Formation of oximes from carbonyl compounds (ketones or aldehydes). The patents were found in 564/259.
Patent US2237365 (http://l2.espacenet.com/dips/viewer?PN=US2237365&CY=gb&LG=en&DB=EPD)
high yield, oximes
Patent US2283150 (http://l2.espacenet.com/dips/viewer?PN=US2283150&CY=gb&LG=en&DB=EPD)
example with 95% yield
Patent US2350318 (http://l2.espacenet.com/dips/viewer?PN=US2350318&CY=gb&LG=en&DB=EPD)
ex. 4 Raney Ni
Patent US2562205 (http://l2.espacenet.com/dips/viewer?PN=US2562205&CY=gb&LG=en&DB=EPD)
> 90% yield
Patent US3429920 (http://l2.espacenet.com/dips/viewer?PN=US3429920&CY=gb&LG=en&DB=EPD)
buffered medium
Patent US3457354 (http://l2.espacenet.com/dips/viewer?PN=US3457354&CY=gb&LG=en&DB=EPD)
2,4,5-trimethoxyamphetamine ex III A & B
Patent US3808275 (http://l2.espacenet.com/dips/viewer?PN=US3808275&CY=gb&LG=en&DB=EPD)
presence of tin compound
Patent US3821303 (http://l2.espacenet.com/dips/viewer?PN=US3821303&CY=gb&LG=en&DB=EPD)
NH2OH produced in situ
Patent US4015011 (http://l2.espacenet.com/dips/viewer?PN=US4015011&CY=gb&LG=en&DB=EPD)
amphetamines, ex. 12 oxime
Patent US4707294 (http://l2.espacenet.com/dips/viewer?PN=US4707294&CY=gb&LG=en&DB=EPD)
NH2OH in alcohol
Patent US6235935 (http://l2.espacenet.com/dips/viewer?PN=US6235935&CY=gb&LG=en&DB=EPD)
high purity/yields
Patent US6462235 (http://l2.espacenet.com/dips/viewer?PN=US6462235&CY=gb&LG=en&DB=EPD)
ketone, H2O2, NH3, catalyst
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
Here's something from
Chemische Berichte vol. 26 page 1904 (1893)
on the reduction of phenylacetoxime with sodium amalgam
beta-Phenyläthylamin
Eine alkololische Lösung von 9.4 g Phenylacetoxim wurde nach un nach mit 500 g 2 1/2 pCt. Natriumamalgam versetzt und die Flüssigkeit durch Zugiessen von Eisesssig stets angesäuert. Ueberschreitet die Temperatur der Lösung nicht 20º, so ist bei dem Zusatze der ersten Hälfte des Amalgams nur eine geringe, beim Hinzufügen der zweiten Hälfte aber eine lebhafte Wasserstoffentwicklung wahrzunehmen.
Die gelb gefärbte Flüssigkeit wurde nach der Reduction von dem Alkohol durch Eindampfen befreit und der Rückstand mit Wasser erwärmt. Ungelöst blieb etwas unverändertes Oxim; das Filtrat schied auf Zugabe von Kalilauge ein aufschwimmendes braun gefärbtes Oel ab, das nach dem Trennen mittels Aether fractionirt wurde. Farbloses Liquidum vom Siedepunkt 197-198º bei 725 Druck.
Ausbeute 7.5 g vom destillirten Amin, was etwa 90 pCt. der theoretischen Menge entspricht.
Das Phenyläthylamin wurde in die Acetyl- und Benzoylverbindung übergeführt und diese mit Phosphorpentoxyd zu den Dihydroisochinolinderivaten condensirt.
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
Here's my translation/interpretation:
An alcoholic solution of 9.4 g phenylacetoxime was gradually added to 500 g of sodium amalgam and the liquid was kept acid by addition of glacial acetic acid. The temperature stayed under 20º. When the first half of the amalgam was added there was little reaction, but after the second half of the amalgam was added there was a vigorous production of hydrogen.
The yellow colored liquid was freed from the alcohol after the reduction by evaporation and the residue was warmed in water. Unreacted oxime remained undissolved. The filtrate when treated with KOH produced a brown oil (floating on top), after separation of ether medium (extracted with ether?). Colorless liquid bp 197-198º at 725 pressure.
Yield 7.5 g of distilled amine, about 90 % theoretical corresponding amount.
The phenylethylamine was converted to the acetyl and benzoyl derivatives and condensed to dihydroisoquinoline derivatives using phosphorus pentoxide.
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
One reference I have says oximes can be reduced using NaHg/EtOH114, aluminum amalgam57 and zinc and acetic acid122 (among other ways).
references:
57. Cerchez and Dumitresco-Colesiu, Bull. soc. chim., (5) 1, 852 (1934)
114. Houben-Weyl, Die Methoden der organischen Chemie, (II) p. 350 (1925)
122. Kanao, J. Pharm. Soc. Japan, 49, 157 (1929): 50, 24 (1930)
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
http://community.webshots.com/photo/28229010/38035795iPyrNq (http://community.webshots.com/photo/28229010/38035795iPyrNq)
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
This patent gives an example for reducing vanillyl oxime to the amine using NaHg/CH3COOH.
Patent US1329272 (http://l2.espacenet.com/dips/viewer?PN=US1329272&CY=gb&LG=en&DB=EPD)
BTW, you can make sodium amalgam by electrolysing an aqueous NaOH solution using a mercury cathode (ie. at the bottom of a beaker with an insulated wire (bare at the end) going into the mercury like I tried many beers ago with success). Air and H2O decomposes NaHg so its best to use it asap or store it in an inert atmosphere or under mineral oil, etc.
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)
The hardest thing to explain is the obvious
Please tell me this patent hasn´t been posted before. No hits in TFSE anyway.
Patent GB1062299 (http://l2.espacenet.com/dips/viewer?PN=GB1062299&CY=gb&LG=en&DB=EPD)
1-(3,4-dihydroxyphenyl)-2-propanone oxime is made from the nitrostyrene
and reduced to the N-hydroxyamphetamine under very mild conditions.
I don´t need to mention what can be made from this amphetamine very easily.
Do I? ;)