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Bicyclo[3 3 1]nonan-2-ol from 4-Cyclooctenylmethyl Toluenesulfonate.

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the latter a r e only weakly basic owing to t h e electron attraction of the triple bond. T h e quaternary N-alkynylammonium
salt which is presumably initially formed f r o m triethylene diainine a n d phenylchloroacetylene can condense in a subsequent reaction with a further mole o f tertiary a m i n e [61
to form 12).
trate gave a 35
yield of ethyl 4-hydroxy-2-phenylaminoquinoline-3-carboxylate (5) a s pale yellow needles from dilute ethanol, m . p . 185-187 " C .
Received, May 25th, 1964
[Z 741/574 IEI
German version: Angew. Chem. 76,537 (1964)
Ethyl 4-chloro-2-phenylaminoquinoline-3-carboxylate
(6)
was prepared in 94 5; yield by refluxing 0.1 g of ( 5 ) with
2 ml of redistilled phosphorus oxychloride for 10 min; colorless needles from dilute ethanol, m.p. 62-63 "C.
[ I ] Heterosubstituted Acetylenes, Part 7. - Part 6: If. G. Viehe
and M . Reinstein, Angew. Chem. 76, 537 (1964); Angew. Chem.
internat. Edit. 3, 506 (1964).
[2] H . G . Viehe, Patent Applications.
131 Cf. references cited i n [ I l , and V. I. Isanik, Zh. obsh. Khim.
( U . S . S . R . )33. 1697 (1963); V. Wolf'and F. Kou.itz, Liebigs Ann.
Chern. 638, 33 ( I 960).
[ I ] H . G. Viehe and E. Fronchimont, Chem. Ber. 95, 319 (1962).
[5] G. R . Ziegler, C. A. Welch, C. E. Orzech, S . Kikkauw, and
S . I. Miller, .I. Amer. chem. SOC.85, 1648 (1963); C. E. Orzech,
C. A. U'elcli, G. R . Ziegler, J. I . Dickstein, and S. I . Miller, ibid.
84, 2020 (1962); A . K . Kuriirkose and S . 1. Mil!er, Tetrahedron
Letters 1962, 905.
[61 Cf. also: S. D. Ross, J. J . Bruno, and R. C. Peterson, J . Amer.
chem. SOC.85, 3999 (1963).
A New Synthesis of Dibenzotb,g1-[1,81naphthyridones
By Dr. A. K . Mallams [*]
Department of Chemistry, University of t h e Witwatersrand,
Johannesburg (South Africa)
Dziebiwhkiand D y n l f k [ I ] isolated t h e dibenzo[b,g]-[I ,8]naphthyridone ( 4 ) from t h e mixture of compounds obtained by
heating acetanilide with diphenylurea. T h e present new synthesis gave excellent yields o f dibenzo[b,g]-[I ,8]naphthyridones without a n y by-products.
When 2 g of ethyl x-(N,N'-diphenylguany1)acetoacetate (1)
[2] were heated with 20 g of polyphosphoric acid a t 140 " C for
I h , a 94
yield of 1 I-methyldibenzo[b,g]-[l,8]naphthyrid12(5H)-one ( 3 ) was obtained as yellow needles f r o m aqueous
acetic acid, m. p. 304-308 'C (decomp.). T h e use of smaller
a m o u n t s of polyphosphoric acid gave lower yields of ( 3 ) . T h e
latter was insoluble in hot dilute alkali b u t soluble in h o t
mineral acids. Ethanolic solutions of (3) exhibit yellow-green
fluorescence.
'x
( 1 ) : R' = CHJCO
(2): R' = COOC&
H,C,-NH-C=N-C,H,
I
R'CH-COOC&
"
1
;
Treatment of 0.2 g o f (5) with 2 g of polyphosphoric acid a t
140'C for I h afforded a quantitative yield of ( 4 ) .
1 I-Chlorodibenzol[b,g]-l,8]naphthyrid-12(5H)-one ( 7 ) was
obtained analogously in 65 yield o n refluxing 0.1 g of ( 4 )
with 6 ml of redistilled phosphorus oxychloride for 3 h ; pale
yellow needles from ethanol, m. p. > 400 "C.
[Z752/569 1El
Received, May 25th, 1964
German version: Angew. Chem. 76, 646 (19641
["I Present address: Organic Research Division, African Explosives and Chemical Industries, Modderfontein, Transvaal,
South Africa. The author wishes to thank the Sir Ernest Oppenheimer Memorial Trust for the award of a research fellowship.
[ I ] K . Dziewwriski and W. Dyrnek, Roczniki Chem. 20,38 (1946).
[2] .'M Traube and A . Eyme, Ber. dtsch. chem. Gcs. 32, 3176
(I 899).
[ 3 ] V . E. Tishchenko and N . V . Koshkin, Zh. obshch. Khim. 4,
1021 (1934).
Bicyclo[3,3,1Inonan-2-01 from
4-Cyclooctenylmethyl Toluenesulfonate
By Doz. D r . M. H a n a c k and Dipl.-Cheni. W. Kaiser
Chemisches lnstitut der Universitiit Tubingen (Germany)
2-Acetoxybicyclo~3,2,l]octaiieis formed by acetolysis of 3cycloheptenylmethyl p-bromobenzeiiesulfonate [I]. 4-Cyclooctenylmethyl derivatives also give rise to bicyclic reaction
products by transanular participation of t h e double bond
during solvolysis.
4-Cyclooctenylmethanol (m. p. o f p-nitrobenzoate 52-53 'C)
is readily obtained f r o m 4-cyclooctenecarboxylic acid [2].
T h e alcohol was converted into t h e tosylate ( I ) (Tos =
S O ~ C ~ H J C Hm
~ .)p, . 29-3OoC, which was solvolysed at
60 "C for 48 hours in glacial acetic acid plus sodium acetate.
T h e acetate obtained was reduced with LiAIH4 t o give some
unidentified hydrocarbons a n d 60 :( of a n alcohol fraction
which consisted predominantly of bicyclo[3,3,l]nonan-2-ol
(2) [ 3 ] . Oxidation of t h e alcohol gave bicyclo[3,3, Ilnonan-2one [3,4] plus 18
of another ketone, presumably bicyclo[4,2,l]nonan-2-one. T h e participation of t h e double bond is
(3): R 2 = CH,
(4):
(7):
R2 = OH
R2 = C1
(5): R 2 = O H
(6): R2 = C1
When 2 g of ethyl N,N'-diphenylguanylmalonate (2) [2,3]
were heated with 20 g of polyphosphoric acid a t 1 4 0 ° C for
I h , a quantitative yield of 1 I-hydroxydibenzo[b,g]-[1,8]naphthyrid-l2(5N)-one (4) was obtained as yellow needles
from acetic acid, m . p . > 400°C. Smaller a m o u n t s of polyphosphoric acid (10 g) resulted in lower yields of ( 4 ) . When
the reaction was stopped after 20 niin by pouring t h e reaction
mixture i n t o 80 ml of cold water, t h e insoluble product ( 4 )
was obtained in 20 ;{ yield. Neutralization of t h e acidic filAnXew.
cheni. i n t e r w t . Edit.
/
V o f . 3 (1964) / No. 8
also shown by the r a t e of acetolysis of ( I ) . T h e reaction proceeds fifty times as fast a s acetolysis o f cyclooctanylmethyl
toluenesulfonate.
Received. May 29th, 1964
[Z 744/576 IE]
German version: Angew. Cheni. 76, 572 (1964)
[ I ] G . LeNj., Seances Acad. Sci. 251, 1.526 (1960); cf. also S .
Winstein and P . Carter, J . Amer. chem. SOC.83, 4485 (1961).
[2] G. Stork and N. K . Lnnrlesnion, J. Amer. chem. SOC.8 5 , 5129
(1963).
[3] H . Meerwein, F. K i d , G. Klos,yen, and E. Schoh, J. prakt.
Chem. [2] 104, 161 (1922).
141 J. P . Ferris and N . C . Miller, J. Amer. chern. SOC.85, 1325
(1963).
583
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toluenesulfonate, cyclooctenylmethyl, bicycle, nona
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