DE193634C - - Google Patents
Info
- Publication number
- DE193634C DE193634C DENDAT193634D DE193634DA DE193634C DE 193634 C DE193634 C DE 193634C DE NDAT193634 D DENDAT193634 D DE NDAT193634D DE 193634D A DE193634D A DE 193634DA DE 193634 C DE193634 C DE 193634C
- Authority
- DE
- Germany
- Prior art keywords
- ether
- alcohol
- cyanohydrin
- solution
- dilute
- 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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- 239000002253 acid Substances 0.000 claims description 4
- 229910001023 sodium amalgam Inorganic materials 0.000 claims description 4
- LTYRAPJYLUPLCI-UHFFFAOYSA-N 2-hydroxyacetonitrile Chemical class OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 claims description 3
- -1 aromatic ethanolamines Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- IBGBGRVKPALMCQ-UHFFFAOYSA-N Protocatechuic aldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 5
- ULSIYEODSMZIPX-UHFFFAOYSA-N Phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 5
- 229960003371 protocatechualdehyde Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NNICRUQPODTGRU-UHFFFAOYSA-N Mandelonitrile Chemical compound N#CC(O)C1=CC=CC=C1 NNICRUQPODTGRU-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000001264 neutralization Effects 0.000 description 3
- 229950006768 phenylethanolamine Drugs 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N 2-Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N Potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000001035 methylating Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
- C07C215/28—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
- C07C215/30—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PpENTSCHRIFTPUBLICATION
KLASSE 12 q. GRUPPE 32./WCLASS 12 q. GROUP 32./W
Verfahren zur Darstellung von aromatischen Äthanolaminen.Process for the preparation of aromatic ethanolamines.
Die Reduktion von Cyanhydrinen zu Alkoholbäsen ist bisher noch nicht bekannt geworden. Dies ist begründet in der bei den Oxynitrilen leicht erfolgenden Abspaltung von Blausäure oder in der eintretenden Verseifung. In einem Falle, nämlich bei der Reduktion des Mandelsäurenitrils, wurde außerdem nicht Phenyläthanolamin, sondern Phenyläthylamin erhalten (FiIeti & Piccini, Gaz. chim. ital. ίο 1878,446; 1879, 294, und Ber. 12 [1879],The reduction of cyanohydrins to alcohol bases has not yet become known. This is due to the easy elimination of hydrocyanic acid with the oxynitriles or the saponification that occurs. In one case, namely in the reduction of mandelonitrile, phenylethanolamine was not obtained, but phenylethylamine (FiI eti & Piccini, Gaz. Chim. Ital. Ίο 1878,446; 1879, 294, and Ber. 12 [1879],
s. 297). - :p. 297). -:
Es wurde indessen gefunden, daß es bei vorsichtig geleiteter Reduktion mittels Natriumamalgam gelingt, Cyanhydrine aromatischer Aldehyde und Ketone in die entsprechenden Äthanolbasen überzuführen. Es ist in dem Verfahren erhöhte Temperatur und Anwesenheit größerer Mengen freier Säure zu vermeiden. ^LIt has been found, however, that with carefully directed reduction by means of sodium amalgam succeeds in converting cyanohydrins of aromatic aldehydes and ketones into the corresponding ethanol bases. It is elevated temperature and presence of larger amounts of free acid in the process to avoid. ^ L
ao Man erhält so beispielsweise aus Benzaldehydcyanhydrin das Phenyläthanolamin oder Aminomethylphenylcarbinol : , ; .ao This gives phenylethanolamine or aminomethylphenylcarbinol, for example, from benzaldehyde cyanohydrin: .
C0H5-CH(OH)-CH2-NH^.C 0 H 5 -CH (OH) -CH 2 -NH ^.
von dem Kolshorn (Ber. 37 [1904], S. 2483) einige Derivate beschrieben hat, und aus Protocatechualdehydcyanhydrih das O-Dioxyphenyläthanolnmin, das mit der aus Aminoacetobrenzcatechin durch Reduktion (Patent 157300, Kl. 12 q) erhältlichen Verbindung identisch ist.von dem Kolshorn (Ber. 37 [1904], p. 2483) has described some derivatives, and from Protocatechualdehydcyanhydrih the O-Dioxyphenyläthanolnmin, which with that from Aminoacetobrenzcatechin by reduction (patent 157300, cl. 12 q), the compound obtainable is identical is.
In eine Lösung von 10 Teilen Mandelsäurenitril in 150 Teilen verdünntem Alkohol trägt man unter Rühren und Abkühlen 400 Teile 4prozentiges Natriumamalgam allmählich ein, indem man durch gleichzeitiges Zutröpfeln von verdünnter Essigsäure die Flüssigkeit möglichst neutral hält. Nach beendeter Reduktion wird der Alkohol verdampft und die angesäuerte Flüssigkeit zur Entfernung von Verunreinigungen mit Äther ausgeschüttelt. Durch überschüssige konzentrierte Natronlauge wird dann das entstandene Phenyläthanolamin ölig abgeschieden und mit Äther aufgenommen. Nach dem Abdestillieren des. Äthers hinterbleibt die Base als farbloses öl, das nach einigem Stehen kristallinisch erstarrt. Das Chlorhydrat des Phenyläthanol- amins bildet farblose, in Wasser leicht mit neutraler Reaktion lösliche Kristalle, die bei 176 bis 177° schmelzen. Das Pikrat schmilzt .'.■ bei 153 bis 154° .In a solution of 10 parts of mandelonitrile in 150 parts of dilute alcohol, 400 parts of 4% sodium amalgam are gradually added while stirring and cooling, keeping the liquid as neutral as possible by simultaneously adding dilute acetic acid. After the reduction is complete, the alcohol is evaporated and the acidified liquid is shaken out with ether to remove impurities. The phenylethanolamine formed is then deposited in an oily form with excess concentrated sodium hydroxide solution and taken up with ether. After the ether has been distilled off, the base remains as a colorless oil which solidifies in a crystalline manner after standing for a while. The chlorohydrate of phenylethanolamine forms colorless crystals which are easily soluble in water with a neutral reaction and which melt at 176 to 177 °. The picrate melts . '■ at 153 to 154 °.
ι Teil· Protocatechualdehydcyanhydrin wird in 20 Teilen verdünntem Alkohol gelöst. Zu dieser Lösung gibt man unter guter Kühlung und Umrühren 30 Teile 4prozentiges Natriumamalgam in kleinen Portionen; gleichzeitig sorgt man durch fortwährendes Zutröpfeln von verdünnter Salzsäure dafür, daß die Flüssigkeit möglichst neutral bleibt. Die vom Quecksilber getrennte Lösung wird durch Abdämpfen im Vakuum konzentriert und, nachdem nichtbasische Produkte durch Ausschütteln mit Äther entfernt sind, das entstandene o-Dioxyphenyläthanolamin mit Ammoniak gefällt. Nach einigem Stehen saugt man die Base ab und wäscht sie mit Wasser, Alkohol und jÄther aus. Sie kann durch Part · Protocatechualdehyde cyanohydrin is dissolved in 20 parts of dilute alcohol. 30 parts of 4 percent sodium amalgam are added in small portions to this solution, with good cooling and stirring; At the same time, dilute hydrochloric acid is continually added to ensure that the liquid remains as neutral as possible. The solution separated from the mercury is concentrated by evaporation in vacuo and, after non-basic products have been removed by shaking with ether, the resulting o-dioxyphenylethanolamine is precipitated with ammonia. After standing for a while, the base is suctioned off and washed off with water, alcohol and ether . She can get through
überführen in das kristallisierte Oxalat gereinigt werden.transferred to the crystallized oxalate to be purified.
o-Dioxyphenyläthanolamin bildet ein weißeso-Dioxyphenylethanolamine forms a white color
Kristallmehl, das bei 1910 unter Zersetzung schmilzt. Die Base ist in Wasser schwer, in Alkohol und Äther sehr schwer löslich,Crystal flour which melts at 191 0 with decomposition. The base is poorly soluble in water, very poorly soluble in alcohol and ether,
. leicht löslich in verdünnten Säuren und ätzenden Alkalien. Das Chlorhydrat ist amorph; seine verdünnte Lösung wird durch. Easily soluble in dilute acids and caustic alkalis. The hydrochloride is amorphous; its dilute solution is through
ίο Eisenchlorid intensiv grün gefärbt. Das Oxalat bildet farblose Kriställchen, die bei 1750 schmelzen und sich leicht in Wasser lösen.ίο Ferric chloride has an intense green color. The oxalate forms colorless small crystals which melt at 175 0 and easy to dissolve in water.
Bei der Einwirkung methylierender Agentien auf die Base bildet sich das Dioxyphenyläthanolmethylamin. When methylating agents act on the base, the dioxyphenylethanolmethylamine is formed.
Das bisher nicht beschriebene Protocatechualdehydcyanhydrin kann ebenso wie Benzaldehydcyanhydrin dargestellt werden, indemThe previously not described protocatechualdehyde cyanohydrin can be used just like benzaldehyde cyanohydrin can be represented by
ao man die Bisulfitvcrbindung des Protecatechualdchyds mit Cyankalium umsetzt, oder indem man nach Ultee (Ber. 39 [1906], S. 1856) auf Protocatechualdehyd Blausäure in Gegenwart einer Spur Kaliumcarbonat einwirken läßt.see also the bisulfite compound of the protecatechial chloride with potassium cyanide, or by following Ultee (Ber. 39 [1906], p. 1856) Protocatechualdehyde hydrocyanic acid is allowed to act in the presence of a trace of potassium carbonate.
Sobald der Aldehyd gelöst ist, nimmt man das gebildete Cyanhydrin mit Äther auf. Die ätherische Lösung wird zur Entfernung von unverändertem Protocatechualdehyd mit Bisulfitlösung geschüttelt. Das nach dem Abdestillieren des Äthers zurückbleibende Protocatechualdehydcyanhydrin erstarrt nach einigem Stehen zur rotbraunen Kristallmasse, die leicht Blausäure abspaltet und bei IOO bis 105 ° schmilzt. In Wasser, Alkohol und Äther ist das Nitril leicht löslich, unlöslich dagegen in Benzol und Ligroin.As soon as the aldehyde is dissolved, the cyanohydrin formed is taken up with ether. the Essential solution is used to remove unchanged protocatechualdehyde with bisulfite solution shaken. The protocatechualdehyde cyanohydrin remaining after the ether has been distilled off After standing for a while, it solidifies to a red-brown crystal mass, which easily splits off hydrogen cyanide and at 100 to 105 ° melts. Nitrile is easily soluble in water, alcohol and ether, but it is insoluble in benzene and ligroin.
Die neuen Verbindungen bilden therapeutisch verwertbare Substanzen.The new compounds form therapeutically usable substances.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE193634C true DE193634C (en) |
Family
ID=456849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT193634D Active DE193634C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE193634C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006059903A1 (en) * | 2004-12-02 | 2006-06-08 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| EP1698648A1 (en) * | 2005-03-01 | 2006-09-06 | DSM IP Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
-
0
- DE DENDAT193634D patent/DE193634C/de active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006059903A1 (en) * | 2004-12-02 | 2006-06-08 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| US7678876B2 (en) | 2004-12-02 | 2010-03-16 | Dsm Ip Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
| EP1698648A1 (en) * | 2005-03-01 | 2006-09-06 | DSM IP Assets B.V. | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound |
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