DE153861C - - Google Patents
Info
- Publication number
- DE153861C DE153861C DENDAT153861D DE153861DA DE153861C DE 153861 C DE153861 C DE 153861C DE NDAT153861 D DENDAT153861 D DE NDAT153861D DE 153861D A DE153861D A DE 153861DA DE 153861 C DE153861 C DE 153861C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- phenyl
- methyl
- alcohol
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 claims description 3
- 230000002378 acidificating Effects 0.000 claims description 2
- 239000003638 reducing agent Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N Phosphoryl chloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229960000583 Acetic Acid Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical group N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 1
- KTFGWHSLIOZEKH-UHFFFAOYSA-N 5-benzyl-1H-pyrazole Chemical compound C=1C=CC=CC=1CC1=CC=NN1 KTFGWHSLIOZEKH-UHFFFAOYSA-N 0.000 description 1
- IJPFBRONCJOTTA-UHFFFAOYSA-N 5-chloro-1H-pyrazole Chemical compound ClC1=CC=NN1 IJPFBRONCJOTTA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- MFSIEROJJKUHBQ-UHFFFAOYSA-N O.[Cl] Chemical compound O.[Cl] MFSIEROJJKUHBQ-UHFFFAOYSA-N 0.000 description 1
- VFBFBYISKAUZNI-UHFFFAOYSA-N S.[Sn] Chemical compound S.[Sn] VFBFBYISKAUZNI-UHFFFAOYSA-N 0.000 description 1
- 101710019204 TIMM10 Proteins 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J Tin(IV) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
- C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
- C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Das durch Umsetzung von i-Phenyl-3-methyl-4-benzolazo-5-pyrazolon mit Phosphoroxychlorid erhältliche Phenylmethylbenzolazochlorpyrazol geht nach den Beobachtungen von Michaelis und Leonhardt (Ber. d. D. ehem. Ges. 36, 3597) unter der Einwirkung von Zinkstaub und Natronlauge in Phenylmethylbenzolazopyrazol über, es wird also das Chlor leicht durch Wasserstoff ersetzt. Demgegenüber war nicht vorherzusehen, daß unter anderen Reduktionsbedingungen das Chlor im Molekül erhalten bleibt, aber die Benzolazogruppe gespalten wird, so daß das bisher unbekannte Phenylmethylamidochlorpyrazol entsteht.The reaction of i-phenyl-3-methyl-4-benzolazo-5-pyrazolone Phenylmethylbenzolazochlorpyrazole obtainable with phosphorus oxychloride goes according to the observations von Michaelis and Leonhardt (Ber. d. D. formerly Ges. 36, 3597) under the influence from zinc dust and caustic soda to phenylmethylbenzolazopyrazole, so it becomes that Chlorine easily replaced by hydrogen. In contrast, it was not foreseeable that under other reduction conditions the chlorine remains in the molecule, but the benzene azo group is cleaved, so that the previously unknown phenylmethylamidochloropyrazole is formed.
Es wurde gefunden, daß die Darstellung dieser Verbindung gelingt, indem man Phenylmethylbenzolazochlorpyrazol mit sauren· Reduktionsmitteln behandelt. An Stelle des Benzolazoderivates können natürlich andere Arylazoderivate in dem Verfahren verwendet werden.It has been found that this compound can be prepared by adding phenylmethylbenzolazochloropyrazole treated with acidic reducing agents. Instead of the benzene azo derivative, others can of course Arylazo derivatives can be used in the process.
Zur Darstellung der neuen Verbindung verfährt man beispielsweise wie folgt:To display the new connection, proceed as follows, for example:
IO Teile i-Phenyl^-methyl^-benzolazo-IO parts i-phenyl ^ -methyl ^ -benzolazo-
5-chlorpyrazol und 4 Teile granuliertes Zinn werden mit 10 Teilen Alkohol Übergossen, 5 Teile konzentrierter Salzsäure und 5 Teile konzentrierter Zinnchlorürlösung zugegeben und gerührt. Die Reaktion beginnt von selbst und wird durch Erwärmen auf dem Wasserbad zu Ende geführt.5-chloropyrazole and 4 parts of granulated tin 10 parts of alcohol are poured over them, 5 parts of concentrated hydrochloric acid and 5 parts concentrated tin chloride solution added and stirred. The reaction starts by itself and is completed by heating on the water bath.
Die entstandene neue Base kann in üblicher Weise nach Entfernung des Zinns durch Schwefelwasserstoff und Eindampfen der Lösung (zweckmäßig im Vakuum) in Form des kristallinischen salzsauren Salzes isoliert werden. Dies läßt sich aus Alkohol umkristallisieren. Aus der wäßrigen Lösung des Chlorhydrats scheidet überschüssiges Alkali die freie Base als Öl ab, das sich in Äther aufnehmen läßt. Beim Abdestillieren des Äthers erhält man dann das Phenylmethylamidochlorpyrazol als Öl, das bald zur Kristallmasse erstarrt.The resulting new base can in the usual way after removing the tin Hydrogen sulfide and evaporation of the solution (expediently in vacuo) in the form of the crystalline hydrochloric acid salt can be isolated. This can be recrystallized from alcohol. Excess alkali separates the free alkali from the aqueous solution of the chlorohydrate Base as an oil that can be absorbed in ether. Receives when the ether is distilled off one then the Phenylmethylamidochlorpyrazol as an oil, which soon becomes crystal mass stiffens.
Es kristallisiert aus Petroläther in Tafeln, die bei 490 schmelzen; in Alkohol und Äther ist es leicht löslich. Sein Chlorhydrat kristallisiert aus Alkohol in Blättchen, deren Zersetzungspunkt bei 2200 liegt; mit salpetriger Säure gibt es eine Diazoverbindung.It crystallizes from petroleum ether in tablets that melt at 49 0; it is easily soluble in alcohol and ether. Its chlorine hydrate crystallizes from alcohol in flakes, the decomposition point of which is 220 ° ; with nitrous acid there is a diazo compound.
In gleicher Weise gestaltet sich das Verfahren, wenn an Stelle des Phenylmethylbenzolazochlorpyrazols ein anderes I-Phenyl-3-methyl-4-arylazo-5-chlorpyrazol sauer reduziert wird.The process works in the same way if phenylmethylbenzolazochloropyrazole is used instead another I-phenyl-3-methyl-4-arylazo-5-chloropyrazole acid is reduced.
I -Phenyl-3 -methyl-4-0-toluolazo-5-chlorpyrazol (3 Teile) werden mit Alkohol (10 Teile)I-phenyl-3-methyl-4-0-toluene-azo-5-chloropyrazole (3 parts) are mixed with alcohol (10 parts)
und 5Oprozentiger Essigsäure (ιο Teile) angerührt und unter Zusatz von Eisenfeile (3 Teile) auf dem Wasserbad erwärmt. Dann verdünnt man mit heißem Wasser, filtriert und dampft ein. Aus dem Rückstand kann durchSoda das Phenylmethylamidochlorpyrazol frei gemacht und in Benzol aufgenommen werden. Von beigemengtem o-Toluidin ist es durch Destillation mit Wasserdampf zu trennen.and 50 percent acetic acid (ιο parts) stirred and heated on a water bath with the addition of iron files (3 parts). Then it is diluted with hot water and filtered and evaporates. The phenylmethylamidochloropyrazole can be obtained from the residue by means of soda can be set free and absorbed in benzene. From added o-toluidine it is to be separated by distillation with steam.
Das vorerwähnte Phenylmethyl-4-o-toluolazochlorpyrazol wird durch Einwirkung von diazotiertem o-Toluidin auf Phenylmethylpyrazol und Erhitzen des so entstehenden Phenylmethyl-o-toluolazopyrazolons (1 Teil) mit Phosphoroxychlorid (1Y2 Teil) auf ioo° erhalten; jenes Toluolazochlorpyrazolon bildet orangegelbe Nädelchen, die bei 970 schmelzen; das o-Toluolazopyrazolon bildet rote, bei 183° schmelzende Nädelchen. Den genannten o-Toluolazoderivaten entsprechen die mit p-Phenetidin erhältlichen Derivate i-Phenyl^-methyl-zj.-p-phenetolazo-5-pyrazolon, das feine orangerote Nadeln vom Schmp. 1590 bildet, und das i-Phenyl-s-methyl-zi-p-phenetolazochlorpyrazol, das bei 123° schmilzt und in orangegelben Blättchen kristallisiert.The aforementioned phenylmethyl-4-o-toluene-azochloropyrazole is obtained by the action of diazotized o-toluidine on phenylmethylpyrazole and heating of the phenylmethyl-o-toluene-azopyrazolone (1 part) with phosphorus oxychloride (1Y 2 part) to 100 °; Toluolazochlorpyrazolon that forms orange-yellow needles, melting at 97 0; the o-toluolazopyrazolone forms red needles that melt at 183 °. The o-toluene azo derivatives mentioned correspond to the derivatives i-phenyl ^ -methyl-zj.-p-phenetolazo-5-pyrazolone, which forms fine orange-red needles of melting point 159 0 , and i-phenyl-s- methyl-zi-p-phenetolazochloropyrazole, which melts at 123 ° and crystallizes in orange-yellow flakes.
Beispiel III.Example III.
Zur Reduktion des Phenetolazochlorpyrazols löst man es in zehnfacher Menge Eisessig (90 Prozent) und trägt unter Rühren Zinkstaub ein. Man erwärmt auf dem Wasserbad, übersättigt die filtrierte entfärbte Lösung mit Ätznatron und schüttelt mit Äther aus. Von beigemengtem Phenetidin kann das Amidochlorpyrazol durch Wasserdampf getrennt und durch Kristallisation des Chlorhydrats rein gewonnen werden.To reduce the phenetolazochloropyrazole, it is dissolved in ten times the amount of glacial acetic acid (90 percent) and introduces zinc dust while stirring. One warms up on the water bath, oversaturated the filtered decolorized solution with caustic soda and shake out with ether. The amidochloropyrazole can be separated from the added phenetidine by steam and can be obtained pure by crystallization of the chlorohydrate.
Die neue Verbindung ist von technischem Interesse, da sie durch Methylierung und Einwirkung von Alkali in das Phenyldimethyldimethylamidopyrazolon übergeführt werden kann.The new compound is of technical interest because it is methylated and acted upon can be converted from alkali into the phenyldimethyldimethylamidopyrazolone can.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE153861C true DE153861C (en) |
Family
ID=420450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT153861D Active DE153861C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE153861C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5163710A (en) * | 1991-10-28 | 1992-11-17 | Chirtel Stuart J | Roller skating pole |
-
0
- DE DENDAT153861D patent/DE153861C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5163710A (en) * | 1991-10-28 | 1992-11-17 | Chirtel Stuart J | Roller skating pole |
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