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Novel One-Step Synthesis of Oxocyclopentanecarboxylates through Electroreduction of Cinnamate Derivatives.

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F. Duus in D. Barton, W. D. Ollis:
Comprehensive Organic Chemistry, Bd. 3, Pergamon
Press, Oxford 1979, S. 373.
/2/
G. C. Barrett, in Lit. / 7 / , S. 55.
/3/ F. C. V. Larsson, S.-0. Lawesson, Tetrahedron 28
(1972), 5341; zit. Lit.
/ 4 / H. B. Henbest, S . A. Khan. Chem. Commun. 1968,1036;
D. Arndt in Houben-Weyl-Miiller; Methoden der Organischen Chemie, Bd. IV/lb, Thieme, Stuttgart 1975,
S. 647.
/5/ In Zhnlicher Weise lien sich aus 1,3-0xathiolan-S.S-dioxid Formaldehyd freisetzen: K. Schank. R. Wilmes,
G. Ferdinand,
2. Sulfur Chem. 8 (1973). 397.
/6/ T. Kauffmann, Angew. Chem. &. (19741, 715;
Chem. Int. Ed. Engl. 9,
627 (1974).
/7/ R. Mayer, H. Berthold, _Chem. E. 96 (1963), 3096.
/I/
Table 1.
Solvent
Isolated Yields(%)
3a
___
_
74
76
23
m3a
IMF
IMX)
i-hcH
45
9
MeoH
trace
87.5% aq.a-i3G4
75% aq.CH3G4
50% aq.a-i,CN
*
trace
trace
30
7s
77
2
72
15
6
61
The reaction was carried out using a copper plate as a cathode in
a variety of solvent containing Et4NOTS as a supporting electrolyte
at l0-lSoCuntil 4.0 F/mol electricity was passed.
m.
a.
H. Staudinger, H. Freudenberger,
B.
(1943) 573.
/9/ A . Schonberg in Houben-Weyl-Miiller: Methoden der
Organischen Chemie, Bd. IX, Thieme, Stuttgart 1955,
S. 706; zit. Lit.
/ l o / A . Schonberg, E. Frese, K.-H. Brosowski,
Vol.
w. e.
2 (19621, 3077.
For instance, 2-carbomethoxy-3,4-diphenylcyclopentanone2% was
exclusively obtained in a 74-76%yield from methyl cinnamate 5' in
acetonitrile or N,N'-dimethylformamide wiiile the electroredution of
*%Hn
'SH
cH3cN( or DMF )
16.
ter Fassung am
2.
September. in erweiterNovember
1982 /Z
1s in
methanol gave dimethyl 3,4-diphenyladipate$g /2/ in a 75% yield as an
only product.
+2e. &-cathode
Eingegangen am
L@*
2a
__
=.
/8/
Effect of Solvent Systems in Electroreductlon of
C6H5-
C H a -CDY?i5
Y=74-76%
2a
-
148 S /
Y=75%
30
-
The results of the similar electroreductive cyclization/4/ of a variety
of cinnamate derivatives & - l h are s m r i z e d in Table 2.
-
69
-
-
zu zitieren als
Angew. Chern. Suppl.
1983,70- 74
Q Verlag Chemie GmbH, D-6940 Weinhelm, 1983
0721 422718310101 007os02 50/0
Substituent
Ar
a
-
Electroredution of Cinnamate Derivatives la-&.to
2-Carbomethoxycyclopentanones &Zh in DMF*
Table 2
to be cited as
Angew. Chern. Suppl.
1983, 70-74
71
'SH5
I
Isolated Yield
of &-ZB (%I
76
R
H
Novel One-Step Synthesis of Oxocyclopentanecarboxylates
through Electroreduction of Cinnamate Derivatives
64
By Ikuzo Nishiguchi' and Tsuneaki Hirashima
It has been w e l l conceived that electrochemical reduction of a,@unsaturated esters in an aqueous solution usually gives the corresponding
hydrdimers, adipic acid derivatives, as the main products /1,2/.
In this study, 2-carboalkoxycyclopentanones2 were fomed in moderate to
g o d yields through electroreductionof cinnarrate derivatives 1.
?he present method may possess high potentiality in organic synthesis as
a facile one-step preparation of some cyclopentanone derivatives from
readily available starting a.6-unsaturated esters.
1
-
Y: 52-7%
h
p-C1C6H4
H
75
mp
("C1
126-127
83- 87
75- 80
131-133
101-104
121-123
115-116
134-13s
Electroreduction was conducted using a Ql plate as a cathode in DMF
containing Et4NlXs as a supporting electrolyte at 1O-1S0C with stirring
until 4.0 F/mol of electricity was passed.
**Fyridinyl
Furthemre, a mixture consisting of an uniequivalent mole of methyl
p-chlorocimamate&h and dimethyl 2.3-diphenyladipate 2% was electrochemically reduced under the similar conditions t o obtain some informations on the reaction pathway of the present reductive cyclization. As a
result, the dimeric cyclization product g$ was exclusively fomed in a
74% yield ,and 3%
- _ was quantitatively recovered accompanying no formation
of 2%.
2
-
show in Table 1, remarkable solvent effect was observed in the
present electroreductivedmerization.
As
*
Dr. I. Nishiguchi, Dr. T. Hirashima
Osaka Municipal Technical Research Institute
1-6-50,Mrinomiya, Jyoto-!a, Osaka, Japan 536
-
70
-
%(quantitative
recovery)
-
72
-
a(Y:74%)
-
J
This controlled experiment clearly showed that the reaction may proceed
via a dimeric anionic intermediate such as 4 /S/, which yields the
cyclization product 2 o r the simple hydrodimer 2 depending upon the
proton-donating ability of the solvent system, and also denies the
possibility of Dieclanann condensation of 2 under the reaction conditions.
Ar
1
I
Dieses Manuskript ist
zu zitieren als
This manuscript is
to be cited as
Angew. Chern. Suppl.
Angew. Chern. Suppl.
i983,75-a3
1983,75-a3
0 Verlag Chernie GmbH.0-6940Weinheam. 1983
0721 4227183101010075102.5010
r
2-Benzyl-1-phosphaazulen
G. Markl+ und E. Seidl
Vom Azulen
-
dem klassischen Vertreter der nichtalternieren-
den aromatischen Kohlenwasserstoffe - wurden inzwischen alle
R
durch Ersatz einer Methingruppe durch Stickstoff moglichen
-3
Typical Procedure
5 isomeren Monoazaazulene als Grundkorper oder in substituier-
A solution of 20g (0.067 mole) of tetTaethylarmmnim p-toluene-
Entsprechende Phosphaazulene, in
ter Form synthetisiert /l/.
sulfonate in 80 ml of anhydrous acetonitrile was placed in cathodic
(64 ml) and anodic(l6 ml) chambers of a electrolysis cell equipped with
copper(cathm3e) and platinum(anode) electrodes, reference electrode, and
a ceramic diaphragm.
To the catholyte was added 1.62g(0.01 mole) of
The catholyte was stirred with a magnetic bar
methyl cinnamate &.
and electrochemically reduced at the cathode potential of - 1 . S - 2 . 2 V
vs. SCE under the external cwling with a water bath until 4.0 F/ml of
The usual unrk-up gave Z-carbomethoxy-3,4electricity was passed.
diphenylcyclopentanone 28 in a 74% yield, mp 126-127OC : nmr(CDC13, pp)
2.b-3.0(m., ZH), 3.0-4.0(m., 3H), 3.7(s.. 3H), 7.2(s., 1OH).
denen eine Methingruppe durch 3-bindigen Phosphor der Xoordinationszahl 2 ersetzt ist, sind bis heute nicht bekannt.
Da inzwischen aber sowohl stabile 6 - wie 5-gliedrige aromatische Phosphorheterocyclen mit 3-bindigem Phosphor der
Koordinationszahl 2 dargestellt werden konnten / 2 / , war
auch an der Existenzfahigkeit von Phosphaazulenen nicht zu
zweifeln.
Wir berichten nunmehr iiber eine erste Synthese dieser neuen
*Prof. Dr. Gottfried Mlrkl, Dipl.chem. Ernst Seidl, Institut
for Organrsche Chemie der Universitat, Universitatsstr. 31,
D-8400 Regensburg.
-
73
-
-
References and Notes
/1/ (a) M.M.Baizer,Ed.,'Organic Electrochemistry", bhrcel Dekker,New
York, N.Y. , 1 9 7 3 , 399-412:
~~
(b) L.Eberson and H.&fer,'Topics
in
Chrrent Chemistry,Zl,Organic Electmchuniste, Springer-Verlag,
Berlin Heidelberg New York,l97l,pp 117-127:(c) N.L.Weinberg,'wnique of Electroorganic Synthesis", Part 11, Wiley, N e w York, N.Y.,
1974,pp 87-136,and others cited therein.
/ 2 / M.M.Baizer and J.M.Anderson, J.Electmchm.Soc. ,111, 223(1964).
/3/ (a) E.L.Totton, R.C .Freeman, and T.L.Yarbro,-€in.,
26, 343
(1961) :(b) J.P.Petrovich, M.M.Baizer, and M.R.Ort, J.Electrochem.
Soc., 116, 749(1969).
/4/ A l l the products were isolated and identified by specroscopic and/or
elemental analyses.
/ 5 / M.M.Balzer, J.P.Petrovich, and D.A.Tyssee, J. Electrochem. Soc.,ll7,
173(1970)
75
-
Verbindungsklasse. Das nach R.B. Dran et a1 / 3 /
dargestellte
Gemisch von 1-Vinyl- und 2-Vinyl-1.3,s-cycloheptatrien
"/%
__
(Vhn. 4 0 / 6 0 ) reaqiert mit Benzyldlchlorphosphan in Gegenwart
Yon Cu-Stearat in einer Mc Cormack-Cyclisierung / 4 /
(Reak-
tionszeit etwa 4 Wochen) zu dem Gemisch der isomeren 1-Benzyl-1 ,1-dichlor-tetrahydro-1 A5-phosphaazulene
+/s,
_ _ das
sich aus der Losung der Edukte in Petrolether (Sdp. 50-70 O C )
zunachst schmierig, dann farblos kristallin abscheidet:
Received March 9, 1981,
revised October 22, 1982
/Z
406
S/
Die Benzyl-dichlorphosphorane
-
konnen zu den Phosphanoxiden
hydrolysiert werden, durch direkte Dehydrochlorierung von
-
mit a-Picolin in Methylenchlorid/Petrolether /5/ erhalt man
ein Gemisch der 1-Benzyl-dihydro-1-phosphaazulene
(Sdp.
-
74 -
?r
125 oC/10-2 Torr):
-
76 -
& und 2
_
_
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step, synthesis, cinnamate, one, oxocyclopentanecarboxylates, novem, electroreductive, derivatives
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