CH104677A - Process for the preparation of p.oxy-amylphenylmethylamine. - Google Patents
Process for the preparation of p.oxy-amylphenylmethylamine.Info
- Publication number
- CH104677A CH104677A CH104677DA CH104677A CH 104677 A CH104677 A CH 104677A CH 104677D A CH104677D A CH 104677DA CH 104677 A CH104677 A CH 104677A
- Authority
- CH
- Switzerland
- Prior art keywords
- ether
- base
- acid
- vinegar
- amylphenylmethylamine
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000052 vinegar Substances 0.000 claims description 4
- 235000021419 vinegar Nutrition 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910001023 sodium amalgam Inorganic materials 0.000 claims description 3
- QIGLJVBIRIXQRN-UHFFFAOYSA-N DL-leucine ethyl ester Natural products CCOC(=O)C(N)CC(C)C QIGLJVBIRIXQRN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- QIGLJVBIRIXQRN-ZETCQYMHSA-N ethyl (2s)-2-amino-4-methylpentanoate Chemical compound CCOC(=O)[C@@H](N)CC(C)C QIGLJVBIRIXQRN-ZETCQYMHSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- -1 methoxyl residue Chemical group 0.000 description 1
- PTECIXPBVVDNOU-UHFFFAOYSA-N molecular bromine;hydrate Chemical compound O.BrBr PTECIXPBVVDNOU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
- C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von p # Ogy-amylphenylmethylamin. p . Oxy-amylphenylmethylamin von der Formel
EMI0001.0005
ist bis jetzt nicht bekannt.
Es wurde nun gefunden, da.ss, wenn man das Kondensations produkt aus Leu,cinäthylester mit Anisalde <B>hyd</B> ! mit Natriumamalgam reduziert, völlig verseift, mit Mineralsäure die p . Methoxy- benzyl-a-Aminobutylessigsäure ausfällt, diese durch Erhitzen in das p . Methoxy-a@myl- phenylmethylamin überführt und aus diesem Körper die Methylgruppe durch Kochen mit Bromwasserstoffsäure abspaltet, der ,gesuchte Körper entsteht.
EMI0001.0018
wird ,gewaschen und getrocknet und gibt beim Erhitzen auf zirka 200' glatt die p.Methoxy-amylphenylmetliylaminbase. Nun mehr wird die Methylgruppe aus dem Me- thoxylrest durch dreistündiges Kochen mit. der dreifachen Menge konzentrierter Brom wasserstoffsäure abgespalten. Beispiel: 90 gr Leucinäthylester werden mit 81 gr Anisaldehyd versetzt. Die Mischung er wärmt sich, und es tritt Wasserabscheidung ein.
Das trübe Reaktionsgemisch wird mit 400 gr Alkohol versetzt und portionen- weise mit 850 gr 8 %igem Natriumamalgam reduziert. Das Gemisch wird alsdann noch zirka '/2 Stunde auf denn Wasserbacl erwärmt bis zur vollständigen Verseifung. Darauf wird mit Mineralsäure, genau neutralisiert.
Die abgeschiedene p . Methoxy-benzyl-a- Aminobutylessigsäure von der Formel Beim Erkalten erstarrt die Lösung zu einem Kristallbrei, der abgenutscht und aus Wasser umkristallisiert wird.
Das p . Oxy- am.ylphenylmethylaminbromhydrat schmilzt bei 152 , Die Analyse ergab folgendes Re sultat:
EMI0001.0052
Brom <SEP> berechnet: <SEP> 29,1
<tb> Brom <SEP> .gefunden: <SEP> 28,9 Aus der wässerigen Lösung des Bromhydra- tes wird die freie Base durch Zusatz von Ammoniak gefällt. Die Base ist unlöslich in Wasser, sehr leicht löslich in Alkohol, Äther und Essigäther. Sie kann aus einem Gemenge von Benzol und Essigäther in Form von wei ssen Blättchen vom Schmelzpunkt 73' bis 74 erhalten werden.
Process for the preparation of p # Ogy-amylphenylmethylamine. p. Oxy-amylphenylmethylamine of the formula
EMI0001.0005
is not yet known.
It has now been found that if the condensation product of leu, cinethylester with anisalde <B> hyd </B>! reduced with sodium amalgam, completely saponified, with mineral acid the p. Methoxybenzyl-a-aminobutyl acetic acid precipitates, which is transferred to the p. Methoxy-a @ myl-phenylmethylamine is transferred and the methyl group is split off from this body by boiling with hydrobromic acid, which creates the body we are looking for.
EMI0001.0018
is, washed and dried and gives the p.Methoxy-amylphenylmetliylaminbase when heated to about 200 '. The methyl group is now more from the methoxyl residue by boiling for three hours with. split off three times the amount of concentrated hydrobromic acid. Example: 90 g of leucine ethyl ester are mixed with 81 g of anisaldehyde. The mixture warms up and water separates out.
The cloudy reaction mixture is mixed with 400 grams of alcohol and reduced in portions with 850 grams of 8% sodium amalgam. The mixture is then heated to water for about 1/2 hour until saponification is complete. Then it is precisely neutralized with mineral acid.
The secluded p. Methoxy-benzyl-a-aminobutyl acetic acid of the formula When it cools, the solution solidifies to form a slurry of crystals that is suction filtered and recrystallized from water.
The p. Oxy-am.ylphenylmethylamine bromohydrate melts at 152, the analysis gave the following result:
EMI0001.0052
Bromine <SEP> calculated: <SEP> 29.1
<tb> Bromine <SEP>. found: <SEP> 28.9 The free base is precipitated from the aqueous solution of the bromine hydrate by adding ammonia. The base is insoluble in water, very easily soluble in alcohol, ether and vinegar ether. It can be obtained from a mixture of benzene and vinegar ether in the form of white flakes with a melting point of 73 to 74.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH104677T | 1923-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH104677A true CH104677A (en) | 1924-05-01 |
Family
ID=4363544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH104677D CH104677A (en) | 1923-03-24 | 1923-03-24 | Process for the preparation of p.oxy-amylphenylmethylamine. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH104677A (en) |
-
1923
- 1923-03-24 CH CH104677D patent/CH104677A/en unknown
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