A Novel Rearrangement Around The (P N) Double Bond1')
A Novel Rearrangement Around The (P N) Double Bond1')
(2a) c1
I
-
between I9F and ’H is observed and from the NMR spectra
of this compound one obtains 6, = - 3.77 ppm (2 doublets), H3C N(CH3)z
3,_,=10.8 Hz, S,= -52.9ppm (2 quadruplets), I I
F S O z - N - P = O + (CH,),SiCl
= -4.5 Hz, 6 = - 6.2 ppm (2 quadruplets) [external stand- I
c1
ard: (CH,),Si, CFCl,, or 85% H,PO,]. The structures of
(3)
the chlorosulfonyl derivatives could be confirmed by mass
spectrometry: for (2c) there were observed, besides the mol- The product ( 3 ) distills unchanged at 59°C/0.01 torr
ecule ion 245 (673, the characteristic fragments at m/e= 244 Preparation of ( 2 a ) :
[FSO,NCH,POCI, (6%)], 210 [FSO,NCH,POCl
(100%)], 146 [NCH,POCI, (91%)], 130 [NCH,PCl, FSO,N=PCl, (0.1 mol) is dissolved in CH,Cl, (500 ml).
(36%)], 128 [ClSO,NCH, (26%)], and 117 [POCI, (74%)]. Then the flask is cooled in ice, and CH,OH diluted with
This reaction can be applied to other (P=N) double bonds. CH,Cl, (250 ml) is dropped in slowly with stirring. When
addition is complete, the mixture is boiled under reflux
It was not possible to differentiate the (P=N) stretching for an hour, to complete removal of HCl. Finally diethyl
vibration of ( l a ) and the (P-0)stretching vibration of ether (50ml) is added and the whole is heated for about
( 2 a ) in their IR spectra. For ( 2 a ) , bands were observed 20 minutes under reflux.The ether and CH,Cl, are removed
at ca. 2960s, 1450vs, 1425vs, 1290vs, 1220vs, 1050vs, in a vacuum and the residue is distilled in an oil-pump
910 vs, 805 vs, 695 vs, 600 vs, 560 vs, 530 s, 515 vs, 455 m, vacuum. Yield: 21 g (90%). ( 2 b ) is formed as by-product.
and 400 s (cm- I). Received: March 2,1971 [Z 383 IE]
German version: Angew. Chem. 83, 365 (1971)
Compounds (2) cannot be prepared from N-(halosulfo-
ny1)alkylamines and phosphorus trichloride in the pres-
[l] Phosphorus Compounds, Part 63.-Part 62: H. W Roesky and
ence of a tertiary amine. Compound ( 2 a ) reacts with L. F . Grimm, Chem. Commun., in press.
(CH,),SiN(CH,), in 1 :1 molar ratio with loss of chlorotri- [2] Houben- Weyl-Miiller: Methoden der organischen Chemie. Thieme-
methylsilane : Verlag, Stuttgart 1964, Vol. XII/2, p. 528.
C O N F E R E N C E R EPO R TS
Macromolecular Colloquium
The Macromolecular Colloquium was held at Freiburg/Br. (Germany), February 25-27, 1971
Detection of Grafting and Crosslinking of the tion, and then determining the insoluble fraction and its
Elastomer Phase in Two-Phase Systems swelling behavior and composition.