CH357722A - Process for the preparation of a new hydrazine derivative - Google Patents
Process for the preparation of a new hydrazine derivativeInfo
- Publication number
- CH357722A CH357722A CH357722DA CH357722A CH 357722 A CH357722 A CH 357722A CH 357722D A CH357722D A CH 357722DA CH 357722 A CH357722 A CH 357722A
- Authority
- CH
- Switzerland
- Prior art keywords
- hydrazine
- methyl
- piperidyl
- isopropylidene
- solution
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 150000002429 hydrazines Chemical class 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- JIQXKYSNGXUDJU-UHFFFAOYSA-N propan-2-ylidenehydrazine Chemical compound CC(C)=NN JIQXKYSNGXUDJU-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Description
Verfahren zur Herstellung eines neuen Hydrazin-Derivates
Es wurde gefunden, dass man zum neuen co- (l Methyl-piperidyl-4)- (o-n-caproyl-hydrazin gelangen kann, indem man (l-Methyl-piperidyl-4)-hydrazin mit Aceton umsetzt, das entstandene oo-(l-Methyl-piperi- dyl-4)-'-isopropyliden-hydrazin mit n-Capronsäure- chlorid'acyliert und aus dem so entstandenen co- (l- Methyl-piperidyl-4)-?-n-caproyl-?'-isopropyliden-hydrazin die Isopropylidengruppe abspaltet.
Beispiel G (1-Methyl-piperidyl-4)-?-n-caproyl-hydrazin 100 g (1-Methyl-piperidyl-4)-hydrazin werden in 300 cm3 Aceton unter Kühlung gelöst und die Lösung 1/2 Stunde am Rückfluss zum Sieden erhitzt. Eindampfen der Lösung im Vakuum liefert das co-(l- Methyl - piperidyl - 4) -?' - isopropyliden - hydrazin in quantitativer Ausbeute. Es kristallisiert beim Abkühlen in Nadeln. Das Rohprodukt wird nicht weiter gereinigt, sondern gleich acyliert.
Die Lösung von 18, 73 g oo-(l-Methyl-piperidyl- 4)-co'-isopropyliden-hydrazin in 100 cm3 Methylenchlorid wird unter Rühren und Kühlung mit einer Lösung von 14, 88 g n-Capronsäurechlorid in 25 cm3 Methylenchlorid versetzt. Nach beendeter Zugabe wird das Gemisch 4 Stunden bei Zimmertemperatur weitergerührt, dann mit 20proz., auf-10 abgekühlter, mit Kochsalz gesättigter NatronTauge ausgeschüttelt, über Natriumsulfat getrocknet und im Vakuum eingedampft.
Der Rückstand wird im Hochvakuum fraktioniert, wobei das ? -(1-Methyl-piperidyl-4)-?-n caproyl-o,'-isopropyliden-hydrazin unter 0, 03 mm Hg bei 128-133 bergeht
20, 44 g (,)- (1-Methyl-piperidyl-4)-?-n-caproyl-?'isopropyliden-hydrazin werden in 100 cm3 90proz.
¯thanol gelöst und in die Lösung unter Eiskühlung Chlorwasserstoff eingeleitet bis zur stark sauren Reaktion auf Kongopapier. Nach einstündigem Stehen bei Zimmertemperatur wird die Lösung im Vakuum bei 12 mm Hg und bei einer Badtemperatur von 40 bis 50 fast zur Trockne eingedampft, der Rückstand in Methylenchlorid aufgenommen, die Methylenchlo- rid-Lösung mit 20proz., auf-10 abgekühlter, mit Kochsalz gesättigter Natronlauge ausgeschüttelt, über Natriumsulfat getrocknet und im Vakuum eingedampft. Der kristalline Rückstand, das ?-(1-Methyl piperidyl-4)-oo-n-caproyl-hydrazin, wird aus Ather Petroläther umkristallisiert. Verwachsene Nadeln, Smp. 84-85 .
PATENTANSPRUCH
Verfahren zur Herstellung von ?-(1-Methyl-pipe ridyl-4)-co-n-caproyl-hydrazin, dadurch gekennzeichnet, dass man (l-Methyl-piperidyl-4)-hydrazin mit Aceton umsetzt, das entstandene co- (l-Methyl-piperi- dyl-4)-?'-isopropyliden-hydrazin mit n-Capronsäure- chlorid acyliert und aus dem so entstandenen M- (l- Methyl-piperidyl-4)-co-n-caproyl-cu -isopropyliden-hy- drazin die Isopropylidengruppe abspaltet.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the preparation of a new hydrazine derivative
It has been found that the new co- (l-methyl-piperidyl-4) - (on-caproyl-hydrazine) can be obtained by reacting (l-methyl-piperidyl-4) -hydrazine with acetone, the oo- ( l-methyl-piperidyl-4) -'- isopropylidene-hydrazine with n-caproic acid chloride'acylated and from the co- (l-methyl-piperidyl-4) -? - n-caproyl -? '- isopropylidene hydrazine splits off the isopropylidene group.
Example G (1-methyl-piperidyl-4) -? - n-caproyl-hydrazine 100 g (1-methyl-piperidyl-4) -hydrazine are dissolved in 300 cm3 of acetone with cooling and the solution is refluxed for 1/2 hour Boiling heated. Evaporation of the solution in vacuo yields the co- (l-methyl-piperidyl-4) -? ' - isopropylidene - hydrazine in quantitative yield. It crystallizes in needles on cooling. The crude product is not purified any further, but acylated straight away.
The solution of 18.73 g of oo- (l-methylpiperidyl-4) -co'-isopropylidene hydrazine in 100 cm3 of methylene chloride is mixed with a solution of 14.88 g of n-caproic acid chloride in 25 cm3 of methylene chloride while stirring and cooling . When the addition is complete, the mixture is stirred for a further 4 hours at room temperature, then extracted with 20% sodium hydroxide solution cooled to 10 and saturated with sodium chloride, dried over sodium sulfate and evaporated in vacuo.
The residue is fractionated in a high vacuum, whereby the? - (1-Methyl-piperidyl-4) -? - n caproyl-o, '- isopropylidene hydrazine goes below 0.03 mm Hg at 128-133
20.44 g of (,) - (1-methyl-piperidyl-4) -? - n-caproyl -? 'Isopropylidene hydrazine are 90% in 100 cm3.
¯thanol dissolved and hydrogen chloride passed into the solution while cooling with ice until a strongly acidic reaction on Congo paper. After standing for one hour at room temperature, the solution is evaporated to almost dryness in vacuo at 12 mm Hg and a bath temperature of 40 to 50, the residue is taken up in methylene chloride, and the methylene chloride solution is 20%, cooled to -10, with sodium chloride Shaken out saturated sodium hydroxide solution, dried over sodium sulfate and evaporated in vacuo. The crystalline residue, the? - (1-methyl piperidyl-4) -oo-n-caproylhydrazine, is recrystallized from ether, petroleum ether. Intergrown needles, m.p. 84-85.
PATENT CLAIM
Process for the production of? - (1-Methyl-pipe ridyl-4) -co-n-caproyl-hydrazine, characterized in that (l-methyl-piperidyl-4) -hydrazine is reacted with acetone, the co- ( 1-methyl-piperidyl-4) -? '- isopropylidene-hydrazine acylated with n-caproic acid chloride and from the M- (1-methyl-piperidyl-4) -co-n-caproyl-cu -isopropylidene -hydrazine splits off the isopropylidene group.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH354441T | 1958-05-06 | ||
| CH357722T | 1958-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH357722A true CH357722A (en) | 1961-10-31 |
Family
ID=25737141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH357722D CH357722A (en) | 1958-05-06 | 1958-05-06 | Process for the preparation of a new hydrazine derivative |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH357722A (en) |
-
1958
- 1958-05-06 CH CH357722D patent/CH357722A/en unknown
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