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Bis(trimethylsilyl)aminophosphane.

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The high reactivity towards oxidative attack, e . g . nucleophilic substitution at the phosphorus atom makes 2 an
extremely interesting synthon. For example, 2 smoothly
reacts with carbon disulfide or sulfur with increase in coordination number of the phosphorus to give 3I5land 4'", respectively, while reaction with dichlorophosphanes affords
access to p-functional diphosphanes such as 5[" and with
thiols yields mercaptophosphanes such as 6I5l.
H C1
5 ( hle3Si)2K-P-P-R
R'S-PH2
1: = T t . i ~ a i ~ r e t h ~ l p i p e r ~ i d y 1
R' = Ethyl
6
Experimenral
Bis(trimethylsilyl)aminophosphane**
By Edgar Niecke* and Reinhold Riiger
The stability['] and synthetic potentialI2l of the secondary
aminophosphane N.N.N'-tris(trimethy1silyl)diaminophosphane stimulated our investigations into the synthesis of a
primary aminophosphane.
We have now obtained bis(trimethylsilyl)aminophosphane 2 as the first representative of this class of compounds by selective F/H exchange in bis(trimethy1si1yl)aminodifluorophosphane l''] with LiA1H4/HN(iPr)2.
(kIe3Si),N-PF,
1
-
(1\1e3Si),N-PH2
- LIAIF,(NR~)~.~
2
All experiments were carried out under an inert gas with
rigorous exclusion of air and moisture. The solvents were
re-purified and dried by column chromatography on AlzOz
(super I , basic).-2:
LiAIH4 (1.14 g, 30 mmol) and
HN(iPr)? (2.2 g, 20 mmol) are added to a solution of I
(6.97 g, 30 mmol) in pentane (60 mL) at -20°C. The mixture is stirred and treated with 10 mL of THF, which initiates reaction (evolution of gas). Stirring is continued for a
further 24 h, during which time the mixture is allowed to
warm to room temperature. Solvent and product are collected under oil-pump vacuum in three cold traps ( - 10,
-50, - 196"C), whereby the residue is heated to 50°C. 2
condenses at - 10 and -50°C together with solvent residues. Fractional distillation under vacuum furnishes 3. I5 g
(16 mmol P 53%) of pure 2.
Received: August I I . 1981 [Z 970 IE]
German version: Angew. Chem. 94 (1981) 70
R = CH(CH3)2
2 is a water-clear, highly pyrophoric liquid, which is
stable up to at least 100°C. Its composition is confirmed
by elemental analysis and by its mass spectrum [70 eV: m l z
193 ( M + ,30%), 192 ( M + - H, 2.3), 191 ( M + - H2, l.5), 178
( M +-Me, 100) etc. The H2P-NSi2 skeletal framework
can be deduced from the following characteristic IR absorptions of gaseous 2: 2260 m, 2255 sh v,,,,(PH2), 1070 m
6(PH2), 981 m v(PN), 903 s v.,,(NSi2), and 479 cm-I m
v,( NSi2).
The triplet structure of the signal at 6 = -59.3
('JHp=189.4 Hz) in the "P-NMR (30% in CD2C12, H,PO4
ext.) proves the presence of a PHI-group; the amine ligand
leads to a stronger deshielding of the phosphorus nucleus
than in primary p h o ~ p h a n e s ~The
~ ~ . 'H-, "C{IH}- and
'"Sil'H}-NMR spectra (30% in CD2CI2,TMS int.) show the
signal to be expected for free rotation about the P-N
bond: ' H : 6=0.29 ( 4 J H p = 1.1 Hz), 4.75 (IJ,+p=
189.5 Hz);
I 3 C: 6 = 1.14 (3JcI,=5.3 Hz), and "Si: 6 = 10.41 (2Js,I'=10.8
Hz).
62
Fakultit fur Chemie d e r Universitat
Postfach 8460, D-4800 Bielefeld (Germany)
Thic work was supported by the Deutsche Forschungsgemeinschaft a n d
the Fonds d e r Chemischen Industrie.
0 Verlag Chemie GmhH. 6940 Weinheim. 1982
(1976) 99.
151 " P - N M R : 3: 6 = 2 . 4 (I.'Jt,,,=496 Hz); 4: A= -0.4 (t. 'J,,,.=490 Hz): 5
(preferred stereoisomer): S=61.1 (d, d , 'J,.I.=IS1 Hz, '5,,,.=35 Hz); 6.0
(d, d, 'JIT=151 Hz, 'J,,1.=201.5 Hz): 6: S= - 115 (11. ' J , , p = 193 Hz,
Jtl1$=7..3Hz).
Palladacycloalkanes by
Oxidative Coupling of 3,3-Dimethylcyclopropene
with Palladium(0) Compounds**
By Paul Binger*, Holger Michael Biich, Reinhard Benn,
and Richard Mynott
Transition metal-catalyzed cyclooligomerization of alkenes proceeds smoothly and in high yields if the double
['I Dr. P. Binger,
[*] Prof. Dr. E. Niecke, Dr. R. Ruger
[**I
[ I ] E. Niecke, G. Ringel. Angew. Chem. 89 (1977) 501: Angew. Chem. In/. Ed.
Engl. 16 (1977) 486.
[21 E. Niecke, A. Nickloweit-Luke, R. Ruger, Angew. Chem. 93 (1981) 406:
Angen'. Chem. I n / . Ed. Engl. 20 (1981) 385; Z . Na/urforrch. 366. 1566
(1981): Phosphorus and Sulfur, in press.
131 W. Flick, Diplomarbeit, Universitat Gottingen 1973.
141 J. F. Brazier, D. Houalla, M. Loenig, R. Wolf, Top. Phosphorus Chem. 8
[**I
H. M. Biich, Dr. R. Benn, Dr. R. Mynott
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelm-Platz I . D-4330 Mulheim a. d. Ruhr (Germany)
Metallacycloalkanes, Part 4. This work forms a p a n of a thesis by H. M.
Buch, Universitat Kaiserslautern, planned for 1982.-Pan 3: [I].
0 5 7 0 - 0 8 ~ ~ / 8 2 / 0 1 0 1 - 0 0 6S 2OI2.50/0
Angew. Chem. I n / . Ed. Engl. 21 i1982j No. I
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