CS220345B2 - Method of producing 2-methylthio-4-aminopyrimidine - Google Patents
Method of producing 2-methylthio-4-aminopyrimidine Download PDFInfo
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- CS220345B2 CS220345B2 CS603081A CS603081A CS220345B2 CS 220345 B2 CS220345 B2 CS 220345B2 CS 603081 A CS603081 A CS 603081A CS 603081 A CS603081 A CS 603081A CS 220345 B2 CS220345 B2 CS 220345B2
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- methylthio
- formula
- amino
- aminopyrimidine
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- HGGXLEAHOVIYKT-UHFFFAOYSA-N 2-methylsulfanylpyrimidin-4-amine Chemical compound CSC1=NC=CC(N)=N1 HGGXLEAHOVIYKT-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- AOBVZYNKWONVRH-UHFFFAOYSA-N 4-amino-2-methylsulfanylpyrimidine-5-carboxylic acid Chemical compound CSC1=NC=C(C(O)=O)C(N)=N1 AOBVZYNKWONVRH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QINRQIZOBCQKAZ-UHFFFAOYSA-N ethyl 4-amino-2-methylsulfanylpyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)N=C1N QINRQIZOBCQKAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 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 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- SNNHLSHDDGJVDM-UHFFFAOYSA-N ethyl 4-chloro-2-methylsulfanylpyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)N=C1Cl SNNHLSHDDGJVDM-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WXRSVVFYNXEDCM-UHFFFAOYSA-N 2-ethoxycarbonyl-3-[(2-methylsulfanylpyrimidin-4-yl)amino]prop-2-enoic acid Chemical compound CCOC(=O)C(C(O)=O)=CNC1=CC=NC(SC)=N1 WXRSVVFYNXEDCM-UHFFFAOYSA-N 0.000 description 1
- UYHSQVMHSFXUOA-UHFFFAOYSA-N 2-methylthiouracil Chemical compound CSC1=NC=CC(O)=N1 UYHSQVMHSFXUOA-UHFFFAOYSA-N 0.000 description 1
- DFOHHQRGDOQMKG-UHFFFAOYSA-N 4-chloro-2-methylsulfanylpyrimidine Chemical compound CSC1=NC=CC(Cl)=N1 DFOHHQRGDOQMKG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- -1 RЬO Chemical compound 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HDIWKNXVBQPJCO-UHFFFAOYSA-N ethyl 2-methylsulfanyl-6-oxo-1h-pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=C(SC)NC1=O HDIWKNXVBQPJCO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- YCWDQAKDVQNVAR-UHFFFAOYSA-N ethyl pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=CN=CN=C1 YCWDQAKDVQNVAR-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 159000000018 pyrido[2,3-d]pyrimidines Chemical class 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- IGTCYZWXXQDFQA-UHFFFAOYSA-M sodium;5-hydroxypent-2-enoate Chemical compound [Na+].OCCC=CC([O-])=O IGTCYZWXXQDFQA-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Vynález se týká způsobu výroby 2-methylthio-4-aminopyrimidinu vzorce IThe invention relates to a process for the preparation of 2-methylthio-4-aminopyrimidine of the formula I
2-methylthi0'-4-amino-pyrimidin je cenným meziproduktem při syntéze farmakologicky účiných antibakteriálních sloučenin, z nichž některé jsou popsány v britském patentovém spisu č. 1 129 358, v německém zveřejňovacím spisu č. 2 341 146 a 2 238 325. Některé z nich se používají jako vynikající uroantíseptické prostředky, například kyselina pyromidinová vzorce2-Methylthio-4-amino-pyrimidine is a valuable intermediate in the synthesis of pharmacologically active antibacterial compounds, some of which are described in British Patent Specification No. 1,129,358, in German Publication Nos. 2,341,146 and 2,238,325. among them, excellent uroantisseptic agents are used, for example pyromidine acid of the formula
a kyselina pypemidinová vzorceand pypemidine acid of the formula
OO
Zη μ m - с. ·- · !L (IZη μ m - с. · - ·! L
I kterážto posledně uvedená sloučenina je obzvláště účinná proti Pseudomonas aeruginosa.However, the latter compound is particularly active against Pseudomonas aeruginosa.
Ze způsobů syntézy výše uvedených derivátů pyrido(2,3-d)pyrimidinu je nejvhoidnější Gould-Jacobsova cyklizace ethylesteru kyseliny N- (2-methylthio-6-pyrimidinyl) aminomethylenmalonové, na 5,8-dihydro-6-ethoxykarbioinyl-2-methylthiioi-5-oxopyrido(2,3-d)pyrimidin, který se v dalším reakčním stupni alkylu je, například ethyl jiodidem, načež následuje hydrolýza za vzniku příslušné kyseliny. Poité se methylthioškupina této kyseliny, nahradí nukleofilní substitucí piperazinylovou nebio některou jinou skupinou.Of the methods for the synthesis of the above pyrido (2,3-d) pyrimidine derivatives, the most rapid is the Gould-Jacobs cyclization of N- (2-methylthio-6-pyrimidinyl) aminomethylenemalonic acid ethyl ester to 5,8-dihydro-6-ethoxycarbioinyl-2-methylthio -5-oxopyrido (2,3-d) pyrimidine, which in the next reaction step of the alkyl is, for example, ethyl iodide, followed by hydrolysis to give the corresponding acid. If the methylthio group of this acid is used, it is replaced by nucleophilic substitution with piperazinyl or some other group.
220343220343
Hlavním meziproduktem při této syntéze ]e 2-methylthio-4-aminopyrimidln.The major intermediate in this synthesis was 2-methylthio-4-aminopyrimidine.
Podle postupu, popsaného Wheelerem a Bristolem v časopisu Am. Chem. Journal, 33, str. 447 (1905), je možno tuto sloučeninu připravit reakcí 2-methylthio-4-hydroxypyrimidinu s oxychloridem fosforečným POC13 při teplotě 110 °C. Na vzniklý 2-methylthío-4-chlorpyrimidin se pak působí v uzavřeném systému při teplotě 120 °C a za tlaku 2 MPa ethanolbvým roztokem amoniaku za vzniku 2-methylthio-4-aminopyrimidi· nu.Following the procedure described by Wheeler and Bristol in Am. Chem. Journal, 33, p. 447 (1905), may be prepared by reacting 2-methylthio-4-hydroxypyrimidine with phosphorus oxychloride POCl 3 at 110 ° C. The resulting 2-methylthio-4-chloropyrimidine was then treated in a sealed system at 120 ° C and 20 psi with ethanolic ammonia to give 2-methylthio-4-aminopyrimidine.
Výchozí 2-methyllthio-4-hydroxypyrimidin se získá reakcí sulfátu 2-methyl-2-thtopseudomočoiviny s enolátem sodným ethylesteru kyseliny 3-hydrOixypropenové za mírných reakčních podmínek (Wheeler, Merriam, Am. Chem. Jour,, 29, str. 480 /1901/). Příprava eniolátu sodného ethylesteru kyseliny 3-hydroxypropepnové reakcí ethylacetátu, ethylformiáitu a rozptýleného sodíku v xylenovém roztoku při teplotě 35 °C byla popsána Wislicénusem, v časopisu Ber. d. Chem. Ges., 20, str. 2933 (1887). Při této exothermní reakci může dojít к samovznícení rozptýleného sodíku; toto nebezpečí se zvyšuje vznikajícím plynným vodíkem při reakci. Proto jsou nezbytná přísná opatření při této reakci.The starting 2-methyl- 1- thio-4-hydroxypyrimidine is obtained by reacting 2-methyl-2-thtopseudourea sulfate with sodium 3-hydroxyethylpropenoate enolate under mild reaction conditions (Wheeler, Merriam, Am. Chem. Jour, 29, p. 480) (1901). The preparation of the sodium enolate of 3-hydroxypropepenic acid ethyl ester by reaction of ethyl acetate, ethyl formate and dispersed sodium in xylene solution at 35 ° C has been described by Wislicenus, Ber. d. Chem. Ges., 20, 2933 (1887). In this exothermic reaction, scattered sodium may spontaneously ignite; this danger is increased by the hydrogen gas produced during the reaction. Therefore, strict measures are necessary in this reaction.
Celkový výtěžek při syntéze 2-methylthio4Total yield for 2-methylthio 4 synthesis
-4-aminopyrimidinu je 15,8 %, vztaženo n&-4-aminopyrimidine is 15.8% based on
thioimočovinu.thioimurea.
Účelem vynálezu je poskytnout způsob výroby 2-methylthiO-4-aminopyrimidinu za mlírných reakčních podmínek v dobrém výtěžku bez nebezpečí výbuchu.The purpose of the invention is to provide a process for the preparation of 2-methylthio-4-aminopyrimidine under mild reaction conditions in good yield without the risk of explosion.
Způsob podle vynálezu к výrobě 2-methylthior-4-aminopyrimidinu vzorce I spočívá v tom, že se 2-methylthio-4-chlor-5-ethoxykarbonylpyrimidin nechá reagovat s amoniakem v ethanolovém roztoku při teplotě místnosti, vzniklý 2-methylthio-4-amino-5-ethoxykarbonylpyrimidin, který je novou sloučeninou, se hydrolyzuje v alkalickém prostředí při teplotě v rozmezí 60 až 100 °C, načež se vzniklý 2-methylthio-4-amino-5-karbOKypyrimidín dekarboxyluje v přítomnosti chinolinu a práškové mědi jakožto katalyzátoru při teplotě v rozmezí 230 až 235 °C.The process according to the invention for the preparation of 2-methylthior-4-aminopyrimidine of the formula I is characterized by reacting 2-methylthio-4-chloro-5-ethoxycarbonylpyrimidine with ammonia in ethanol solution at room temperature to form 2-methylthio-4-amino The 5-ethoxycarbonylpyrimidine, which is a novel compound, is hydrolyzed in an alkaline medium at a temperature in the range of 60-100 ° C, after which the resulting 2-methylthio-4-amino-5-carbOKypyrimidine is decarboxylated in the presence of quinoline and copper powder as a catalyst. in the range of 230 to 235 ° C.
Dekarboxylaci je též možno provést za použití činidel, jako jsou kysličník olovlčitý РЬОг, N,N-dimethylanilin nebo prášková měď, v Ν,Ν-dimethylanilinu v přítomnosti rozpouštědel, jato je toluen, xylen, dimethylfarmamid atd., nebo bez rozpouštědel. Výhodně se však tato reakce provádí v přítomnosti chinolinu a práškové mědi.Decarboxylation can also be carried out with reagents such as lead oxide, RЬO, N, N-dimethylaniline or powdered copper, in Ν, dim-dimethylaniline in the presence of solvents such as toluene, xylene, dimethylpharmamide, etc., or without solvents. Preferably, however, this reaction is carried out in the presence of quinoline and copper powder.
Výtěžek 2-m|ethylthio-4-aminopyrimidinu je 29,5 % teorie, vztaženo' na thiomočovinu.The yield of 2-methylthio-4-aminopyrimidine is 29.5% of theory, based on thiourea.
Způsob podle vynálezu je možno znázornit tímto reakčním schématem.The process according to the invention can be illustrated by this reaction scheme.
N^^COOC^ NH3/C£HSQHCOOC ^ N ^^ NH 3 / C H £ S QH
(lil)(lil)
CH3SCH 3 S
(IV)' соон(IV) 'соон
NHZ NH Z
COOC^HsCOOC ^ Hs
NH2 ~NH 2 ~
&5° (?5 ° (?
Výchozí sloučenina 2-methylthio-4-chlor-5-ethoxykarbionylpyrimidin je známou sloučeninou. Byla připravena E. Petersem a spol. (Cancer Research 19, str. 729 až 737 /1959/, C. A. 54, 6732c) chlorací 2-methylthió-4-hydrioxy-5-ethoxykarbonylpyrimldinu, který se připravuje kondenzací sulfátu 2-methyl-2-thiopseudomiočoviny s diethylesterem kyseliny ethoxymethylenmatonové v přítomnosti hydroxidu sodného. Sulfát 2-methyl-2-thiopseudomočovÍny se připravuje methylací thiomočoviny dimethylsulfátem (výtěžek 94 %). Celkový výtěžek 2-methylthilo-4-chlor-5-ethoxykarbonylpyrimidinu je 65,5 % teorie, počítáno na thiomočovinu.The starting compound 2-methylthio-4-chloro-5-ethoxycarbionylpyrimidine is a known compound. It was prepared by E. Peters et al. (Cancer Research 19, 729-737 (1959), CA 54, 6732c) by chlorination of 2-methylthio-4-hydroxy-5-ethoxycarbonylpyrimidine prepared by condensation of 2-methyl-2-thiopseudomionate sulfate with diethyl ethoxymethylenmatonic acid ester in the presence of sodium hydroxide. 2-Methyl-2-thiopseudurea sulphate was prepared by methylating thiourea with dimethyl sulphate (yield 94%). The total yield of 2-methylthilo-4-chloro-5-ethoxycarbonylpyrimidine is 65.5% of theory, calculated on thiourea.
Vynález je blíže objasněn dále uvedeným příkladem provedení, na nějž však vynález není nikterak omezen.The invention is illustrated by the following non-limiting example.
PříkladExample
a) 2-methylthio-4-ammo-5-ethoxykarbonylpyrimidini(a) 2-methylthio-4-amino-5-ethoxycarbonylpyrimidinium
23,2 g 2-methylthio-4-chlor-5-ethoxykarbonylpyrimidinu se suspenduje ve 235 ml ethanolu. Za míchání se po dobu 1 hodiny nechá při teplotě místnosti tímto roztokem probublávat plynný amoniak. Vzniklá bílá sraženina se odfiltruje a promyje ethanolem, čímž se získá 16,5 g v záhlaví uvedené sloučeniny o teplotě tání v rozmezí 130 až 134 °C. Výtěžek odpovídá 83,4 % teorie.23.2 g of 2-methylthio-4-chloro-5-ethoxycarbonylpyrimidine are suspended in 235 ml of ethanol. Ammonia gas was bubbled through the solution at room temperature with stirring for 1 hour. The resulting white precipitate was filtered off and washed with ethanol to give 16.5 g of the title compound, mp 130-134 ° C. Yield: 83.4%.
b) 2-methylthio-4-amino-5-karboxypyrimidinb) 2-methylthio-4-amino-5-carboxypyrimidine
Suspenze 213 g 2-methylthio-4-amino-5-ethoxykarbonylpyrimidinu ve 142 ml 7% roztoku hydroxidu sodného se zahřívá půl hodiny při teplotě 85 °C. Přidáním kyseliny octové se pH čirého reakčního roztoku upraví na hodnotu 5 a vzniklá sraženina se odfiltruje. Tím se získá 19 g v záhlaví uvedené sloučeniny o teplotě tání v rozme-A suspension of 213 g of 2-methylthio-4-amino-5-ethoxycarbonylpyrimidine in 142 ml of 7% sodium hydroxide solution was heated at 85 ° C for half an hour. The pH of the clear reaction solution was adjusted to 5 by the addition of acetic acid and the resulting precipitate was filtered off. This affords 19 g of the title compound, m.p.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| YU202080A YU41728B (en) | 1980-08-11 | 1980-08-11 | Process for preparing 2-methylthio-4-amino pyrimidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS220345B2 true CS220345B2 (en) | 1983-03-25 |
Family
ID=25556514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS603081A CS220345B2 (en) | 1980-08-11 | 1981-08-11 | Method of producing 2-methylthio-4-aminopyrimidine |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5759875A (en) |
| CS (1) | CS220345B2 (en) |
| DD (1) | DD201895A5 (en) |
| ES (1) | ES8303359A1 (en) |
| PL (1) | PL134157B1 (en) |
| PT (1) | PT73498B (en) |
| SU (1) | SU999968A3 (en) |
| YU (1) | YU41728B (en) |
-
1980
- 1980-08-11 YU YU202080A patent/YU41728B/en unknown
-
1981
- 1981-08-03 ES ES504501A patent/ES8303359A1/en not_active Expired
- 1981-08-07 PL PL23253181A patent/PL134157B1/en unknown
- 1981-08-10 PT PT7349881A patent/PT73498B/en unknown
- 1981-08-10 SU SU813324050A patent/SU999968A3/en active
- 1981-08-11 DD DD23252981A patent/DD201895A5/en unknown
- 1981-08-11 JP JP56124826A patent/JPS5759875A/en active Pending
- 1981-08-11 CS CS603081A patent/CS220345B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES504501A0 (en) | 1983-02-01 |
| PL232531A1 (en) | 1982-04-26 |
| JPS5759875A (en) | 1982-04-10 |
| ES8303359A1 (en) | 1983-02-01 |
| PL134157B1 (en) | 1985-07-31 |
| YU202080A (en) | 1983-02-28 |
| SU999968A3 (en) | 1983-02-23 |
| PT73498B (en) | 1982-10-28 |
| PT73498A (en) | 1981-09-01 |
| DD201895A5 (en) | 1983-08-17 |
| YU41728B (en) | 1987-12-31 |
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