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Europium as an Alkaline Earth Metal.

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calcium turnings (99.5
purity, from sam e source) and red
phosphorus o r resublirned arsenic o r germanium (99.999 y~L
purity, from Messrs. Schuchardt) in stoichiometric proportions by heating a t l l O O 0 C for 24 h in evacuated quartz
ampoules. Magnesium nitride an d calcium nitride were
produced by passing gaseous ammonia over magnesium or
calcium turnings a t 850 OC.
T h e starting materials were mixed in I : 1 molar ratios an d
compressed under a pressure of 10000 kg/cmz o r sintered
in evacuated quartz tubes a t 1000°C for 48 h .
The gases resulting f r o m th e hydrolysis were identified by
mass spectroscopy [2]. I n order t o preclude decomposition
o f readily labile hydrides before their introduction into the
spectrometer, the crystalline mixed phases were decomposed
with 2 N HCI with cooling (0 "C) in an evacuated apparatus
directly within th e instrument. Apart from th e known
hydrides of phosphorus, arsenic, nitrogen, a n d germanium,
the following products were obtained:
Imidodiphosphinatometal Chelates,
Neutral Complexes withcarbon-Free Chelate Rings
By D r . A. Schmidpeter, Dip1.-Chem. R. Bohm, a n d
cand. chem. H. Groeger
Institut fur Anorganische Chemie
der Universitat Munchen (Germany)
Only a few metal chelates a r e known in which t h e ring
contains no carbon. I n the course of o u r work on heterocycles
containing P an d N [ l ] , we have piepared several co mp o u n ds
of a new type ( I ) . Here the d o n o r functions X a r e bridged by
-(CsHj)zP-N- P(C6H5)2- grOllpS.
(c(jH5)z75N.g(c&5)z
q;,i
xxI
I
,-
P3HS,As3H5, and PH2AsH2 from Mg,Pz/Mg3Asz;
P3H~,PH2NH2,PH(NH2)2,P(NH2)3,
and PzH3NH2 from Mg3PdMg3Nz;
As3H5, AsHzNH2, AsH(NHd2, and As(NH2)3 from MgsAsziMglN2;
P3H5 and GeH3PHr [3] from CaGe/Ca3Pz,
As3Hs and GeH3AsH2 131 from CaCe/Ca3As~;
GeHlNH2 and GeH2(NH2)2 from CaGe/Ca,Nz.
Received, July 29th, 1964
[ Z 8211642 IEI
German version: Angew. Chem. 76, 860 (1964)
[I] P . Royen and C . Rocktaschel, Angew. Chem. 76, 302 (1964);
Angew. Chem. internat. Edit. 3, 314 (1964). The two mixed
hydrides Si2GeHe and SiGe2H8 described in this publication as
"hitherto unknown" had actually been prepared previously by
C. S. G . Phillips, P . Powell, J . A . Semlyen, and P . L.Timms, 2.
analyt. Chem. 197, 202 (1963) from an Mg/Si/Ge alloy and
identified by gas chromatography. Cf. also C . S. G . Phillips and
P . L.Timms, Analyt. Chern. 35, 505 (1963); P. L . Timms, C. C .
Simpson, and C. S. G . Phillips, J. chern. SOC.(London) 1964, 219
1467.
[2] We wish to thank Dr. W. Mosch for carrying out the mass
spectrographic investigations.
[ 3 ] I . E Drake and W . L . Jolly, Chem. and Ind. 1962, 1470. Here
the compounds were prepared from Monogermane and phosphine or arsine by a silent electrical diszharge.
Reaction of Amide Acetals with Isocyanates.
The Synthesis of Parabanic Acid 0,N-Acetals
By Prof. Dr. H. Bredereck, Dr. G . Simchen a n d
cand. chem. E. Goknel
lnstitut fur Organische Chemie an d Organisch-Chemische
Technologic
der Technischen Hochschule Stuttgart (Germany)
In the course of o u r investigations o n th e reaction of acetals
of carboxamides with cumulative double-bond systems, we
reacted dirnethylformamide diethyl acetal ( I ) with isocyanates
by heating a mixture of the components (molar ratio 1 : 1) at
100-130 "C for several hours. 0,N-Acetals of 1,3-disubstituted parabanic acids [(2a), m .p . 1 2 0 °C ; (Zb), m.p. 93 "Cl
were obtained in 80 t o 85
yield, with elimination of
ethanol (as urethane).
( C6%)
Color
NH
Cu
0
S
S
Zn
Ni
Cd
blue
colorless
brown
colorless
I M.P.
T
2p$p(
[T
c 6H5) 2
I
178-180 (decomp.)
228-229.5
265-266 (decomp.)
309-311 (decomp.)
A green precipitate separates from a methanolic solution
of tetraphen~limid3diphosphinic diimide hydrochloride
N[(Cf,H5)2PNH2]2CI [2] an d CuC12.2 H 2 0 o n treatment with
sodium methoxide. Careful hydrolysis of this precipitate
yields (In). C o mp o u n d ( I h ) is formed from tetraphenylimidodiphosphinic acid N[(ChH5)2PO]2H [3] a n d zinc dust
in boiling benzonitrile. Compounds ( I c ) a n d ( I d ) are precipitated from a methanolic solution of NiC11.6 H 2 0 or
CdC12,H20 by potassium tetraphenyldithioimidcdiphosphinate K N [ ( C ~ H ~ ) ~ P S141.
]Z
T h e compounds a r e insoluble in wate:, a n d can be crystallized from polar organic solvents and benzene. According
to osmometric a n d cryoscopic molecular-weight determinations, ( I n ) an d ( I b ) are n o t associated. Further ligands,
e.*y. pyridine, can ad d o n t o ( I c ) .
Received, August 25th, 1964
[ Z 814/649 1El
German version: Angew. Chem. 76, 860 (1961)
Translated by Express Translation Service, London
[ I ] Cf. A . Schmidpeter, K . D i d / , and R. B o h , Angew. Chem.
76, 605 (1964).
[2] I. I. Bezman and J . H . Smalley, Chem. and Ind. 1960, 839;
H . H . Sisler, H . S . Ahuja, and N . L. Smith, Inorg. Chem. I , 84
(1962).
[3] E. Fluck and F. L. Goldmann, Chem. Ber. 96, 3091 (1963).
[4] A. Schmidpeter and H . Groeger, unpublished work.
Europium as an Alkaline Earth Metal
By Prof. Dr. W. Klemm, Dipl.-Chem. H . Kock, and
W. Miihlpfordt
Anorganisch-Chemisches Institut
der Universitiit Munster (Germany)
+
(20): H = C & ;
RNHCOOCzH5
(2b): R = CGH,,
[ Z 812/647 IEI
Received, August 17th, 1964
German version: Angew. Chem. 76, 861 (1964)
Translated by Express Translation Service, London
704
According t o their atomic volumes, europium a n d ytterbium
d o not fit into t h e series of t h e rare earth metals b u t resemble
t h e alkaline-earth metals; their magnetic behavior also
indicates that they contain the species M2+, but not M3+ [I].
T h e atomic volume of Eu lies between those of C a and
Sr, b u t closer t o C a ; however, ELI does not crystallize
in t h e face-centered cubic system like C a and Sr, but in the
body-centered cubic system like Ba
Angew. Chent. internat. Edit.
Vol. 3 (1964) No. 10
B~haViOrof europium towards ealcium [ I a] : Extensive mixed
crystal formation occurs in th e system Ca/Eu. T h e lattices
a re face-centered fr o m 0 t o ab o u t 55 atom-',: of Eu, an d
body-centered from ab o u t 60 t o 100 a t o m - % of Eu. Th e
miscibility ga p for samples obtained by rapid cooling of t h e
melt is only a few atoms percent. T h e variation of the lattice
constants of the mixed crystals with a high Eu content roughly
corresponds t o that of Vegard's straight line for bodycentered cubic Ca (stable only at high temperatures), the
volume of which does n o t differ appreciably f r o m t h at of
face-centered cubic Ca. T h e face-centered mixed crystals with
a high calcium content behave, as regards their lattice
constants, as if the volume o f Eu with a (hypothetical) facecentered crystal structure were a few percent m o r e t h an
the body-centered variety.
Behavior towords magnesium [I b] : M g an d C a form an MgzCa
phase, while in the system Mg/Sr, besides MgzSr, th e phase
Mgl7Srr a n d one or t w o phases in t h e range MgSSr-Mg4Sr
also occur [2]. T h e existence of MgSr is th e subject of
controversy [3]. W e were able t o detect th e following phases
by X-ray methods in the system Mg/Eu: Mg17Eu2 [4], one or
t wo phases between Mg5Eu a n d Mg&,
Mg2Eu [4], a n d
MgEu (stable only below 500 "C). In this behavior, therefore,
Eu resembles Sr, and not Ca. Th e lattice constants of MgZEu
[MgZnZ-type ( C 14), D:h-P63/mmc; a = 6.379; c = 10.308 A]
lie between those of Mg2Ca [a = 6.23; c = 10.12 A] an d
Mg2Sr [a = 6.439; c = 10.494 A], a n d rather closer t o the
latter. T h e values for Mg17Eu2 [Nil7Thz-type, Dih-P63/
m mc ; a = 10.49; c = 10.33 A] an d Mg17Sr2 [a = 10.533; c =
10.341 A] a re particularly similar. However, th e lattice
constant of MgEu [Csl-type (B 2), Oi-Pm3m; a = 4.102 A ]
is not strictly compatible with th e value given by Nowutny
[3] for MgSr [a = 3.908 A]. Whereas Mgl7Eu2 is practically
volume-additive, the formation o f Mg2Eu a n d MgEu is
accompanied by a pronounced contraction; th e electronegativities of Sr an d Eu must therefore be somewhat different IS]. T h u s europium behaves towards magnesium as a
typical alkaline earth metal, closely related t o strontium.The
extent t o which the alloys mentioned contain th e species
Eu2+ is being investigated 161.
T h e variation of t h e lattice constants in t h e case of t h e
MBel3 phases (NaZnl3-type, OE-Fm3c; EuBel3: a = 10.300
A [71; CaBel3: a = 10.312 A [8]; SrBe13: a = 10.470 A 191)
indicates that E u occurs in th e trivalent state. This will also
be checked by magnetic measurements.
Received, August 24th, 1964
[Z 813/648 IE]
German version: Angew. Chem. 76, 862 (1964)
Translated by Express Translation Service, London
Preparation of Thioamides from Alkenylamines
and Sulfur at Room Temperature
By Prof. D r . Roland Mayer an d J . Wehl
Institut fur Organische Chemie
der Technischen Universitat Dresden (Germany)
Elemental sulfur reacts with alkenylamines in some polar
solvents (preferably dimethylformamide) a t r o o m temperature a n d atmospheric pressure t o give thioamides. The
yields from vinylamines of type ( I ) a r e ab o u t 75 74; those
from propenylamines o f type (2) lie between 20 an d 60 7;.
Ketialkenylamines a n d ,amines derived from aldehydes react
differently under these conditions.
This useful variant of t h e Willgerodt-Kindler reaction can
start directly f r o m ketones, which ar e treated in t h e conventional manner with a secondary amine a n d sulfur, a
catalyst, e.g. y-toluenesulfonic acid, then being added t o
accelerate t h e formation of t h e alkenylamine. Examples:
a) N-(a-styry1)morpholine (18.5 g), sulfur (3.5 g), a n d dimethylformamide (20 ml) a r e mixed together. T h e solution
rapidly turns dark brown an d loses its turbidity. After
standing overnight at 15-2OoC,it is poured into 100 ml o f a
1 : 1 methanol/water mixture an d cooled t o at least 0 'C. A
crude product [ I ] separates o u t a n d is crystallized from 50
methanol, giving (31, R '= C6H5, R2 = -(CHz)z-O-(CH&
-,
m.p. 79-79.5"C, in 75 % yield (16.3 9).
b) A mixture o f acetophenone (12.0 g), p-toluenesulfonic
acid (0.5 g). morpholine (18 g), an d sulfur (3.2 g), is refluxed
for 3 h at 130 " C an d then poured into 50 ml of methanol and
cooled to 0 ° C . Wo r k - u p as above yielded 20.7 g (94 %,) of the
same product (3). A control experiment without catalyst
afforded a yield of only 49 %.
Received, September 14th, 1964 [Z 825/645 IEI
German version: Angew. Chem. 76, 861 (1964)
-
-~
~~~
[I]A separate report will be given on a yellow impurity C16H12S2
formed in this reaction.
[I] W. Klemm and H. Eommer, Z . anorg. allg. Chem. 231, 138
(1937).
[ 1 a] Experiments by H . Kock, preliminary experiments by R. de
Medicis.
[I b] Experiments by W. Miih/pfordt.
[2] M . Hansen: Constitution of Binary Alloys. 2nd Edition,
McGraw-Hill, New York 1958. J . V . Florio, N . C. Baenzinger,
and R. E. Rundle, Acta crystallogr. 9, 367 (1956), assumed the
phase MgsSr-Mgl7Sr2(Nil7Th2-typ).
[ 3 ] H. Nowotny, Z. Metallkunde 34, 247 (1942).
[4] Our conclusions regarding Mg l~Eu 2t MgrEu were confirmed
recently by synthesis of these substances by P . I. Kripyakevich,
E. I . Gladyshevskii, 0 . S. Zarechnyuk, V . I. Evdokimenko, I. I.
Zalufskii, and D . P . Frankevich, Soviet Physics Crystallogr. 8,
477 ( I 964) (English translation).
[5] Cf. G. Gnutzmann, F. W. Dorn, and W. Klemm, Z . anorg.
allg. Chem. 309, 224 (1961).
[6] As found by A . LandeNi, Z . anorg. allg. Chem. 330,230 (1964),
Eu appears bivalent in EuA12, EuGa2, EuIn2, and EuT12, whereas
Yb3'-, as well as Ybzf, is present in YbA12.
[7] E. I . Glodyshevskii, P. I. Kripyakevich, and D . P . Frankevich,
Soviet Physics Crystallogr. 8, 628 (1964) (English translation).
[8] T. W . Baker and J. Williams, Acta crystallogr. 8 , 519
(1955).
[9] SrBel3 was synthetised recently by D. Kunze (Ph.D. Thesis,
Universitat Munster, 1964).
Angew. Chem. internot. Edit.
/
Val. 3 (I964) / No. 10
Products of the Thermolysis of Sulfenic Acid
Derivatives
By Prof. Dr. Roland Mayer a n d H.-J. Frey
Institut fur Organische Chemie
der Technischen Universitat Dresden (Germany)
Sulfenic acid derivatives ( I ) ar e sensitive t o heat a n d can
therefore b e distilled, if a t all, only in a good vacuum [I]. W e
have found t h at these compounds decompose between 60
a n d l l O ° C as indicated in the following equation. While
705
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