0% found this document useful (0 votes)
70 views

A Novel Rearrangement Around The (P N) Double Bond1')

1) The document describes the synthesis and properties of alkyl dichloro-N-(halosulfonyl)iminophosphates (1) and their rearrangement to N-alkyl-N-(halosulfonyl)aminodichlorophosphoric esters (2) upon heating. 2) Compounds (1) are obtained in high yields via the reaction of trichloro-N-(fluorosulfonyl)iminophosphorane or N-(chlorosulfonyl) analog with alcohols but cannot be distilled without decomposition. 3) Upon heating compounds (1) in diethyl ether or dioxane, they rearrange to the

Uploaded by

Ihsan Nur Aripin
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (0 votes)
70 views

A Novel Rearrangement Around The (P N) Double Bond1')

1) The document describes the synthesis and properties of alkyl dichloro-N-(halosulfonyl)iminophosphates (1) and their rearrangement to N-alkyl-N-(halosulfonyl)aminodichlorophosphoric esters (2) upon heating. 2) Compounds (1) are obtained in high yields via the reaction of trichloro-N-(fluorosulfonyl)iminophosphorane or N-(chlorosulfonyl) analog with alcohols but cannot be distilled without decomposition. 3) Upon heating compounds (1) in diethyl ether or dioxane, they rearrange to the

Uploaded by

Ihsan Nur Aripin
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 2

For their replacement we used both a double reaction of nitrogen pyramid (cf. also [2]).

Hindered rotation around


metalated N,N'-dimethylhydrazine with organosilicon hal- the Si-N bond is unlikely because the compound
ides and fission of Si-N bonds by (CH,),Sk, compounds.

-if N-inversion is rapid only Si-N and not N-N hind-


H,C CH, X = CH30, t-C,H,, CsH5 ered rotation can be recognized in the 'H-NMR spectrum
I I 2 X-(CH,),SiCI
-shows only one signal for the Cl(CH,),Si group in
Li-N-N-Li
- 2 LiCl
H3C CH3 toluene down to - 75 OCL7].
I 1
X- (CH3),Si-N-N-Si(CH,),-X
The height of the energy barrier to N-N rotation in (1) is
apparently influenced by electronic and not by steric
effects. This became clear because restricted rotation
around the N-N bond of compounds ( I d ) - (1 f ) could
be demonstrated only with ligands @=Cl, Br, or C6H,)
that are electron-attracting in aliphatic or aromatic com-
pounds. Further, the AG Tc values increase parallel to
the increase in ( - I ) effect of the ligands X=C1, Br, and
ill x B. p. ("C/torr) v(CH,),Si ("C)[a] AGqC C6H5.
(Hz) (kcal/mole) Received: February 22, 1971 [Z 382 IE]
German version: Angew. Chem. 83, 364 (1971)
(a) CH,O 74-7815
(b)[b] (CH,),N 81-84/3
ic) tert-C,H, 98-100JO.7
(d) C,H, 120-121JO.07 2.5 7 15.4 +0.3[c]
(el CI 46-4711 131 3.7 47 17.4k0.3
A Novel Rearrangement around the (P=N) Double
If) Br 60-61/0.5 4.2 42 17.1i 0 . 3
Bond1']
[a] +2"C.
[b] ( I b ) was prepared from ( l e i and dimethylamine. By Herbert W Roesky and Walter Grosse Bowing[*]
[c] Since the width of the (CH,),Si signals at height is 2.0 Hz one
must correct the values according to [ 6 ] ; we have k, = 3.0 and AG?< Trichloro-N-(fluorosu1fonyl)iminophosphoraneor the N -
=15.7+0.3. (chlorosulfonyl) analog reacts with an equivalent amount
of methanol or ethanol in methylene dichloride to yield
alkyl dichloro-N-(halosulfony1)iminophosphates(1).
In contrast to hydrazine derivatives containing C,H,CH,
or (CH,),CH groups[41,the compounds ( I ) permit for the
first time a systematic variation of the ligand serving as I
probe in dynamic 'H-NMR spectroscopic studies. In the
XSOZN-PCI, + ROH --+XSQN-P-O-R + HCI

spectra of ( l a ) - ( l c ) the protons of the CH, groups


bound to the Si atom are isochronous not only at different
concentrations and in various solvents (chloroform to
-4O"C, chlorobenzene to - 30°C, benzene to I O T , ethyl- , X-SQ-N-P-0
Y1
ene dichloride and o-dichlorobenzene to 20°C) but also in t 1 1
R C1
toluene to - 75 "C, which contraindicates that the chemical (2)
shifts of the two CH, signals are accidentally equivalent;
however, for ( I d)-(I f ) they remain anisochronous
[(CH,),Si doublet] in various solvents and at various con- B. p. ("Cltorr) Yield (%)
centrations. This might be due to hindered rotation around (a) X=F, R=CH, (2a) 29"CIO.l 90
(b) X=F, R=C,H, (2b) 31 'C/O.Ol 95
the N-N or Si-N bond or to an N-inversion that is slow (c) X=Cl, R=CH, (2c) 58°C/0.01 95
on the NMR time scale. The latter can be excluded by the id) X=Cl, R=C2H, (2d) 68"C/0.01 80
AG! values (see Table), especially as an N-bound silyl
group decreases the inversion barrierr51by flattening the
The compounds ( 1 ) can be obtained in high yield but
cannot be distilled without decomposition; they can be
[ I ] 0. J . Scherer and R. Schmitf, J. Organometal. Chem. 16, P 11 (1969). characterized by their NMR spectra and by elemental
[2] 0. J . Scherer and W JaiisAen, Chem. Ber. 103, 2784 (2970). analysis. No 'H-19F coupling was observed for ( 1 a ) or
[3] H.Bock, Z . Naturforsch. 17b, 423 (1962); this author first obtained ( I b ) . The 'H- and "F-NMR spectra afford the following
the compound by gas-phase reaction of N,N'-dimethylhydrazine with
dichlorodimethylsilane; 'H-NMR data were not given.
data for ( I a) :
[4] a) G. J . Bishop, B. J. Price, and I . 0. Sutherland, Chem. Commun.
1967, 672; b) J . R. Fletcher and I . 0. Sutherland, ibid. 1969, 706; c ) 6 , = -4.46 ppm (doublet), J H - p = 17.5 Hz, 6,= - 58.7 ppm (doublet),
M . J. S. Dewar and W E . Jennings, J. Amer. Chem. SOC.91,3655 (1969); JF_,=4.5 Hz.
d) J . E. Anderson, D. L.Grifith, and J . D. Roberts, ibid. 91,6371 (1969);
e) M . J. S. Dewar and W B. Jennings, Tetrahedron Lett. 1970, 339.
[5] For problems of N-inversion see: H. Kessler, Angew. Chem. 82, Migration of the alkyl group has not hitherto been observ-
237 (1970); Angew. Chem. internat. Edit. 9, 219 (1970); b) A . Rauk,
L. C.Allen, and K . Mislow, Angew. Chem. 82,453 (1970); Angew. Chem.
ed on alcoholysis of trichloroiminophosphoranes[".
internat. Edit. 9,400 (1970); c) J . M . Lehn, Fortschr. Chem. Forsch. 15, If the compounds ( I ) are heated in diethyl ether or dioxane,
311 (1970).
they rearrange to N-alkyl-N-(halosu1fonyl)aminodichloro-
[6] H . Friebolin, H. G . Schmid, S. Kabuss, and W Faisst, Organic
Magnetic Resonance I , 147 (1969).
[7] On rapid N-inversion, Si-N hindered rotation will not be ob- [*I Univ.-Doz. Dr. H. W. Roesky and Dip1.-Chem. W. Grow Bowing
servable in the 'H-NMR spectra if the compound has the gauche con- Anorganisch-Chemisches Institut der Universitat
formation (CH, ligand eclipsed with Cl). 34 Gottingen, Hospitalstrasse 8/9 (Germany)

344 Angew. Chem. internat. Edit. / Vol. I0 (1971) / No. 5


phosphoric esters (2). Compounds ( 2 a ) -( 2 d ) are
colorless liquids which, unlike their isomers ( I ) , distill
unchanged in an oil-pump vacuum. For ( 2 a ) a coupling
H3C C1
I I
FSOz - N - P -0 + ( CH3)3 - SiN(CH,)2

(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

From the lectures:

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.

By Lothar Bohn“] It will now be shown that information on grafting and


crosslinking can also be obtained in the original material
It is well known that the toughness of brittle, hard materials in the solid state. The difference in shrinkage of the glass
can be improved by the incorporation of a finely divided and rubber phases on cooling from the melt can lead to
soft phase. As an essential condition for the effect of the “thermal stress”, which affects the glass transition of the
rubbery soft phase, it is always plain that the two immiscible elastomer phase. This is discussed for the case of rubber-
polymer phases must be strongly bonded at the contact modified styrene/acrylonitrile copolymers (ABS). The im-
surface. Some crosslinking in the rubber phase is sometimes portance of the “thermal stress” to the fracture mechanism,
also regarded as important. Attempts are made to achieve particularly to the initiation of crazing, is also discussed.
adhesion between the phases, e. g. by graft copolymeriza-
tion, polymer chains corresponding to the hard basic
component being grafted onto a previously prepared Thermodynamics of the Cooperative Transformations
rubber latex. of Biopolymers in Solution
The method normally used in the past for the determination By Th. Ackermann“’
of the grafting and crosslinking state in such a material
One of the characteristics of typical biopolymers is that
consists in breaking it down by trying to bring it into solu- the thermal transformation process from a highly ordered
[‘I Dr. L. Bohn [*] Prof. Dr. Th. Ackermann
Farbwerke Hoechst AG., G 832 Institut fur Physikalische Chemie der Universitat
6230 Frankfurt/Main 80 (Germany) 78 Freiburg, Hebelstrasse 38 (Germany)

Angew. Chem. internat. Edit. / Vol. I0 (1971) J N o . 5 345

You might also like