DE208255C - - Google Patents
Info
- Publication number
- DE208255C DE208255C DENDAT208255D DE208255DA DE208255C DE 208255 C DE208255 C DE 208255C DE NDAT208255 D DENDAT208255 D DE NDAT208255D DE 208255D A DE208255D A DE 208255DA DE 208255 C DE208255 C DE 208255C
- Authority
- DE
- Germany
- Prior art keywords
- eugenol
- isoeugenol
- acetamide
- och
- acetamides
- 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.)
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- RRAFCDWBNXTKKO-UHFFFAOYSA-N Eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 20
- -1 N-substituted aminomethyl compounds Chemical class 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 239000005770 Eugenol Substances 0.000 claims description 10
- 229960002217 Eugenol Drugs 0.000 claims description 10
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 150000003869 acetamides Chemical class 0.000 description 4
- 230000001476 alcoholic Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LRKYLKBLUJXTFL-UHFFFAOYSA-N 1-(piperidin-1-ylmethyl)piperidine Chemical compound C1CCCCN1CN1CCCCC1 LRKYLKBLUJXTFL-UHFFFAOYSA-N 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N Chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002690 local anesthesia Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- M 208255 KLASSE 12 o. GRUPPE- M 208255 CLASS 12 or GROUP
Dr. ALFRED EINHORN in MÜNCHEN.Dr. ALFRED EINHORN in MUNICH.
Verfahren zur Herstellung N-substituierter Aminomethylverbindungen des Eugenol-Process for the preparation of N-substituted aminomethyl compounds of eugenol
und Isoeugenolacetamids.and isoeugenol acetamides.
Es wurde gefunden, daß die Acetamide des Eugenols und Isoeugenol sich mit Formaldehyd und sekundären aliphatischen Basen im SinneIt has been found that the acetamides of eugenol and isoeugenol react with formaldehyde and secondary aliphatic bases in the sense
, Co HK der folgenden Gleichung zu neuen Basen, den N-substituierten Aminomethylverbindungen des 35 Eugenol- und Isoeugenolacetamids umsetzen:, Co H K of the following equation to convert to new bases, the N-substituted aminomethyl compounds of eugenol and isoeugenol acetamides:
O6H3-O C H3 . ■O 6 H 3 -OCH 3 . ■
XO-C H2-CO-N H2 + C H2O + HNRR1 X OC H 2 -CO-N H 2 + CH 2 O + HNRR 1
/C3 H5 = H2O + C6H3^O CH3 XO · CH2. C O. NH . C H2. NRR1. / C 3 H 5 = H 2 O + C 6 H 3 ^ O CH 3 X O • CH 2 . C O. N H. C H 2 . NRR 1 .
Dabei ist es gleichgültig, ob man die drei Komponenten direkt aufeinander einwirken läßt, oder ob man den Formaldehyd zuvor an die Acetamide oder an die sekundären Basen bindet und also entweder dann die N-Mono- oder -Dimethylolverbindungen der Acetamide mit den sekundären Basen oder aber die Methylolverbindungen oder die Me- 45 thylendiverbindungen der sekundären BasenIt does not matter whether the three components interact directly or whether the formaldehyde is previously transferred to the acetamides or to the secondary ones Bases binds and then either the N-mono- or -dimethylol compounds of the Acetamides with the secondary bases or the methylol compounds or the Me- 45 ethylene compounds of the secondary bases
RR1NCH2OH bzw. (RR1NJ2 CH2 RR 1 NCH 2 OH or (RR 1 NJ 2 CH 2
mit den Acetamiden zur Reaktion bringt. Die vorerwähnten Umsetzungen entsprechen 50 den Gleichungen:reacts with the acetamides. The aforementioned conversions correspond to 50 the equations:
,C3 H5
C6 H3^-O C H3 , C 3 H 5
C 6 H 3 ^ -OCH 3
CO-NH.CH2OH + HNRR1 CO-NH.CH 2 OH + HNRR 1
C 3 H.5
= H2O + C6H3^O CH C 3 H. 5
= H 2 O + C 6 H 3 ^ O CH
SO . C H2. CO - N H. C H2- N R R1, S O. CH 2 . CO - N H. CH 2 - NRR 1 ,
/C3 H5
C6 H3-- O C H / C 3 H 5
C 6 H 3 - OCH
C H2. CΌ · N (C H2O H)2 + H N RR1 C H 2 . CΌ · N (CH 2 OH) 2 + HN RR 1
= H2 O + CH2O = H 2 O + CH 2 O
/rOCH,/ rOCH,
C H2- C O · N H - C H2- N R R1,CH 2 - CO NH - CH 2 - NRR 1 ,
/C3 H5 3^-O C H3 x0 · C H2- C 0 - N H% + H 0 C H2N R R1 / C 3 H 5 3 ^ -OCH 3 x 0 • CH 2 - C 0 - NH % + H 0 CH 2 NRR 1
= H2O+ C6H/= H 2 O + C 6 H /
H5 H 5
33
C H2-C 0'NH-C H2-N RR1,CH 2 -C 0'NH-C H 2 -N RR 1 ,
/C3 H5 / C 3 H 5
3^O-CH2-CO-NH2 + CH2(NRR1J2 3 ^ O-CH 2 -CO-NH 2 + CH 2 (NRR 1 J 2
/CSH5 HNRR^C6H3(OCH3 X0 - C H2- C O - N H · C H2- N R R1. / C S H 5 HNRR ^ C 6 H 3 (OCH 3 X 0 - CH 2 - CO - NH • CH 2 - NRR 1 .
Die N - substituierten Aminornethylverbindungen des Eugenol- und Isoeugenolacetamids besitzen die Fähigkeit, lokale Anästhesie zu erzeugen und sollen als Medikamente Verwendung finden.The N - substituted amino methyl compounds of eugenol and isoeugenol acetamides have the ability to produce local anesthesia and are intended to be used as drugs Find.
Das Eugenolacetamid ist schon in der Patentschrift 65393 beschrieben, das Isoeugenolacetamid läßt sich durch Einwirkung von Ammoniak auf den Isoeugenolessigsäureäthylester oder durch Kochen-molekularer Mengen Isoeugenol, Chloracetamid und Ätzkali in alkoholischer Lösung herstellen; es kristallisiert aus absolutem Alkohol in Nädelchen vom Schmelzpunkt 1540.The eugenolacetamide is already described in the patent specification 65393, the isoeugenolacetamide can be produced by the action of ammonia on the isoeugenolacetic acid ethyl ester or by boiling molecular amounts of isoeugenol, chloroacetamide and caustic potash in alcoholic solution; It crystallized from absolute alcohol in needles of melting point 154 0th
Bei der Einwirkung einer wäßrigen Lösung von Formaldehyd auf Eugenolacetamid in Gegenwart von Kaliumcarbonat usw. entsteht das N-DimethyloleugenolacetamidUpon the action of an aqueous solution of formaldehyde on eugenol acetamide in In the presence of potassium carbonate, etc., the N-dimethyloleugenol acetamide is formed
/C H2- C H: C H2 3^-O C H3 X0 - C H2- C O - N (C H2O H)2;/ CH 2 - CH: CH 2 3 ^ -OCH 3 X 0 - CH 2 - CO - N (CH 2 OH) 2 ;
es bildet Kristalle, die bei 570 schmelzen, und verliert leicht, z. B. beim Umkristallisieren aus Benzol, 1 Molekül Formaldehyd und geht in das N-Monomethyloleugenolacetamidit forms crystals that melt at 57 0 and easily loses, e.g. B. when recrystallizing from benzene, 1 molecule of formaldehyde and goes into the N-monomethyloleugenol acetamide
.C H2 - C H \ C H2 C6(.CH 2 - CH \ CH 2 C 6 (
H3(OCH3 H 3 (OCH 3
XO -CH2-C O -NH (CH2OH) X O -CH 2 -CO -NH (CH 2 OH)
über, welches sich in Nadeln abscheidet und bei 90 bis 91 ° schmilzt.about, which is deposited in needles and melts at 90 to 91 °.
Die N-Dimethylolverbindung des Isoeugenolacetamids :The N-dimethylol compound of isoeugenol acetamide :
.CHiCH-CH3 .CHiCH-CH 3
C6H3(OCH3 C 6 H 3 (OCH 3
^O-C H2-C O-N (CH2O H)2 ^ OC H 2 -C ON (CH 2 OH) 2
läßt sich wie die entsprechende Eugenolverbindung darstellen, sie kristallisiert aus Benzol in Nadeln vom Schmelzpunkt 108 bis 1090 und spaltet beim Erhitzen Formaldehyd ab.can be represented, it crystallized from benzene in needles melting at 108-109 0 and splits off formaldehyde upon heating as the corresponding Eugenolverbindung.
Man kocht in alkoholischer Lösung 6 g N-Monomethyloleugenolacetamid und 2 gPiperidin, oder 5 g Eugenolacetamid mit 2 g Formaldehydlösung von 40 Prozent und 2 g Piperidin, oder 5 g Eugenolacetamid mit der entsprechenden Menge PiperidomethanolBoil 6 g of N-monomethyloleugenol acetamide and 2 g of piperidine in an alcoholic solution, or 5 g eugenol acetamide with 2 g formaldehyde solution of 40 percent and 2 g piperidine, or 5 g of eugenol acetamide with the corresponding amount of piperidomethanol
C5H10-N-CH2OH,
oder Methylendipiperidin C 5 H 10 -N-CH 2 OH,
or methylenedipiperidine
(C5H10N)2CH2,(C 5 H 10 N) 2 CH 2 ,
die durch Umsetzung von Piperidin mit Formaldehyd entstehen, 1 bis 2 Stunden am Rückflußkühler. Nach dem Abdestillieren des Lösungsmittels verbleibt ein gelbes öl, das mit φ verdünnter Salzsäure digeriert wird; nicht basische Produkte bleiben dann ungelöst. Aus der Lösung wird das Eugenolacetpiperidylmethylamid durch Pottasche abgeschieden und in Äther aufgenommen. Die ätherische Lösung wird mit Wasser durchgeschüttelt und dann verdunstet. So erhält man die neue Verbindung als öl, welches zu Kristallen vom Schmelzpunkt 48 bis 5 2° erstarrt. Das salzsaure Salz des Eugenolacetpiperidylmethylamids kristallisiert aus Aceton in weißen Nädelchen vom Schmelzpunkt 142 bis 1440 und ist in Wasser leicht löslich.formed by the reaction of piperidine with formaldehyde, 1 to 2 hours on the reflux condenser. After the solvent has been distilled off, a yellow oil remains, which is digested with φ dilute hydrochloric acid; non-basic products then remain undissolved. The eugenolacetpiperidylmethylamide is deposited from the solution by means of potash and taken up in ether. The ethereal solution is shaken with water and then evaporated. The new compound is thus obtained as an oil which solidifies to form crystals with a melting point of 48 to 5 2 °. The hydrochloric acid salt of the Eugenolacetpiperidylmethylamids crystallized from acetone in white needles of melting point 142-144 0 and is readily soluble in water.
2 g Dimethylolisoeugenolacetamid und 1 g Diäthylamin werden in alkoholischer Lösung 3 Stunden unter Rückfluß gekocht, dann dunstet man ein und erhält ein öliges Reaktionsprodukt, das mit verdünnter Salzsäure behandelt wird, wobei sich ev. etwas Isoeugenolacetamid abscheidet, das man abfiltriert. Fügt man nun kohlensaures Kali zur sauren Lösung, so scheidet sich das Isoeugenolacetdiäthylaminomethylamid 2 g of dimethylolisoeugenol acetamide and 1 g Diethylamine are refluxed in alcoholic solution for 3 hours, then it evaporates and an oily reaction product is obtained, which with dilute hydrochloric acid is treated, some isoeugenolacetamide possibly separating out, which is filtered off. If one adds carbonate of potash to the acidic solution, the isoeugenolacetdiäthylaminomethylamid separates
CH:CH-CH3 CH: CH-CH 3
C ti.3 C ti. 3
XO-CH2.CO-NH-CH2-N (C2H5)2 X O-CH 2 .CO-NH-CH 2 -N (C 2 H 5 ) 2
zunächst als öl ab, es wird aber bald fest und wird beim Umkristallisieren aus Aceton in Nädelchen erhalten, die bei 75 bis 760 schmelzen; es liefert' ein Pikrat, welches ausinitially as an oil from, but it is soon realized and obtained upon recrystallization from acetone in needles, melting at 75-76 0; it delivers a picrat which out
Aceton in gelben Nadeln kristallisiert und bei 1340 schmilzt.Acetone crystallized in yellow needles, and melts at 134 0th
Beispiel III.Example III.
Man kocht 5 g Dimethylolisoeugenolacetatamid und 3 g Piperidin in alkoholischer Lösung ι bis 2 Stunden und verarbeitet die Reaktionsmasse wie vorbeschrieben.5 g of dimethylolisoeugenol acetate amide and 3 g of piperidine are boiled in alcoholic solution ι to 2 hours and processed the reaction mass as described above.
Das so erhältliche Isoeugenolacetpiperidylmethylamid The isoeugenolacetpiperidylmethylamide obtainable in this way
CHiCH-CH3 CHiCH-CH 3
Ce Hs\~O C Hs Ce Hs \ ~ OCH s
XO · C H2- C O · N H - C H2. N C5 H10 X O • CH 2 - CO • NH - CH 2 . N C 5 H 10
bildet Kristalle, die bei 58 bis 6i° schmelzen und in den meisten Lösungsmitteln leicht löslich sind. Das salzsaure Salz kristallisiert in weißen Blättchen und schmilzt bei 164 bis i66°, es ist in Alkohol und Aceton schwer, in Wasser leicht löslich.forms crystals which melt at 58 to 61 ° and are easily soluble in most solvents. The hydrochloric acid salt crystallizes in white flakes and melts at 164 to 166 °, it is difficult in alcohol and acetone, in water easily soluble.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE208255C true DE208255C (en) |
Family
ID=470300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT208255D Active DE208255C (en) |
Country Status (1)
| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2911440A (en) * | 1955-06-14 | 1959-11-03 | Geigy Chem Corp | Eugenol glycolic acid and isoeugenol glycolic acid amides |
-
0
- DE DENDAT208255D patent/DE208255C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2911440A (en) * | 1955-06-14 | 1959-11-03 | Geigy Chem Corp | Eugenol glycolic acid and isoeugenol glycolic acid amides |
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