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Heterocyclics from Ethoxymethylenecyanamide and Ethoxymethyleneurethane.

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Alkynyl Derivatives of Aluminum
Preparation of Germyl-lithium Diammoniate and
Potassium Dihydrogen Antimonide
By Dr. P. Binger
By Priv.-Doz. Dr. t i Amberger and Dr. H. Boeters
Max-Planck-Institut fur Kohlenforschung,
Mulheim-Ruhr (Germany)
lnstitut fur Anorganische Chemie
der llniversitit Miinchen (Germany)
Trialkylaminates of dialkylaluminum hydride react smoothly with 1-alkynes a t 20-40 "C in excess trialkylamine to give
the aminates of dialkylalkynylaluminum ( I ) .
Germane reacts quantitatively with lithium in liquid NH3 to
yield germyl-lithium diammoniate (I).
+ GeH4
-0.5 H2
. -----,LiGeHy xNH3
- (x--2) N H3
----> LiGeHs.2 NH3
Similarly, both hydrogen atoms of acetylene can be smoothly the RzAl-group, a stable monoaminate with double
molecular weight being formed. At 10O-12O0C, trialkylaluminum trialkylaminates also give(l), R1H being eliminated.
The known addition of AI-H- and Al-C-bonds onto triple
bonds [l] does not occur in the presence of amines. In contrast, etherates of dialkylaluminum hydride react with 1alkynes only above 100"C, but then addition of the alkynes
onto the triple bond occurs predominantly as a result of
dissociation of RzAIH.OR2. Etherates of trialkylaluminum
do not react under these conditions.
The free dialkylalkynylaluminum compounds can be obtained from the aminates by exchange with trialkylaluminum
as shown in (a) forathepropynyl derivative.
+ A1R3
Diethylpropynylaluminum (b.p. 50 oC/O.OO1 mm) and bis-
(triethy1aluminum)-N-methylmorpholine (b.p. 90 oC/O.OO1
mm) can be readily separated by distillation. Alkali trialkylalanates [M(R3AlH)] react smoothly with 1-alkynes at
50-60 OC without any catalyst (diethylamine [2], lithium
hydride [3]) to give M(R~AICECR). Both hydrogen atoms
of acetylene react and it is not possible to stop the reaction
at the stage of monosubstitution [M(R3AIC=CH)].
2 Na(R3AIH)
+ H C r CH
+ 2 Hz
R = C2H5
The reaction of sodium bis(triethyla1uminum)acetylene (2)
with diethylaluminum chloride gives 1,2-bis(diethylaluminum)acetylene, a white powder which is insoluble in hydrocarbons.
+ 2 RzAlCl + R2AI-C=C-AlRl+
2 AIR3
+ 2 NaCl
R = C2Hs
This compound, which is probably polymeric as a result of
association via Al-C2-AI-bridges, forms a monoetherate of
double molecular weight.
Gaseous germane is passed into a solution of lithium in NH3
just above the melting point of the mixture (-77.7 "C) until
decolorization occurs (after about 45 min for 0.005 g-atom of
Li). The vapor pressure of GcH4 at 77 "C (1350 mm of Hg) is
greater than that of NH3 (48 mm). The NH3 is then sublimed
off at -78.2"C to1 eave ( I ) as a pale grey, stable solid. On
warming ( I ) to room temperature, ammonia (2 moles) is
evolved and a melt is formed above a solid phase. On
standing for some time at 20"C, or more quickly by heating
at 250°C, the solid phase decomposes with evolution of
hydrogen and change of color from yellow, through brown,
to red. Germane is not liberated.
Stibine reacts quantitatively with potassium in liquid NH3
to form potassium dihydrogcn antimonide (2).
K-t SbH3
-0.5 HZ
However, it is not possible to introduce gaseous stibine into
the metal solution at -77"C', since it has a lower vapor
pressure at -77 "C (34 mm) than NH, has. If excess stibine
is condensed over the frozen solution of the metal, antimony
separates out. These inconveniences can be avoided if the
stibine is passed into the metal solution at --77 "C at a partial
pressure of about 10 mm together with propane until decolorization occurs (50 min for 0.01 g-atom of K). The
hydrogen released into the gaseous mixture can de determined
readily by freezing out the C:IHs and NH3. The NH3 is then
sublimed off at --78.2 "C. A residue of (2) remains as a stable,
red-brown solid. On warming to room temperature, its
color changes to black, with cvolution of hydrogen.
Received. August 6th, 1963
[Z 555/409 IE]
German version: Angew. Chem. 75, 860 (1963)
Heterocyclics from Ethoxymethylenecyanamide
and Ethoxymethyleneurethane
By Dr. R. Gompper, Dr. H. E. Noppel, and H. Schaefer
Institut f i r Organische Chemie und Organisch-chemische
Technologie derTechnischen Hochschule Stuttgart (Germany)
Ethoxymethylenecyanamide (I) and ethoxymethyleneurethane (2) are obtained in 85 and 90 '%, yield respectively by
heating cyanamide or urethane with orthoformic ester [in the
presence of a little BF3 for (2)]
+ HC(OR2)j
R 2 0 -CH=N-RI
( 1 ) ; R'-:CN;
Received, August 2nd, 1963
[Z 559/401 IE]
(2) : R1= C02R2; R2 = CZHS
German version: Angew. Chem. 75, 918 (1963)
[ I ] G . Wilke and H . Miiller Liebigs Ann. Chem. 629,222 (1960).
[2] G. B. Smith, D. H . McDaniel, E. Biehl, and C. A . Hollingsworth, J. Amer. chem. SOC.82, 3560 (1960).
[3] P. Chini, A . Buradel, E. Puuluzzi, and M. De Malde, Chim. e
Ind. 44, 1220 (1962); Chem. Abstr. 58, 13973h (1963).
and are suitable starting materials for simple syntheses of
1,2,4-triazoles, s-triazines, and pyrimidines.
(3) is obtained in 60 '%,
yield from (I) and phenylhydrazinc i n boiling benzene. In the
analogous reaction with ( 2 ) , phcnylhydrazinomethyleneurethane is initially formed (7 I
and on heating in diphenyl
Atigew. Cizem. interiicii. Edit. 1 Vol. 2 (1963)
No. 11
ether is c y c l k d to I-phenyl- 1,2,4-triazol-5-one (4) (yield:
81 %). 1,2,4-Triazol-5-one results directly from (2) and
hydrazine in 60 7; yieid.
( I ) reacts with dimedone, 2-hydroxy-l,4-naplitIioqt1inone,
anthrone and 8-naphthol.
(31, Y = NH2
or (4). Y = OH
is very reactive. This is shown by the fact that
Compound (f)
polyhydric phenols (contrary t o the reaction of their alkali
salts with carbon disulfide [2]) react according to the number
of hydroxyl groups. Thus 3 moles of (I) react with phloroglucinol in 83 yield. Under the same conditions, (I) reacts
with enamines, e.g. with I ,3,3-trimethyl-2-methylene-indoline to give (5) in 30 'i:yield, with indole to give (6) in 41 x
yield, and with tertiary aromatic amines, such as N,N-dimethylaniline [3].
.s-Triazines are not only obtained from open-chain amidines;
N-cc-pyridyl-N'-ethoxycarbonylformamidine, which is prepared almost quantitatively by heating cc-aminopyridine with
(2) to approx. IOO"C, is converted on addition to boiling
diphenyl ether into pyrido[ I ,2 - u] - s-triazin - 4 - one in 41 %
In contrast to tautomerizable enamines, such as $-aminocrotonic ester (5) or I ,3-dimethyl-4-aminouracil (6), which
react directly with (2) at 100 -120°C to yield pyrimid-4-ones
[(7) in 4 0 % yield, (8) in 86 yield], aromatic primary
amines react with (2) to yield formamidines; their cyclization
to quinazol-4-ones requires heating in diphenyl ether.
A r = P-CloH7; X
2-Methylthio-l,3-benzdithioliummethyl sulfate (7) reacts
with phenols even more readily than (1). By reaction
of (7) with phenol, S,S'-phenylene-w,w-dimercapto-p-benzoquinone methide [4] is formed in 75 '%,yield. The condensation of trithionium salts with dimethylaniline could not be
applied to phenols [51.
Tris(methylthi0)- and methylthiobis(phenylthio)carbenium
methyl sulfate (from dimethyl or diphenyl trithiocarbonate,
respectively, and dimethyl sulfate) form crystal violet with
dimethylaniline. They react, although more slowly than (7)
and (I), with compounds possessing active methylene groups
and with phenols.
Received, August 15th, 1963
[Z 567/391 IE]
German version Angew. Chem. 75, 919 (1963)
The yields are sometimes satisfactory (Ar = a-naphthyl, 51 %,;
(3-naphthyl, 89 x ; 2-anthry1, 94
but occasionally poor
(Ar = C6H5, 10 7:);now and then merely decomposition of
the formamidine is observed.
[Z 562/393 TE]
Received, August 15th, 1963
German version: Angew. Chem. 75, 918 (1963)
Syntheses with Tris(alkylary1thio)carbeniumSalts
[I] R. Gompper and W. Tiipf, Chcm. Ber. 95, 2861 (1962).
[2] R. Gompper and R. Schmidt, Angew. Chem. 74, 780 (1962);
Angew. Chem. internat. Edit. I, 596 (1962).
[3] Reaction of 2-methylthio-5-methyl-I,3-benzdithiolium perchlorate with dimethylaniline: see L. Soder and R. Wizinger,
Helv. chim. Acta 42, 1733, 1779 (1959).
[4] Preparation see W . R. Hurtley and S. Smiles, J. chem. SOC.
(London) 1926, 1821 ; IY27, 534.
[ 5 ] U.Schmidt, R . Scheuring, and A . Liiflringhaus, Liebigs Ann.
Chem. 630, 116 ( I 960).
By Doz. Dr. R. Gompper and Dipl.-Chem. E. Kutter
A Macrocyclic Azo Dye
lnstitut fur Orgdnische Chernie und Organisch-chemische
Technologie der Technischen Hochschiile Stuttgart
[l, 21 uses tris(alkylary1thio)carbenium salts as intermediates. The latter are readily obtained by heating trithiocdrbonic acid esters with
al kylating agents (dimethyl sulfate, ethyl tosylate etc.). The
carbenium salts react readily, on heating in pyridine/triethylamine or glacial acetic acid/pyridine, with compounds possessing sufficiently acidic methylene groups or with phenols.
Thus (I) reacts with malononitrile to give (2) (90 yield),
with I,3-dimethylbarbituric acid to give (3) (84 x, yield), and
with 2,h-di-t-butylphenol t o give ( 4 ) (47 yield). Similarly
A new route to ketene mercaptals
Angew. Cltern. intcvmt. Edit.
V o l . 2 (1963)
No. I I
By Dipl.-lng. J. Jarkovsk? and Dr. Z. J. Allan
Research Institute for Organic Syntheses,
Pardubice-Rybitvl (Czechoslovakia)
We have found h a t a cyclic azo dyestuff is formed in quantitative yield when compounds with suitably spaced groups
and suitable bond angles are reacted according to the RuggliZiegler dilution principle. I-(m-Aminobenzoy1amino)-8hydroxynaphthalenc-3,6-disulfo1iic acid [ I ] was coupled with
its diazoniiim derivative in aqueous NaHCO3. The azo cornpound ( I ) was precipitated with NaCl and purified by crystdllixation (from acctone/water I :9).One iiiillimole of (I) was di-
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ethoxymethylenecyanamide, ethoxymethyleneurethane, heterocyclic
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