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Isomerization of 1 3-Diphenyl-2 2-dichloroaziridine.

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ation by splitting offaldeh5de even when, as in the case of the
formaldehyde compound, the b. p. of the hemiacetal ( 3 ~ is
higher than that of the acctal (2a).
With amines, hydrazines, and thiols, the corresponding types
ofmixed acetal are formed, viz. ( 4 ) - ( 7 ) , e . g . from (Zo):
(4) R =- CH,, R I N = pipertdine,
b p. 61-62 "CjIO mni
N R - N R I ( 5 ) R=- CH,, h.p. 46"C/t2mni
(6) R = CH?, R'= C4H9, b.p. 74 'C/IOnim
o r from (3151
(7) K
CH,, R' - C T H ~b.p.
101 'C/23 iniii
The acetals can be split by acyl chloridcs, just as Bu/inw a n d
Haitke [3] found for aminals, e . g . :
+ Ph-CO
+ Ph -CO-NR-OR
( 2 a)
-1- RO
RO RN C H z - C I
Received, M a y Ihth, 1963
[Z 5081339 IE]
German version: Angew. Chem. 75, 640 (1963).
Isomcrization of 1,3-Diphenyl-2,2dichloroaziridine
By Professor Dr. H . W. Heine and Amos B. Smith TI1
Department o f Chemistry, Bucknell University,
Lewisburg, Pennsylvania (I J.S.A.) and lnstitut fur Organische
Chcmic tlcr llniverstitiit K6ln (Germany)
Unstable I,I -dichlorocqcli,i71.ol,ancs that quickly isomerize
into 2,3-dichloro- I-propcnc systems have been postulated as
intermediates in the reaction of dichlorocarbene with cyclobutene [I] a n d ben7ofuran 121. That I,l-dilialocyclopropaiies
can indeed undergo such isomeriaations has recently been confirmed by the preparation and thermal conversion of 6,6-dibromobicyclo[3,1 ,O]hexanc into 2,3 -dibromcyclohexene [3].
W e wish t o report the first cxamplc of a similar type of isonierization with an aziridinc system: 2 g of 1,3-diphenyI-2,2dichloroaziridine ( 1 ) [4] was rciluxcd in 20 ml of toluene for
24 hours, and the toliiene was evaporated in vacuo. Purification of the product by rapid distillation in micro distillation
equipment yielded N-phcnyl-cr-plienyl-cr-chloroacetiniidoyl
chloride (
2), b.p. 146 -148"C/0.2 mm. Distillation must be
very rapid and the distillation column short in order t o prevent charring.
[ I ] Communication No. I5 on Hydroxylamine Derivatives;
Communication No. 14: G . Zinner, Arch. Pharmaz. in the press;
Communication No. 13: G. Zinner, Arch. Pharmaz. 296, 57
[2] Present address: lnstitut fur Pharmazie und Lebensmitlelchemie der Universitat Miinster/Westfalen (Germany).
[3] H . Bohme and K . Hnrtke, Chem. Ber. 93, 1305 (1960).
Isolation of the Diphenylphosphorus Radical
By Doz. Dr. Ulrich Schmidt, Dr. F. Geiger,
DipLChem. Asmus Muller, and Dipl.-Chem. K. Markau
Chemisches Laboratorium der UniversitLt und lnstitut fur
Elektrowerkstoffe der Fraunhofer-Gesellschaft,
FreiburglBreisgau (Gcrniany)
Simple organic phosphorus radicals which d o not contain
other hetero-atoms have not yet been prepared. There were,
however, strong indications for their existence, even if shortlived [I].
Using the same practical methods which led t o the isolation
o f the phenylsulfur radical [21, we succeeded in identifying the
diphenylphosphorus radical. When evaporating tetraphenyldiphosphine is irradiated with short-wave ultraviolet light at
0.01 m m H g a n d the vapor condcinsed immediately behind
the zone of irradiation o n a cold linger cooled with liquid
nitrogen, diphenylphosphorus condenses as a faintly pink
transparent film which loses its color only at 170'K after
30 min. The diphenylphosphorus radical is therefore equal in
thermal stability to arylsulfur radicals substituted by phenyl
or by electron donors [ 3 ] . In the same way, photolytic cleavage of the P-H bond in diphcnylphosphine yields the diphenylphosphorus radical.
Electron spin resonance measurements a t 77'K showed a
strong signal with a weakly anisotropic g-factor (g = 2.009).
Received, M a y 17th, 1963
Received, M a y 27th, 1963
[Z 513/3361EJ
German vwsioii: Angew. Chem. 75, 669 (1963).
[ I ] Unpublished studios of E. VugeI and H . Kiefer reported by
E. Vugel, Angew. Chem. internal. edit. 2, I (1963).
[2] W, E. Parham, C . G. Fri/z, K . W. Soeder, and R . M . Dudson,
J. org. Chemistry 28, 577 (1963).
[3] J. Sunnenherg and S. Wim/ein, J. org. Chemistry 27, 748
( I 962).
[41 E. K . Fields and J . M . Siridri, Chem. & Ind. 1959, 1216.
[5] A . G. Cuokand E. K . Ficld.s,.I. org. Chemistry27, 3686 (1962).
[Z 506/334 IEl
German version: Angew. Chem. 75, 640 (1963).
[ I ] For references see E. Muller, H . Eggensperger, and K . Sche$
ler, Liebigs Ann. Chem. 658, 103 (1962).
[2] U. Schmidt and A . Muller, Angew. Chem. 75, 299 (1963);
Angew. Chem. internat. Edit. 2 , 2 1 6 (1963).
[3] U. Schmidt, A . Muller, and K . Markau, Tetrahedron Letters,
in the press.
( 3 ) in
Hydroiysis of the o i l gavr: ~.-chloro-cc-plienylacetanilide
95 yield; treatment o f ( 3 ) with PC15 gave (2) plus a slight
impurity cvidenccd by two additional peaks in the infrared
spectrum which could not he eliminated by distillation.
The infrared spectrum of (2) had an expected absorption band
at 1680 cm-1, i.c. in thcrcgion where iniido chloridcs absorb,
c . g . N-methylbenLiniidoyl chloride has a peak a t 1678 cm-1.
The band at 737 cni-1, ascribed by F;c,Zd~,andSnndri [4] t o the
'CC12 group of the dichloro;wiridine, is still discernible in the
&rude acetimidoyl chloride but not in the distilled product.
rearrange into cc-chloro-aphenylacetanilides in water 14,5].tmido chlorides such as (2)
would be plausible intermediates for this rearrangement.
By Dr. I<. B. King and M. B. Bisnette
Mellon Institute, I'illsburgh, Pennsylvania (U.S.A.)
W e have obtained benzoferrocene ( I ) a s a red-viotet stable
crystalline solid (m. p. 74 -76"C, subl. ca. 70"C/0.1 mm) in
yields of up t o 9 f/, of pure malcrial by treating iron(l1) chloride
simultaneously with solutions of sodium indenide a n d sodium
Angew. Chetrr. ititcv'nut. Edit.
Val. 2 (1963) / Nu. 7
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dichloroaziridine, isomerization, diphenyl
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