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Distillable N-Hemiacetals N--Hydroxyalkyl-N O-dialkylhydroxylamines.

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For analytical purpose?, evaporation was continued to dryness and the total residue decomposed with water. On14 one
gaseous decomposition product was formed, namely methane,
its presence being established by infrared spectroscopy. The
volume of CH4 was determined by measurement of pressure.
The aqueous solution of the residue was transparent; its acid
reaction (pH approx. 2) is due to the presence of hydroiodic
acid. The average value for the ratio of HI:CH4 was 1:2.95.
The titanium content, which was determined gravimetrically,
was somewhat too high owing to thermal decomposition.
N o unequivocal statement can yet be made about the course
of the reaction. However, the occurrence of CH3I as a reaction
product indicates that B CH3 group of the Ti(CH3)4 is not
simply exchanged for the iodine atom of CF3I.
pyrazolenines (2). On heating ( I n ) in 9UCUO in triethylenegl)col dimethyl ether, (2u) distilled in 36 % yield from
the reaction mixture. The structurc assignment of (2a) (b. p.
75 OCj5l mm) is based on spectral data (infrared; strong band
at 1640 cm-I, =C-H 3095 cm- I , ultraviolet: Amax = 257 mp,
E = 2250; 350 mp, E = 270; NMR: singlet 8.65 T, doublet
7.63~,quadruplet3.70r,J=1.6cps) [2]. On heatingsolid (10)
in VUCCIO to 130°C, (2b) was ohtained in 68 % yield (b.p.
63 0C/0.0Z5 mm; infrared: strong hand at 1652 cm-1; ultraviolet: Amax
272 mp, E = 3530; 347 mlJ, E = 300; N M R :
singlet 8.78 7 , multiplets at 8.28, 7.72, and 7.03 T) [2].
Received, May Sth, 1963
[Z 500/332 IE]
German version: Angew. Chem. 75, 576 (1963).
A New Process for the Formation of P-P Bonds
By Doz. Dr. W. Kuchen and Dipl.-Chem. W. Griinewald
Institut fiir Anorganische Chemie und Elektrochemie der
Technischen Hochschble Aachen (Germany)
PBr3 and PSBrj react with magnesium in dieth>l ether to give
MgBr2-etherate and red phosphorus [I] as well as a product
with the overall composition (PS), [2]. Analogously, tetraphenylcyclotetraphosphine [3] artd tetraphenyldiphosphine
[4] are formed from ChHsPBrz and (C6H&PBr, respectively,
in good yield.
+ Mg
2 (C6Hs)zPBr t Mg
( C ~ H S P4) ~MgBrz
$- MgBrz
These reactions occur smoothly even at room temperature.
An ether/benzene mixture is used as solvent, and the MgBr2
dissolved in the reaction solution as the etherate is precipitated by addition of dioxan.
Treatment ofthe reaction mixture obtained according to equation 2 with sulfur leads to practically quantitative yields of tetraphenyldiphosphine di-P-sulfide (C6H&P(S)-P(S)(C6H&
[4]. The phenylphosphorus bromides required for the reaction
are easily prepared by equilibrating the chlorides, which are
readily available, with PBr3 at 100 -200 "C and then continuously distilling both PC13 and the phosphorus chlorobromides PBr3-, CI, (n = I or 2) which are also formed out of the
equilibrium mixture. The yields of ChH5PBr2, b.p. 124 to
126 'C/1 I mm, and (C,jH&P&r, h.p. 140--141"C/35 mm are
approximately 90 %.
The reaction of phosphorus bromides with magnesium thus
provides a further means of synthetizing P-P bonds and supplements the few preparative methods so Far available [5].
Received, May 9 t h , 1963 [Z 501/333 IEI
German version: Angew. Chern. 75, 576 (1963).
W. Kuchen and H . G . Beckers, unpublished experiments.
W. Kuchen and H . G. Beckers, Angew. Chem. 71, 163 (1959).
W. Kuchen and H . Buchwald, Chem. Ber. 91,2296 (1958).
W. Kuchen and H . Buchwald, Chem. Ber. 91,2871 (1958).
Review: J . E . Hiiheey, J. chem. Educat. 40, 153 (1963).
Preparation of Pyrazolenines and their Photolysis
to Cyclopropenes
Both (2u) and (2b) are stable under conditions leading to
pyrolytic rearrangements of phenylsubstituted pyrazolenines
[3]. Compound (20) distillsunchanged at 147-148 "C/760mm
and ( 2 b ) can be distilled in vucuo at 225 " C .
Irradiation with a Hanovia high pressure mercury lamp at
I3 "C led to formntion of cyclopropenes (3) by elimination of
nitrogen. The known I ,3,3-trimethj lcyclopropene (3u) [4]
was obtained from (2u) in 65 yield. Compound (2b) gave
a n almost quantitative yield of the new bicyclic compound (3b)
(b.p. 56'C/12 mm). The structure of (3h) follows unambigously from its infrared spectrum (band at 1840 cm-1 (m), a
region typical for cjclopropene slteletal vibrations [4]) and its
NMR spectrum (singlet at 8.85 5 and multiplets at 8.25 and
7.70 T) [2].
Received, M a y I5th, 1963
[ Z 505/335 JE]
German version: Angew. Chem. 75, 640 (1963).
[ I ] G . L. Closs and L. E. Closa, .I.Arner. chem. Soc. 83, 2015
[2] Satisfactory elemental analyses were obtaincd for these compounds.
[3] J. van Alphen, Recueil Trav. chim. Pays-Bas 62, 485 (1943);
R . Hiittel, J. Riedl, H . Martin, and K. Frunke, Chem. Ber. 93,
1425, 1433 (1960).
[4] G. L. Closs and L. E. Closs, J . Amer. chem. SOC.83, 1003
Distillable N-Hemiacetals:
[1 ]
By Prof. Dr. G. Zinncr and Apotheker W. Rilter
lnstitut fiir Pharmazentische Chcmie und Lebensmittelchemie
der Universitiit MarburglLahn (Germany) [2]
Oil treatment of N,O-dinlethylhydroxy!amine ( I ) with aldehydes in a molar ratio of 2: I , we obtained -- in addition to
the anticipated acetals (2) -- the corresponding herniacetals
(3) in yields 30-50 '%,.
RO-RN--\I -1- R' -CHO
By Prof. Dr. G. L. Closs and Dr. W. Boll
R = CH,
b) R = CsH7
George Herbert Jones Laboratory, The University of Chicago,
Chicago ( U S A . )
We observed ring closure of N-sodium salts of p-toluenesulfonylhydrazones o f a$-unsaturated carbonyl compounds (1)
[ I ] followed by elimination of sodium toluenesulfinate to give
Angew. Chem. intermit. E d i t . / Vol. 2 (1963)
/ No. 7
(Za) h.p.40"C\3Omm
b) b . p 62"C/12 mm
( 3 a i h.p. 5OoC/30mm
b) b.p. 28"C/12 mtii
These new types of hemiacetals can be distilled without de
composition in contrast to the usual N-heniiacetals, and do
not tend to yield the symmetrical acetals by disproportion-
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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dialkylhydroxylamines, distillable, hydroxyalkyl, hemiacetal
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