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Lithium Aluminium Tetrakis(diethylphosphide).

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di(alkoxycarbony1)oxazoles (2) in 60-70 % yield. These
esters are hydrolyzed by aqueous barium hydroxide a t
50-70 'C or by ether/ethanolic sodium hydroxide at roomtemperature to yield the barium or disodium salt of the
COOR
I
co
N
COOR
CHOH
!o
,.J
COOR
T 7
'O/
COOR
121
(1)
It has now been found that interaction of u,P-unsaturated
dicarboxylic acids, their anhydrides or esters with thiourea
in a methanolic solution saturated with hydrogen chloride or
hydrogen bromide results in ring-closure and formation of
2-imino-4-oxo-3,5H-1,3-thiazine-6-carboxylicesters.
In the above scheme, R is preferably CH3 or CzHs, while R'
may be, for example, CH3, C2H5, n-C4H9, (CH&CH,
C H ~ ( C H ~ ) I & Hor
~ , C6Hll. When R and R' are unlike,
transes terification occurs.
(31
oxazole-4,5-dicarboxylic acid. By heating the anhydrous
R
C1 isopropanol/
ethanol 1 : 1
Cl ethanol
C1 isopropanol/
pet. ether 1 :1
C1 acetonel
pet. ether 1 : 1
C1 acetone
[I] J. W.Cornforth and R. H. Cornforth, J. chem. SOC.(London)
1947,96.
121 E. F. Hartree, J. Amer. chem. SOC. 75, 6245 (1953).
C1 acetonel
pet. ether 1 :1
Lithium AIuminum Tetrakis(diethy1phosphide)
Anorganisch-chemisches lnstitut
der Universitat MSnster (Germany)
With 1 mole of LiP(CzH& (I), AIC13 forms the crystalline
trimer [ C I ~ A - P ( C ~ H S [2];
) ~ ] however,
~
with 3 moles of (I),
it gives a viscous substance (2) having an AI:P ratio of 1:3.
With 4 moles of(l), AICb reacts in ether at room temperature
according to the equation:
AICI,
+ 4 LiP(CzH5)z
*
+ 3 LiCI.
LiAIp(CzH~)214
I78
(decomp.)
180-181
(decomp.)
165-167
(decomp.)
199-200
(decomp.)
148-149
(decomp.)
150
(decomp.)
197-198
(decornp.)
CI n-propanol
(23711202 IE]
By Prof. Dr. G. Fritz [l] and DipLChem. G.Trenczek
Yield
I
salts in quinoline with equimolar amounts of quinoline
sulfate in the presence of cupric oxide or copper powder as
catalyst, we obtained oxazole (3) in 50-70 % yield directly,
without isolating the relatively labile oxazole-4,5-dicarboxylic
acid.
Received, October 24tb, 1962
I
M.p.[%I
89
59
79.2
70.5
75
54
62
The compounds cited in the Table are convertible, irrespective of the substituent R , into 2-imino-4-oxo-3,5H-l,3thiazine-6-carboxylic acid, m.p. 244-245 OC, using 5 N
hydrochloric acid at 80 "C. With methanolic ammonia, the
thiazine derivatives yield the corresponding 6-carbonamide
(m.p. 222'C). A patent covering this method is pending.
Received, October 28th, 1962 [Z 3951198 IE]
[I] K. Bekringer and P. Zillikens, Liebigs h a . Chem. 574, 140
(1951).
[2] A. Huntsch, Liebigs Ann. Chem. 296, 94 (1897).
(3)
(1)
On concentrating the ether solution, colorless, well-formed
crystals of lithium aluminum tetrakis(diethy1phosphide) (3)
result: these are recrystallised from diethyl etherlpentane,
m.p. 224-226OC (in a sealed tube); yield 71 %. Compound
(3) is also formed from the viscous product (2) with a further
mole of (1). It is spontaneously idammable in the atmosphere, stable in nitrogen, very soluble in ether, and insoluble
in benzene and pentane. The X-ray diagram of (3) is clearly
distinguishable from that of LiP(C2H&.
Received, October 26th, 1962
[Z 376/201 IE]
[I] New address: Institut fur Anorganische und Analytische
Chemie, Universitlt GieBen, Germany.
121 G. Fritz i n d G. Trenctek, Z. anorg. allg. Chem. 313,236 (1961).
A Simple Synthesis of 2-Imin0-4-0~0-3,5H-1,3thiazine-6-carboxylicEsters
By Dr. R. Zimmermann
Preparation of Aminoarsines by Transamination
By Dr. H. J.Vetter and Priv.-Doz. Dr. H. NBth
lnstitut fiir Anorganische Chemie
der Universitat Munchen (Germany)
-
The (H3C)zN ligands in tris(dimethylamino)arsine,
Asm(CH3)2]3 (I) [l], can be successively substituted by
reaction with substances possessing N-H bonds. Compounds
of the type X-NH2 react with ( I ) as follows:
(H3C)zN--As-N-X
2 As[N(CHdzh
+ 2 HzNX -+
I
I
X-N-AS-N(CH&
+ 4(HsC)zNH.
I
n-CdH9
GHs
C&)CO
N(CH3)z
163-165
213-215
-
undist. oil
110 subl. in vucm
165 subl. in vucuo
106/2 mm.Hg
380.2
420.2
476.2
354.1
385
415
-
356
Abteilung Allgemeine Organica, Chemische Werke Albert,
Wiesbaden-Biebrich (Germany)
According to Behringer and Zillikens [l], in alcoholic
solution, a,a-unsaturated monocarboxylic esters and isothiourea hydrochloride [2] yield open-chain isothiuronium
salts.
N
I
NHz
Angew.
X = C1, Br
Chem. internat. Edit. I Vol. I (1962)
II
NWHX
1 No.
12
663
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