CH371121A - Process for the preparation of 1-substituted 3-methyl-pyrazolone (5) compounds - Google Patents
Process for the preparation of 1-substituted 3-methyl-pyrazolone (5) compoundsInfo
- Publication number
- CH371121A CH371121A CH7055959A CH7055959A CH371121A CH 371121 A CH371121 A CH 371121A CH 7055959 A CH7055959 A CH 7055959A CH 7055959 A CH7055959 A CH 7055959A CH 371121 A CH371121 A CH 371121A
- Authority
- CH
- Switzerland
- Prior art keywords
- pyrazolone
- compounds
- substituted
- methyl
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- JRQMRDBHOIOIIL-UHFFFAOYSA-N 3-methyl-1,5-dihydropyrazol-4-one Chemical class CC1=NNCC1=O JRQMRDBHOIOIIL-UHFFFAOYSA-N 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 title description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- -1 aromatic sulfamides Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- NGUYDTBNGCDFEI-UHFFFAOYSA-N 2-phenyldiazenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1N=NC1=CC=CC=C1 NGUYDTBNGCDFEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- SXRSNXAUVPHKSG-UHFFFAOYSA-N C(CC(=O)C)(=O)NS(=O)(=O)N Chemical class C(CC(=O)C)(=O)NS(=O)(=O)N SXRSNXAUVPHKSG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical group OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- CNXXUGXCLRRGMF-UHFFFAOYSA-N octane-1-sulfonohydrazide Chemical compound CCCCCCCCS(=O)(=O)NN CNXXUGXCLRRGMF-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
Verfahren zur Herstellung von 1-substituierten 3-Methyl-pyrazolon- (5)-verbindungen
Es ist bereits bekannt, dass Phenylhydrazin mit Diketen zum I-Phenyl-3-methyl-pyrazolon- (5) kondensiert. Weiterhin ist bekannt, dass aromatische Sulfamide mit Diketen unter Biltdung von Acetoacetylsulfamiden reagieren.
Es wurde nun gefunden, dass man in einer einzigen Stufe neue l-substituierte 3-Methyl-pyrazolon- (5)-verbindungen mit der allgemeinen Formel
EMI1.1
worin R einen gegebenenfalls substituierten Aryl-oder n-bzw. iso-Alkylrest bedeutet, herstellen kann, wenn man Diketen mit Ammoniak oder primären Amines intermediär zum Acetessigsäureamid bzw. seinen N Substitutionsprodukten umsetzt und in der gleichen Phase auf das Umsetzungsprodukt ein entsprechen- des Sulfonsäurehydrazid, vorzugsweise unter gelindem Erwärmen, einwirken lässt.
Sulfonsäurehydrazide, die sich zur Herstellung der neuen 3-Methyl-pyrazolon- (5)-verbindungen eignen, sind beispielsweise Benzolsulfonsäurehydrazid, Naphthalin-sulfonsäure- (2)-hydrazid, Azobenzolsul- fonsäure- (4)-hydrazid sowie deren beispielsweise durch Halogen, Nitro-, Carbonsäure-, Sulfonsäure-, Acetylamino-oder Alkylgruppen substituierte Deri- vate, weiterhin die Alkylsulfonsäurehydrazide. Als Vertreter seien unter anderem d'as n-Octyl-, n-Dode cyl-und das n-Octadecylsulfonsäurehydrazid genannt.
Die neuen N-Sulfonyl-pyrazolone- (5) sind analogen Reaktionen zugänglich, wie die bis dahin bekannten direkt substituierten Pyrazolone- (5).
Die nach dem erfindungsgemässen Verfahren her gestellten Pyrazolon- (5)-verbindungen eignen sich für die gleichen Verwendungszwecke wie die nach den bisher bekannten Verfahren hergestellten.
Beispiel 1
In einem mit Rührer, Tropftrichter, Thermometer und Rückflusskühler versehenen Dreihalskolben werden 12 Gewichtsteile konz. Ammoniak und 75 Ge wichtsteile Wasser vorgelegt und unter äusserer Eis kuhlung und Rühren 21 Gewichtsteile Diketen langsam eingetropft, so dass die Temperatur 10 C nicht übersteigt.
Anschliessend werden innerhalb von 30 Minuten 43 Gewichtsteile Benzolsudonsäurehydlrazid bei langsam ansteigender Temperatur unter Rühren eingetragen und daraufhin noch 2 Stunden lang auf 40-5 () o C erwärmt. Nach dem Stehen über Nacht hat sich ein schwach gelb gefärbtor Niederschlag abge- schieden, welcher nach dem Umkristallisieren blass rosafarbige stumpfe Nädelchen ergibt, die bei 157 bis 159 C unter Zersetzung schmelzen.
Die Rohausbeute beträgt etwa 87%.
Beispiel 2
In 85 Gewichtsteil'en 5% igem wässrigem Ammoniak werden bei 5-10 C unter Rülhren 21 Gewichtsteile Diketen allmählich eingetragen. Darauf werden bei Raumtemperatur 52 Gewichtsteile n-Octansulfon- säurehydrazid portionsweise zugegeben und d'as Reak- tionsgemisch noch 6 Stunden elxng auf 60 C unter weiterem Rühren erwärmt. Der galbe Niederschlag wird durch Lösen in wässriger Sodälosung, Ausfällen mit verdünnter Salzsäure und anschliessendem Umkristallisieren gereinigt. Man erhält danach ein fast farbloses Kristallpulver mit einem Schmelzpunkt von 86 C.
Die Ausbeute beträgt 69 %.
Process for the preparation of 1-substituted 3-methyl-pyrazolone (5) compounds
It is already known that phenylhydrazine condenses with diketene to give I-phenyl-3-methyl-pyrazolone- (5). It is also known that aromatic sulfamides react with diketene to form acetoacetyl sulfamides.
It has now been found that new l-substituted 3-methylpyrazolone (5) compounds with the general formula can be obtained in a single step
EMI1.1
wherein R is an optionally substituted aryl or n- or. iso-alkyl radical means, if diketene is reacted with ammonia or primary amines as an intermediate to acetoacetic acid amide or its N substitution products and a corresponding sulfonic acid hydrazide is allowed to act on the reaction product in the same phase, preferably with gentle heating.
Sulfonic acid hydrazides, which are suitable for the preparation of the new 3-methylpyrazolone (5) compounds, are, for example, benzenesulfonic acid hydrazide, naphthalene sulfonic acid (2) hydrazide, azobenzenesulfonic acid (4) hydrazide and their, for example, halogen, Nitro, carboxylic acid, sulfonic acid, acetylamino or alkyl group-substituted derivatives, furthermore the alkylsulfonic acid hydrazides. Representatives that may be mentioned include n-octyl, n-dodecyl and n-octadecylsulfonic acid hydrazide.
The new N-sulfonyl-pyrazolone- (5) are accessible analogous reactions as the previously known directly substituted pyrazolone- (5).
The pyrazolone (5) compounds produced by the process according to the invention are suitable for the same purposes as those produced by the previously known processes.
example 1
In a three-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser, 12 parts by weight of conc. Ammonia and 75 parts by weight of water were initially charged and 21 parts by weight of diketene were slowly added dropwise with external ice cooling and stirring, so that the temperature does not exceed 10 C.
Then, over a period of 30 minutes, 43 parts by weight of benzenesudonic acid hydlrazide are added with stirring at a slowly increasing temperature and then heated to 40-5 ° C. for a further 2 hours. After standing overnight, a pale yellow colored precipitate has separated out, which after recrystallization gives pale pink-colored dull needles which melt at 157 to 159 ° C. with decomposition.
The raw yield is about 87%.
Example 2
21 parts by weight of diketene are gradually introduced into 85 parts by weight of 5% strength aqueous ammonia at 5-10 ° C. with stirring. Then 52 parts by weight of n-octanesulfonic acid hydrazide are added in portions at room temperature and the reaction mixture is heated for a further 6 hours at 60 ° C. with continued stirring. The yellow precipitate is purified by dissolving it in aqueous soda solution, precipitating it with dilute hydrochloric acid and then recrystallizing it. An almost colorless crystal powder with a melting point of 86 ° C. is then obtained.
The yield is 69%.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD5896559 | 1959-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH371121A true CH371121A (en) | 1963-08-15 |
Family
ID=5477342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH7055959A CH371121A (en) | 1959-01-21 | 1959-03-07 | Process for the preparation of 1-substituted 3-methyl-pyrazolone (5) compounds |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH371121A (en) |
-
1959
- 1959-03-07 CH CH7055959A patent/CH371121A/en unknown
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