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Condensation Products of Squaric Acid and Azulenic Hydrocarbons.

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azolium salts, to form deeply colored 1,2-derivatives of
cyclobutenedione of general formula (49), such as that
shown in example (50) "261.
(SO), - C H = R :
0
CH=R
- C H = (N' D
o P L H=R
(49)
&H,
(51), -CH=R:
bcH,
H
Diacetoxycyclobutenedione (22) [I71 also reacts with
pyrroles to give yellow 1,2-dipyrrylcyclobutenediones
(51), as well as cyclotrimethine dyes of the type (40) [171.
We are grateful to the management of Chemische Werke
Hiils AG for permission to publish this report, and to
Prof. H. Hellmann and Dr. A . Schmidt for their helpful
interest.
Received: July 7th, 1966
[A 543 IE]
German version: Angew. Chem. 78, 927 (1966)
Translated by Express Translation Service, London
[26] H. E. Sprenger, personal communication.
C 0M M U N I CAT I 0 N S
Oxidation of Sulfoxides with Hydroperoxides
By Dr. L. Kuhnen
Forschungslaboratorien, Chemische Werke Hiils AG.,
Marl (Germany)
Dedicated ta Professor F. Broich on his 60th birthday
Organic hydroperoxides oxidize sulfides to sulfoxides. Addition of excess of oxidizing agent does not lead to the formation of sulfones [ I ] .
However, sulfides and sulfoxides can be oxidized by equimolar amounts of organic hydroperoxides in the presence of
vanadium, molybdenum, or titanium compounds to sulfones
in almost quantitative yields. The sulfides and sulfoxides dissolved if convenient in benzene, ethyl acetate or ethanol are mixed with the catalyst and heated to 5O-7O0C, the
organic hydroperoxide being then added slowly. The reaction,
which is sometimes strongly exothermic, is complete as soon
as only traces of peroxide can be detected with potassium
iodide in the reaction mixture. The sulfones are then isolated
by crystallization or distillation.
For example, oxidation of thioanisole ( I ) in benzene with
t-butyl hydroperoxide in the presence of molybdenyl acetylacetonate produces methyl phenyl sulfone (2) in 98 % yield.
Oxidation of dimethyl sulfoxide (3) with cumyl a-hydroperoxide in the presence of vanadium pentoxide gives dimethyl sulfone (4) in 91 % yield.
Condensation Products of Squaric Acid and
Azulenic Hydrocarbons
By Dr. W. Ziegenbein and Dr. H.-E. Sprenger
Forschungslaboratorien der Chemische Werke Hiils AG.,
Marl (Germany)
Dedicated to Professor F. Broich on his 60th birthday
On reaction of squaric acid (1,2-dihydroxycyclobutenedione)
in, e.g., butanol, with azulene or a homologue thereofrll
there is surprisingly smooth formation of condensation
products, to which we assign the limiting structure ( I ) on the
basis of elemental analysis and spectroscopic results [21 and
in analogy with the products synthesized from squaric acid
with pyrroles, resorcinol, and phloroglucinol[31.
OC
( l a ) - ( l c ) are precipitated as sparingly soluble
crystals with a green metallic luster. Their solutions in dimethylformamide are intensely blue to green.
Preparation of 4-(I-azuleniumyIidene)-2-(l-azulenyl)-3-oxoI-cyclobutenolate ( l a )
Unsaturated sulfides such as ally1 n-butyl sulfide or diallyl
sulfide can be oxidized selectively to unsaturated sulfones.
In contrast to conventional oxidation procedures, these
reactions proceed without the presence or formation of water
or carboxylic acids.
Received: April 28th, 1966
[ Z 225 IE]
German version: Angew. Chem. 78, 9 3 1 (1966)
Publication delayed at the author's request
[I] L. Baternan and K. R . Hargrave, Proc. Roy. SOC. (London),
Ser. A 224, 389, 399 (1954); K. R. Hargrave, ibid., Ser. A 235,
55 (1956).
Angew. Chem. internat. Edit. 1 VoI. 5 (1966)
1 No. 10
A mixture of 1.92 g (0.015 mole) of azulene, 0.86 g (0.007
mole) of squaric acid, 60 ml of butanol, and 40 ml of benzene
is refluxed for 5-7 hr with continuous removal of the water
formed. After evaporation to one-third of the original volume
the crystals that separate are filtered off and washed with
methanol and light petroleum. Drying then affords 2.25 g
(90 %) of material, which is purified by dissolution in hot
benzonitrile and precipitation with ether; Amax = 680 mp
(E = llOOOO), 460 (3440), 394 (7560), 366 (9500), 311 (17200),
284 (18500) (in chloroform).
Compounds ( I b) and ( I c ) are obtained analogously. The
last-mentioned can be purified by dissolution in warm,
893
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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