DOI:10.1080/10426500600754794

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Phosphorus, Sulfur, and Silicon
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Studies on Organophosphorus
Compounds: The Synthesis of
[1,3,2]-Diazaphospholes and
[1,3,2]-Oxaazaphospholes
O. A. Omran a & H. M. Moustafa a
a Chemistry Department , Sohag, Egypt
Published online: 01 Feb 2007.
To cite this article: O. A. Omran & H. M. Moustafa (2006) Studies on
Organophosphorus Compounds: The Synthesis of [1,3,2]-Diazaphospholes and [1,3,2]-
Oxaazaphospholes, Phosphorus, Sulfur, and Silicon and the Related Elements, 181:11,
2519-2528, DOI: 10.1080/10426500600754794
To link to this article: http://dx.doi.org/10.1080/10426500600754794
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Phosphorus, Sulfur, and Silicon, 181:2519–2528, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500600754794
Studies on Organophosphorus Compounds:
The Synthesis of [1,3,2]-Diazaphospholes
and [1,3,2]-Oxaazaphospholes
O. A. Omran
H. M. Moustafa
Chemistry Department, Sohag, Egypt
A number of spiro[cyclopentane (cyclohexane, and cycloheptane)-1,4ꢀ-perhydro-
[1,3,2]diazaphosphole] derivatives (3a–c, 5a–c, 11a–c, and 12a–c) and spiro-[cy-
clopentane (cyclohexane, and cycloheptane)-1,4ꢀ-perhydro[1,3,2]oxaazaphos-phole]
derivatives (7a–c) were prepared via an interaction of 2,4-bis-(4-methoxy-phenyl)-
1,3,2,4-dithiaphosphetane-2,4-disulphide (1) with substances containing two func-
tional groups.
Keywords 1-Phenylamino-1-cyanocycloalkanes; 2,4-bis-(4-methoxyphenyl)-1,3,2,4-
dithiaphosphetane-2,4-disulphide
INTRODUCTION
It is well known that 2,4-bis-(4-methoxyphenyl)-1,3,2,4-dithiaphos-
phetane-2,4-disulphide (Lawesson’s Reagent, [LR]) is a most effective
and versatile thiation reagent for different cabonyl compounds.1−5 The
nucleophiles attack LR at the phosphorus atom and form phosphorus
heterocycles.6−9 In view of the latest development and also in con-
tinuation of our study of phosphorus hetero-cycles,10−13 In this arti-
cle it was of interest to synthesize spiro[1,3,2]diazaphospholes and
spiro[1,3,2]oxaazaphospholes from the reaction of LR with other classes
of substrates with two functional groups.
RESULTS AND DISCUSSION
The reaction of 1-phenylamino-1-cyanocyclopentane(cyclohexane, and
cyclo-heptane)14 (2a–c) with LR (1) in boiling acetonitrile afforded
2ꢀ-(4-methoxy-phenyl)-4ꢀ-phenylspiro[cyclopentane (cyclohexane, and
Received February 26, 2006; accepted April 16, 2006.
Address correspondence to H. M. Moustafa, Chemistry Department, Faculty of Sci-
ence, Sohag, Egypt. E-mail: hassa20002000@yahoo.com
2519

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O. A. Omran and H. M. Moustafa
cycloheptane)-1,4ꢀ-perhy-dro[1,3,2]diazaphosphole]-2ꢀ,5ꢀ-disulfides
(3a–c). The reaction pathway was assumed to proceed via a nucle-
ophilic attack of the amino group on the phosphorus of LR followed by
a P-SH addition to the nitrile group and subsequent rearrangement,16
which yielded compounds 3a–c (cf. Scheme 1). The IR spectra of
compounds 3a–c showed the absence of bands corresponding to cyano
groups while exhibiting the characteristic absorption band at 651, 642,
and 659 cm−1 for P S, respectively. 1H NMR spectra of compounds
3a–c exhibited a singlet at 3.9 ppm corresponding to OCH3 (cf. Table I).
SCHEME 1
The treatment of compounds 2a–c with sodium metal in ethanol
afforded the corresponding amines 4a–c in good yield. IR spectra of
compounds 4a–c showed the absence of absorption bands correspond-
ing to CN groups and the appearance of new bands corresponding to
1
NH2 groups (3163–3412 cm−1). The H NMR (CDCl3) spectra of com-
pounds 4a–c are in agreement with the proposed structure (cf. Table I).
Compounds 4a–c were allowed to react with LR (1) in anhydrous ben-
zene at 80◦C to give 2ꢀ-(4-methoxyphenyl)-3ꢀ-phenylspiro[cyclopentane

2521

2522

2523

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O. A. Omran and H. M. Moustafa
(cyclohexane, and cycloheptane)-1,4ꢀ-perhydro[1,3,2]diazaphosphole]-
2ꢀ-disulfi-des (5a–c). As to the mechanism for the formation P-
heterocycles 5a-c, it is suggested that a nucleophilic attack on LR to
give the intermediate, which at elevated temperature looses H2S to
give, compounds 5a-c (cf. Scheme 2). The structures of these products
were based on spectroscopic data and elemental analysis (cf. Table I).
Compounds 6b,c were synthesized by Desai,15 and this synthe-
sis can be carried out in another route via the diazotization of
compounds 4b,c. Also, the diazotization of compound 4a gave 1-
anilinocyclopentanemethanol (6a). Compounds 6a–c were then sub-
mitted to the reaction with LR in anhydrous benzene to give
2ꢀ-(4-methoxyphenyl)-3ꢀ-phenylspiro[cyclopentane (cyclohexane, and
cycloheptane)-1,4ꢀ-perhydro[1,3,2]oxaazaphosphole]-2ꢀ-disulfides (7a–
c) (cf. Scheme 2). The structures of the new products have been elu-
cidated via analytical results and spectroscopic data (cf. Table I).
Moreover, the addition of compounds 4a–c to phenyl isocyanate
and/or phenyl isothiocyanate in ethanol at 26◦C afforded the opened
products 8a–c and 9a-c, respectively, via an addition of the amino
groups of compounds 4a–c to the isocyanate or isothiocyanate (cf.
Scheme 2). The cyclized products 10a–c were obtained by refluxing com-
pounds 8a–c and/or 9a–c in N,N-dimethylaniline. The IR and 1H NMR
spectra of these compounds confirm the proposed structures (cf. Table I).
The reaction of compounds 8a–c and/or 9a–c with LR in refluxing
p-xyl-ene afforded 2ꢀ(4-methoxyphenyl)-3ꢀ-phenylspiro[cyclopentane
(cyclohexane and cycloheptane)-1,4ꢀ-perhydro[1,3,2]diazaphosphole]-
1-ylphenylaminomethane-1-ones (11a–c) and 2ꢀ(4-methoxyphenyl)-
3ꢀ-phenylspiro[cyclopentane (cyclohexane and cycloheptane)-1,4ꢀ-
perhydro[1,3,2]diazaphosphole]-1-ylphenylaminometha-ne-1-thiones
(12a–c), respectively. The same products 11a–c and 12a–c were also
obtained through the reaction of compounds 5a–c with phenyl iso-
cyanate and/or phenyl isothiocyanate in boiling benzene. The structure
of compounds 11a–c and 12a–c were confirmed on the basis of their
elemental and spectral analyses (cf. Table I).
EXPERIMENTAL
The Synthesis of 2ꢀ-(4-Methoxyphenyl)-4ꢀ-phenylspiro
[cyclopentane (Cyclohexane and Cycloheptane)-1,4ꢀ-
Perhydro[1,3,2]diazaphosphole]-2ꢀ,5ꢀ-disulfides (3a–c):
General Procedure
2,4-bis-(4-methoxyphenyl)-1,3,2,4-dithiaphosphetane-2,4-disulphide
(LR, 1) (2.02 g; 0.005 mole) and 1-phenylamino-1-cyanocyclopentane

Diazaphospholes and Oxaazaphospholes
2525
SCHEME 2

2526
O. A. Omran and H. M. Moustafa
(cyclohexane, and/or cycloheptane) (2a–c) (0.01 mol) were dissolved
in acetonitrile (80 mL). The reaction mixture was refluxed for 6 h,
concentrated and cooled the precipitate was filtered off, dried, and
recrystallized from the suitable solvent to give compounds 3a–c.
The Synthesis of 1-Anilinocyclopentane(cyclohexane,
and Cycoheptane)methyl-amine l4a–c: General Procedure
To a solution of the proper nitrile 2a–c (1.0 g) in absolute ethanol (10
mL) was added 1.5 g of clean sodium. When all the sodium reacted
(10–15 min.), the reaction mixture was cooled to about 20◦C, and 15
mL of conc HCl was added. The reaction mixture was concentrated and
cooled and 20 mL of 40% NaOH was added dropwise with shaking to
the reaction mixture. The formed amine was extracted with chloroform
and purified by distillation.
The Synthesis of 1-Anilinocyclopentane (Cyclohexane and
Cycloheptane)methanol 6a–c: General Procedure
To a stirred ice-cooled solution of the proper amine (4a–c) (0.01 mole) in
8 mL of conc HCl was added portionwise (0.83 g, 0.012 mole) of NaNO2.
The mixture was kept at r.t. for 30 min and then poured onto crushed ice.
The obtained solution was neutralized with NH4OH, and the separated
oil was extracted with chloroform and purified by distillation to give
compounds 6a–c.
The Synthesis of 2ꢀ-(4-Methoxyphenyl)-3ꢀ-phenylspiro
[cyclopentane(cyclohexane and cycloheptane)-1,4ꢀ-Perhydro-
[1,3,2]diazaphosphole]-2ꢀ-disulfides (5a-c) and 2ꢀ-(4-
methoxyphenyl)-3ꢀ-phe-nylspiro[cyclopentane(cyclohexane
and Cycloheptane)-1,4ꢀ-perhydro[1,3,2]oxaazaphosphole]-2ꢀ-
disulfides (7a–c): General Procedure
A mixture of the proper amine (4a–c) (0.01 mole) and/or the proper
hydroxylderivative (6a–c) (0.01 mole) and 2,4-bis-(4-methoxyphenyl)-
1,3,2,4-dithiaphosphetane-2,4-disulphide (LR, 1) (2.02 g, 0.005 mole)
in dry benzene (80 mL) was refluxed for 5 h, concentrated, and cooled.
The formed precipitate was filtered off, dried, and recrystallized from
the suitable solvent to give compounds 5a–c and 7a–c, respectively.
The Synthesis of Compounds 8a–c and 9a–c: General
Procedure
To a stirred solution of the proper amine 4a–c (0.01 mole) in 30 mL
of absolute ethanol was added phenyl isocyanate (1.19 g, 0.01 mole)

Diazaphospholes and Oxaazaphospholes
2527
or phenyl isothiocyanate (1.35 g, 0.01 mole). The reaction mixture was
stirred at r.t. for 1 hour. The formed precipitate was filtered off, dried,
and recrystallized from the suitable solvent to give compounds 8a–c
and 9a–c, respectively.
The Synthesis of 3ꢀ-Phenyl-2ꢀ-phenylaminospiro
[cyclopentane(cyclohexane and Cycloheptane)-1,4ꢀ-(3ꢀ,5ꢀ-
dihydroimidazoles)] (10a–c): General Procedure
Compound 8a–c and/or 9a–c (0.01 mol) was refluxed in N,N-
dimethylaniline (10 mL) for 12 h. The solvent was concentrated, cooled,
and filtered off. The solid product was recrystallized from the suitable
solvent (cf. Table I).
The Synthesis of 2ꢀ-(4-Methoxyphenyl)-3ꢀ-
phenylspiro[cyclopentane(cyclohexane and
Cycloheptane)-1,4ꢀ-Perhydro[1,3,2]diazaphosphole]-1-
ylphenylamino-methane-1-ones (11a–c) or –1-thiones (12a–c):
General Procedure
2,4-bis-(4-methoxyphenyl)-1,3,2,4-dithiaphosphetane-2,4-disulphide
(LR, 1) (2.02 g; 0.005 mole) and the proper compound 8a–c and/or 9a–c
(0.01 mol) were dissolved in p-xylene (60 mL). The reaction mixture
was refluxed for 6 h, concentrated, and cooled; the precipitate was
filtered off, dried, and recrystallized from the proper solvent to give
compounds 11a–c and 12a–c, respectively.
The Alternate Synthesis of Compounds 11a–c and 12a–c:
General Procedure
Compound 5a–c (0.01 mol), phenyl isocyanate and/or pheny isothio-
cyanate (0.01 mol) and dry benzene (70 mL) were refluxed together
for 3 h when colorless crystals separated out, which were filtered and
washed with warm benzene to afford compounds 11a–c and 12a–c.
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