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Anions and Freee Radicals of Acidic Hydrocarbons and their Aza-isologues.

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Anions and Free Radicals of Acidic Hydrocarbons
and their Aza-isologues
x)
Richard Kuhn, Heidelberg (Germany)
Replacement of one fluorene residue in the "acidic" compound bis(bipheny1ene)propene by a 4 If-cyclopenta[d,e,flphenanthrene residue gives rise to the two isomers (I) (m.p.
376 mp) and (2) (m.p. 196-197"C,
252-254OC. hmax,
Amax, = 346 mp) (F.A. Neugebuucr). Acids convert (2) into
(I). With bases, compounds (I) and (2) give the same red
anion (3) (hmax, = 555 mp), which on neutralisation yields
(1) and (2) in an approximately I :I ratio [I].
-
( I ) (Phe)C=CH-CH(Biph)
l-tQj (Phe)CH-CH-C(Biph)
e
(3) (Phe)C!=CH-C4Biph)
(2)
(Phe)C=CH-&Biph)
(4)
(5) (Phe)C=CH-UCH3)(Biph)
(Phe)C(CH&CH=C(Biph)
(6)
(7) (Phe)CoCH-CH(Phe)
(Phe)C=CH-&Phe)
18)
e r
(Phe)C-CH=QBiph)
.
Methylation of (1) and (2) leads to (5) (m.p. 207-208 "C,
hmaxl= 380 my; yield ca. 56%) and (6) (mp. 245-247 'C,
hmaxl= 348 my, yield ca. 28
vicr the common anion (3).
Discharge of the anion (3) gives il mixture of dimeric hydrocarbons CSsH34, which dissociate weakly in solution into the
orange radicals (4) (Xmaxl = 515 mp). Orange radicals (8),
which are nearly insensitive to oxygen, are formed by dissociation of a dimeric hydrocarbon C(,2H34 (m.p. 282-285 "C)
which is obtained by discharge of the red anion (Xmax, =
555 mp) of (7) (m.p. 276-277"C, ha,,
= 376 mp) (electron
spin resonance spectra, K. H. Huusser).
The red compound (9) (m.p. 147-148 "C), which is obtained
from fluorenone hydrazone and glutacondialdehyde, gives a
r
(Phe)&H-C(Biph)
[I] Phe = 4,5-phenanthrylene, Biph
=
Biphenylene.
(Biph)C=N-NH-CH-CH-CH=CH-CH-N-N=C(Biph)
(9)
green anion; its dissociation constants, however, are not
greater than those of the m-isologues previously described
121.
[GDCh-Ortsverband Berlin (Germany),
November 26th, 19621
[VB 671/65 IE]'
--
_
.
121 R. Kuhn, hgew. Chem. internat. Edit. 1. 602 (1962).
SELECTED ABSTRACTS
'
First prospects for successful chemotherapy of virus diseases
have appeared. R. Thiel and A. Wacker have succeeded in
curing a disease of the cornea of the eye, caused by a virus,
by a method that had first been used by ff. E. Kaujman.
Drops of a 0.1 % aqueous solution of the deoxyriboside of
iodouracil were applied several times daily to the affected eye.
The virus incorporates the "fitlse" nucleoside into its nucleic
acid in place of natural thymine. Its capacity for multiplication is thereby destroyed, and the virus becomes photosensitive, so that it can be killed by repeated irradiation of the
eye with a special daylight lamp. / Klin. Monatsbl. Augenheilkunde augeniirztl. Fortbild., No. 11 (1962) / -Hg.
[Rd 413/115 IE]
'Lbe preparation of epoxides from substituted pquinooes and
liazometbane is reported by B. Eisicrt, H.Fink, and Anneliese
%fuller.The speed of reaction increases along the series tetra.ndo-. tetrabromo-, tetrachloro-, and tetrafluoro-pbenzoquinone. Tetramethoxy-, tetra-acctoxy-, 2,6-dimethoxy-3,5
dibromo-, and 2,6-dimethoxy-p-benquinone also yield
epoxides. 2,5-Dimethoxy-p-benzoquinone,
in which the two
methoxyl groups are involved in a vinylogous ester isomerism,
does not react with diazomethane. Naphthaquinones which
are substituted with chloro-, bromo-, or methoxyl groups in
the 2- and 3-positions can also be converted into epoxides.
Naphthaquinones which are substituted solely in the 2-position react vio their double bond in the 2,3-position to form
pyrazoline derivatives. Some of the epoxides thus obtained
can be isomerized to aldehydes with boron trifluoride etherate, and hydrogenated to p-hydroxybenzyl alcohols. Boiling
with 50% hydrochloric acid yields formaldehyde and the original quinone./Chem. Ber. 95,2403 (1962)/-W. [Rd 424/121 IE]
Zinc acetylides have been syntheiimd by R. Nust, 0. Kiinzel,
and R. Mufler. The reaction between diphenylzinc and phenylacetylene (l:2) in ether gives an 80 % yield of bis(pheny1ethynyl)zinc. In liquid NH3, this forms a colorless, crystalline
ammoniate, Zn(C=CC6Hs).N H3. Reaction of (C&ls)zZn and
C&sC=CH in a 1:1 molar ralio gives an approx. 80%
yield of phenyl-phenylethynylzinc.G H s Z ~ C E C G H ~m., p.
132.5-1335°C (decomp.). In ether, as in liquid NH3, this
compound decomposes into diphenylzinc and bis(pheny1ethyny1)zinc. Zinc amide suspended in liquid NH3 reacts
with acetylene to give the crystallinu ammoniate of diethynylzinc, Zn(C=CH)rNH,, which is very soluble in liquid NH3
(non-electrolyte). The infrared spectra display the expected
vc-c frequencie-s. / Chem Ber. 95, 2155 (1962) / -Ma.
[Rd 357/111 IE]
Angew. Chem. internat. Edit. / Vol. 2 (1963) I No. 3
2-Benzyl-5,7-dinitrothiazolo[5,4-b]quinol-9-one,the first thiazoloquinolone with a functional group a t C-9, was synthetized
by J. Dines, M . FZrcZsan, and G. Ciudan. 2-Chloro-3,5-dinitrobenzoic acid was condensed with 2-benzyl-5-aminothiazole in warm ethanol to give 3,5-dinitro-N-(tbenzy1-5thiazoly1)anthranilicacid in 62% yield, m.p. 204OC. Following the procedure for classical acridone syntheses, the ring
was closed with phosphorus oxychloride to give the thiazoloquinolone in 58% yield, m.p. 238-239°C. The substance.
forms a hydrochloride as well as silver, potassium, and piperidinium salts (mp. 216-217"C, decomp.). With methyl
iodide, the silver salt gives the N-methyl derivative of the
quinolone in 28 % yield, m.p. 233-235 O C . 1 Chem. Ber. 95,
251 1 (1962) / W.
[Rd 416/118 IE]
Cyclic dimers of maleic anhydride and its derivatives were
synthetized by G. 0.Schenck, W. Hurtmann, S.-V. Monnsjefd,
W. Metzner, and C. H. Krauch using il photoreaction with
benzophenone as sensitizer (high pressure mercury arc, glass
apparatus, argon; solvent: dioxan or benzene). The photochemical cycloaddition of these dienophiles, which does not
proceed - or only very slowly - in the absence of benzophenone (I), leads to symmetrical cyclobutadiene derivatives
of type (2) (a: R R' = CH3, X = 0 ; b: R CH3, R = H
or v i c e v e r s a , X = O ; c : R - R ' = H , X - O ; d : R = R ' CH3, X = NH;e: R =R'= H,X = N.--GHs;f:R = R = H,
X = N-C~HH). Cyclobutadiindene (98.5 %; m.p. 113OC).
the photodimer of indene, was obtained in particularly high
quantum yield (0.9 based on the yield of benzopinacolone in isopropanol). The photosensitized addition of dimethylmaleic anhydride onto furan surprisingly takes place
in the a,p-position and leads to 6,7-dimethyl-4-oxabicyclo[3,2,0]hept-2-ene6,7-dicarboxylicanhydride (3), m. p. 153O C .
The adducts of dimetbylmaleic anhydride onto ethylvinyl
ether and of indene onto coumarin are obtained in an analogous manner. The dehydrogenating action of activated ( I ) ,
-
-
(2)
(3)
which normally leads to the formation of, for instance, the
dioxan adduct of (I), is suppressed in the presemce of the
above mentioned dienophiles. / Chem. Ber. 95,1642 (1962) /
-Ku.
[Rd 368/114 IE]
163
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