CH357721A - Process for the preparation of a new hydrazine derivative - Google Patents
Process for the preparation of a new hydrazine derivativeInfo
- Publication number
- CH357721A CH357721A CH357721DA CH357721A CH 357721 A CH357721 A CH 357721A CH 357721D A CH357721D A CH 357721DA CH 357721 A CH357721 A CH 357721A
- Authority
- CH
- Switzerland
- Prior art keywords
- hydrazine
- methyl
- piperidyl
- isopropylidene
- solution
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000002429 hydrazines Chemical class 0.000 title claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000010933 acylation Effects 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 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
- 239000000155 melt Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010992 reflux Methods 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung eines neuen Hydrazin-Derivates
Es wurde gefunden, dass man zum neuen ?- (1 Methyl-piperidyl-4)-?-pivaloyl-hydrazin gelangen kann, indem man (l-Methyl-piperidyl-4)-hydrazin mit Aceton umsetzt, das entstandene co-(l-Methyl-piperi- dyl-4)-co'-isopropyliden-hydrazin mit Pivalinsäure- chlorid acyliert und aus dem so entstandenen ?-(1 Methyl - piperidyl-4)-?-pivaloyl-?'-isopropyliden-hydrazin die Isopropylidengruppe abspaltet.
Beispiel ?-(1 -Methyl-piperidyl-4)-?-pivaloyl-hydrazin
100 g (1-Methyl-piperidyl-4)-hydrazin werden in 300 cm3 Aceton unter Kühlung gelöst und die Lösung 1/. Stunde am Rückfluss zum Sieden erhitzt. Eindamp- fen der Lösung im Vakuum liefert das M- (l-Methyl- piperidyl-4)-co'-isopropyliden-hydrazin in quantitativer Ausbeute. Es kristallisiert beim Abkühlen in Nadeln. Die Verbindung kann destilliert werden und siedet bei 68-70 /0, 3 mm Hg. Zur Acylierung wird jedoch das kristalline Rohprodukt direkt weiterverwendet.
Die Lösung von 71, 5 g ?-(1-Methyl-piperidyl-4) a/-isopropyliden-hydrazin in 300 cm3 Chloroform wird unter Rühren und Kühlung (Innentemperatur von 0-5 ) mit einer Lösung von 50, 95 g Pivalin- säurechlorid in 50 cm3 Chloroform versetzt. Nach beendeter Zugabe wird die Lösung 5 Stunden bei Zimmertemperatur weitergerührt, dann mit 20proz. eiskalter, mit Kochsalz gesättigter Natronlauge ausgeschüttelt, über Natriumsulfat getrocknet und im Vakuum zur Trockne eingedampft.
Der ölige Rück- stand wird im Hochvakuurn destilliert wobei das co- (l Methyl-piperidyl-4)-co-pivaloyl-og'-isopropyliden-hy- drazin unter 0, 4 mm Hg bei 139-142 übergeht und in der KÏlte kristallinisch erstarrt.
58, 77 g oo-(1-Methyl-piperidyl-4)-oo-pivaloyl-co'- isopropyliden-hydrazin werden in 300 cm3 90proz.
¯thanol gelöst und in die Lösung unter Eiskühlung Chlorwasserstoff bis zur kongosauren Reaktion eingeleitet. Darauf wird die Lösung 1 Stunde bei Zim- mertemperatur stehengelassen und im Vakuum eingedampft, wobei das Hydrochlorid kristallisiert. Der Rückstand wird in Chloroform aufgenommen, die Chloroformlösung mit 20proz., auf-5 abgekühlter, mit Kochsalz gesättigter Natronlauge geschüttelt, über Natriumsulfat getrocknet und im Vakuum zur Trockne eingedampft. Der kristalline Rückstand wird aus Äther umkristallisiert. a- (l-Methyl-piperidyl-4)- co-pivaloyl-hydrazin bildet glänzende Blättchen und schmilzt bei 120-122 .
PATENTANSPRUCH
Verfahren zur Herstellung von co- (l-Methyl-pipe ridyl-4)-o)-pivaloyl-hydrazin, dadurch gekennzeich- net, dass man (1-Methyl-piperidyl-4)-hydrazin mit Aceton umsetzt, das entstandene o-(l-Methyl-piperidyl-4)-?'-isopropyliden-hydrazin mit Pivalinsäurechlo- rid acyliert und aus dem so entstandenen < M- (l-Me- thyl-piperidyl-4)-m-pivaloyl-cu'-isopropyliden-hydra- zin die Isopropylidengruppe abspaltet.
@@@@@@@
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the preparation of a new hydrazine derivative
It was found that the new? - (1-methyl-piperidyl-4) -? - pivaloyl-hydrazine can be obtained by reacting (l-methyl-piperidyl-4) -hydrazine with acetone, the co- (l -Methyl-piperidyl-4) -co'-isopropylidene hydrazine is acylated with pivalic acid chloride and the isopropylidene group is split off from the? - (1 methyl - piperidyl-4) -? - pivaloyl -? '- isopropylidene hydrazine .
Example? - (1 -Methyl-piperidyl-4) -? - pivaloyl-hydrazine
100 g of (1-methyl-piperidyl-4) hydrazine are dissolved in 300 cm3 of acetone with cooling and the solution 1 /. Heated to reflux for an hour. Evaporation of the solution in vacuo gives the M- (1-methylpiperidyl-4) -co'-isopropylidene hydrazine in quantitative yield. It crystallizes in needles on cooling. The compound can be distilled and boils at 68-70 / 0.3 mm Hg. For acylation, however, the crystalline crude product is used directly.
The solution of 71.5 g? - (1-methyl-piperidyl-4) a / -isopropylidene hydrazine in 300 cm3 chloroform is mixed with a solution of 50.95 g pivaline with stirring and cooling (internal temperature from 0-5) acid chloride in 50 cm3 chloroform. After the addition is complete, the solution is stirred for a further 5 hours at room temperature, then at 20 percent ice-cold sodium hydroxide solution, saturated with sodium chloride, extracted, dried over sodium sulfate and evaporated to dryness in vacuo.
The oily residue is distilled in a high vacuum, the co- (1 methyl-piperidyl-4) -co-pivaloyl-og'-isopropylidene hydrazine passing over below 0.4 mm Hg at 139-142 and crystalline in the cold stiffens.
58.77 g of oo- (1-methyl-piperidyl-4) -oo-pivaloyl-co'-isopropylidene hydrazine are 90% in 300 cm3.
Dissolved ethanol and passed hydrogen chloride into the solution while cooling with ice until a Congo-acidic reaction was achieved. The solution is then left to stand for 1 hour at room temperature and evaporated in vacuo, the hydrochloride crystallizing. The residue is taken up in chloroform, the chloroform solution is shaken with 20% sodium hydroxide solution cooled to -5 and saturated with sodium chloride, dried over sodium sulphate and evaporated to dryness in vacuo. The crystalline residue is recrystallized from ether. a- (l-Methyl-piperidyl-4) - co-pivaloyl-hydrazine forms shiny flakes and melts at 120-122.
PATENT CLAIM
Process for the preparation of co- (l-methyl-pipe ridyl-4) -o) -pivaloylhydrazine, characterized in that (1-methyl-piperidyl-4) hydrazine is reacted with acetone, the o- (l-Methyl-piperidyl-4) -? '- isopropylidene-hydrazine acylated with pivalic acid chloride and from the <M- (l-methyl-piperidyl-4) -m-pivaloyl-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 |
|---|---|---|---|
| CH357721T | 1958-03-31 | ||
| CH354441T | 1958-05-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH357721A true CH357721A (en) | 1961-10-31 |
Family
ID=25737140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH357721D CH357721A (en) | 1958-03-31 | 1958-03-31 | Process for the preparation of a new hydrazine derivative |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH357721A (en) |
-
1958
- 1958-03-31 CH CH357721D patent/CH357721A/en unknown
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