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Synthesis of N N N-Trisubstituted Amidines Quaternary Amidinium Salts and Aminal Esters.

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assuming that the relationship may be linearly extrapolated,
the radius of the proton in (11) is almost zero. The correlation
between the location of the absorption band and the ionic
radius of the central ion points to a steric effect. We assume
that the molecule is spread in the plane so that the valency
angle at the meso C-atom becomes larger than normal.
An analogous situation exists in the case of aza-compounds,
in which the meso-methine group is substituted by a trigonal
The t-butyl group was introduced as a new protecting group
for phosphoric acid in nucleotides. t-Butyl nucleotides are
obtainable by the trichloroacetonitrile method [3], e.g. the
t-butyl esters of 5'-AMP (60% yield) and of 3'4hymidylic
acid (75 %). The protecting group can be removed with 20 %
acetic acid in 45 min at 60 "C.
Nucleotides protected by other means were obtained in 60%
yields by the reaction of 3'-adenylic acid or 3'-uridylic acid
with diphenyldiazomethane:
c s@
0.9 5
19 600
I 8 900
17 500
3'-AMP i- (QHs)~CNZ +
Received, March 14th. 1962
' d H
O = L Q
Received, March 27 th. 1962
[Z 265/91 1El
[I] 3rd. Communication.- 2nd. Communication: G. Scheibe et
al., Angew. Chem. 73, 273 (1961).
121 G. Scheibe and W. Riess, Chern. Ber. 92, 2189 (1959).
[3] G. Scheibe and H . J. Friedrich, Z . Elektrochem. 64, 720
(1960); 65, 851 (1961).
[Z 270/102 IE]
[*I From a paper delivered to the Basler Chemische Gesellschaft
(Bask Chemical Society) on Dec. 21 st. 1962.
[II'R. B. Woodward and R . A . Olofson, J. Amer. chem. SOC.83,
1010 (1961).
1.21 F. Cramer, H. Schaller, and H . A . Staab, Chem. Ber. 94, 1612
[3] F. Cramer and G. Weimann, Chern. Ber. 94, 996 (1961).
[4] G. Scheibe, Angew. Chem. 73, 383 (1961).
New Syntheses of 2,4-Disubstituted s-Triazines
New Phosphorylation Reactions and Protecting
Groups for Nucleotides
By Prof. Dr. F. Cramer, Dipl.-Chem. H. NeunhoeKer,
Dipl.-Chem. K. H. Scheit, cand. ing. G. Schneider,
and cand. ing. J. Tennigkeit [*]
Institut fur Organische Chemie
der Technischen Hochschule Darmstadt (Germany)
N-Methyl-5-phenylisoxazoliummethyl sulphate (I) [l] in the
presence of a base yields compound (11), which combines with
phosphoric acid to form (HI), an excellent phosphorylating
agent of the enol-phosphate type.
The following compounds were prepared: methyl phenyl
phosphate (89 % yield),ethyl phenyl phosphate (70%), isopropyl phenyl phosphate (73 %), benzyl phenyl phosphate(8 1 %).
The reaction can also be applied to the synthesis of nucleotide esters and hence to oligonucleotide synthesis.
Nucleotide imidazolides [2] are starting materials for the
synthesis of nucleotide derivatives. AMP imidazolide (IV,
R = adenine) reacts with orthophosphate to give ADP
(95 %) and with flavin mononucleotide to give flavin adenine
dinucleotide, FAD (67 %). UMP imidazolide (IV, R = uracil)
with glucose-1-phosphate yields the coenzyme uridine diphosphoglucose UDPG (677;). IMP irnidazolide leads to the
corresponding thymidine diphosphoglucose (70 %I.
By Prof. Dr. H. Bredereck, Dr. F. Effenberger, and
Dip1.-Chem. A. E. Hofmann
Institut fur Organische Chemie und Organisch-Chemische
Technologie, Technische Hochschule, Stuttgart (Germany)
With the syntheses of s-triazine and N-substituted s-triazines
[I], we have also described the preparation of 2,4-diamino-striazine from guanidine carbonate and formamide. We have
now succeeded in obtaining, in good yields, numerous 2,4-disubstituted triazines by reacting urea, guanidine, substituted
guanidines, benzamidine, and S-methylisothiourea with formylating agents (trisformaminomethane, orthoformic ester,
dimethylformamide diethylacetal).
Heating urea with trisformaminomethane or orthoformic
ester led to 2,4-dihydroxy-s-triazine,
which until now has been
very difficult to prepare 121. Guanidine formed 2,4-diaminos-triazine with dimethylforrnamide diethylacetal; likewise,
butylguanidine gave 2,4-bisbutylamino-s-triazine,phenylguanidine gave 2,4-dianilino-s-triazine, and p-tolylguanidine
formed 2,4-di-p-toluidino-s-triazine.
The reaction of benzamidine with ethyl formate or dimethylformamide diethylacetal yielded 2,4-diphenyl-s-triazine.
Finally, 2-methylmercapto-4-amino-s-triazine,
a compound
which we have previously reported, was obtained by heating
S-methylisothiourea with dimethylformamide diethylacetal.
Received, April 2nd. 1962
[Z 260/95 IE]
[I] H . Bredereck, 0. Smerr, and R . Gompper, Chern. Ber. 94,
1883 (1961).
[2] I. Flumen!, R. Promel, and R . H . Martin, Helv. chim. Acta
42, 487 (1959); H . Biltz and E. Gieseler, Ber. dtsch. chem. Ges.
46, 3410 (1913).
Synthesis of N,N,N'-Trisubstituted Amidines,
Quaternary Amidinium Salts and Aminal Esters
By Prof. Dr. H. Bredereck, Dr. F. Effenberger,
and DipLChem. G. Simchen
Institut fur Organische Chemie und Organisch-Chemische
Technologie, Technische Hochschule, Stuttgart (Germany)
Complexes of N,N-disubstituted acid amides with dialkyl sulfates [l] can, uflder mild conditions, be converted to N,N,N'trisubstituted amidinium salts [2] by reaction with primary
Angew. Chem. internat. Edit. I Vol. I (19621 / No. 6
33 1
amines, and to quaternary amidinium salts [3 --61 by reaction
with secondary amines.
Thus, compound (I) with methylamine gave N,N,N'-trimethylformamidinium methyl sulfate (90 % yield), from
which the hitherto unknown, free trimethylformamidine
(b.p. 108 "C/740 mm.; ng = 1.4490) can be obtained in good
Compound (I) and dimethylamine form N,N,N',N'-tetramethylformamidinium methyl sulfate (94 % yield). Using
sodium methylate, this compound can be converted in equally
good yields into the highly reactive bis(dimethy1amino)methoxymethane (b.p. 128OC; n g = 1.4158), which is an
aminal ester [5].
cu. P
C H 3 S 0 & + NaOCH3 + H-C-O-CHJ
+ CH3S04Na
CH 3
polarization of the phosphorescence was measured and
compared with that of the fluorescence. In the same way,
the polarization of the spectrally resolved luminescence was
determined at constant excitation wavelength as a function of
wavelength. The apparatus will be described in greater detail
in the Zeitschrift fur Angewandte Physik.
The phosphorescence of phenanthrene and its derivatives, of
triphenylene, and of coronene is strongly negatively polarized
for all absorption bands. The numerical value of the degree
of polarization is only slightly dependent upon the particular
compound and upon the conditions of measurement; it lies
between - 0.15 and - 0.20. For quinoline, the value is
only - 0.08 and at higher concentrations it approaches
zero. The degree of polarization of the phosphorescence is
for all the compounds investigated independent of the absorption wavelength and almost constant.
The curve for the degree of polarization of the spectrally
resolved phosphorescence shows that the 0-0-transitions of
the phosphorescence are negatively polarized with respect
to the 0-0-transitions in the long-wave absorption band. No
essential change is introduced into the degree of polarization
by superposition of vibration bands.
The results indicate that, for the substances investigated so
far, the electron oscillators of triplet-singlet phosphorescence
are nearly perpendicular to the oscillators of the singlet
system. Since the latter, from all the evidence gathered so far,
lie in the plane of the molecule, it follows that the tripletsinglet phosphorescence of these compounds is polarized
perpendicular to the molecular plane. It has been shown by
Weissman [6] that dipole transitions are involved.
Further investigations are being made to elucidate these
Received, Aprll 6th 1962
These reactions also take place with dialkyl sulfate complexes
of higher acid amides, as well as with other amines.
Received, April 2nd. 1962
IZ 259/94 IE]
[l] H. Bredereck, F. Efenberger, and G. Simchen, Angew. Chem.
73, 493 (1961).
[2] H . Bredereck, R. Gompper, K . Klemm, and H . Rempfer, Chem.
Ber. 92, 837 (1959).
[3] Z . Arnold, Coll. Czech. chem. Commun. 24,760 (1959).
[4] 2.Arnold and F. Sorm, Coll. Czech. chem. Commun. 23, 452
[ 5 ] I). H. Clemens and W. D. Emmons, J. Amer. chem. SOC.83,
2588 (1961).
[6] H.Edhme and F. Soldan, Chem. Ber. 94, 3109 (1961).
[Z 261/98 IE]
[I] Th. Forster: Fluoreszenz organischer Verbindungen. Vandenhoeck und Rupprecht, Gottingen 1951.
[2] V . A. Pifipovich, Opt. and Spectr. 10, 104 (1961).
[3] R. Williams,J. chem. Physics 30, 319 (1961).
[4] 5'. J. Weissman, J. chem. Physics 8, 1258 (1950).
[ 5 ] F. Dorr and M . Held, Angew. Chem. 72, 287 (1960).
[6] S.Freed and S. J. Weissman,Physic. Review 60, 440 f 1941).
Pyrroline by the 1.4-Addition of Imene
to Butadiene [*I
By Prof. Dr. R. Appel and Dr. 0. Buchner
Anisotropy of the Triplet-Singlet
Phosphorescence of Aromatic Compounds
By Priv.-Doz. Dr. F. D6rr and Dipl.-Chem. H. Gropper
Physikalisch-chemischesInstitut der Technischen Hochschule
Miinchen (Germany)
It is found that the oscillators responsible for phosphorescence in dyes do not lie in the same plane as the absorption
and fluorescence oscillators.
While the phosphorescence spectra of numerous compounds
have been accurately investigated, little has been known up
to the present time concerning polarization of this luminescence in dyes [1,2], phenanthrene and naphthalene [3], and
dibenzoylmethane [4] complexes. We used a well-known
method [5,6] for the determination of the relative positions
of the electron osqillators for the investigation the phosphorescence polarization of aromatic compounds. Frozen
solutions of phenanthrene. 5,6-benzoquinoline, 7,8-benzoquinoline, 0-, m-, p-phenanthroline, benzoquinoxaline, triphenylene, coronene, and quinoline were investigated (10-4 to
10-3 M in ethanol, temperature approximately 105 OK). They
were excited to luminescence by linearly polarized light in the
different absorption bands. Then the relative degree of
Anorganisch-Chemisches Institut
der Universitat Heidelberg (Germany)
A recent report by V. Franzen [I] on the 1,4-addition of
methylene to butadiene prompts us to communicate results
that we obtained in 1960 [21 on the 1,4-addition of imene [31
to butadiene. The former is isolectronic with methylene.
Hydroxylamine-0-sulphonicacid was treated with sodium
methylate in methanol into which butadiene had previously
been passed over a long period of time. On working-yp by
steam and fractional distillation, a small amount of distillate
coming over in the range 65-93"C, and consisting principally of methanol and a little pyrroline was obtained. The
pyrroline was identified by gas chromatography through
comparison with an authentic sample prepared by reduction
of pyrrole.
We assume that the imene, formed according to equation (I),
reacts directly, with butadiene (equation 2) in a 1,Caddition.
Angew. Chem. internat.
Edit.1 Vol. 1 (1962) 1 No. 6
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salt, aminals, synthesis, esters, amidine, quaternary, amidinium, trisubstituted
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