Author Topic: Zinc reductions of benzyl alcohol esters  (Read 77 times)

Doc B

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Zinc reductions of benzyl alcohol esters
« on: April 01, 2013, 08:18:53 AM »
I have been unable to locate the JoC vol 26, pp99 reference UF gives in relation for this reaction so in addition to being appreciative should it be made available, I was wondering what the wise wasps think of its feasibility as an alternative to Birch or Nagi style reductions?

20g of a benzyl alcohol is heated with 130ml of formic acid for a few hours to form the ester. To which is added 40g of zinc dust with 40ml of water. The mixture is refluxed for 5hrs, after which it is cooled, filtered and made basic with sodium hydroxide. The formyl amide (1) is extracted with an organic solvent (2) and then hydrolyzed at reflux with 40ml hydrochloric acid for 2hrs. After which the (3) mixture is left to cool and then added drop wise to a strong sodium hydroxide solution. A brown liquid layer floats at the top of the mixture and water is added to dissolve and solids formed. The mixture is then shaken vigorously for 5min then extracted with organic solvent again. The extract is fractionally distilled under reduced pressure to obtain the product.

Questions

(1) will the formyl amide be red?
(2) Extracted from organic solvent with the HCl(aq) or reflux the whole shebang?
(3) Black coloured?

Doc B

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Re: Zinc reductions of benzyl alcohol esters
« Reply #1 on: April 01, 2013, 08:21:45 AM »
Also it's stated that 95% formic acid is used to form the ester. Is there any reason why the ~88% obtainable from glycerol & Oxalic acid wouldn't be suitable?

Polonium

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Re: Zinc reductions of benzyl alcohol esters
« Reply #2 on: April 01, 2013, 01:34:35 PM »
Here's your reference:

Reactions of 2-Benzhydrylphenylacetic Acid; A New Pyrone Synthesis
R. L. LETSINGER , J. D. JAMISON , A. S. HUSSEY
J. Org. Chem., 1961, 26 (1), pp 97–102
DOI: 10.1021/jo01060a023

Doc B

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Re: Zinc reductions of benzyl alcohol esters
« Reply #3 on: April 01, 2013, 02:46:21 PM »
Thank you kindly, Polonium! :-D