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Biosynthesis of Lupinine.

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We therefore subjected the open analogue, triphenylmethane
(III), to the action of potassium in ether and in dioxan and
to our surprise, established cleavage here, too, whereas sodium was again without effect. The potassium compounds
were treated with carbon dioxide on this occasion, and in this
way up to 50 % of diphenylacetic acid (V) was obtained alongside triphenylacetic acid (IV). It is presumed that a cleavage
caused by the potassium metal takes place first. On account
of its great reactivity, the phenylpotassium formed in this way
will immediately metallate compound 111, so that the foilowing reaction sequence is probable:
</
GHsK
+,7
(CsWsCH
111
of I1 consumed 2 moles of periodate with liberation of 1 mole
of formic acid. Thus, a sugar containing nitrogen instead of
oxygen in the semi-acetal ring has been prepared for the first
time.
Received, September 17th, 1962
[Z 346/178
IE]
[l] H. Paulsen, Angew. Chem. internat. Edit. I, 454 (1962).
Biosynthesis of Lupinine El]
co2
+ (GHshCHK -+
(GH5)zCH-COOH
By Ing. M. SouEek and Doz. Dr. H. R. Schiitte
V
4- (GHs)aCK
co
--%
(GHs)~C-COOH
IV
In any case, benzoic acid could not be found among the reaction products.
Diphenylmethane is cleaved more slowly and only to a small
extent (about 1 %): the carbonated product very probably
contains phenylmalonic acid, because the resulting mixture
of acids is odorless at first and acquires the characteristic
strong odor of phenylacetic acid only after long standing. It
will not be discussed here how the phenylmalonic acid is
formed, but in this connection it may be pointed out that
phenylmalonic acid is also formed in the reaction of benzylsodium with carbon dioxide [2] Tetraphenylmethane is also
cleaved by potassium - actually more rapidly and more fully
than 111, but the mixture of acids obtained after carbonation
has a more complicated composition. However up to 5 % of
IV and 13 % of V were obtained from it.
Received, September 17tb, 1962 [Z 347/179 IEI
Deutsche Akademie der Wissenschaften zu Berlin
Institut fur Biochemie der Pflanzen, Halle/Saale (Germany)
and Institute for Physical Chemistry of the Czechoslovakian
Academy of Sciences, Prague (Czechoslovakia)
According to our earlier studies, lupinhe can arise from
cadaverine or lysine in Lupinus Iuteus [2]. On administering
cadaverine-(l,5-14C), to the plants the CHzOH-group of this
alkaloid contained about one-quarter of the specific radioactivity of the whole alkaloid, which would agree with the
theory of formation from 2 molecules of cadaverine or lysine
[the small crosses in the Iupinine formula correspond to the
assumed distribution of activity after application of cadaverine-(1,5-14C)].
To verify this theory, lupinine obtained after administration
of cadaverine-(1,5-'4C) was subjected to exhaustive methylation and a Hofmann degradation; the mixture of bases from
the degradation was ozonized and the formaldehyde produced extracted as its dimedone derivative. This formaldehyde
corresponds to the C-2 and C-10 of lupinine and should also
contain a quarter of the specific radioactivity of the lupinine.
[l] W. Theilacker and U.Berger-Brose, unpublished work.
[2] H. Gilman, H. A . Pacevitz, and 0 . Baine, J. Amer. chem. SOC.
62, 1516 (1940).
Preparation of 5-Acetamido-5-deoxyD-xylopiperidinose
By Dr. H. Paulsen
Institut fur Organische Chemie,
Chemisches Staatsinstitut, Universitat Hamburg (Germany)
Lupinine
Lupininemethiodide (371 mg) was converted into the base
5,6-Diacetamidohexoses exist preferentially in the furanose
with 10 ml of Dowex 1 (OH-) and after evaporation, pyroform. On treatment with acid, 5,6-diaminohexoses, are translyzed at 10 mm Hg and with a bath temperature of 200°C,
with elimiformed into 2-aminomethyl-5-hydroxypyridine,
whereby 163 mg of degradation base distilled over and were
nation of water [l]. Partiai hydrolysis of 5-acetamido-5-dethen ozonized in 5 ml of acetic acid. The resulting solution
oxy-l,2-O-cyclohexylidene-~-xylofuranose
(I) leads to a mixwas diluted with 50 ml of water and distilled into aqueous
ture of crystalline 5-acetamido-5-deoxy-~-xylopiperidinose dimedone solution, producing 36 mg of formaldimedone. The
(11; m.p. 154 "C, [a]g = -19.5 ") and a syrup of 5-acetamidolatter was recrystallized to constant radioactivity, just as the
5-deoxy-~-xylofuranose(111; [a15 = +32.5 ") in a ratio of 2:l.
lupininemethoidide had been. The specific radioactivities of
Compounds I1 and 111 are isolable, are stable in neutral sohthe lupininemethiodide and the formaldimedone are sumtion, and do not isomerize into one another. In acid solution,
marized in Table 1.
the equilibrium I1 + 111 is established starting from either
Table 1. Specific radioactivities
pure I1 or 111, the process being slow at room temperature but
very fast at 70 "C.
OH
I\
><p
'0
-0
,
-OH
d
HCI
HO-
0
HO-
ip-/
I
-OH
W
I
Compound
/OH
,
I
Lupininemethiodide
Formaldimedone
HO-
NAc H8
I
--OH
!
0
I
NHAc
I
I1
The bands of the -NH- group present in the infrared spectrum of 111are absent in that of 11. Four acetylatable hydroxyl groups were detected in the piperidinose 11; three were
found in the furanose 111. A benzylpiperidinoside derivative
Angew. Chem. internal. Edit. I Vol. 1 (1962) I No. I1
1 Spec. Activity
1.121.106 counts/min/rnMol
0.289.106 counts/min/mMol
I Obs.
1
100 %
25.4 %
I Theor.
1
100 %
25 %
The fact that the C-2 and C-10 each contain a quarter of the
radioactivity of the lupinine molecule confirms the theory
that in L. Luteus, lupinine can arise from two molecules of
cadaverine 121.
Received, September 17th, 1962 [Z 351/180 IE]
[l] Part 8 of the series ,,Zur Biosynthese der Lupinenalkaloide"
(The biosynthesis of lupin alkaloids); Part 7: H. 17.Schurre and
Ch. Schafer, Naturwissenschaften48, 669 (1961).
[2] H. R. Schutte, Arch. Pharmaz. 293, 1006 (1960).
597
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