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Condensation Products of Squaric Acid and Tertiary Aromatic Amines.

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concentrated sulfuric acid and precipitation with ethanol.
( l b ) : Amax = 770 m p (E = 132000), 440 (10400), 384 (7780),
3 16 (16400) (chloroform) ;
( I c) : Amax = 720, 465, 405, 380, 316,262 m p (chloroform).
Received: February loth, 1966 [Z 165/997 IE]
German version: Angew. Chem. 78, 937 (1966)
Publication delayed at the authors' request
[ I ] We thank Professor K. Hafner, Darmstadt, and Dr. E. Klein
(Dragoco, Holzminden) for samples of azulene.
[2] We are indebted to Dr. Th. Bohm-Giissl and Mr. G . Peitscher
for measurement and interpretation of the spectra.
[ 3 ] A . Treibs and K . Jakob, Angew. Chem. 77, 680 (1965);
Angew. Chem. internat. Edit. 4,694 (1965).
( l c ) , hmax = 624, 417, 387, 367, 306, 261 m p (chloroform)
(Id), principal absorption band: 621 m p (methanol).
Received: February 18th. 1966 [Z 166/998 IE]
German version: Angew. Chem. 78, 937 (1966)
Publication delayed at the authors' request
[l] A . Treibs and K. Jacob, Angew. Chem. 77, 680 (1965);
Angew. Chem. internat. Edit. 4,694 (1965).
[2] We thank Dr. Bohm-Gossl and Mr. G. Peitscher for measurement and interpretation of the spectra.
Addition of Epoxides to 2-Imidazolines
By Dr. R. Feinauer
Forschungslaboratorien, Chemische Werke Hiils AG.,
Marl (Germany)
Condensation Products of Squaric Acid and
Tertiary Aromatic Amines
By Dr. H.-E. Sprenger and Dr. W. Ziegenbein
Forschungslaboratorien der Chemische Werke Hiils AG,
Marl (Germany)
Dedicated to Professor F. Broich on his 60th birthday
Reaction of squaric acid (dihydroxycyclobutenedione) with
phenols (resorcinol, phloroglucinol) and reactive pyrroles
affords deeply colored condensation products to which
respectively a p-quinonoid and a betaine structure
have
been ascribed.
We have found that tertiary aromatic amines also condense
smoothly as nucleophilic reagents with squaric acid, intensely
blue to green, high-melting products being formed to which
we assign the polar structures (la) to ( I d ) on the basis of
elemental analysis and spectroscopic findings [21 and in
analogy with the condensation products from squaric acid
and pyrroles. Structures ( l a ) to ( I d ) are to be regarded as
limiting formulae.
The products are very slightly soluble in alcohol or ether,
more soluble in dimethylformamide and dimethy! sulfoxide.
Dedicated to Professor F. Broich on his 60th birthday
Epoxides react with cyclic imidoic esters with formation of
dioxaazabicycloalkanes [I]. Addition of epoxides to cyclic
thioimidoyl esters takes place similarly; in the case of
2-thiazolines, however, a subsequent reaction leads to 2,5disubstituted 2-oxazolines [21.
We have studied the reaction of epoxides with cyclic amidines
and have found that 4-oxa-1,6-diazabicyclo[3.3.O]octanes(2)
are formed smoothly from epoxides and 1-phenyl-2-imidazolines ( I ) .
R
140
125
150
150
150
150
1
18
79
92
86
85
66
107- 108
114-1 15
171- 172
174-176
135-136
212-213
0.2
0.4
0.2
0.05
0.05
0.1
1.5615
1.5519
1.5920
1.5800
1.5428
1.5071
The components are heated without a solvent to the temperatures given in the table, and the 4-oxa-l,6-diazabicyclo[3.3.0]octanes formed are isolated by distillation. Cyclic
carbonates of 1,Zdiols may be used instead of the epoxides,
since under the reaction conditions they lose COz and are
converted into epoxides. The products are viscous, usually
yellow oils that are readily hydrolysed by aqueous acids or
aqueous alkali. Their structures were proved by elemental
analyses, IR spectra, and degradative reactions.
-(CH&OH
4CHzhOH
-CHZ-C~HS -CH2-C6H5
-(CHZ)~-O-(CHZ)~-
decomp. >230
(decomp.)
decomp. >250
274-276
Preparation of 2-(p-dimethyIaminophenyl)-4-(dimethylimonio2,5-cyclohexadienyIidene)-3-oxo-l-cyclobutenolate
(la)
11.4 g (100 mmoles) of squaric acid and 24.2 g (200 mmoles)
of N,N-dimethylaniline are heated with 150 ml of 1-butanol
and 60 ml of benzene under reflux until a total of 3.6 ml of
water has distilled off azeotropically. The mixture becomes
deep blue. After cooling to 20 "C the condensation product,
which is precipitated as small blue crystals, is filtered off and
washed several times with light petroleum (boiling range
35-45 "C); yield 9.2 g (60 %); A,,
= 628, 414, 389, 366,
306, 263 m p (chloroform).
Compounds (1b)-(ld) can be prepared analogously. Compound (Id) can be recrystallized from ethylene glycol.
( l b ) , principal absorption band : 640 mp (methanol)
894
Received: July 7th, 1966
[Z 287 IE]
German version: Angew. Chem. 78, 938 (1966)
____
[I] R . Feinauer and W . See/iger, Liebigs Ann. Chem., in press.
[2] R . Feinauer, Angew. Chem. 78, 938 (1966); Angew. Chem.
internat. Edit. 5, 894 (1966).
Synthesis of A2-Oxazolines by Reaction of
Epoxides with A2-Thiazolines
By Dr. R. Feinauer
Forschungslaboratorien der Chemische Werke Hiils AG,
Marl (Germany)
Dedicated to Professor F. Broich on his 60th birthday
Epoxides add to 2-oxazolines with formation of 4,6-dioxa-l-azabicyclo[3.3.O]octanes(4) [I]. However, by reaction
of epoxides with 2-thiazolines (1) we obtained 2,5-disubstiAngew. Chem. internat. Edit. 1 Vol. 5 (1966)
1 No. 10
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acid, squaric, condensation, product, amines, aromatic, tertiary
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