DE279194C - - Google Patents
Info
- Publication number
- DE279194C DE279194C DENDAT279194D DE279194DA DE279194C DE 279194 C DE279194 C DE 279194C DE NDAT279194 D DENDAT279194 D DE NDAT279194D DE 279194D A DE279194D A DE 279194DA DE 279194 C DE279194 C DE 279194C
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- derivatives
- parts
- homopiperonylamine
- aralkylated
- 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
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- YOJQZPVUNUQTDF-UHFFFAOYSA-N Hydrastinine Chemical class C1=C2C(O)N(C)CCC2=CC2=C1OCO2 YOJQZPVUNUQTDF-UHFFFAOYSA-N 0.000 claims description 2
- RRIRDPSOCUCGBV-UHFFFAOYSA-N Methylenedioxyphenethylamine Chemical class NCCC1=CC=C2OCOC2=C1 RRIRDPSOCUCGBV-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N Phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 230000002378 acidificating Effects 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 150000002829 nitrogen Chemical group 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N Isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IOEPOEDBBPRAEI-UHFFFAOYSA-N 1,2-dihydroisoquinoline Chemical class C1=CC=C2CNC=CC2=C1 IOEPOEDBBPRAEI-UHFFFAOYSA-N 0.000 description 1
- OJYQVFSOTGWSQR-UHFFFAOYSA-N C1OC=2C=C(C=CC=2O1)N(C=O)C(C)C Chemical compound C1OC=2C=C(C=CC=2O1)N(C=O)C(C)C OJYQVFSOTGWSQR-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N Ethyl iodide Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- JVr 279194 KLASSE Mp. GRUPPE^ K'4, - JVR 279194 CLASS GROUP Mp ^ K'4.
Firma E. MERCK in DARMSTADT. Verfahren zur Darstellung von Hydrastininderivaten, Patentiert im Deutschen Reiche vom 24. Dezember 1912 ab. E. MERCK company in DARMSTADT. Process for the preparation of hydrastinine derivatives, patented in the German Empire on December 24, 1912.
Es wurde gefunden, daß die N-Formylderivate der nach dem Verfahren des Patents 274350, Kl. 12 q, sehr leicht und vorteilhaftIt has been found that the N-formyl derivatives according to the method of the patent 274350, class 12 q, very light and advantageous
darstellbaren C-Alkyl-N-alkyl- oder aralkyl- 35 homopiperonylamine der allgemeinen Formel:representable C-alkyl-N-alkyl- or aralkyl- 35 homopiperonylamine of the general formula:
.0.0
CH2
\CH 2
\
CH2-CH(Alkyl).N: CH 2 -CH (alkyl) .N :
(R = Alkyl oder Aralkyl)(R = alkyl or aralkyl)
,R
XOH, R
XOH
4040
. 45. 45
beim Behandeln mit sauren Kondensationsmitteln, wie Phosphorpentoxyd, Phosphorpentachlorid, Aluminiumchlorid oder Chlorzink, inwhen treating with acidic condensing agents such as phosphorus pentoxide, phosphorus pentachloride, Aluminum chloride or zinc chloride, in
3 · 4-Dihydroisochinolinderivate, die am Kohlenstoffatom 3 (Formelbild untenstehend) Alkylreste enthalten, übergeführt werden können:3 · 4-dihydroisoquinoline derivatives attached to the carbon atom 3 (formula below) contain alkyl radicals, can be converted:
CH,CH,
CH,CH,
CH-AlkylCH-alkyl
CHCH
+ HCl = CH2 + HCl = CH 2
NRNO
CH-AlkylCH-alkyl
+ H2O.+ H 2 O.
5555
OCHOCH
Ferner können an Stelle der obenerwähnten, j lierten Ausgangsstoffe die N-Formylderivate 60 am Stickstoff bereits alkylierten oder aralky- der primären Basen der Formel:Furthermore, instead of the abovementioned starting materials, the N-formyl derivatives 60 on the nitrogen already alkylated or aralky the primary bases of the formula:
CHCH
C H2-C H (Alkyl)· N H2 CH 2 -CH (alkyl) • NH 2
65.65.
(ebenfalls nach dem Verfahren des Patents 274350, Kl. 12q, darstellbar) nach der Gleichung:(can also be represented using the method of patent 274350, class 12q) according to the equation:
CH9 CH 9
CH- AlkylCH-alkyl
-f HCl = CH,-f HCl = CH,
NHNH
OCHOCH
zuerst in 3-alkyüerte 3 · 4-Dihydroisochinolinderivate übergeführt und dann am Stickstoffatom alkyliert oder aralkyliert werden.first in 3-alkylated 3 · 4-dihydroisoquinoline derivatives converted and then alkylated or aralkylated on the nitrogen atom.
Die Kondensation der am Stickstoff bereits alkylierten oder aralkylierten Formylderivate zu Dihydroisochinolinderivaten war nicht vorauszusehen. The condensation of the formyl derivatives already alkylated or aralkylated on the nitrogen to dihydroisoquinoline derivatives could not be foreseen.
Außerdem bedeutet das Verfahren infolge der leichten Zugänglichkeit der AusgangsstoffeIn addition, the process means due to the easy accessibility of the starting materials
CH-AlkylCH-alkyl
+ H2O+ H 2 O
NHClNHCl
im Gegensatz zur Herstellung der am Kohlenstoff nicht substituierten Derivate des Homopiperonylamins einen wesentlichen technischen Fortschritt.in contrast to the preparation of the unsubstituted carbon derivatives of homopiperonylamine a significant technical advance.
ι Teil 3 · 4-Methylendioxy-N-methylformylisopropylamin ι Part 3 · 4-methylenedioxy-N-methylformylisopropylamine
CHCH
CH2-CH(CHg)-NCH 2 -CH (CHg) -N
CH3
COHCH 3
COH
(derbe, weiße Kristalle aus Petroläther vom Schmelzpunkt 53 bis 54°) wird in 5 Teilen Xylol gelöst und in der Siedehitze 3 Teile Phosphorpentoxyd in 3 Anteilen innerhalb ι Stunde zugegeben. Nach beendeter Reak-(coarse, white crystals of petroleum ether with a melting point of 53 to 54 °) is divided into 5 parts Dissolved xylene and boiling 3 parts of phosphorus pentoxide in 3 parts within ι hour added. After the end of the reaction
tion ist eine gelbrote Masse entstanden. Das Xylol wird davon abgegossen und der Rückstand in Eiswasser gelöst. In dieser Lösung befindet sich die Isochinolinbasetion, a yellow-red mass has arisen. The xylene is poured off and the residue dissolved in ice water. The isoquinoline base is located in this solution
CHv CH-CH,CHv CH-CH,
CH3
OHCH 3
OH
als Metaphosphat. Sie wird aus der Lösung mit Alkalilauge gefällt und mit Äther aufgenommen. Nach dem Verdampfen der Lösung bleibt die Base als Öl zurück, das nach der Reinigung in eine weiße kristallinische Masse übergeht.as metaphosphate. It is precipitated from the solution with alkali lye and absorbed with ether. After evaporation of the solution, the base remains as an oil which, after purification, turns into a white crystalline mass transforms.
Die Kristalle schmelzen bei 105 bis 106 °.The crystals melt at 105 to 106 °.
Das überchlorsaure Salz kristallisiert aus Wasser oder Alkohol in langen, ganz schwach gelbgrün gefärbten Nadeln, die bei 215 bis 216 ° schmelzen.The overchloric acid salt crystallizes from water or alcohol in long, very pale yellow-green colored needles, which are at 215 to 216 ° melt.
ι Teil 3 · 4-Methylendioxyphenyl-N-formylisopropylamin (lange, weiße Nadeln aus Alkohol vom Schmelzpunkt 94 bis 95 °) wird in 7 Teilen Toluol gelöst und bei Siedehitze mit 3 Teilen Phosphorpentoxyd in 3 Anteilen innerhalb Y2 Stunde versetzt. Das in Toluol unlösliche rohe Reaktionsprodukt wird mit Eis versetzt und mit Äther ausgeschüttelt. Die rote fluorescierende Lösung des Metaphosphats der IsochinolinbasePart 3 · 4-methylenedioxyphenyl-N-formylisopropylamine (long, white needles made of alcohol with a melting point of 94 to 95 °) is dissolved in 7 parts of toluene and 3 parts of phosphorus pentoxide are added in 3 parts at boiling point within 2 hours. The crude reaction product, which is insoluble in toluene, is mixed with ice and extracted with ether. The red fluorescent solution of isoquinoline base metaphosphate
CHCH
JCH-CH3 JCH-CH 3
wird stark alkalisch gemacht und ausgeäthert. Der Rückstand wird unter vermindertem Druck destilliert. Die Base geht unter 4,5 mm Druck bei 140 bis 142 ° als farbloses öl über, das in der Vorlage in weißen Nadeln erstarrt, die nach dem Kristallisieren aus Petroläther bei 60 bis 61 ° schmelzen. Bei einstündigem Erhitzen auf 100° mit der molekularen Menge Jodäthyl in ätherischer Lösung erhält man das Jodäthylat, das aus Alkohol in gelben Nadeln vom Schmelzpunkt 211 bis 212 ° kristallisiert.is made strongly alkaline and etherified. The residue is under reduced pressure distilled. The base goes over under 4.5 mm pressure at 140 to 142 ° as a colorless oil, which in the template solidified in white needles, which formed after crystallization from petroleum ether Melt 60 to 61 °. When heated to 100 ° for one hour with the molecular amount Ethyl iodine in ethereal solution gives iodine ethylate, which is obtained from alcohol in yellow needles crystallized from melting point 211 to 212 °.
Claims (1)
COHR.
COH
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE279194C true DE279194C (en) |
Family
ID=535130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT279194D Active DE279194C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE279194C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022150525A1 (en) | 2021-01-06 | 2022-07-14 | Awakn Life Sciences | Mdma in the treatment of alcohol use disorder |
-
0
- DE DENDAT279194D patent/DE279194C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022150525A1 (en) | 2021-01-06 | 2022-07-14 | Awakn Life Sciences | Mdma in the treatment of alcohol use disorder |
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