CS225550B1 - Preparation of 1,2,3-triazole-4-carboxamide - Google Patents
Preparation of 1,2,3-triazole-4-carboxamide Download PDFInfo
- Publication number
- CS225550B1 CS225550B1 CS813382A CS813382A CS225550B1 CS 225550 B1 CS225550 B1 CS 225550B1 CS 813382 A CS813382 A CS 813382A CS 813382 A CS813382 A CS 813382A CS 225550 B1 CS225550 B1 CS 225550B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- triazole
- carboxamide
- formula
- preparation
- aminopyrimidine
- Prior art date
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- OSKSVLBJJXQUPI-UHFFFAOYSA-N 2h-triazole-4-carboxamide Chemical compound NC(=O)C1=CNN=N1 OSKSVLBJJXQUPI-UHFFFAOYSA-N 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 5
- XWLBYEBHQNSCKA-UHFFFAOYSA-N 5-amino-1h-pyrimidin-6-one Chemical compound NC1=CN=CN=C1O XWLBYEBHQNSCKA-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- -1 alkali metal nitrite Chemical class 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000005005 aminopyrimidines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Description
Vynález ae týká způsobu výroby 1,2,3-triazol-4-karboxamidu vzorce IThe invention relates to a process for the preparation of 1,2,3-triazole-4-carboxamide of the formula I
ze 4-hydroxy-5-aminopyrimidinu níže uvedeného vzorce II za podmínek diazotace.from 4-hydroxy-5-aminopyrimidine of formula II below under diazotization conditions.
Deriváty 1,2,3-triazolu lze podle údajů literatury připravovat reakcí příslušně substituovaných acetylenů s kyselinou dusíkovodíkovou /Oliveri-Mandala E., Coppola A,, Gazz.chim. ital. 40, II, 441 (1911)/ nebo s trimethylsilýlazidem /L. Birkofer, A. Ritter, P« Richter, Chem.Ber. 96, 2750 (1963)/. Výchozí deriváty acetylenů jsou však relativně špatně přístupné a při prvním způsobu k reakci používaná kyselina dusíkovodíková je silně esplosivní.1,2,3-triazole derivatives can be prepared by reaction of appropriately substituted acetylenes with nitric acid / Oliveri-Mandala E., Coppola A, Gazz. Italian. 40, II, 441 (1911) (or with trimethylsilyl azide). Birkofer, A. Ritter, P. Richter, Chem.Ber. 96, 2750 (1963)]. However, the starting derivatives of acetylenes are relatively poorly accessible and the first method used for the reaction is strongly esplosive.
Autoři vynálezu nyní neočekávaně zjistili, že při reakci kyseliny dusité se 4-hydroxy-5-aminopyrimidinem vzorce II dochází k přesmyku výchozího pyriraidinu za vzniku 1-formyl-1,2,3-triazol-4-karboxamidu, který snadno, za podmínek mírné hydrolýzy, přechází na 1,2,3-triazol-4-karboxamid vzorce I.The present inventors have now unexpectedly found that the reaction of nitrous acid with 4-hydroxy-5-aminopyrimidine of formula II results in a rearrangement of the starting pyriraidine to give 1-formyl-1,2,3-triazole-4-carboxamide which easily, under mild conditions hydrolysis to the 1,2,3-triazole-4-carboxamide of formula I.
Podle vynálezu se 1,2,3-triazol-4-karboxamid vzorce I dá vyrábět tím způsobem, že se 4-hydroxy-5-aminopyrimidin vzorce II OH nh2 (II)According to the invention, 1,2,3-triazole-4-carboxamide of the formula I can be produced by the process of 4-hydroxy-5-aminopyrimidine of the formula II OH nh 2 (II)
225 550 uvede v kyselém prostředí, při teplotě -5 °C až +10 °C, do reakce s dusitanem alkalického kovu, a vyloučený produkt, který je směsí 1,2,3-triazol-4-kařboxamidu s jeho 1-formylderivátem, se překrystalizuje z vody.225 550 reacts with an alkali metal nitrite in an acidic medium, at a temperature of -5 ° C to +10 ° C, and the precipitated product which is a mixture of 1,2,3-triazole-4-carboxamide with its 1-formyl derivative, is recrystallized from water.
Reakce se provádí za podmínek diazotace: aminopyrimidin vzorce II se suspenduje ve 2 až 10 molekvivalentech, výhodně ve 3 molekvivalentech, silné anorganické kyseliny, například kyseliny chlorovodíkové, sírové nebo £luoroborité, a při teplotě -5 až +10 °C, výhodně při 0 až +5 °C se přikape 35 až 45 % (hmotnostní %) roztok 1 molekvivalentu dusitanu sodného nebo draselného, nebo se po částech vnese 1 molekvivalent pevného dusitanu sodného nebo draselného. Výchozí látka přejde do roztoku a po několika hodinách se vyloučí produkt, který se odfiltruje a překrystalizuje z horké vody; při tom dojde k odhydrolýzování formylové skupiny a získá se jednotný triazol vzorce I.The reaction is carried out under diazotization conditions: the aminopyrimidine of formula II is suspended in 2 to 10 mol equivalents, preferably 3 mol equivalents, of a strong inorganic acid, for example hydrochloric, sulfuric or fluoroboric acid, and at a temperature of -5 to +10 ° C, preferably at 0 a solution of 1 mol equivalent of sodium or potassium nitrite is added dropwise to + 5 ° C, or 1 mol equivalent of solid sodium or potassium nitrite is added in portions. The starting material goes into solution and after a few hours the product precipitates, which is filtered off and recrystallized from hot water; in this case, the formyl group is dehydrolyzed and a uniform triazole of the formula I is obtained.
1,2,3-Triazol-4-karboxamid je vhodnou výchozí látkou pro přípravu biologický aktivních látek·1,2,3-Triazole-4-carboxamide is a suitable starting material for the preparation of biologically active substances.
Výchozí 4-hydroxy-5-aminopyrimidin vzorce II je známá _ látka a dá se připravit například podle československého £k<^ho OiťfcdčCo/ έί76£7-θ£) nebo způsobem podle M.P.V. Boarlandové a J.F.W. McOmieho, J.Chem.Soc. 4942 (1952).The starting 4-hydroxy-5-aminopyrimidine of formula (II) is a known compound and can be prepared, for example, according to Czechoslovakia or according to M.P.V. Boarland and J.F.W. McOmie, J. Chem. 4942 (1952).
Způsob přípravy podle vynálezu je blíže objasněn v následujícím příkladu, který však rozsah vynálezu žádným způsobem neomezuje.The preparation process of the present invention is illustrated in more detail in the following example, which is not intended to limit the scope of the invention in any way.
Příklad 1Example 1
K suspenzi 4-hydroxy-5-aminopyrimidinu (5,5 g, 0,05 mol) v koncentrované kyselině chlorovodíkové (15 g, 36 % hmotnostních; 0,15 mol) se za míchání a chlazení, při teplotě 0 až +5 °C přikape roztok dusitanu sodného (3,6 g 0,0525 mol) ve vodě (5 ml); pevná látka při tom přejde do roztoku. Reakční směs se míchá 4 hodiny při uvedené teplotě a pak se nechá stát přes noc při teplotě místnosti. Vyloučený produkt se odfiltruje a překrystalizuje z vroucí vody. Získá se 3,4 g (výtěžek 61 %)To a suspension of 4-hydroxy-5-aminopyrimidine (5.5 g, 0.05 mol) in concentrated hydrochloric acid (15 g, 36% by weight; 0.15 mol) was stirred and cooled at 0 to +5 ° C dropwise a solution of sodium nitrite (3.6 g 0.0525 mol) in water (5 ml); the solid goes into solution. The reaction mixture was stirred at this temperature for 4 hours and then allowed to stand overnight at room temperature. The precipitated product is filtered off and recrystallized from boiling water. 3.4 g (61% yield) are obtained.
1,2,3-triazol-4-karboxamidu ve formě bezbarvých krystalků o teplotě tání 255 až 259 °Cj UF spektrum (v 0,1 M NaOH):1,2,3-triazole-4-carboxamide in the form of colorless crystals, m.p. 255-259 ° C. UF spectrum (in 0.1 M NaOH):
= 233, logg - 3,98.= 233, logg = 3.98.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS813382A CS225550B1 (en) | 1982-11-15 | 1982-11-15 | Preparation of 1,2,3-triazole-4-carboxamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS813382A CS225550B1 (en) | 1982-11-15 | 1982-11-15 | Preparation of 1,2,3-triazole-4-carboxamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS225550B1 true CS225550B1 (en) | 1984-02-13 |
Family
ID=5431498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS813382A CS225550B1 (en) | 1982-11-15 | 1982-11-15 | Preparation of 1,2,3-triazole-4-carboxamide |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS225550B1 (en) |
-
1982
- 1982-11-15 CS CS813382A patent/CS225550B1/en unknown
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