CH148289A - Process for the preparation of 6,7-dioxymethylene-3-methyl-1- (3'.4'-dioxymethylenebenzyl) -isoquinoline. - Google Patents
Process for the preparation of 6,7-dioxymethylene-3-methyl-1- (3'.4'-dioxymethylenebenzyl) -isoquinoline.Info
- Publication number
- CH148289A CH148289A CH148289DA CH148289A CH 148289 A CH148289 A CH 148289A CH 148289D A CH148289D A CH 148289DA CH 148289 A CH148289 A CH 148289A
- Authority
- CH
- Switzerland
- Prior art keywords
- dioxymethylene
- isoquinoline
- methyl
- prisms
- dioxymethylenebenzyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
- C07D217/18—Aralkyl radicals
- C07D217/20—Aralkyl radicals with oxygen atoms directly attached to the aromatic ring of said aralkyl radical, e.g. papaverine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Description
Verfahren zur Darstellung. von 6,7-Dioxymethylen-3-methyl-1-(3' . 4'-dioxymet1)ylen- benzyl)-isochinolin. Es ist bekannt (Bischler und Napieralski, Fer. d. deutsch. chem. Gesellschaft, 26 (1893) 1903, Pictet und Finkelstein, Ber. d. deutsch.
chem. Gesellschaft, 42 (1909) 1979), dass Säureamide, welche aus Phenylessigsäuren und 1 - Phenyl - 2 - aminoäthanen gekuppelt worden sind, unter dem Einfluss kondensie render Mittel, wie Chlorzink, Phosphor- pentoxyd, Phosphoroxychlorid in Benzyl- dihydroisochinoline überführbar sind.
Es wurde nun gefunden, dass Säureamide, welche als basische Komponente das 1-Me- t:liy lendioxyphenyl-2-amino-propan (D. R. P. Nr.2743,50) enthalten, ebenfalls unter dem Einfluss kondensierender Mittel in Benzyl- clihydroisochinoline übergehen. Diese waren noch nicht bekannt.
Durch Dehydrierung derselben können Basen erhalten werden, welche dem Papaverin an therapeutischer Wirkung überlegen sind, während die be reits bekannten Verwandten des Papaverins für medizinische Verwendung nicht geeignet waren (Mahnich und Walther, Archiv d. Pharm. 265 (1927), S. 3).
Es war bereits bekannt. dass Di- und Te- trahydropapaverin sich mittelst Palladium zum Papaverin dehydrieren lassen (Spaet u. Burger, Ber. d. deutsch. chem. Ges. 60 (192i7), 704); aber in diesem Falle tragen die bei den Kohlenstoffatome, deren einfache Bin dung in eine doppelte überführt werden soll, noch je zwei Wasserstoffatome.
Im vorlie genden Falle handelt es sich nun um eine Dehydrierung, bei welcher eines jener H Atome durch eine Alkylgruppe ersetzt ist, wodurch die Dehydrierung erschwert bezw. unter Umständen unmöglich gemacht wird.
Hervorragende, dem Papaverin über legene therapeutische Wirkungen zeigt vor allem das noch nicht. bekannte 6,7-Dioxy- methylen-3-methyl-1-(3' . I'-clioxymethylen- benzyl) - isochinolin, welches erfindungsge mäss dadurch hergestellt wird, dass man das Säureamid, gebildet aus 1-(3'. 4'-Dioxy-mP- thylenphenyl)-2-aminopropan und 3,4-Dioxy- methylen-phenylessigsäure, mit sauren Kon densationsmitteln behandelt und die so ge wonnene Base mit fein verteiltem Palladium dehydriert.
<I>Beispiel:</I> <B>10</B> Teile des genannten Amids CH202 = C,H3-CH2-CH(CH3)-NH-CO-CH2- CJH3 = 02CH2 (F. =146 ) werden in 1,80 Teilen heissen Toluols gelöst und mit 6 Tei len Phosphoroxychlorid 3 Stunden auf etwa 100 erhitzt.
Das Reaktionsprodukt, welches sich als dunkle, zum Teil kristallisierte Masse abscheidet, wird vom Toluol abge trennt und mit 100 Teilen Wasser unter Er wärmen eine halbe Stunde gerührt, mit Kohle filtriert und der Kristallisation über lassen. Das Hydrochlorid der neuen Base scheidet sich in Prismen ab, welche bei 23.7 unter Zersetzung schmelzen. 1.0 Teile der selben werden mit 1 Teil Palladiummooar Stunden bei etwa 1$0 gerührt. Die Schmelze wird in heisser 4 % iger Salzsäure gelöst, mit Kohle gereinigt und der Kristalli sation überlassen.
Das Hydrochlorid schei det sich in Prismen ab, welche bei<B>1159</B> schmelzen. Die freie Base kristallisiert aus Methanol, Äther oder Benzol in glänzenden Prismen vom Schmelzpunkt 140 . Sie ist leicht löslich in kaltem Methylenchlorid.
EMI0002.0022
Method of representation. of 6,7-dioxymethylene-3-methyl-1- (3 ', 4'-dioxymet1) ylene-benzyl) -isoquinoline. It is known (Bischler and Napieralski, Fer. D. German. Chem. Society, 26 (1893) 1903, Pictet and Finkelstein, Ber. D. German.
chem. Gesellschaft, 42 (1909) 1979) that acid amides which have been coupled from phenylacetic acids and 1 - phenyl - 2 - aminoethanes can be converted into benzyl dihydroisoquinolines under the influence of condensing agents such as zinc chloride, phosphorus pentoxide, phosphorus oxychloride.
It has now been found that acid amides, which contain the 1-meta-t: liy lendioxyphenyl-2-aminopropane (D. R. P. No. 2743.50) as a basic component, also convert to benzyl clihydroisoquinolines under the influence of condensing agents. These were not yet known.
By dehydrating them, bases can be obtained which are superior to papaverine in terms of therapeutic effect, while the already known relatives of papaverine were not suitable for medical use (Mahnich and Walther, Archiv d. Pharm. 265 (1927), p. 3) .
It was already known. that di- and tetrahydropapaverine can be dehydrated to papaverine by means of palladium (Spaet and Burger, Ber. d. German. chem. Ges. 60 (192i7), 704); but in this case the carbon atoms whose single bond is to be converted into a double bond each have two hydrogen atoms.
In the present case it is a dehydrogenation in which one of those H atoms is replaced by an alkyl group, which makes the dehydrogenation more difficult or more difficult. may be made impossible.
Above all, this does not yet show excellent therapeutic effects superior to papaverine. known 6,7-dioxymethylene-3-methyl-1- (3 '. I'-clioxymethylene benzyl) isoquinoline, which according to the invention is produced by the amide formed from 1- (3', 4 '-Dioxy-mP-thylenephenyl) -2-aminopropane and 3,4-dioxymethylene-phenylacetic acid, treated with acidic condensation agents and the base thus obtained is dehydrated with finely divided palladium.
<I> Example: </I> <B> 10 </B> parts of the amide mentioned CH202 = C, H3-CH2-CH (CH3) -NH-CO-CH2-CJH3 = 02CH2 (F. = 146) dissolved in 1.80 parts of hot toluene and heated to about 100 for 3 hours with 6 parts of phosphorus oxychloride.
The reaction product, which separates out as a dark, partially crystallized mass, is separated from the toluene and stirred with 100 parts of water while warming for half an hour, filtered with charcoal and allowed to crystallize. The hydrochloride of the new base separates out in prisms, which melt at 23.7 with decomposition. 1.0 parts of the same are stirred with 1 part of palladium for a few hours at about 1%. The melt is dissolved in hot 4% hydrochloric acid, cleaned with charcoal and left to crystallize.
The hydrochloride is deposited in prisms, which melt at <B> 1159 </B>. The free base crystallizes from methanol, ether or benzene in shiny prisms with a melting point of 140. It is easily soluble in cold methylene chloride.
EMI0002.0022
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEM111600D DE550122C (en) | 1929-08-24 | 1929-08-24 | Process for the production of pellets of 1-benzyl-3-methylisoquinoline |
Publications (1)
Publication Number | Publication Date |
---|---|
CH148289A true CH148289A (en) | 1931-07-15 |
Family
ID=7327290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH148289D CH148289A (en) | 1929-08-24 | 1930-03-08 | Process for the preparation of 6,7-dioxymethylene-3-methyl-1- (3'.4'-dioxymethylenebenzyl) -isoquinoline. |
Country Status (3)
Country | Link |
---|---|
AT (1) | AT131117B (en) |
CH (1) | CH148289A (en) |
DE (1) | DE550122C (en) |
-
1929
- 1929-08-24 DE DEM111600D patent/DE550122C/en not_active Expired
-
1930
- 1930-03-01 AT AT131117D patent/AT131117B/en active
- 1930-03-08 CH CH148289D patent/CH148289A/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE550122C (en) | 1932-05-10 |
AT131117B (en) | 1933-01-10 |
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