CH337828A - Process for the preparation of amides of eugenolglycolic acid and isoeugenolglycolic acid - Google Patents
Process for the preparation of amides of eugenolglycolic acid and isoeugenolglycolic acidInfo
- Publication number
- CH337828A CH337828A CH337828DA CH337828A CH 337828 A CH337828 A CH 337828A CH 337828D A CH337828D A CH 337828DA CH 337828 A CH337828 A CH 337828A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- eugenolglycolic
- amides
- preparation
- isoeugenolglycolic
- Prior art date
Links
- 239000002253 acid Substances 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 5
- 150000001408 amides Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005770 Eugenol Substances 0.000 claims description 4
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkenyl radical Chemical group 0.000 claims description 4
- 229960002217 eugenol Drugs 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 claims 2
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 claims 2
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- AQILMXQXJGRJQJ-UHFFFAOYSA-N 2-hydroxyacetic acid 2-methoxy-4-prop-1-enylphenol Chemical compound C(CO)(=O)O.C=1(C(O)=CC=C(C=CC)C1)OC AQILMXQXJGRJQJ-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000002082 anti-convulsion Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJKVUAPQJNAYFE-UHFFFAOYSA-N n-(4-chlorophenyl)-2-hydroxy-n-methylacetamide Chemical compound OCC(=O)N(C)C1=CC=C(Cl)C=C1 AJKVUAPQJNAYFE-UHFFFAOYSA-N 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Amiden der Eugenolglykolsäure und Isoeugenolglykolsäure
Gegenstand vorliegenden Patentes ist ein Verfahren zur Herstellung von Amiden der Eugenolglykolsäure und Isoeugenolglykolsäure der Formel
EMI1.1
worin R den Allyl-oder Propen-(l)-ylrest, Rj einen durch Halogen und/oder Methoxygruppen substituierten Phenyl-oder Benzylrest, R2 Wasserstoff oder einen Alkyl-oder einen Alkenylrest, bedeuten, mit therapeutisch interessanten hypnotischen, analgetischen, sedativen, anticonvulsiven und anästhetischen Eigenschaften.
Das Verfahren ist dadurch gekennzeichnet, dass man Eugenol-oder Isoeugenolglykolsäure oder ein reaktionsfähiges funktionelles Derivat dieser Säuren auf ein primäres oder sekundäres Amin der Formel
EMI1.2
einwirken lässt.
Geeignete reaktionsfähige funktionelle Derivate der Eugenolglykolsäure und Isoeugenolglykolsäure sind beispielsweise deren Halogenide und gemischte Anhydride mit niedrigen organischen Carbonsäuren, insbesondere Essigsäure, sowie deren Ester, insbesondere die niederen Alkylester und Phenylester. Die Umsetzungen werden zweckmässig in Lösungs-oder Verdünnungsmitteln durchgeführt. Als Lösungsmit- tel für die Umsetzungen mit Säurehalogeniden und -anhydriden kommen einerseits inerte organische Lösungsmittel wie Ather oder Benzolkohlenwasserstoffe und anderseits Wasser, für die Umsetzungen mit Säureestern auch Alkohole in Betracht.
Als säure- bindende Mittel können bei den Reaktionen mit Säurehalogeniden oder gemischten Anhydriden in organischen Lösungsmitteln ein Überschuss an dem umzusetzenden Amin oder auch eine tertiäre organische Base, wie Pyridin oder Dimethylanilin, in Wasser überdies auch anorganische Stoffe, wie Natriumoder Kaliumcarbonat, Verwendung finden.
Als Ausgangsstoffe der Formel II kommen z. B.
2-Chlor-anilin, 3-Chlor-anilin, 4-Chlor-anilin, 2, 5 Dichlor-anilin, 4-Brom-anilin, o-Anisidin, m-Anisidin, p-Anisidin, N-Methyl-, N-Äthyl-, N-n-propyl-, N-isopropyl-, N-n-Butyl-, N-Isobutyl-, N-sec. Butyl-, N-n-Amyl-, N-Iosamyl-, N-n-Hexyl-, N-Allyl-, N Crotyl-und N-Methallyl-2-chlor-anilin,-3-chlor- anilin,-4-chlor-anilin,-2, 5-dichlor-anilin,-4-bromanilin,-o-anisidin,-m-anisidin,-p-anisidin in Betracht.
Beispiel
In eine Lösung von 24 Teilen Eugenolglykolsäurechlorid in 150 Volumteilen abs. Ather lässt man unter Rühren und Kühlen mittels einer Kälte- mischung eine Lösung von 29 Teilen N-Methyl-pchlor-anilin in 50 Volumteilen abs. Äther eintropfen.
Nach beendigter Zugabe des Amins kocht man das Reaktionsgemisch etwa 1/2 Stunde am Rückfluss, kühlt dann ab und versetzt mit 100 Teilen Wasser.
Man trennt die ätherische Lösung ab, wäscht sie mit verdünnter Salzsäure, verdünnter Natriumcarbonatlösung und Wasser, trocknet sie über Natriumsulfat und destilliert das Lösungsmittel ab. Bei der Destillation des Rückstandes erhält man Eugenol glykolsÏure-N-methyl-p-chlor-anilid Kp0,005 168 bis 173 .
In gleicher Weise erhält man auch : Eugenolglykolsäure-N-äthyl-p-chlor-anilid,
Fp. 48-49 , EugenolglykolsÏure-N-n-propyl-p-chlor-anilid,
Fp. 81-82 , Eugenolglykolsäure-N-n-butyl-p-chlor-anilid,
Fp. 74-75 , EugenolglykolsÏure-N-Ïthyl-3',4'-dichlor-anilid,
Fp. 70-71¯, Eugenolglykolsäure-N-äthyl-p-brom-anilid
Kp0,0005 175-178¯, EugenolglykolsÏure-N-Ïthyl-p-anisidid
Kp0,0005 175-163¯.
Process for the preparation of amides of eugenolglycolic acid and isoeugenolglycolic acid
The present patent relates to a process for the preparation of amides of eugenolglycolic acid and isoeugenolglycolic acid of the formula
EMI1.1
where R is the allyl or propene (l) -yl radical, Rj is a phenyl or benzyl radical substituted by halogen and / or methoxy groups, R2 is hydrogen or an alkyl or an alkenyl radical, with therapeutically interesting, hypnotic, analgesic, sedative, anticonvulsive ones and anesthetic properties.
The process is characterized in that eugenol or isoeugenol glycolic acid or a reactive functional derivative of these acids with a primary or secondary amine of the formula
EMI1.2
can act.
Suitable reactive functional derivatives of eugenolglycolic acid and isoeugenolglycolic acid are, for example, their halides and mixed anhydrides with lower organic carboxylic acids, especially acetic acid, and their esters, especially the lower alkyl esters and phenyl esters. The reactions are expediently carried out in solvents or diluents. Suitable solvents for the reactions with acid halides and anhydrides are, on the one hand, inert organic solvents such as ethers or benzene hydrocarbons and, on the other hand, water, and for the reactions with acid esters also alcohols.
Acid-binding agents in the reactions with acid halides or mixed anhydrides in organic solvents can be an excess of the amine to be reacted or a tertiary organic base such as pyridine or dimethylaniline, and inorganic substances such as sodium or potassium carbonate in water.
As starting materials of the formula II, for. B.
2-chloro-aniline, 3-chloro-aniline, 4-chloro-aniline, 2, 5 dichloro-aniline, 4-bromo-aniline, o-anisidine, m-anisidine, p-anisidine, N-methyl-, N- Ethyl-, Nn-propyl-, N-isopropyl-, Nn-butyl-, N-isobutyl-, N-sec. Butyl-, Nn-amyl-, N-isosamyl-, Nn-hexyl-, N-allyl-, N-crotyl- and N-methallyl-2-chloro-aniline, -3-chloro-aniline, -4-chloro-aniline , -2, 5-dichloro-aniline, -4-bromaniline, -o-anisidine, -m-anisidine, -p-anisidine.
example
In a solution of 24 parts of eugenolglycolic acid chloride in 150 parts by volume of abs. A solution of 29 parts of N-methyl-pchloro-aniline in 50 parts by volume of abs is left in ether with stirring and cooling by means of a cold mixture. Drip in ether.
When the addition of the amine is complete, the reaction mixture is refluxed for about 1/2 hour, then cooled, and 100 parts of water are added.
The ethereal solution is separated off, washed with dilute hydrochloric acid, dilute sodium carbonate solution and water, dried over sodium sulfate and the solvent is distilled off. When the residue is distilled, eugenol glycolic acid-N-methyl-p-chloro-anilide Kp0.005 168 to 173 is obtained.
In the same way you also get: eugenolglycolic acid-N-ethyl-p-chloro-anilide,
Fp. 48-49, eugenolglykolsure-N-n-propyl-p-chloro-anilide,
Mp. 81-82, eugenolglycolic acid-N-n-butyl-p-chloro-anilide,
M.p. 74-75, eugenolglycolic acid-N-ethyl-3 ', 4'-dichloro-anilide,
Mp. 70-71¯, eugenolglycolic acid-N-ethyl-p-bromo-anilide
Kp0.0005 175-178¯, eugenolglycolic acid-N-ethyl-p-anisidide
Kp0.0005 175-163¯.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH335398T | 1956-05-24 | ||
| CH337828T | 1956-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH337828A true CH337828A (en) | 1959-04-30 |
Family
ID=25736734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH337828D CH337828A (en) | 1956-05-24 | 1956-05-24 | Process for the preparation of amides of eugenolglycolic acid and isoeugenolglycolic acid |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH337828A (en) |
-
1956
- 1956-05-24 CH CH337828D patent/CH337828A/en unknown
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