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Cross-linked Poly-(p-lithiumstyrene) a reagent for the Preparation of Organo-lithium Compounds.

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Effect of Ultraviolet Light on the Biosynthesis of
Polyphenylalanine
By Prof. Dr. A. Wacker, Priv.-Doz. Dr. D. Jacherts,
and Dr. Blanda Jacherts
lnstitut fur Therapeutische Biochemie
der Universitat Frankfurt/Main (Germany)
The preferential dimerisation of adjacent uracil molecules in
a polynucleotide chain on irradiation with ultraviolet light
[ l ] may serve as the basis of a sequence analysis of code
triplets necessary for protein synthesis [2], insofar as these
contain two uracil molecules. With this method we can also
test whether the code of the messenger ribonucleic acid
(m-RNA) is complementary to that of the deoxyribonucleic
acid and the transfer ribonucleic acid (transfer-RNA).
Uracil should have adenine, which is resistant to ultraviolet
radiation, as its complementary base.To test thisweinvestigated the sensitivity of incorporation of phenylalanine, which is
dependent on the code triplet uracil-uracil-uracil [3] (Tablel).
Table 1. Dependence of incorporation of phenylalanine-[3-14Cl on
ultraviolet irradiation of different fractions of the biosynthetic system
131. DL-Phenylalanine-[3-'4C]. specific activity 1 mC/mmole. UV-dose =
3.5X lo4 erg/mmZ. A polynucleotidephosphorylase from HeLa-cells was
used for polymerizing the uridine-diphosphate
Experimental system
Phenylalanine-[3-14Cl
incorporated after
20 min. [countshin.]
I.
2.
3.
4.
5.
6728
I847
2393
7664
3021
Complete system
System without polyuridylic acid
System -k polyuridylic acid, UV-irradiated
System
100-S-fraction, UV-irradiated
System ribosomes, UV-irradiated
+
+
Cross-linked poly-(p-lithiumstyrene) also corresponds to
phenyl-lithium in reactivity. It can serve as a starting material
for the synthesis of ion-exchange resins containing special
functional groups [3], or it may be used in place of butyllithium for metallation and halogen-lithium exchange reactions. Benzene is a suitable solvent; ether or tetrahydrofuran
are better. Cross-linked poly-(p-lithiumstyrene) does not
react in aliphatic hydrocarbons.
With the new reagent one can, for example, convert fluorene
into fluorene-9-carboxylic acid, phenylacetylene, p-bromophenylacetylene and p-vinylphenylacetylene into the corresponding phenylpropiolic acids, and diphenylene oxide
into diphenylene oxide-4-carboxylic acid. Halogen-lithium
exchange reactions may be illustrated by e . g . the conversion
of 1-iodonaphthalene into 1-naphthoic acid and of p-iododiphenyl ether into p-phenoxybenzoic acid.
The preparative value of cross-linked poly-(p-lithiumstyrene)
lies in its insolubility, which simplifies the separation of
reaction products from excess reagent.
Received, July 30th, 1962
[Z 319/151 IEI
[ I ] D. Braun, Makromolekulare Chem. 30, 85 (1959).
[Z] Cf. D. Braun, Angew. Chem. 73, 197 (1961).
As may be seen from Table 1 , the m-RNA [4] and the
ribosomes are inactive after irradiation, whereas the transferRNA is resistant to ultraviolet light. Hence, it may be concluded that the adjacent uracil molecules in the code triplet
of the m-RNA are altered (dimerised) photochemically. The
hypothesis of the complementary code adenine-adenineadenine in the transfer-RNA appears to be valid, since the
transfer-RNA, as expected, is resistant to ultraviolet irradiation.
Received, July 16th, 1962
iodostyrene, styrene and divinylbenzene in the molar ratio
1 : 1 :0.02 (the polymerisation is initiated with benzoyl
peroxide). The resultant polymers can be converted almost
quantitatively into cross-linked poly-(p-lithiumstyrene) by
stirring for several hours, at room temperature, with a
benzene solution of butyl-lithium (in 3- to 4-fold molar
excess). Addition of ether facilitates filtration of the polymer
which is somawhat swollen in benzene. By repeated washing
and filtration in a nitrogen atmosphere it can be obtained
pure and free from soluble organo-lithium compounds of
low molecular weight.
[ Z 314/149 IEI
[ I ] A . Wacker, H . Dellweg, and E. Lodemann, Angew. Chem. 73,
64 (1961); A . Wacker, L. Trager, and D . Weinblum, ibid. 73, 65
(1961); A . Wacker, D . Weinblum,L . Trager, and Z . H . Moustafa,
.
I
molec.
.
Biology 3, 790 (1961).
[2] M. W . Nirenberg and J. H . Matthaei, Proc. nat. Acad. Sci.
U.S.A. 47, 1588 (1961); P . Lengyel, J. F. Speyer, and S . Ochoa,
ibid. 47, 1936 (1961).
[31 M. W . Nirenberg and J. H . Matthaei, Proc. nat. Acad. Sci.
U.S.A. 47, 1588 (1961).
[4] L . Grbssmann (personal communication) independently also
found inhibition of polyphenylalanine synthesis after ultraviolet
irradiation:of polyuridylic acid.
[3] D. Braun, Lecture at the Symposium on Anomalous Reactions on Exchange Adsorbents, Weimar (Germany)April 1961.
P-Amindethylationof Malonic Esters with Aziridines
By Dr. H. Stamm
Institut fur Pharmazeutische Chemie und Lebensmittelchemie
der Universitat Marburg (Germany)
In contrast to the numerous aminoethylations with aziridines
on hetero-atoms, only a few examples of aminoethylations on
carbon are known [1,2].
By heating l-phenethylaziridine (I, R' = C S H ~ - C ~ H ~and
-)
LiOCZH5 with a large excess of diethyl malonate (11, R=H)
to 100-130 OC, I-phenethyl-3-ethoxycarbonyl-2-pyrrolidone
TN7
I,
R
+
'
COrCzH5
R-C-H
R
LIOCZH~
3
COrC2H5
1\N/\\oI-
COzC2Hs
I
Cross-linked Poly-(plithiumstyrene), a Reagent
for the Preparation of Organo-lithium Compounds
By Dr. D. Braun and Dip1.-Ing. E. Seelig
R
IIIa H
IIIb CHn
IIIc H
Deutsches Kunststoff-Institut Darmstadt (Germany)
Treatment of linear poJy-(p-iodostyrene) with butyl-lithium
yields poly-(p-lithiumstyrene) [l], a polymeric organometallic
compound whose reactivity is similar to that of phenyllithium [2].
Cross-linked homopolymers and copolymers based on p iodostyrene can be obtained by pearl polymerisxtion of p Angew. Chem. internnt. Edit.
Vol. I (1962) I No. 9
(Iila) is formed, infrared bands at 1689-1691 cm-1 (lactamcarbonyl, weakly split) and at 1735 cm-1 (ester-carbonyl),
yield: 20-25 %. Likewise, but with lower yield, 111b can be
obtained from diethyl methylmalonate (11, R-CHd, and
1-phenyl-3-ethoxycarbonyl-2-pyrrolidone
(IIIc) from diethyl
malonate and l-phenyl-aziridine. Compound I l k crystallised
after about 3 months, m.p. 57.5 "C. The carbonyl bands of
509
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