W. L.

Brown

ANNUUM)
PERFECTION PIMIENTO (CAPSICUM
THE RED PIGMENT IN THE
CHEMISTRY OF PEPPER PIGMENTS:
A CONTRIBUTION TO THE
ARTICLE:
1935, 110:91-94. J. Biol. Chem.

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A CONTRIBUTION TO THE CHEMISTRY OF PEPPER
PIGMENTS*
THE RED PIGMENT IN THE PERFECTION PIMIENTO
(CAP~ICUM ANNTJ~M)
BY W. L. BROWN
(From the Department of Chemistry, Georgia Agricultural Experiment
Station, Experiment)
(Received for publication, March 20, 1935)
Zechmeister and von Cholnoky (1) were the first to show that
the red pigment of the capsicum fruits was not a hydrocarbon.
Their analyses indicated the formula C34H4803, which they called
capsanthin. Later work (2) caused them to revise the formula to
C&I~oO~. Finally (3), by chromatographing the synthetic esters
of capsanthin on CaCO+ they were able to isolate a purer prepara-
tion which, on analysis, indicated a formula of GoH6803, thus
placing capsanthin in the Go series of polyene pigments. They
(4) worked on Japanese chillies (Cap&cum frutescens jczponicum)
also, and isolated a red pigment which corresponded with the
capsanthin isolated from Hungarian paprika.
While both the Perfection pimiento and the pepper used for the
production of paprika in Hungary are generally considered to be
varieties of Capsicum annuum, the pimiento fruit is quite different
from that of the paprika. The pimiento fruit is ox heart and coni-
cal in shape, is about 9 cm. long, 8 cm. in maximum diameter, and
the shell is 4 to 8 mm. thick. There is no pungency in any part of
this variety, as even the placenta and seed are free of capsaicin.
So far as is known, the work of Zechmeister and von Cholnoky
on capsanthin has not been confirmed by other investigators. The
Perfection pimiento is a different type of pepper from that used in
their studies. For these reasons, and because of the importance of
* Published with the approval of the Director as paper No. 40, Journal
Series.
91

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92 Pepper Pigments
the pimiento canning industry in the United States, it was thought
advisable to isolate and examine the red pigment of the pimiento.
EXPERIMENTAL
Isolation of Pigment-The cores were removed from the pimi-
entos, the shells were ground coarsely, washed, and pressed to
remove part of the sugar which causes difficulty in drying.
The
press-cake was dried at 35 and ground.
A capsanthin content of
1.5 to 3.0 gm. per kilo has been found in various dried pimiento
products, depending upon the ripeness and method of preparation
and the length of the storage period.
Washing and pressing before
drying give a preparation of lower capsanthin content, but one
which dries more readily and is not hygroscopic.
The dried and
ground product was stored at a temperature of 4 in bottles filled
with nitrogen.
In general, the more recent procedure given by Zechmeister and
von Cholnoky (4) was used for the extraction, hydrolysis, and
separation of capsanthin.
All solvents used for recrystallization
were redistilled in a current of nitrogen.
Concentrations were
carried out in vacua in apparatus having ground-in connections.
Preparations were kept in a desiccator by evacuating and allowing
nitrogen to ilow in, this being repeat.ed to insure removal of oxygen.
The desiccators were stored at 4 in the dark. Nitrogen was pre-
ferred to CO2 because of the greater ease with which it may be
freed of oxygen.
Purification for Analysis-All crude preparations were recrys-
tallized twice from CSZ, filtered at the pump, and washed with ice-
cold ether while on the filter to remove tarry matter. Prepara-
tions I and II were recrystallized from hot methanol and yielded
fine brick-red crystals which melted at 173-174 (corrected).
After washing with ice-cold ether, a preparation was partly dis-
solved in hot methanol and filtered, the filtrate yielding on crystal-
lization Preparation III, which had the same appearance and
melting point as Preparations I and II. The undissolved residue
obtained in preparing the solution for crystallizing Preparation III
was dissolved in methanol, filtered, and allowed to crystallize.
The beautiful lustrous blue-black crystals which separated on
cooling were 1 to 2 mm. long and were clusters of thick, arched
rods. This preparation (No. IV) had a melting point of 174-175

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W. L. Brown 93
(corrected) and amounted to about 25 mg. The preparations were
dried in vctcuo over PzO6 and paraffin shavings at 70 in an Abder-
halden drying pistol before melting points were determined and
analyses carried out.
Crystal forms corresponded to those found by Zechmeister and
von Cholnoky. Precipitating from ether with petroleum ether
gave bent needles. Recrystallizing from CS, gave crystals of a
fir twig pattern.
The crystals of Preparation IV were weighed out for analysis
without being ground, which probably accounts for the variation
in the analyses of this preparaGon.
Preparation Z-Found. C 79.99, H 9.91.
Preparation ZZ-Found. C 79.89, H 9.90.
Preparation III-Found. C 80.01, H 10.26.
Preparation IV
3.608 mg. substance: 10.760 mg. CO, and 3.141 mg. Hz0
3.901 : 11.674 3.486
C10H5803. Calculated. C 81.84, H 9.97
Found. 81.33, 81.61, 9.74, 9.99
Preparation IV is probably as pure a preparation of capsanthin
as can be obtained in this manner. According to Zechmeister and
von Cholnoky (3), the carbon content was 0.5 per cent too low in a
preparation with only a trifling heterogeneity. They were able
to improve this only by preparing the dicaprate, chromatographing
its benzine solution, eluting the capsanthin dicaprate zone with
benzine containing a little alcohol, hydrolyzing the dicaprate, and
recovering the purified capsanthin.
Solubility-At room temperature the purified pigment was
fairly soluble in CHC&, ethanol, and methanol, less soluble in ether
and benzene, difficultly soluble in CS2, and almost insoluble in
petroleum ether. It is much more soluble in the hot solvents.
Absorption Spectrum-A solution of 5 mg. of the pigment per
liter of CSS in a 10 mm. cell exhibited absorption bands at 550 to
532 and 513 to 493 rnp.
SUMMARY
The characteristic red coloring matter of the Perfection pimiento
has been isolated and examined. The red pigment from the pimi-
ento was found to be identical with capsanthin isolated from Hun-
garian paprika.

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94
Pepper Pigments
BIBLIOGRAPHY
1. Zechmeister, L., and von Cholnoky, L., Ann. Chem., 464, 54 (1927).
2. Zechmeister, L., and von Cholnoky, L., Ann. Chem., 487, 197 (1931).
3. Zechmeister, L., and von Cholnoky, L., Ann. Chem., 609, 269 (1934).
4. Zechmeister, L., and von Cholnoky, L., Ann. Chem., 469, 1 (1931).

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