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SLater : Tutin.
18. Tutin.
By S. N. SLATER.
Tutin, C,,H,,O,, yields dihydrotutin on hydrogenation and both these substances yield monobromosubstitution products. Parallel reactions have been carried out with picrotoxinin. Tutin gives an acetyl
derivative.
THEisolation of the crystalline poison, tutin, from the leaves and seeds of the three species of Coriaria found in
New Zealand was first reported by Easterfield and Aston (J., 1901, 79, 120), who described i t as a colourless
m. p. 208-209".
It was shown after hydrolysis with dilute mineral acid t o reduce
compound, C,,H,,O,,
Fehling's solution and t o give an amorphous precipitate with phenylhydrazine. Methoxy-groups were absent.
Concentrated sulphuric acid gave a blood-red coloration with a saturated aqueous solution of tutin and treatment with slaked lime destroyed the poison.
Workers in Japan have since described the isolation of " coriarine " from Coriaria japonzca, A. Gray.
Kinoshita ( J . C h e w . SOC.
Japan, 1930, 51, 9 9 ; 1931, 52, 171) gives the molecular formula C12H1405,
m. p. 212",
and states t h a t a mixed m. p. with tutin which has been further purified shows no depression. On acetylation
with acetic anhydride and pyridine an acetyl derivative, m. p. 240", was obtained. The benzoyl derivative
melted a t 170'5". Hydrogenation with platinum in acetic acid yielded hydrotutin, m. p. 240" ; acetyl derivative, m. p. 185O; benzoyl derivative, m. p. 182-185".
Kariyone and Sat0 ( J . Pharm. SOC.
Ja p a n , 1930, 50, 659; 1930, 51, 134) give the m. p. of coriarine as 212The crystalline forms were identical. AS a
213" and t h a t of tutin from New Zealand sources as 211-212".
:i1
20
0
2400
Tutin in water.
2700
Bromopicrotoxinin
in chloroform.
( T h e E of bromoW i n is >1 at
Z~OOA.)
result of analyses the molecular formula C,,Hla06 was suggested, which is close t o t h a t of coriamyrtin, C1,H1,O,,
and picrotoxinin, C,,H,,O 6, both of which are related pharmacologically t o tutin.
Following a n improved method of extraction tutin was isolated and purified by recrystallisation from alcohol,
The
Analyses agreed with the molecular formula C,,H,,O,.
the purest specimens melting a t 209-210".
absorption spectrum revealed the absence of any strongly absorbing chromophore within the region examined.
Acetylation with acetic anhydride and pyridine gave a monoacetyl derivative, m. p. 177". Hydrogenation of
tutin in alcohol with a palladised norit catalyst proceeded smoothly and yielded dihydrotutin, m. p. 190-192".
Dihydrotutin can be brominated just as readily as tutin (see below), yielding bromohydrotutin, m. p. 257",
and this ready bromination of the dihydro-derivative has been established also in the case of picrotoxinin.
Picrotoxin was hydrogenated in alcohol with a palladised norit catalyst, and the product brominated without
further purification, yielding bromohydropicrotoxinzn, m. p. 255".
I n view of these results it seems doubtful whether the identity of coriarine and tutin has been established.
The author has been unable t o raise the m. p. of tutin t o the figures recorded by Kariyone and Sat0 and by
Kinoshita and there are marked differnces between the m. p.'s of the acetyl and the dihydro-derivatives of the
two substances.
Tutin on treatment with bromine water readily forms a monobromo-substitution product (King, unpublished
work). A closer investigation of this reaction has shown t h a t two substances are actually produced, which have
been designated U - and P-browotutin. The a-form, the main product, melts a t 256-257", and the p-form
at 237". There is thus a marked similarity between this reaction and the bromination of picrotoxinin. The
early literature on the bromination of picrotoxinin (Paterno and Oglialoro, Gazzetta, 1877, 7, 193 ; Schmidt
and Lowenhardt, Ber., 1881, 14, 817; Meyer and Bruger, Rev., 1898, 31, 2958) is confusing, but Horrmann
(Bey., 1912, 45, 2090) states t h a t the action of bromine on either picrotoxin or picrotoxinin yields a mixture of
a- and p-bromopicrotoxinin in which the p-form (needles, decomposing a t 280") predominates. The isolation
of this p-form has been confirmed.
[1943]
The Polysaccharides of Carragheen Moss (Chondrus crispus). Pavt I .
51
As with tutin, the absorption spectra of (3-bromopicrotoxininand a-bromotutin revealed the absence of any
strongly absorbing chromophore within the region examined. Of the two halogen derivatives, that from
picrotoxinin showed the stronger absorption.
EXPERIMENTAL.
Isolation of Tutin.-The dried leaves and stems of Coriaria lurida were boiled for 3 hours with water, and the aqueous
liquor concentrated in a continuous flow evaporator. After saturation with sodium chloride and filtration through
sand the extract was run in a fine stream through an upwardly moving column of ether (ca. 8 feet) in a continuous extraction apparatus designed by Mr. C. G. Martin, MSc. The ethereal extract was evaporated to dryness, and the residue
dissolved in the minimum quantity of water, neutralised with sodium bicarbonate, and extracted eight times with
ether. The dried (sodium sulphate) extracts left on distillation a crystalline product. When this was extracted with ether
(Soxhlet), practically pure tutin separated in the boiling flask, m. p. 209-210" after repeated crystallisation from alcohol
(Found : C, 61.4; H, 6.2. C1,Hl,06 requires C, 61.2; H, 6.1%). There was no colour produced with ferric chloride
and no reaction with dinitrophenylhydrazine ; alkaline permanganate was slowly decolorised and ammoniacal silver
nitrate was reduced on heating. When tutin was distilled with zinc dust, extensive charring occurred and only a small
quantity of distillate was obtained ; this appeared to be phenolic in nature.
AcetyZtutin.-Tutin
(0-5 g.), acetic anhydride (2.5 c.c.), and pyridine (1 c.c.) were heated a t 140" for 14 hours, the
product diluted with water, and the acetyl derivative recrystallised from aqueous methyl alcohol; m. p. 177" after shrinking and softening (Found : C, 60.5 ; H, 6-2. C1,H,,O, requires C, 60-7 ; H, 5.95y0).
Dihydrotutin.-Tutin
(0.5 g.) in ethyl alcohol was shaken with palladised norit in hydrogen (absorption, 41 C.C.;
theo. for 1 double bond, 38 c.c.). After filtration and removal of the solvent the product was crystallised from methyl
alcohol, yielding dihydrotutin, m. p. 190-192", together with small quantities of material of lower m. p.
Bromohydrotutin.-Dihydrotutin
(0.33 g.), dissolved in water and treated with excess of bromine water, gave a white
substance (0.32 g.), m. p. 257" (decomp.), unchanged by recrystallisation from methyl alcohol (Found : C, 48.4; H,
5.1 ; Br, 21.6. C,,Hl,06Br requires C, 48-0; H, 5.1 ; Br, 21.376). Mixed with a-bromotutin (see below), it melted at
ca. 235".
L3romohydropicrotoxinin.-Picrotoxin (0.5 g.) was shaken with palladised norit in alcohol in hydrogen and when no
further contraction took place the catalyst was filtered off and the solvent removed. The residue, dissolved in water,
gave with excess of bromine water a white precipitate which, after recrystallisation from alcohol, yielded bromohydropicrotoxinin in needles, m. p. 255" (decomp.) after softening (Found : Br, 20.9. Cl,Hl,O,Br requires Br, 21.4%).
(1.0 g.) was dissolved in boiling water, and bromine water added in excess. The
Bromination of 7'utin.-Tutin
material which separated was filtered off and dried (Found : C, 48.7 ; H, 4.8 ; Br, 21.4. CI,Hl,06Br requires C, 48.3 ;
H, 4.6; Br, 21.4%). Yield, 0.84 g.-fraction I. On standing, the aqueous mother-liquor deposited a further crop of
crystalline material (0.12 g.-fraction 11). The aqueous mother-liquor was evaporated to small bulk; small nodules
were slowly deposited (0.08 g.-fraction 111).
Fraction I : M. p. 247" (decomp.). Recrystallisation from methyl alcohol raised the m. p. t o 256" (decomp.) :
a-bromotutin (Found : Br, 2 1.7yo).
Fraction I1 : M. p. 230" (decomp.). Recrystallisation from ethyl alcohol raised the m. p. t o 237" (decomp.) :
8-bromotutin (Found : Br, 21-1yo).
Fraction 111 : M. p. ca. 230" (decomp.). Recrystallisation from ethyl alcohol raised the m. p. to 257" (decomp.).
Bromopicrotoxznzn.-Picrotoxin (0.5 g.) was dissolved in boiling water, and bromine water added. After cooling to
room temperature, the precipitate was filtered off and dried-0.29 g., m. p. wide decomposition range up to 259". After
repeated crystallisation from alcohol p-bromopicrotoxinin was obtained in fine needles, m. p. 282" (decomp.).
The expenses of this investigation have been met by a grant from the Hutton Memorial Research Fund of the Royal
Society of New Zealand. The author is indebted to Mr. C. L. Carter for microanalyses and to Mr. W. S. Metcalf for
spectrographic examinations.
UNJVERSITY
OF OTAGO,DUNEDIN,
NEW ZEALAND.
[Received, J a n u a ~ y26th, 1942.1

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The Polysaccharides of Carragheen Moss (Chondrus crispus). Pavt I .

[Received, J a n u a ~ y26th, 1942.1

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