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Detergent Action of Hydroxylated Fatty Esters of Sucrose.

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Using a n opitical method according to Briegleb [3], we were
able to prove the existence of a 1:l-complex KO2- in
aqueous solution. The stability constant of this weak complex
can be estimated to be K'," = 1.0 I/mole. From solubility
data [4] we calculated K2C5 " = 0.8 I/mole.
The results show [51 that the yellow adducts are charge
transfer complexes of the Mulliken type [6], in which the
iodide ions act as donors and the SOz- molecules as acceptors.
Infrared spectroscopic measurements in acetonitrile led to
the same result [2]. It was possible to calculate the complete
term diagram of the complex [5,7]: WN = AH = -1.68,
W,J = -0.12, W1 = 77.68, WE = 82.16 kcal/mole. Although
we failed to obtain any indication of a n addition compound
in the course of tensimetric analysis of a solution o f iodine
in liquid SO2 at -61.5 "C [S], low-temperature spectra of
this solution (yrZ= 7 . 7 10-5)
~
did show a definite shift of the
iodine bands towards the blue; this shift increases with
decreasing temperature. The maximum value for the iodine
band is 493.5 m p at -14.7"C, 490 m p at -41.8"C, and
482.5 m p at -73.5 "C. The bathochromic shift of the iodine
band is taken as definite evidence for the formation of a
charge transfer complex according to the equation :
x
12
+ Y so2 + mx. (SOZ),.
The stoichiometric relationships of the complex are still
unknown; its stability is low. Its enthalpy of formation at
--15 'C is estimated [ 5 ] at AH = -2 kcal/mole and therefore
corresponds to the stability of iodine/aromatic complexes. In
this complex, the iodine molecule acts as donor, the SO2
molecule as acceptor. There are some other instances of this
unusual donor function of the iodine molecule, viz. the
autocomplex of iodine I4 [9] and the complex cation I3+ [lo].
[S] See also G . Jander and H . Mesech, Z. physik. Chem. I83A,
121 (1939).
[9] G . Kortiim and H. Koffer, 2. Elektrochem., Ber. Bunsenges.
physik. Chem. 67, 67 (1963).
[lo] J. Arotsky, H. C. Mischra, and M. C. R. Symons, J. chern.
SOC.(London) 1962,2582.
Detergent Action of Hydroxylated Fatty Esters of
Sucrose
By Dr. H. Simonis and Dr. R. M. lsmail
Forschungslaboratorium der Firma H. J. Zimmer,
Frankfurt/Main (Germany)
Fatty esters of sucrose containing one or more hydroxyl
groups in the fatty acid residue are characterized not only by
outstanding detergent action but are also completely degraded
by bacteria [I]. The monohydroxy-, dihydroxy-, and tribydroxystearic esters of sucrose, whose even-numbered fatty
acid residues contain 14- 22 carbon atoms, were prepared by
hydroxylation of patty esters and catalysed transesterification
with sucrose [2,3] in a polar solvent. The resulting mixtures
contained about 75 "/, mono- and about 25 % diester. The
compounds given in Table 1, for example, were prepared.
Table I . Properties of hydroxylated fatty esters of sucrose.
Fatty acid
Received, July 16th, 1963
[Z 544/370 IEI
German version: Angew. Chem. 75, 792 (1963).
[I] Part 111 of the series on Sulfur-Iodine Compounds; Part 11:
J. Jander and G.Tiirk, Chem. Ber. 95, 2314 (1962).
[la] Gmelins Handhuch der anorganischen Chemie. 8th Edit.,
Verlag Chemie, Berlin 1933, Vol. Iodine, p. 401.
[2] See also E. R. Lippincott and F. Eugene, Spectrochim. Acta
(London) 17, 123 (1961).
[3] G. Briegleb: Elektronen-Donator-Acceplor-Komplexe. Molekule und Koordinationsverhindungen in Einzeldarstellungen,
Springer-Verlag, Berlin 1961, p. 199ff.
[4] C. J. J. Fox, Z. physik. Chem. 41, 458 (1902).
[ 5 ] G.Turk, Ph. D. Thesis, Universitiit Freihurg/Breisgau, 1963.
[6] R. S. MuNiken, J. physic. Chem. 56, 801 (1952).
[7] For an explanation o f the individual energy values, see [3,]
p. 3.
12-Hydroxystearic
9,lO-Dihydroxystearic
9,10,12-Trihydroxystearic
Ricinoleic
58.5-61.5
49.0-51.x
55.0-58.s
56.0-60.5
33.3
31.4
33.5
36.5
0.40
0.40
1 .o
0.50
[ I ] Studies under the direction of Prof. KoZbeZ, Berlin, and ProT.
Srhlegel, Cottingen, for which we again express thanks.
[2] L. Osipow, F. dee SneN. D . Marra, and W. C. York, Ind.
Engng. Chem. 48, 1459 (1956).
[3] G. R. Ames, Chem. Reviews 60, 541 (1960).
C O N F E R E N C E REPORTS
~-
~
~
Meeting of Northwest-German Chemistry Lecturers
Braunschweig (Germany), May 18th and 19th, 1963
From t h e proceedings:
A Naturally Occurring Epoxide with Diyne and Enol
Ether Functions
C. Arudt, Berlin (Germany)
In addition to several other spiroketals containing enol ether
and poly-yne functions which were isolated in previous investigations on material from Chrysanthemum leucanthemum
L., a minute amount of a compound was obtained whose
structure was not determined.
The molecular formula was found to be C15H1205. Besides
the enol ether bands, only an acetyl residue can he recognized
as a functional group from its infrared spectrum. Since this
substance has one oxygen atom more than previous comAnxew. Chem. internat. Edit.
I Vol. 2 (1963) I No. 9
pounds in this series, this oxygen must be in an ether bond.
On ozonisation, as expected, 3,5-heptadiynoic acid was
produced. Very mild saponification yielded an alcohol. Reaction with sodium methoxide gave a diol with an ether
grouping. Since epoxides in the allylic position are split by
sodium methoxide, structure ( I ) would be a possibility for
the epoxide.
€13c:--c;c
-(.'-C-CII
q
OAc
Nuclear magnetic resonance spectra o f the natural material
and of its reaction products are i n complete agreement with
this formulation.
549
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