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Course of the Microbial Conversion of Cobalamine Analogues into Vitamin B12.

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significant a s passive Q-switches i n t h e production o f giant
laser pulses [S].
x-Aminoalkylation of White Phosphorus 111
[ Z 970/796 1EI
Received: April 20th, 1965
German version: Angew. Chem. 77, 546 (1965)
By Dr. Ludwig Maier
Monsanto Research SA., Zurich (Switre;land)
[ I ] We thank Dr. C. Jutz for providing the dye.
[2] F. Baumgartner, E. Gunrher, and G. Scheibe, 2. Elektrochem.,
Ber. Bunsenges. physikal. Chem. 60, 570 (1956).
[3] J. Heiss, Ph.D. Thesis, Technische Hochschule Munchen,
1964.
[4] Cf. C. Scheibe. J . Heiss, and K . Feldmann, Angew. Chem. 77,
545 (1965); Angew. Chem. internat. Edit. 4 , 525 (1965).
[S] See, e. g. , F. P . Scliafer and W. Schmidt, Z . Naturforsch. 190,
1019 (1964).
In continuation of studies o n the direct synthesis of organophosphorus c o m p o u n d s from elemental phosphorus [2] we
have found t h a t the reaction of white phosphorus with N hydroxymethyldialkylamines provides a simple method of
preparing tertiary phosphine oxides. Phosphonic and phosphinic acids and s o m e t i x e s even the tertiary phosphine are
formed $: by-products.
2 P4 t- 19 R2NCH2OH
RzNCHzPO(0H)z
Course of the Microbial Conversion of Cobalamine
~
Analogues into Vitamin B I [l]
By Dr. P. Renz
Lehrstuhl fur Biochemie und Biotechnologie
de; Technischen Hochschule Stuttgart (Germany)
Dcdicoted tu Prof. K . Bernhauer
on the occasion of'his 65th birthdnjr
+ 3 ( R z N C H Z ) ~ P O ( O H+)(R2NCH2)3P i 3 ( R z N C H ~ ) ~ P =fO7 HzO
T h e yields of tertiary phosphine oxide depend upon the
ratios of t h e reagents a n d upon t h e solvent ilsed. T h e highest
yield is obtained with a molar ratio phosphorus: N-hydroxymethyldialkylamine of 2:s a n d with 50
aqueous alcohol
a s solvent at 80 "C for 1-8 h ; t h e phosphine oxide is isolated
byextrzction with benzfne or ether and recrystallization from
hexane or petroleum ether.
x,
Cobamides containing various benzimidazole or purine
bases, e.g. (2) or (3), a r e converted i n t o vitamin 8 1 2 ( I ) by
Prupiuiiibacterirtm shermanii in t h e presence of 5,6-dimethylbenzimidazole 121.
Yield
[%I
Go ( ~ ) C N
I
L
O='-O(b@-(a)
HOH,C
I
lCo1
( I ) , B = 5,6-Dimethylbenzimidazole
I Z ) , B = Adenine
( 3 ) , B = Benzirnidazole
[Co]= Cobinarnide moiety
T h e bond (c) must remain intact during this process, for
when [3IP]-adenylcobamide (2) [3] is transformed i n t o ( I )
by P . shermanii [2], 93.5
of t h e radioactivity recurs in ( I ) .
In order t o differentiate between t h e t w o remaining possible
positions of cleavage, viz. bonds (a) a n d (b), we synthesized
[~4C]-benzimidazolylcobamide
(3) from cobinamide, benzimidazole, a n d [U-14c]-D-g~UCOSeusing P . shermnnii. It was
shown by degradation with cerium hydroxide [ S ] t h a t all t h e
radioactivity I4264 counts/rnin/mg] was present in t h e
ribosyl residue.
-(CH2)4-(CH2)5-CH2CH2OCH2CH2-
151-153
119-120
160- 161.3
44.6
18.2 [cl
3.2
35.0
31.2
20.3
-43.2
- S l . O :-0.5
-50.6
[a] Based on the amount of white phosphorus used.
Ibl Based o n 85 % H3PO4 as internal standard.
Ic] In addition, 5.1 % [(C~HJ)ZNCHZ],P,
b . p . 1 lo--! 15 "C/1.2 mm.
was also isolated.
[Z 972/798 l E ]
Received: May 7th, 1965
German version: Angew. Chem. 77, 549 (1965)
. .~
.
[ I ] Organophosphorus Compounds, Part 19.-Part IS: L . Maier.
Helv. chim. Acta, in the press.
[2] L. Maier, Angew. Chem. 71, 574 (1959); Helv. chim. Acta 46.
2026 ( 1963).
A New Synthesis of y-Pyrones
T h e vitamin B12 ( 1 ) formed from t h e 14C-labelled (3) was
not radioactive [2]. It must therefore be t h e b o n d (b) that is
split during this transformation. T h e complete nucleoside is
apparently replaced by preformed or-ribazole.
By Dip].-Chem. H. Schiefer a n d Prof. Dr. G. Henseke
This conclusion is supported by t h e observation that 2ribazole can be detected in cultures [6] of P . shermcinii a n d
r-ribazole-5-phosphate in extracts [7] from t h e s a m e microorganism.
When phenylethynyl ketones ( I ) a r e acylated u i t h carboxylic
esters in t h e presence of strongly basic condensing reagents,
e.g. sodium or sodium ethoxide, sodio derivatives o f pdiketones a r e obtained which on protonation mostly cyclize
immediately t o y-pyrone derivatives (2n-g).
Received: April 20th. 1965
[Z 977/803 IE]
German version: Angew. Chem. 77, 547 (1965)
Publication deferred until now at the author's request
Institut fur Organische Chemie
der Bergakademie Freiberg (Germany)
C6H5-CsC -CO-CH,-R'
[ I ] Biosyntheses in the Cobalamine Series, Part 7.-Part 6:
K. Bernhauer, E. Becher, G. Gross, and G. Wilharm, Biochem.
Z . 332, 562 (1960).
[2] K . Bernhauer, E. Becher, and G. Wilharm, Arch. Biochern.
Biophysics 83, 248 (1959).
[3] Prepared from [32P]-cobinamide phosphate [4].
[4] F. Wagner, Biochem. Z . 336, 99 (1962); F. Wagner and
D. G/atzle, ibid., in the press.
151 W . Friedrich and K. Bernhauer, Chem. Ber. 89, 2507 (1956).
161 H . C. Friedmann and D . L . Harris, Biochem. biophys. Res.
Comrnun. 8, 164 (1962).
[7] H . C. Friedmann and D. L . Harris, J. biol. Chemistry 240,406
(1965).
Angew. Chem. internat. Edit.
/
Vol. 4 (1965) / No. 6
iR2-COOC2H5
(la), R' = H
( l b ) , R' = CH,
527
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course, vitamins, b12, microbial, cobalamin, conversion, analogues
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