DD258814A1 - PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE - Google Patents
PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE Download PDFInfo
- Publication number
- DD258814A1 DD258814A1 DD30092487A DD30092487A DD258814A1 DD 258814 A1 DD258814 A1 DD 258814A1 DD 30092487 A DD30092487 A DD 30092487A DD 30092487 A DD30092487 A DD 30092487A DD 258814 A1 DD258814 A1 DD 258814A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- heteroaryl
- alkyl
- formula
- aminothiazoles
- aralkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- 150000008361 aminoacetonitriles Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims abstract description 3
- 239000003973 paint Substances 0.000 claims abstract 2
- 239000012988 Dithioester Substances 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- -1 2-substituted 5-aminothiazoles Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- LKFXYYLRIUSARI-UHFFFAOYSA-N 1,3-thiazol-5-amine Chemical compound NC1=CN=CS1 LKFXYYLRIUSARI-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000005022 dithioester group Chemical group 0.000 claims 1
- FSXWCUSOFGPQKK-UHFFFAOYSA-N ethanebis(thioic s-acid) Chemical class SC(=O)C(S)=O FSXWCUSOFGPQKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 2
- 229950003476 aminothiazole Drugs 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von neuen 2-Heteroaryl-5-aminothiazolen, die in der pharmazeutischen und Farbenindustrie Anwendung finden koennen. Das Ziel der Erfindung, bisher unbekannte 2-Heteroaryl-5-aminothiazole der Formel III, in der R2H, Alkyl, Aryl, Aralkyl, CN, CONH2, CO2Alkyl bedeutet, in einem einfachen Verfahren zu synthetisieren, wurde dadurch geloest, dass Heteroaryldithioester der Formel I mit Aminoacetonitrilen der Formel II gegebenenfalls unter Anwendung eines Loesungsmittels und einer Hilfsbase umgesetzt werden. Die Aminoacetonitrile koennen in freier Form oder als Salze zur Anwendung kommen. Formel IIIThe invention relates to a process for the preparation of novel 2-heteroaryl-5-aminothiazoles which can find application in the pharmaceutical and paint industry. The object of the invention to synthesize hitherto unknown 2-heteroaryl-5-aminothiazoles of the formula III, in which R 2 is H, alkyl, aryl, aralkyl, CN, CONH 2, CO 2 alkyl, in a simple process, was achieved by reacting heteroaryldithioesters of the formula I can be reacted with aminoacetonitriles of formula II optionally with the use of a solvent and an auxiliary base. The aminoacetonitriles can be used in free form or as salts. Formula III
Description
Pleteroaryl - C.Pleteroaryl - C.
worin R = Alkyl, Aralkyl, CH2COOR1 und R1 = H, Alkyl, Aralkyl, bedeuten, mit Aminoacetonitrilen der Formel H2N-CHR2-CNwherein R = alkyl, aralkyl, CH 2 COOR 1 and R 1 = H, alkyl, aralkyl, with aminoacetonitriles of the formula H 2 N-CHR 2 -CN
worin R2 = H, Alkyl, Aryl, Aralkyl, CN, CONH2, CO2Alkyl bedeutet, gegebenenfalls unter Anwendung eines Lösungsmittels zur Umsetzung gebracht werden und daraus bislang noch unbekannte 2-Heteroaryl-5-aminothiazole der Formelwherein R 2 = H, alkyl, aryl, aralkyl, CN, CONH 2 , CO 2 alkyl, optionally be reacted using a solvent and from it yet unknown 2-heteroaryl-5-aminothiazole of the formula
Heteroaryl—^heteroaryl ^
!ET! ET
in der R2 die oben genannte Bedeutung hat, entstehen. Als günstige Lösungsmittel haben sich Alkohole erwiesen. Unter Umständen ist es vorteilhaft, zur Beschleunigung der Cyclisierung katalytische Mengen einer Hilfsbase zuzusetzen. Die Aminoacetonitrile werden am besten, soweit möglich, in freier Form eingesetzt, können aber auch aus ihren Salzen durch Zugabe einer starken nicht zur Reaktion befähigten Base vor oder während der Reaktion freigesetzt werden.in which R 2 has the meaning given above arise. Alcohols have proved to be favorable solvents. It may be advantageous to add catalytic amounts of an auxiliary base to accelerate the cyclization. The aminoacetonitriles are best used as far as possible in free form, but may also be released from their salts by the addition of a strong unreactive base before or during the reaction.
Allgemeine Synthesevorschrift:General Synthesis Instructions:
0,01 mol Heteroaryldithioester werden in Ethanol (60-20OmI) heiß gelöst, mit 0,011 mol Aminoacetonitril versetzt und bis zur Gelbfärbung der Lösung gekocht (max. 10 Min). Dann erhitzt man gegebenenfalls unter Zusatz von 5 Tropfen Triethylamin weiter, wobei man einen Teil des Lösungsmittels abdestilliert. Das Aminothiazol fällt gewöhnlich innerhalb von 10 Min. aus. Ist dies nicht der Fall engt man die Lösung im Vakuum weiter ein oder gibt bis zur Fällung Wasser dazu.0.01 mol of heteroaryl dithioester are dissolved in ethanol (60-20OmI) hot, treated with 0.011 mol aminoacetonitrile and boiled until the solution turns yellow (up to 10 min). Then, if appropriate, heating is continued with addition of 5 drops of triethylamine, during which part of the solvent is distilled off. The aminothiazole usually precipitates within 10 minutes. If this is not the case, the solution is concentrated further in vacuo or water is added until precipitation.
Das stark fluoreszierende, meist gelbliche Aminothiazol wird abgesaugt, mit wenig Wasser und Ethanol gewaschen. Es fällt in der Regel frei von Nebenprodukten an, kann aber gegebenenfalls durch Umkristallisation weiter gereinigt werden.The strongly fluorescent, usually yellowish aminothiazole is filtered off, washed with a little water and ethanol. It is usually free of by-products, but may optionally be further purified by recrystallization.
Die Tabelle enthält einige Beispiele für diese Umsetzung. Es wurden die Dithiocarbonsäuremethylester I (R = Me) verwendet.The table contains some examples of this implementation. The dithiocarboxylic acid methyl esters I (R = Me) were used.
2-Heteroaryl-5-aminothiazole der Formel III (Beispiel 1-15: R2 = H; Beispiel 16: R2 = Me)2-Heteroaryl-5-aminothiazoles of the formula III (Example 1-15: R 2 = H, Example 16: R 2 = Me)
Bei- Hetaryl spielAt- Hetaryl game
Ausb. in % Umkrist. in Rohschmp. Schmp. in G in 0CY. in % Umkrist. in Rohschmp. In G in 0 C
70 286-29070 286-290
Ethanol 288 -Ethanol 288 -
Scr Me 63 90-202Scr Me 63 90-202
Ethanol 205-207Ethanol 205-207
N; N;
atat
Prop 75 195-215Prop 75 195-215
80 154-I6O80 154-I6O
Ethanol 217-219Ethanol 217-219
Ethanol 159-161Ethanol 159-161
*v* v
Bn 105-128Bn 105-128
n-Hexan 127-128n-hexane 127-128
Bei- ' Hetaryl spielAt- 'Hetaryl game
75 231-23675 231-236
Äthanol 234-236Ethanol 234-236
.80 155-156.80 155-156
Äthanol 155-156Ethanol 155-156
IIII
"IT"IT
85 279-28985 279-289
288-291288-291
TiTi
% Ii% Ii
90 245-25290 245-252
DIEB1 259-261DIEB 1 259-261
Bei- Hetaryl spielAt- Hetaryl game
Ausb. in % Umkrist. in Rohschmp. 0C Schmp. in 0CY. in % Umkrist. in Rohschmp. 0 C in 0 C
PhPh
9090
262-268262-268
267-269267-269
7575
205-225205-225
225-227225-227
<x> 85 261-271<x> 85 261-271
Sthanol/üMF 269-271Ethanol / üMF 269-271
ιτ·ιτ ·
Ii—Ε Ii- Ε
Il95 Il 95
305-315305-315
DMF 310-312DMF 310-312
60 253-25560 253-255
Ethanol 255-256Ethanol 255-256
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD30092487A DD258814A1 (en) | 1987-03-19 | 1987-03-19 | PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD30092487A DD258814A1 (en) | 1987-03-19 | 1987-03-19 | PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD258814A1 true DD258814A1 (en) | 1988-08-03 |
Family
ID=5587582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD30092487A DD258814A1 (en) | 1987-03-19 | 1987-03-19 | PROCESS FOR THE PREPARATION OF NEW 2-HETEROARYL-5-AMINOTHIAZOLENE |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD258814A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389426A1 (en) * | 1989-03-21 | 1990-09-26 | Ciba-Geigy Ag | Nematicides and fungicides |
| WO1997012615A1 (en) * | 1995-10-05 | 1997-04-10 | Warner-Lambert Company | Benzimidazole derivatives as 15-lo inhibitors |
-
1987
- 1987-03-19 DD DD30092487A patent/DD258814A1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389426A1 (en) * | 1989-03-21 | 1990-09-26 | Ciba-Geigy Ag | Nematicides and fungicides |
| WO1997012615A1 (en) * | 1995-10-05 | 1997-04-10 | Warner-Lambert Company | Benzimidazole derivatives as 15-lo inhibitors |
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|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |