CH199906A - Process for the preparation of an imidazole dihydride (4,5) substituted in the 2-position. - Google Patents
Process for the preparation of an imidazole dihydride (4,5) substituted in the 2-position.Info
- Publication number
- CH199906A CH199906A CH199906DA CH199906A CH 199906 A CH199906 A CH 199906A CH 199906D A CH199906D A CH 199906DA CH 199906 A CH199906 A CH 199906A
- Authority
- CH
- Switzerland
- Prior art keywords
- imidazole
- dihydride
- ether
- reaction
- substituted
- Prior art date
Links
- -1 imidazole dihydride Chemical compound 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 229940126601 medicinal product Drugs 0.000 claims 1
- 150000002463 imidates Chemical class 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ACFJNTXCEQCDBX-UHFFFAOYSA-N 2-(3,4,5-trimethoxyphenyl)acetonitrile Chemical compound COC1=CC(CC#N)=CC(OC)=C1OC ACFJNTXCEQCDBX-UHFFFAOYSA-N 0.000 description 1
- VLLSCJFPVSQXDM-UHFFFAOYSA-N 2-phenoxyacetonitrile Chemical compound N#CCOC1=CC=CC=C1 VLLSCJFPVSQXDM-UHFFFAOYSA-N 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- KSRWUMFPVXDJOO-UHFFFAOYSA-N COC=1C=C(CC=2NC=CN=2)C=C(C=1OC)OC Chemical compound COC=1C=C(CC=2NC=CN=2)C=C(C=1OC)OC KSRWUMFPVXDJOO-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical class COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229940066765 systemic antihistamines substituted ethylene diamines Drugs 0.000 description 1
- 210000003371 toe Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Darstellung eines in 2-Stellung substituierten Imidazoldibydrids-(4,6). Imidazoldihydride-(4,5) (Imidazoline) hat man zuerst erhalten durch Erhitzen der Salze von aliphatischen 1,2-Diaminen mit Fett säuren. Es liess sich jedoch für diesen Zweck zum Beispiel nicht die Athogyessigsäure ver wenden.
Vor einigen Jahren wurde nun durch die französische Patentschrift Nr. 671362 ein neues Verfahren zur Darstellung von Ver- bindungen dieser Art bekannt. (Vergl. Ghem. Zentralblatt 1980, I., S. 1368, sowie deutsche Patentschrift Nr.<B>512721).</B> Darnach setzen sich Iminoäther höherer Fettsäuren mit Di aminen, wie Äthylendiamin, zu Imidazol- dihydriden-(4,5) um, entsprechend der Glei chung:
EMI0001.0019
Es. zeigte sich, dass auch mit Hilfe dieses Verfahrens nicht 2-Alkylogymethyl- oder 2 Alkylogäthyl-Imidazoldihydride-(4,5), sowie die entsprechenden Imidazoldihydride-(4,5) mit Ogyalkyl- oder Acylogyalkylgruppen er halten werden konnten.
Iminoäther von ur- substituierten niederen Fettsäuren ergaben bei der Kondensation mit Diaminen erst dann gute Ausbeuten, als das erwähnte Verfahren dahin abgeändert wurde, dass man die Um setzung bei Zimmertemperatur unter Durch leiten von Luft zur Entfernung des frei werdenden Ammoniaks vor sich gehen liess.
Wie sich Iminoäther niederer Fettsäuren mit andern, als den oben angegebenen Substituen- ten bei dieser Umsetzung verhalten würden, war nicht ohne weiteres vorauszusehen. Wie gefunden wurde, entsteht aus Carbäthogy- acetiminoäthyläther mit Äthylendiamin glatt das 2-(Carbäthoxy-methyl)-imidazol-dihy- drid-(4,5). Ferner reagieren in diesem Sinne mit guten Ausbeuten die Iminoäther aus Blausäure, Aceto-,
Propio- und Butyro-nitril, renn sie aromatische Reste enthalten. Es kondensiert sich zum Beispiel Phenylformi- minoäther mit Athylendiamin sehr glatt zu 2-Phenyl-imidazoldihydrid-(4,5);
es ist dies umso überraschender, als bei dem ähnlichen Ringschluss zu diesem Imidazoldihydrid-(4,5) aus dem Iminoäther und Bromäthylamin- bydrobromid bei Gegenwart von Natrium- äthylat die Ausbeute gering ist. (Vergl. Stolle, J. prakt. Chem. [N.
F.] 140, 60.) Auch die Iminoäther aus Aryl-aceto-nitrilen eignen sich, obgleich eine Phenylgruppe in ss-Stellung die endständigen Gruppen häufig sehr beweglich macht, für die Kondensation sehr gut. Die Nitrilgruppen können auch ätherartig mit den aromatischen Resten ver knüpft sein, wie z.
B. im Phenoxy-acetonitril; durch Umwandlung derartiger Nitrile in die entsprechenden Imidazoldihydride-(4,5) las sen sich pharmakologisch wirksame, in Was ser schwer lösliche Substanzen (z. B. Salicyl- säurephenylester) in leicht lösliche Verbindun gen überführen.
Während aus dem Imino- äther des ss-Phenoxypropionnitril mit Athy- lendiamin sich sehr leicht das Imidazol- dihydrid-(4,5) bildet, konnte mit dem iso- meren Iminoäther aus ss-Phenyl-ss-oxy-propio- nitril überhaupt kein Imidazoldihydrid-(4,5) erhalten werden;
es verhindert die freie Hy- droxylgruppe als Substituent der Kette die Umsetzung wie in der aliphatischen Reihe. Eine Ausnahme machen die Nitrile, welche die freie Hydroxylgruppe neben dem Phenyl- rest in a-Stellung zur Nitrilgruppe haben, da auch hier der Ringschluss glatt erfolgt. Man kann bei der Kondensation sowohl die freien Iminoäther, als auch ihre Salze verwenden.
An Stelle von Äthylendiamin können auch N - monosubstituierte oder C-substituierte Athylendiamine, wie z. B. N-Methyl-äthylen- diamin, N - Phenyl - äthylendiamin oder 1,2- Propyendiamin Verwendung finden.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Darstellung eines in 2-Stel- lung substituierten Imidazoldihydrids-(4,5), welches dadurch gekennzeichnet ist, dass man einen 3,4,5-Trimethoxyphenylacetiminoäther mit Athylendiamin umsetzt.
Das so gewonnene 2-(3',4',5'-Trimethoxy- benzyl)-imidazoldihydrid-(4,5) bildet farb lose Kristalle vom F. 76 bis 77 - und vom gp.Q,,6 170 bis 171 . Sein Hydrochlorid ist ein farbloses Kristallpulver vom F. 185 bis <B>1860.</B>
Die neue Verbindung kann als Arznei mittel verwendet werden.
Beispiel: 3 Teile 3,4,5-Trimethoxyphenyl-acetimino- äthylätherhydrochlorid der Formel
EMI0002.0101
(hergestellt aus 3,4,5 - Trimethoxy - phenyl- acetonitril), aus dem sich während der Umsetzung 3,4,5-Trimethoayphenyl-acetimo- äthyläther bildet, werden in 15 Teilen ab solutem Alkohol gelöst.
Man fügt ziemlich rasch 1 Teil Athylendiamin hinzu, erhitzt langsam auf<B>100'</B> und hält einige Stunden bei dieser Temperatur. Hernach vertreibt man den Alkohol, versetzt den Rückstand mit ver dünnter Natronlauge und extrahiert er schöpfend mit Benzol. Nach dem Trocknen über Pottasche wird das 2-(3',4',5'-Tri- methozy-benzyl)-imidazoldihydrid-(4,5) der Formel
EMI0002.0122
bei 0,15 mm destilliert.
An Stelle von 3,4,5-Trimethoxyphenyl- acetiminoäthyläther kann ebensogut ein an derer Äther, wie z. B. der Methyl-, Propyl- oder Butyläther Verwendung finden. Statt vom salzsauren Salz des Tri- methoxyphenylacetiminoäthers kann man auch von einem andern Salze wie z. B. vom bromwasserstoffsauren, vom schwefelsauren oder vom methylschwefelsauren Salz aus zehen.
Process for the preparation of a 2-substituted imidazole dibydride- (4,6). Imidazole dihydrides (4,5) (imidazolines) were first obtained by heating the salts of aliphatic 1,2-diamines with fatty acids. Athogyacetic acid, for example, could not be used for this purpose.
A few years ago, the French patent specification No. 671362 made known a new method for representing connections of this type. (Cf. Ghem. Zentralblatt 1980, I., p. 1368, as well as German patent specification no. <B> 512721). </B> According to this, imino ethers of higher fatty acids combine with diamines, such as ethylenediamine, to form imidazole dihydrides (4 , 5) according to the equation:
EMI0001.0019
It. It was found that even with the help of this process it was not possible to obtain 2-alkylogymethyl or 2-alkylogethyl-imidazole dihydrides (4,5), and the corresponding imidazole dihydrides (4,5) with ogyalkyl or acylogyalkyl groups.
Imino ethers of unsubstituted lower fatty acids only gave good yields on condensation with diamines when the process mentioned was changed so that the reaction was allowed to proceed at room temperature while passing air through to remove the ammonia released.
How imino ethers of lower fatty acids with substituents other than those indicated above would behave in this reaction could not be easily foreseen. As has been found, 2- (carbethoxymethyl) imidazole dihydride (4,5) is easily formed from carbethogyacetiminoethyl ether with ethylenediamine. Furthermore, in this sense, the imino ethers from hydrogen cyanide, aceto,
Propio- and butyronitrile, if they contain aromatic residues. For example, phenylformino ether condenses very smoothly with ethylenediamine to give 2-phenylimidazole dihydride (4,5);
This is all the more surprising since the similar ring closure to this imidazole dihydride (4,5) from the imino ether and bromoethylaminobydrobromide in the presence of sodium ethylate, the yield is low. (See Stolle, J. Prakt. Chem. [N.
F.] 140, 60.) The imino ethers from aryl acetonitriles are also very suitable for condensation, although a phenyl group in the s position often makes the terminal groups very mobile. The nitrile groups can also be linked ethereally with the aromatic radicals, such as.
B. in phenoxy-acetonitrile; By converting such nitriles into the corresponding imidazole dihydrides (4,5), pharmacologically active substances that are sparingly soluble in water (e.g. phenyl salicylate) can be converted into easily soluble compounds.
While the imidazole dihydride (4,5) is formed very easily from the imino ether of ss-phenoxypropiononitrile with ethylenediamine, nothing at all could be achieved with the isomeric imino ether from ss-phenyl-ss-oxy-propionitrile Imidazole dihydride (4,5);
the free hydroxyl group as a substituent of the chain prevents the reaction as in the aliphatic series. The nitriles, which have the free hydroxyl group in addition to the phenyl radical in a position to the nitrile group, are an exception, since the ring closure takes place smoothly here too. Both the free imino ethers and their salts can be used in the condensation.
Instead of ethylenediamine, N - monosubstituted or C-substituted ethylenediamines, such as. B. N-methyl-ethylenediamine, N-phenyl-ethylenediamine or 1,2-propylenediamine can be used.
The present patent relates to a process for the preparation of an imidazole dihydride (4,5) substituted in the 2-position, which is characterized in that a 3,4,5-trimethoxyphenylacetiminoether is reacted with ethylenediamine.
The 2- (3 ', 4', 5'-trimethoxybenzyl) -imidazole dihydride- (4,5) obtained in this way forms colorless crystals of 76 to 77 m. Its hydrochloride is a colorless crystal powder from F. 185 to <B> 1860. </B>
The new compound can be used as a medicine.
Example: 3 parts of 3,4,5-trimethoxyphenyl acetimino ethyl ether hydrochloride of the formula
EMI0002.0101
(made from 3,4,5-trimethoxy-phenyl-acetonitrile), from which 3,4,5-trimethoxyphenyl-acetimo-ethyl ether is formed during the reaction, are dissolved in 15 parts of absolute alcohol.
1 part of ethylenediamine is added fairly quickly, heated slowly to <B> 100 '</B> and held at this temperature for a few hours. Then the alcohol is driven off, the residue is mixed with dilute sodium hydroxide solution and extracted with benzene. After drying over potash, the 2- (3 ', 4', 5'-trimethozybenzyl) imidazole dihydride (4,5) of the formula
EMI0002.0122
distilled at 0.15 mm.
Instead of 3,4,5-Trimethoxyphenyl- acetiminoäthyläther can just as well another ether such. B. the methyl, propyl or butyl ethers are used. Instead of the hydrochloric acid salt of the trimethoxyphenylacetiminoether one can also use another salt such as z. B. from the hydrobromic acid, the sulfuric acid or the methylsulfuric acid salt from toes.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE199906X | 1934-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH199906A true CH199906A (en) | 1938-09-15 |
Family
ID=5758875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH199906D CH199906A (en) | 1934-07-31 | 1935-07-23 | Process for the preparation of an imidazole dihydride (4,5) substituted in the 2-position. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH199906A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449354A (en) * | 1967-04-04 | 1969-06-10 | Dow Chemical Co | 2-((2-trifluoromethylphenoxy)methyl)-2-imidazoline |
| US3449357A (en) * | 1967-04-04 | 1969-06-10 | Dow Chemical Co | 2-((2,6-substituted)phenoxymethyl)-2-imidazolines |
-
1935
- 1935-07-23 CH CH199906D patent/CH199906A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449354A (en) * | 1967-04-04 | 1969-06-10 | Dow Chemical Co | 2-((2-trifluoromethylphenoxy)methyl)-2-imidazoline |
| US3449357A (en) * | 1967-04-04 | 1969-06-10 | Dow Chemical Co | 2-((2,6-substituted)phenoxymethyl)-2-imidazolines |
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