CH376512A - Process for the preparation of new pyrazole derivatives - Google Patents
Process for the preparation of new pyrazole derivativesInfo
- Publication number
- CH376512A CH376512A CH260960A CH260960A CH376512A CH 376512 A CH376512 A CH 376512A CH 260960 A CH260960 A CH 260960A CH 260960 A CH260960 A CH 260960A CH 376512 A CH376512 A CH 376512A
- Authority
- CH
- Switzerland
- Prior art keywords
- piperidyl
- methyl
- acetic acid
- benzyl
- benzene
- Prior art date
Links
- 150000003217 pyrazoles Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- -1 acyl acetic acid nitrile Chemical class 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 229960000583 acetic acid Drugs 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000012362 glacial acetic acid Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JHQBLYITVCBGTO-UHFFFAOYSA-N 2-(4-fluorophenyl)acetonitrile Chemical compound FC1=CC=C(CC#N)C=C1 JHQBLYITVCBGTO-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YCJMPRBLQDWITE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-oxo-4-phenylbutanenitrile Chemical compound C1=CC(Cl)=CC=C1C(C#N)C(=O)CC1=CC=CC=C1 YCJMPRBLQDWITE-UHFFFAOYSA-N 0.000 description 1
- PGPFUKMIXWNORQ-UHFFFAOYSA-N 3-oxo-2,4-diphenylbutanenitrile Chemical compound C=1C=CC=CC=1C(C#N)C(=O)CC1=CC=CC=C1 PGPFUKMIXWNORQ-UHFFFAOYSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 150000002969 pentanoic acid esters Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/38—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Verfahren zur Herstellung von neuen Pyrazol-Derivaten Es wurde gefunden, dass man zu neuen Pyrazol- Derivaten der allgemeinen Formel 1,
EMI0001.0002
worin R1 den n-Butylrest oder eine Aralkylgruppe be deutet und R2 für ein Wasserstoff-, Chlor- oder Fluor atom steht, gelangen kann, indem man N-Methyl- piperidyl-4-hydrazin mit einem Acylessigsäurenitril der allgemeinen Formel II,
EMI0001.0006
kondensiert.
Die als Ausgangsmaterialien verwendeten Acyl- essigsäurenitrile der Formel II, worin R1 den n-Butyl- rest oder eine Aralkylgruppe und R2 ein Fluoratom bedeuten, werden hergestellt, indem man 4-Fluor- benzylcyanid in Gegenwart eines alkalischen Konden sationsmittels mit Arylessigsäureäthylestern resp. Va- leriansäureestern umsetzt.
<I>Beispiel 1</I> 1-(N-Methyl-piperidyl-4')-3-benzyl-4-phenyl- 5-amino-pyrazol Zu einer Lösung von 9,4 g α-(Phenyl-acetyl)-ben- zylcyanid in 25 cm3 Eisessig lässt man unter Rühren eine Lösung von 5,6 g N-Methyl-piperidyl-4-hydrazin in 8 cm3 Eisessig so zutropfen, dass die Temperatur 50 nicht übersteigt. Anschliessend wird das Reak tionsgemisch noch 2 Std. bei Zimmertemperatur wei- tergerührt und darauf der Eisessig im Vakuum bei 40-50 abdestilliert.
Der Rückstand wird in 120 cm3 Wasser aufgenommen, die wässerige Lösung mit Na- triumcarbonat alkalisch gestellt und gesättigt und mit total 300 cm3 Benzol ausgeschüttelt. Nach Trocknen über Magnesiumsulfat wird das Benzol im Vakuum entfernt und der Rückstand im Hochvakuum destil liert, wobei das 1-(N-Methyl-piperidyl-4')-3-benzyl- 4-phenyl-5-amino-pyrazol zwischen 201-210 über destilliert und in der Vorlage zu einer glasartigen Masse erstarrt.
Durch Versetzen einer äthanolischen Lösung die ser Pyrazol-Base mit der berechneten Menge einer äthanolischen Lösung von Maleinsäure im Mol-Ver hältnis 1 :2 und anschliessende Zugabe von Äther scheidet sich das 1-(N-Methyl-piperidyl-4')-3-benzyl- 4-phenyl-5-amino-pyrazol-bis-maleinat kristallin aus. Nach zweimaligem Umkristallisieren aus Äthanol schmilzt das Salz bei l44-145 .
<I>Beispiel 2</I> 1-(N-Methyl-piperidyl-4')-3-benzyl-4-(4''-fluor- phenyl)-5-amino-pyrazol Zu einer Lösung von 5,1 g α-(Phenyl-acetyl)- 4-fluor-benzylcyanid in 75 cm3 Eisessig lässt man un ter Rühren eine Lösung von 2,6 g N-Methyl-piperidyl- 4-hydrazin in 3 cm3 Eisessig so zutropfen, dass die Temperatur 50 nicht übersteigt. Anschliessend rührt man das Reaktionsgemisch noch 2 Std. bei Zimmer temperatur, filtriert von etwas ausgeschiedenem α-(Phenyl-acetyl)-4-fluor-benzylcyanid ab, und dampft das Filtrat im Vakuum bei 40-50 ein.
Der Rück stand wird in 100 cm3 Wasser aufgenommen, die wäs- serige Lösung mit Natriumcarbonat alkalisch gestellt und gesättigt und mit total 200 cm3 Benzol ausge schüttelt. Nach Trocknen über Magnesiumsulfat wird das Benzol im Vakuum entfernt und der kristalline Rückstand, das 1-(N-Methyl-piperidyl-4')-3-benzyl- 4-(4''-fluor-phenyl)-5-amino-pyrazol, zweimal aus Benzol umkristallisiert. Smp. l25-127 .
Das als Ausgangsmaterial zur Verwendung gelan gende α-(Phenyl-acetyl)-4-fluor-benzylcyanid (Smp. 105-107 ) wird hergestellt, indem man 4-Fluorben- zylcyanid in Gegenwart von Natriumäthylat in Ätha- nol mit Phenylessigsäureäthylester umsetzt.
<I>Beispiel 3</I> 1-(N-Methyl-piperidyl-4')-3-benzyl-4-(4''-chlor- phenyl)-5-amino-pyrazol Zu einer Lösung von 5,4 g α-(Phenyl-acetyl)- 4-chlorbenzylcyanid in 120 cm3 Eisessig lässt man unter Rühren eine Lösung von 2,6 g N-Methyl-pipe- ridyl-4-hydrazin in 3 cm3 Eisessig so zutropfen, dass die Temperatur 50 nicht übersteigt. Darauf wird das Reaktionsgemisch noch 1 Std. bei Zimmertemperatur und 2 Std. bei 45 weitergerührt und anschliessend das Benzol im Vakuum abgedampft.
Der Rückstand wird in 150 cm3 Wasser aufgenommen, mit Benzol gewaschen, die wässerige Lösung mit Natriumcarbo- nat alkalisch gestellt und gesättigt und mit total 200 cm3 Benzol extrahiert. Nach Trocknen über Ma gnesiumsulfat wird das Benzol im Vakuum entfernt und der Rückstand im Hochvakuum destilliert, wobei das 1-(N-Methyl-piperidyl-4')-3-benzyl-4-(4''-chlor- phenyl)-5-amino-pyrazol unter einem Druck von 0,06 mm Hg bei l90-210 überdestilliert.
Durch Ver setzen einer äthanolischen Lösung von 1-(N-Methyl piperidyl-4')-3-benzyl-4-(4''-chlorphenyl)-5-amino- pyrazol mit einer äthanolischen Lösung von Malein säure im Molverhältnis 1: 2 wird das Bis-maleinat hergestellt. Durch Zugabe von Äther kristallisiert das Salz aus und schmilzt nach zweimaligem Umkristalli sieren aus Äthanol/Äther bei 108-110 .
<I>Beispiel 4</I> 1-(N-Methyl-piperidyl-4')-3-n-butyl-4-(4''-fluor- phenyl)-5-amino-pyrazol Zu einer Lösung von 11,0 g α-Valeroyl-4-fluor- benzylcyanid in 50 cm3 Eisessig lässt man unter Rüh ren eine Lösung von 6,45g N-Methyl-piperidyl-4- hydrazin in 8 cm3 Eisessig so zutropfen, dass die Re- aktionstemperatur 50 nicht übersteigt. Anschliessend wird das Reaktionsgemisch noch 2 Std. bei Zimmer temperatur weitergerührt und darauf der Eisessig im Vakuum bei 40-50 abdestilliert.
Der Rückstand wird in 200 cm3 Wasser aufgenommen, mit total 150 cm3 Äther gewaschen, die wässerige Lösung mit Natrium- carbonat alkalisch gestellt und gesättigt und mit total 350 cm3 Benzol extrahiert. Nach Trocknen über Ma gnesiumsulfat wird das Benzol im Vakuum entfernt und der Rückstand im Hochvakuum fraktioniert, wo bei das 1-(N-Methyl-piperidyl-4')-3-n-butyl-4-(4''- fluor-phenyl)-5-amino-pyrazol unter einem Druck von 0,03 mm Hg bei 160-180 als dickflüssiges, gelbes Öl überdestilliert. Beim Anreiben mit Benzol kristalli siert das Pyrazol-Derivat, das anschliessend noch zwei mal aus dem gleichen Lösungsmittel umkristallisiert wird. Smp. 82-84 .
Das als Ausgangsmaterial zur Verwendung gelan gende α-Valeroyl-4-fluor-benzylcyanid (Sdp. 138 bis 1410/0,1 mm Hg) wird hergestellt, indem man 4-Fluor-benzylcyanid in Gegenwart von Natrium- äthylat in Äthanol mit Valeriansäureäthylester um setzt.
Process for the preparation of new pyrazole derivatives It has been found that new pyrazole derivatives of the general formula 1,
EMI0001.0002
where R1 denotes the n-butyl radical or an aralkyl group and R2 denotes a hydrogen, chlorine or fluorine atom, can be obtained by N-methyl-piperidyl-4-hydrazine with an acyl acetic acid nitrile of the general formula II,
EMI0001.0006
condensed.
The acyl acetic acid nitriles of the formula II used as starting materials, where R1 is the n-butyl radical or an aralkyl group and R2 is a fluorine atom, are prepared by 4-fluorobenzyl cyanide in the presence of an alkaline condensation agent with aryl acetic acid ethyl esters, respectively. Valeric acid esters implemented.
<I> Example 1 </I> 1- (N-methyl-piperidyl-4 ') -3-benzyl-4-phenyl-5-amino-pyrazole To a solution of 9.4 g of α- (phenyl-acetyl ) benzyl cyanide in 25 cm3 of glacial acetic acid, a solution of 5.6 g of N-methylpiperidyl-4-hydrazine in 8 cm3 of glacial acetic acid is added dropwise with stirring so that the temperature does not exceed 50. The reaction mixture is then stirred for a further 2 hours at room temperature and the glacial acetic acid is then distilled off in vacuo at 40-50.
The residue is taken up in 120 cm3 of water, the aqueous solution is made alkaline with sodium carbonate and saturated and extracted with a total of 300 cm3 of benzene. After drying over magnesium sulfate, the benzene is removed in vacuo and the residue is distilled in a high vacuum, the 1- (N-methyl-piperidyl-4 ') -3-benzyl-4-phenyl-5-aminopyrazole between 201-210 distilled over and solidified in the template to a glass-like mass.
By adding an ethanolic solution to this pyrazole base with the calculated amount of an ethanolic solution of maleic acid in the molar ratio 1: 2 and then adding ether, the 1- (N-methyl-piperidyl-4 ') - 3- benzyl-4-phenyl-5-aminopyrazole-bis-maleate crystalline out. After recrystallizing twice from ethanol, the salt melts at 144-145.
<I> Example 2 </I> 1- (N-methyl-piperidyl-4 ') -3-benzyl-4- (4 "- fluorophenyl) -5-amino-pyrazole To a solution of 5.1 g of α- (phenyl-acetyl) -4-fluoro-benzyl cyanide in 75 cm3 of glacial acetic acid are allowed to drop in, with stirring, a solution of 2.6 g of N-methyl-piperidyl-4-hydrazine in 3 cm3 of glacial acetic acid so that the temperature Does not exceed 50. The reaction mixture is then stirred for a further 2 hours at room temperature, some of the α- (phenyl-acetyl) -4-fluoro-benzyl cyanide which has separated out is filtered off, and the filtrate is evaporated in vacuo at 40-50.
The residue is taken up in 100 cm3 of water, the aqueous solution is made alkaline with sodium carbonate and saturated and shaken out with a total of 200 cm3 of benzene. After drying over magnesium sulfate, the benzene is removed in vacuo and the crystalline residue, 1- (N-methyl-piperidyl-4 ') -3-benzyl-4- (4 "- fluorophenyl) -5-aminopyrazole , recrystallized twice from benzene. M.p. l25-127.
The α- (phenyl-acetyl) -4-fluoro-benzyl cyanide (melting point 105-107) which is used as starting material is prepared by reacting 4-fluorobenzyl cyanide in the presence of sodium ethylate in ethanol with phenylacetic acid ethyl ester.
<I> Example 3 </I> 1- (N-methyl-piperidyl-4 ') -3-benzyl-4- (4 "- chlorophenyl) -5-aminopyrazole To a solution of 5.4 g of α- (phenyl-acetyl) -4-chlorobenzyl cyanide in 120 cm3 of glacial acetic acid is allowed to drop in a solution of 2.6 g of N-methylpiridyl-4-hydrazine in 3 cm3 of glacial acetic acid with stirring so that the temperature is 50% does not exceed. The reaction mixture is then stirred for a further 1 hour at room temperature and 2 hours at 45 and the benzene is then evaporated off in vacuo.
The residue is taken up in 150 cm3 of water, washed with benzene, the aqueous solution is made alkaline with sodium carbonate and saturated and extracted with a total of 200 cm3 of benzene. After drying over magnesium sulfate, the benzene is removed in vacuo and the residue is distilled in a high vacuum, the 1- (N-methyl-piperidyl-4 ') -3-benzyl-4- (4' '- chlorophenyl) -5 -amino-pyrazole distilled over under a pressure of 0.06 mm Hg at 190-210.
By Ver put an ethanolic solution of 1- (N-methyl piperidyl-4 ') -3-benzyl-4- (4' '- chlorophenyl) -5-aminopyrazole with an ethanolic solution of maleic acid in a molar ratio of 1: 2 Bis-maleinat is produced. The salt crystallizes out by adding ether and melts after recrystallizing twice from ethanol / ether at 108-110.
<I> Example 4 </I> 1- (N-methyl-piperidyl-4 ') -3-n-butyl-4- (4 "- fluorophenyl) -5-amino-pyrazole To a solution of 11 , 0 g of α-valeroyl-4-fluorobenzyl cyanide in 50 cm3 of glacial acetic acid, a solution of 6.45 g of N-methyl-piperidyl-4-hydrazine in 8 cm3 of glacial acetic acid is added dropwise with stirring so that the reaction temperature is 50% does not exceed. The reaction mixture is then stirred for a further 2 hours at room temperature and the glacial acetic acid is then distilled off in vacuo at 40-50.
The residue is taken up in 200 cm3 of water, washed with a total of 150 cm3 of ether, the aqueous solution is made alkaline with sodium carbonate and saturated and extracted with a total of 350 cm3 of benzene. After drying over magnesium sulfate, the benzene is removed in vacuo and the residue is fractionated in a high vacuum, where the 1- (N-methyl-piperidyl-4 ') -3-n-butyl-4- (4' '- fluorophenyl ) -5-amino-pyrazole distilled over under a pressure of 0.03 mm Hg at 160-180 as a thick, yellow oil. When rubbed with benzene, the pyrazole derivative crystallizes, which is then recrystallized two more times from the same solvent. M.p. 82-84.
The α-valeroyl-4-fluoro-benzyl cyanide (b.p. 138 to 1410 / 0.1 mm Hg), which is used as the starting material, is prepared by treating 4-fluoro-benzyl cyanide in the presence of sodium ethylate in ethanol with ethyl valerate implements.
Claims (1)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU38903D LU38903A1 (en) | 1959-07-03 | ||
| NL253320D NL253320A (en) | 1959-07-03 | ||
| CH7527959A CH373391A (en) | 1959-07-03 | 1959-07-03 | Process for the preparation of new pyrazole derivatives |
| CH260960A CH376512A (en) | 1960-03-08 | 1960-03-08 | Process for the preparation of new pyrazole derivatives |
| GB30802/61A GB939901A (en) | 1959-07-03 | 1960-06-16 | Improvements in or relating to amino pyrazoles |
| GB2123160A GB932812A (en) | 1959-07-03 | 1960-06-16 | Improvements in or relating to amino pyrazoles |
| US38769A US3041342A (en) | 1959-07-03 | 1960-06-27 | Amino-pyrazoles |
| DES69209A DE1150989B (en) | 1959-07-03 | 1960-07-01 | Process for the preparation of 5-amino-pyrazole derivatives |
| BE592550A BE592550A (en) | 1959-07-03 | 1960-07-01 | New derivatives of pyrazole and their preparation |
| FR831821A FR1295363A (en) | 1959-07-03 | 1960-07-01 | New pyrazole derivatives and their preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH260960A CH376512A (en) | 1960-03-08 | 1960-03-08 | Process for the preparation of new pyrazole derivatives |
| CH373046T | 1960-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH376512A true CH376512A (en) | 1964-04-15 |
Family
ID=25690928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH260960A CH376512A (en) | 1959-07-03 | 1960-03-08 | Process for the preparation of new pyrazole derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH376512A (en) |
-
1960
- 1960-03-08 CH CH260960A patent/CH376512A/en unknown
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