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New 4-Hydroxythienopyrimidines.

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anol, and recrystallized as indicated in the Table. Yields:
20-30 %.
solvent pentyl alcohol and of anhydrous aluminum chloride
or concentrated sulfuric acid as catalyst, or by reaction of the
components without a solvent o r catalyst at higher temperatures. Intermediates could not be isolated.
Received: November 7, 1967
[Z 671 IE]
German version: Angew. Chem. 80. 121 (1968)
[*I Prof. Dr.
W. Ried and Dip1.-Chem. W. Kunstmann
Institut fur Organische Chemie der Universitat
6 Frankfurt, Robert-Mayer-Str. 7-9 (Germany)
[**I Read in part at the Symposium on Heterocyclic Compounds
at Reinhardsbrunn on October 11, 1967.
[I] E. J. Smufny, M . C. Caserio, and J. D . Roberts, J. Amer.
chem. SOC.82, 1793 (1960).
[21 Cf., e.g., A.T. Biomquist and E. A . LaLancefte, J. Amer.
chem. SOC.83, 1389 (1961); J. D . Park, S. Cohen, and J. R. Lacher, ibid. 84, 2920 (1962); A . Treibs and K. Jacob, Liebigs Ann.
Chem. 699, 161 (1966); J. Ficini and C. Barbara, Tetrahedron
Letters 1966,6428; J. D. Park and W. C. Frank, J. org. Chemistry
32, 1335 (1967).
Preparation of 4-hydroxythieno [2,3-d]pyrimidines ( I ) :
0.01 mole of 2-amino-3-thiophenecarboxylicester and an
equimolar amount o r slight excess of imidic ester, nitrile, or
formamide were allowed to react under the conditions stated.
After the reaction had occurred, the mixture was cooled for
some time (the product often crystallized from the hot
mixture), added to a little ether, and filtered with suction. The
product was washed with ether and then recrystallized, with
addition of active charcoal, from alcohol or dioxane.
Preparation of 4-hydroxythieno[3,2-d]pyrimidines
(2) :
1.57 g (0.01 mole) of methyl 3-amino-2-thiophenecarboxylate
and a slight excess of imidic ester or formamide were allowed
to react under the stated conditions. Crystallization began
even during the heating of the reaction mixture. The mixture
was then cooled for a short time and the crystalline residue
was filtered off. A second crop of crystals was obtained by
heating the filtrate again for a couple of hours. The combined
crystals were washed with ether and recrystallized from
alcohol or dioxane with addition of active charcoal.
New 4-Hydroxythienopyrimidines
By W. Ried and R . Giesse[*l
Hitherto, little was known about 4-hydroxythienopyrimidines
and they were accessible only by relatively complicated
methods [I]. We have found that 4-hydroxythienopyrimidines
can be obtained, some of them in good yield, from 2-amino3-thiophenecarboxylic esters [2J and 3-amino-2-thiophenecarboxylic esters [31 by reaction with nitriles or their derivatives such as imidic esters, amidines, amidoximes, and acid
amides; the products mostly crystallize as colorless needles.
Received: March 8, 1967
[Z 672 IE]
Publication delayed at the authors' request
German version: Angew. Chem. 80, 122 (1968)
[*I Prof. Dr.
W. Ried and Dip1.-Chem. R. Giesse
Institut fur Organische Chemie der Universitat
6 Frankfurt, Robert-Mayer-Str. 7-9 (Germany)
[11 B. R . Baker, f. P. Joseph, R. E. Schaub, F. J . McEvoy, and
J . H . Williams, J. org. Chemistry 18, 138 (1953).
121 K . Gewald, E. Schinke, and H . Bortcher, Chem. Ber. 99, 94
(1966).
[3] Brit. Pat. 837086 (June 9, 1960), Farbwerke Hoechst;
Chem. Abstr. 54, 24798e, f, g (1960); H . Fiesselmann, German
Pat. 1055007 (April 16, 1959), Farbwerke Hoechst.
4-Hydroxythieno[2,2-d]pyrimidines( I ) are obtained from
2-amino-3-thiophenecarboxylicesters.
OH
CsHs
CI,C
CI3C
C&-CHz
H
Ix
i
H
CZHS
CH3
CH3
H
CzHs
-(CH2)4H
CsHs
214
248
22.0
260
260
I
25
40
50
30
95
Conditions
C~HS-C(NH)OCZHS
ClnC-C(NH)OCH,
Cl3C-CN
C&-CHz-CN
H2N-CHO
4-Hydroxythieno[3,2-d]pyrimidines(2) are obtained from
3-amino-2-thiophenecarboxylicesters.
Decisive for occurrence of the reaction is sufficient basicity
of the nitrogen in the aminothiophenecarboxylic ester in
respect of the carbonium C atom of the nitrile or the nitrile
derivatives. This condition is satisfied by use of the polar
PH,
- A New Ligand in a
Transition Metal Complex
By E. 0. Fischer, E. Louis, and R . J . J . Schneider[*I
Previous experiments have shown that the binuclear complex
compound [V(C0)4PH& containing two PH2 bridges is the
exclusive product when V(CO)6 reacts with PH3, hydrogen
being evolved during the process [I]. We have now succeeded
in incorporating PH3 as a unidentate ligand photochemically
into a metalcarbonyl compound, by exchange of CO for
PH3.
We obtained tricarbonylcyclopentadienylphosphinevanadium(I), T C - C ~ H ~ V ( C O ) ~byP H
UV
~ , irradiation of a solution
COOCH,
I
I
R
I
Cl3C
H
136
I
I
p-HsC-C&-C(NH)OCzHs
Cl3C-C(NH)OCH,
HzN-CHO
14 h/160"C
2 h/130°C
8 h/50'C
15 h/A1C13/b.p.
15 h/b.p.
Conditions
15 h/160"C
12 h/165 "C
12 h/b.p.
Angew. Chem. internat. Edit. / Vol. 7 (1968)
1 No. 2
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