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Lactones by Hydroformylation of Unsaturated Carboxylic Esters.

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COMMUNICATIONS
The Formation of Aniline Black-like Compounds
from Quinonanil-N-chloroi~~e
By Dr. Helmut Gies
Farbwerke Hoechst AG. vormals Meister Lucius & Briining
Frankfurt/Main (Germany)
Published on the occasion of the centenary of the ,founding of
Farbwerke Hoechst on January I l t h , 1963.
In the pure state, quinonanil-N-chloroimide(I) is stable at
2OoC, contrary to data in the literature [I]. When brought
into contact with small amounts of acids, it reacts in solution
or in bulk, sometimes very violently, to form aniline blacklike compounds. This reaction is also initiated by other
compounds which form hydrogen ions during a preliminary
reaction with I. These can be divided into two groups.
Group 1: Primary and secondary amines. These compounds
probably react with I by 1,4-additions in the manner in which
anilidoquinones are formed, e.g. in accordance with equation
(1).
IV
The hydrochloric acid liberated will then act as described in
group 1.
An analogous reaction is known with benzoquinone-bischloroimide [S]. By using reaction (I) with a large excess of
phenol or dimethylanitine, the indo-aniline 111 and the
indamine IV were also successfully prepared and then
reduced with zinc and glacial acetic acid. The reduction
products V and VI were identified by mixed melting points
[6] and by analyzing the acylation products.
V
VI
These reactions of I gain in importance by the fact that they
can also take place in fibres or films made from plastics. This
process is particularly useful with polyester materials. The
resultant black colors are characterized by great fastness.
[Z 363/190 IE]
Received, July 4th. 1962
I
I
HN
I
HN
0
+
I
dH3
The hydrochloric acid liberated reacts with I, forming 1imido benzoquinone-anil [2]. This polymerizes to aniline
black-like compounds by way of emeraldine or azophenine,
depending on the hydrogen ion concentration [l, 31. When I
was treated with excess p-toluidine in alcoholic solution the
crystalline, brown compound I1 was isolated [4].
[l] W . Nover, Ber. dtsch. chem. Ges. 40, 288 (1907).
[2] R. WiZZstutter and E. Mayer, Ber. dtsch. chem. Ges. 37, 1495
(1904).
[3] S. Goldschmidt and B. Wurzschmitt, Ber. dtsch. chem. Ges.
55, 3224 (1922).
[4] 0. Fischer and E. Hepp, Ber. dtsch. chem. Ges. 20, 2480
(1887).
[5] R. Nietzki and R. O m , Ber. dtsch. chern. Ges. 21, 1745
(1888).
[6] G. HeIIer, Liebigs Ann. Chem. 418, 272 (1918).
Lactones by Hydroformylation of Unsaturated
Carboxylic Esters
By Dr. J. Falbe and Prof. Dr. F. Korte
Shell Grundlagenforschung GmbH.
SchloI3 Birlinghoven, Siegkreis (Germany)
\I
I1
There is no formation of azo-compound, as might also have
been expected.
Group 2 : Compounds with mobile hydrogen atoms enabling
them to form stable azo-compounds, e. g. dimethylaniline,
phenol, P-naphthol, o-phenylphenol, phenyl-methyl-pyrazolone and acetoacetanilide. Evidently I reacts with these
compounds to form indo-anilines or indamines, e.g.
(2)
I + o- O H
--+
Aliphatic and alicyclic a$- and P,y-unsaturated carboxylic
esters react with CO/H2 in the presence of catalytic amounts
of dicobalt octacarbonyl, Raney cobalt, or cobalt salts as
catalysts at 200 to 35OOC and 100 to 3 0 0 atm to produce
saturated mono- and bicyclic lactones in yields of 70-90%.
In some instances, it is also possible to use the unsaturated
carboxylic acids directly as starting material. Acrylic esters
give y-butyrolactones while 8-valerolactones are obtained
from vinyl acetates.
H2C=CR1-C
//O
+ ROH
+ CO 4- 2 H z ---+ \1-O‘
(%o
‘OR
R1
R2
\
’
HZDCH-C-C’~
R1
‘OR
+ CO+
/‘O
2Hz
4
1
I
+ ROH
R = CH3, CzHs; R1= H, CH3; RZ = CH3
III
Angew. Chem. internat. Edit. / VoI. 1 (1962) 1 No. 12
With long-chain carboxylic esters, partial migration of the
carbon-carbon double bond takes place under the given
657
reaction conditions. Thus, both y-lactones and &-lactonesare
obtained from unsaturated, a$-unsaturated esters: e.g.
methyl crotonate, gives 72 % 8-valerolactone alongside 20 %
P-methyl-y-butyrolactone, white with P,P-dimethylacrylic
esters, because of complete isomerization, only P-methyl-&valerolactone is obtained in 88.5 % yield.
20 %
0%
72 %
88.5 %
The unsaturated starting materiaIs can be substituted by
alkyl, alkylene, ethoxycarbonyl, and other functional groups.
Alicyclic unsaturated carboxylic esters, such as cyclohexenyl,
cyclopentenyl, and cycloheptenylisobutyric esters, lead to
homologues of iridomyrmecin [ I].
Surprisingly, it was also possible to convert cinnamates into
P-phenyl-y-butyrolactone in 34% yield by employing stoichiometric amounts of the catalyst, although, according to
various authors [2], these esters were not susceptible to
hydroformylation reactions, giving hydrogenation products
only.
Publication withheld until now at the express wish of the
authors.
Received, June 13th. 1962 [Z 359/191IE]
[I J F. Korfe,J. Falbe, and A. Zschocke, Tetrahedron6,201 (1 959).
[2] M . Orchin, Advances in Catalysis 5, 385 (1953); R. Hasek,
Organic Chemical Bulletin, 27 (1955) - published by theResearch
Laboratories of the Eastman Company.
These compounds were prepared from the protected potassium salts or amino acids using the dicyclohexylcarbodiimide method. The yields lay between 65 and 87 %. The
Table 1
Protected peptidester
Peptide
BA-Gly-Gly-OEt
BA-DL-Ser-GlpOEt
BA-DL-Meth-Gly-OEt
BA-L-Leu-Gly-OEt
BA-D-Val-Gly-OEt
AC-DL-Ala-Gly-OEt
CP-~~-Ala-Gly-Gly-0Et
CP-LAla-Gly-OEt
CP-oBz-~~-Ser-Gly-oEt
Gly-Gly-OH [a]
11s-I20
103-106
105-107
97-98
123-126
138-140
83-84
DL-Meth-Gly-OH [a]
~~-Ala-Gly-Gly-0H
[a]
L-Ala-Gly-OH [a, b]
OBZ-DL-S~~-GI~-OH
Abreviations used for the protecting groups: BA = Benzoylacetone;
AC = Acetylacetone; CP = Ethylcyclopentan-2-one-1-carboxylate;
Et = C2H5.
[a] = chromatographicallypure.
[bl M&'= +49.8 (c = 2.6 in water).
cyanomethyl ester method of R. Schwyzer [2] also proved to
be useful. The cyanomethyl esters were prepared by reacting
the potassium salts with chloroacetonitrile.
The protecting groups can be split off by a short treatment
with 2N hydrochloric or acetic acid. Saponification of the
protected peptide esters with aqueous or methanolic potassium hydroxide gives high yields of the potassium salts of the
corresponding peptides.
Received, August 20th, 1962
[Z 344/176IE]
[*I Dedicated to Prof. Ofto Buyer on his 60th birthday.
P-Dicarbonyl Compounds as Protecting Agents
for Amino Groups in Peptides Syntheses [l]
By Prof. Dr. Elisabeth Dane
and Dr. T. Dockner
[*I, Dr. F. Drees, Dr. P. Ksnrad
Institut fur Organische Chemie der Universitiit Munchen
(Germany)
In the presence of methanolic potassium hydroxide, amino
acids react with P-dicarbonyl compounds to give the potassium salts of the corresponding azomethines. We have
found that, among the potassium salts investigated, those
obtained with benzoylacetone, acetylacetone, and ethyl cyclopentan-2-one-l-carboxylateare sufficiently stable to be
suitable for use as protecting groups for amino groups in
peptide syntheses.
The potassium salts of the (3-dicarbonyl-amino acid derivatives can generally be recrystallized from methanol or ethanol,
if necessary with the addition of small amounts of water. The
yields range from 65 to 95 %. In some cases, the protected amino acid derivatives can also be obtained from the
corresponding potassium salts.
The azomethines obtained from the dicarbonyl compounds
can be assumed to have mainly the enamine conformation (I),
[l] German patent application submitted on April 27th, 1961.
[2] R. Schwyzer, B. Iselin, and M . Feurer, Helv. chim. Acta 38, 69
(1955).
A New Synthesis of Condensed Furan Derivatives
By Dr. J. Reisch [I]
Institut fur Pharmazie und Lebensmittelchemie der
Universitat Munster (Germany)
The preparation of condensed furan derivatives from LYalkynyl-P-dicarbonyl compounds has recently been described [2]. Furans are also accessible by the interaction of
1 -phenyl-2-propynol and cyclic P-dicarbonyl compounds (I)
in the presence of concentrated sulfuric acid or boron trifluoride in glacial acetic acid at 100 "C for 30 min. The intermediates (II) cyclize to 111.
P
I
R-CH-COtK
I
stabilized by a hydrogen bond. The infrared spectra of the
azomethines obtained from ethyl glycinate and dicarbonyl
compounds contain NH-absorption bands. The positions of
the NH- and CO-bands of the benzoylacetone and acetylacetone derivatives suggest the existence of especially strong
chelation.
In Table 1 some of the peptide esters synthesized using
P-dicarbonyl protecting groups are summarized.
658
.O
111
Angew. Chem. infernat. Edit. / Vol. I (1962) / N o . 12
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lactones, esters, hydroformylation, carboxylic, unsaturated
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