Syntheses and characterization of ten-membered cyclic and large bite acyclic bis(phosphines)

Article abstract of DOI:10.1080/10426500307891

Reaction of bis(dichlorophosphino)aniline with CH₂ bridged bis(phenols) or substituted diamine gives the 10-membered heterocyclic phosphorochloridities in quantitative yield. The bis(phenols) also react with chlorodiphenylphosphine to afford th

Full text of DOI:10.1080/10426500307891

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Phosphorus, Sulfur, and Silicon and the Related
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Syntheses and Characterization of Ten-Membered
Cyclic and Large Bite Acyclic Bis(phosphines)
Maravanji S. Balakrishna a & Rashmishree Panda a
a Indian Institute of Technology , Bombay, India
Published online: 27 Oct 2010.
To cite this article: Maravanji S. Balakrishna & Rashmishree Panda (2003) Syntheses and Characterization of Ten-Membered
Cyclic and Large Bite Acyclic Bis(phosphines), Phosphorus, Sulfur, and Silicon and the Related Elements, 178:6, 1391-1396,
DOI: 10.1080/10426500307891
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Phosphorus, Sulfur, and Silicon, 178:1391–1396, 2003
C
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print
DOI: 10.1080/10426500390200710
SYNTHESES AND CHARACTERIZATION OF
TEN-MEMBERED CYCLIC AND LARGE BITE
ACYCLIC BIS(PHOSPHINES)
Maravanji S. Balakrishna and Rashmishree Panda
Indian Institute of Technology (Bombay), India
(Received October 14, 2002; accepted December 6, 2002)
Reaction of bis(dichlorophosphino)aniline with CH2 bridged
bis(phenols) or substituted diamine gives the 10-membered hete-
rocyclic phosphorochloridities in quantitative yield. The bis(phenols)
also react with chlorodiphenylphosphine to afford the bulky acyclic
bis(phosphinites).
Keywords: Acyclic; heterocycles; phosphorochloridites; tervalent phos-
phorus centers
The syntheses of the new cyclic phosphorochloridites are interesting
owing to their steric and electronic properties. Here, both the steric
and electronic attributes can be readily altered at phosphorus(III) cen-
ters by carrying out a variety of nucleophilic substitution reactions.
In case of compounds containing P N bonds the steric environment
can be fine tuned by changing the substituents on the aromatic groups
and the nitrogen atom as well. Beside this, acyclic phosphorus com-
pounds with bulky substituents are used widely as homogeneous cata-
lysts in industrial applications. In this context, bis(phosphinites) with
bulky substituents have shown encouraging regioselectivity in organic
5
synthesis.1
In our previous study6 we explored the rich transition metal chem-
istry of heterocyclic phosphorochloridite and its fluoro derivative with
sulfur spacer between the two phenolic groups, where the heterocycles
retain the P Cl and P F bonds after complexation. As a part of our
11
interest7
in designing new P(III) based ligand systems, we report
We are grateful to the Department of Science and Technology (DST), India for finan-
cial support. We also thank the RSIC, IIT, Bombay, and Sophisticated Instrumentation
Facility (SIF), IISc, Bangalore for NMR spectra.
Address correspondence to M. S. Balakrishna, Department of Chemistry, Indian In-
stitute of Technology, Bombay, Mumbai 400 076, India. E-mail: krishna@iit.ac.in
1391

1392
M. S. Balakrishna and R. Panda
here the easy, high-yield, and one-pot syntheses of some novel hetero-
cycles and bulky acyclic bis(phosphinites) containing two tertiary phos-
phine centres.
RESULTS AND DISCUSSION
Stoichiometric reactions of 2,20-methylenebis(2,4-di-alkyllphenol) with
Cl2PN(Ph)PCl2 afford the 10-membered heterocycles, PhN(PCl)2
t
{( OC6H2(R1R2))( -CH2)((R1R2)C6H2O )} (R1, R2 = Bu, 1; R1 = Me,
t
R2 = Bu, 2; R1, R2 = Me, 3) in good yield (Scheme 1). In a simi-
lar way, bis(2-hydroxy-1-naphthyl)methane and N,N0-diphenylethyl-
enediamine react with Cl2PN(Ph)PCl2 to afford the heterocycles
PhN(PCl)2{( OC10H6)
(
CH2)(C10H6O )} (4) and PhN(PCl)2
{ N(Ph)CH2CH2(Ph)N )} (5) respectively.
SCHEME 1

Ten-Membered Cyclic and Large Bite Acyclic Bis(phosphines)
1393
The compounds 1–5 are crystalline white solids, highly air and mois-
ture sensitive both in solid state and in the solution; on exposure to air
they rapidly form the corresponding oxides, which is, confirmed by the
1
31P{ H} NMR spectroscopic studies. The structure and molecular com-
1
position of all the heterocycles were confirmed by NMR (1H, 31P { H})
spectroscopic data and by elemental analyses (Table I).
Reaction of 2,20-thiobis(4,6-di-tert-butylphenol) with two equivalents
of chlorodiphenylphosphine in the presence of triethylamine affords
the expected compound Ph2P( OC6H2(R1R2)2)( S)((R1R2)2C6H2O )-
PPh2 (6) in good yield. Compounds of the type Ph2P( OC6H2(R1R2)2)
t
t
(
CH2)((R1R2)2C6H2O )PPh2, (R1 = R2 = Bu, 7; R1 = Me, R2 = Bu, 8;
R1 = R2 = Me, 9) were obtained in 85–88% yield by reacting the corres-
ponding 2,20-methylenebis(4,6-di-alkylphenol) with chlorodiphenyl-
phosphine (Eq. 1). The analogous bis(naphthol) derivative, bis{2-
(diphenylphosphinoxy)-1-naphthyl} (10) was prepared in a similar way
(Eq. 2). All these compounds 6–10 have been characterized by NMR
(1H, 31P{ H}) spectroscopic studies and the molecular composition
1
have been established by microanalyses (Table I). The coordinatively
unsaturated phosphorus(III) centers present in these compounds
are prone to both oxidation reactions and Lewis base activity. The
oxidation and coordination properties of the compound 10 have been
explored12 and the reactivity and transition metal chemistry of other
compounds is in progress.

1394

Ten-Membered Cyclic and Large Bite Acyclic Bis(phosphines)
1395
EXPERIMENTAL
All synthetic manipulations were carried out under a pure dini-
trogen atmosphere using standard Schlenk techniques. Solvents
were dried and distilled prior to use. Ethers and dichloromethane
were distilled over Na-benzophenone and calcium hydride respec-
tively. 2,20-Thiobis{4,6-di-tert-butylphenol},13 2,20-methylenebis{4,6-
di-alkyl(R1,R2)phenol},14 bis(2-hydroxyl-1-naphthyl)methane15 and
bis(dichlorophosphino)-aniline16 were prepared according to the cited
1
procedures. The 1H and 31P{ H} NMR ( in ppm) spectra were ob-
tained on a VXR 300S spectrometer operating at appropriate frequen-
cies using tetramethylsilane and 85% H3PO4 as internal and exter-
nal references respectively. Positive shifts lie downfield in all cases.
Microanlyses were performed on a Carlo Erba model 1106 elemental
analyser.
Syntheses of Compounds 1–5
Representative Procedure
A
mixture of 2,20-methylenebis{4,6-di-alkyl(R1,R2)phenol}/bis-
(2-hydroxy-1-naphthyl)methane/N,N0-diphenyl
ethylenediamine
(10.0 mmol) and triethylamine (2.10 g, 20.1 mmol) in THF (50 ml)
was added dropwise to a suspension of bis(dichlorophosphino)aniline
(3.0 g, 10.0 mmol) and in THF (30 ml) under nitrogen with vigorous
stirring at 5 C. The reaction mixture was stirred overnight at 25 C.
Triethylamine hydrochloride was filtered off and solvent was removed
under reduced pressure to give crude product as pale white solid,
which was recrystallized from a mixture of CH2Cl2-hexane (3:1).
Syntheses of Compounds 6–10
Representative Procedure
A solution of PPh2Cl (2 mmol) in diethylether or THF (30 ml) was
added dropwise to a mixture of 2,20-thiobis(4,6-di-tert-butylphenol)/2,20-
methylenebis(4,6-dialkylphenol)/bis(2-hydroxyl-1-naphthyl)methane
(1 mmol) and triethylamine (2.1 mmol) also in THF (50 ml) at 0 C
with vigorous stirring. The reaction mixture was warmed to room
temperature and stirring was continued overnight. The triethylamine
hydrochloride was removed by filtration. The solvent was removed
under vacuum to give a white solid of crude product, which was
recrystallized from a mixture of dichloromethane/petroleum ether
(2:1). The physical and analytical data is given Table I.

1396
M. S. Balakrishna and R. Panda
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