Sciencemadness Discussion Board

hydrogenation of cinnamic acid

naome - 6-9-2005 at 14:16

is there an easyer way from cinnamic acid to hydrocinnamic acid?
the preparation of sodium amalgam sounds cool, but i am not fond of working with mercury, and sodium is too valuble (and definatly not otc)

sooooo....
would naoh and zn work?

zn and hcl?

i have lots of pennys

would it reduce the -cooh?


thanks!

Nicodem - 8-9-2005 at 03:41

I doubt Zn/NaOH would work, but Zn/HCl might, most certainly if the Zn is amalgamated. Possibly also with Al-Hg. I have no references at the moment though.

Also, a CTH method perhaps:

http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/c... ?

I would guess the amount of PdCl2 used above is an overkill and on a scale up I would certainly reduce that ratio. Perhaps it works with Pd-C as well. Of course the reaction can also be performed with Raney nickel, electroreduction on a Pb cathode, TiCl3 and some other reduction reagents as well. I would also suggest to check Org. Synth. as I think there is at least one example of this reaction.

[Edited on 8-9-2005 by Nicodem]

S.C. Wack - 8-9-2005 at 05:12

I mentioned Raney alloy in another thread and uploaded articles which are no longer there due to disinterest. One of them got a 95% yield of hydrocinnamic acid by dissolving 10 g. cinnamic acid in 300 ml 10% NaOH heated to 90C, with the gradual addition of Raney alloy. It does not actually say this, that paper refers to others in the series for the procedure.

The Chem Rev one pointed to something pretty much identical at OS.

naome - 8-9-2005 at 11:15

hmmm....
anyone ever try to make theyre own raney nickel?
(i really should utfse, shouldn't i :)
do you need to pulverize it or does the naoh particulate it from the chunks?
raney nickel is amazing, i hear it wont work if all the aluminium is removed.

i may just try amalgamated zn

would amalgamating raney nickel increase its activity, or just make a pyrophoric mercury compound?(!)

Sandmeyer - 8-9-2005 at 11:42

Nose, Atsuko; Kudo, Tadahiro; Chem. Pharm. Bull.; 38; 8; 1990; 2097-2101 used the reduction system of NiCl2*6H2O/Zn dust with the reaction solvent being methanol, after 1 hour they obtained 86% yield of the unsaturated acid.

I would prefer it over Pd for this starting material, considering that 1 kg nickel(II)chloride hexahydrate costs 40 USD.

Too bad I can't acsess Chemical & Pharmaceutical Bulletin of Japan, there are some really good methods published in that journal. Well, maybe someone else can get the above paper for you.

EDIT: It would be cool if someone at sciencemadness could acsess the back-issues of this journal.

[Edited on 8-9-2005 by Sandmeyer]

naome - 9-9-2005 at 11:33

nicl2 is sexy, and cheap.
pd is easy to find, but id rather cover my teeth in it than to hydrogenate cinnamic acid:D
chem. pharm. bull is always elusive but id love to see the procedure.
couldnt one reduce nitro cmpds with nicl2 as well? (maybe its just oximes, still within reach)
could be useful after a nitro-hunsdeiker reaction of the target compound.....

i searched for raney nickel and found the thread Mr.Wack referred to, certainly no disinterest from me! maybe people are too set in their ways to think around corners such as amides.....

i also found the willgerodt reaction for propheonones to hydrocinnamic acids using morpholine and sulphur, seems pretty handy, i can post the procedure if anyone wants...

Vogelzang - 19-8-2009 at 16:26

According to the article Bull. Chem. Soc. Japan 1954 page 480 cinnamic acid can be reduced to hydrocinnamic acid with Urushibara nickel.
See BullChemSocJap1954-p480 in the "Urushibara related" folder here: http://www.4shared.com/dir/2038202/e41cdcd7/sharing.html

Also see http://www.sciencemadness.org/talk/viewthread.php?tid=4236#p...

[Edited on 20-8-2009 by Vogelzang]

Vogelzang - 19-8-2009 at 16:47

I found a dissertation with a process for reducing cinnamic acid using the Clemmensen reduction (attached).

Attachment: hydrocinnamic-Marr.pdf (290kB)
This file has been downloaded 1289 times

S.C. Wack - 19-8-2009 at 17:51

Fieser mentions 80% yields with KI/RP/H3PO4/6 hour reflux.
Acta Chem. Scand. 15, 1200 (1961) uses Raney Ni and 85% hydrazine hydrate, to give 85% isolated yield. The hydrazine can be more dilute given the amount of hot dilute NaOH there.
In JACS 88, 4964 (1966), a yield of 89% was obtained with CrSO4 in warm DMF; world's longest extraction of 3.6 grams of material there.
One of the older CTH articles, JACS 66, 1859 (1944) has benzalacetone and quite a lot of Raney Ni refluxing in ethanol to give 75% yield of the distilled phenylbutanol.
Like many jstage articles, it's open access for that Chem. Pharm. Bull. article above. Other functional group reductions are there as well.

Vogelzang - 20-8-2009 at 11:26

Reduction of cinnamic acid with sodium amalgam.

Annalen der Chemie
http://books.google.com/books?id=ooM8AAAAIAAJ&pg=PA375&a...


Experiment No. 54 Hydrocinnamic acid (note the use of permanganate for testing)
http://books.google.com/books?id=wxxDAAAAIAAJ&pg=PA184&a...

http://books.google.com/books?id=aTsKAAAAIAAJ&pg=PA316&a...

http://books.google.com/books?id=AjlKAAAAMAAJ&pg=PA134&a...

http://books.google.com/books?id=KbdgAAAAIAAJ&pg=PA380&a...

[Edited on 20-8-2009 by Vogelzang]

DJF90 - 21-8-2009 at 00:37

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1...

Vogelzang - 9-9-2009 at 14:59

I found some interesting patents on making Na-Hg electrolytically, electrolytic reduction, reduction of cinnamic acid analogs, etc. The attached article is on continuous electrolytic production of Na-Hg and its use in reduction in a separate compartment (from Journal of Chem. Ed.)

US 1712951 Electrolysis reduction cell

US 1712952 Apparatus for carrying out electrolytic reduction of sugars to alcohols

US 2280887 Process for electrolytic reduction

US 1956950 Manufacture of laevo-1-phenyl-2-methylaminopropanol-1

US 0586729
helical trough

US 1025509
Hg circulation by heat

US 2931830 Beta-(2, 4, 6-triiodo-3-hydroxyphenyl)-propionic acids and preparation thereof

US 3458576 REDUCTION OF ARYLNITROALKENES

US 3529011 ADIPONITRILE PROCESS
fluidized bed

US 1927289 Process for the electrolytic reduction of organic compounds
cinnamic acid. etc.

US 2681363 Hydroxy phenyl aliphatic carboxylic acids and their iodo derivatives
and process forpreparing same
Reduction of the a-methyl-p-hydroxy cinnamic acid with Raney's alloy and aqueous
alkalli (J. Org. Chem. 9, 175 (1944)


US 2500284 Apparatus for electroanalysis

US 3475310 SELF-CLEANING MERCURY ELECTRO



Attachment: JCE1990p0805-electro-Na-Hg.pdf (1.1MB)
This file has been downloaded 929 times

[Edited on 9-9-2009 by Vogelzang]

behemoth - 12-9-2009 at 12:37

According to "A facile direct conversion of aldehydes to esters and amides
using acetone cyanohydrin", Tetrahedron Letters 46 (2005) 8303–8306, cinnamic aldehyde can be converted to hydrocinnamic acid ester directly using cyanide as a mediator.

Abstract—Aromatic aldehydes with electron-withdrawing groups undergo rapid reactions with a variety of alcohols and secondary
amines to afford the corresponding esters and amides, respectively, in high yields, when treated with NaCN or acetone cyanohydrin
and base under ambient reaction conditions. In case of a,b-unsaturated aldehydes, simultaneous reduction of the C@C bond along
with esterification occurred to produce the saturated esters in high yields.

Vogelzang - 16-9-2009 at 16:16

Ber 1914 pages 71-72 German to English translation.

Alpha, beta- hydrocinnamic acid

The hydrogenation was carried out according to Paal-Skita. The cinnamic acid was just neutralized with alkali, after addition of several cubic centimeters of colloidal palladium solution hydrogen under 1 atm. pressure was led in, until a probe (in Soda solution) of permanganate was no longer reduced. Both forms of the cinnamic acid gave the same hydro derivative.

The hydro acid forms beautiful, white, surface rich crystals, which when recrystallized from gasoline melt at 137-138°. After further recrystallization the melting point sank to 132°, whereby from the prisms broad, white needles were obtained. After further recrystallizations we found the melting point always to be 130-131.5°. The substance was already soft before this.

Reduction with sodium amalgam. In the cold or at room temperature the sodium amalgam had over all no effect on the dimethylcinnamic acid. Although, 1 g of the acid could be fully reduced with 3 % amalgam through long warming and shaking on a water bath, whereby 50 times excess of amalgam was necessary. The hydro acid melted at 137-138° and was certainly identical with that described above, although the melting point after recrystallization was not undertaken.


Attachment: Ber1914-p71-72.pdf (210kB)
This file has been downloaded 934 times

Vogelzang - 17-9-2009 at 16:50

TLC of cinnamic acids.



Attachment: JCE1987p0182-TLC.pdf (530kB)
This file has been downloaded 1364 times

Vogelzang - 20-9-2009 at 10:45

McRae and Vining, Can. J. Research, 6, 409 (1932)
listed here http://www.orgsyn.org/orgsyn/prep.asp?prep=CV3P0720

has been uploaded to this post.


Attachment: CanJRes1932-p409-416.pdf (690kB)
This file has been downloaded 1089 times

grind - 28-9-2009 at 02:41

Other procedure for hydrogenation of cinnamic acids (I remember I did it with a methoxy-substituted cinnamic acid) :
At first try whether your cinnamic acid is soluble in NaOH- or in KOH-solution (I used KOH).
Add to 1 mol of your cinnamic acid 10 mol of diluted KOH-solution (or NaOH, depending on the solubility) to get a clear solution. Add Pd/C (sorry I don´t remember the amount, but it was only a little amount). Now you add aluminium (I used grains, do not use fine powder cause it is too reactive). If I remember correctly, I added a tenfold excess of the calculated amount. Stir until the metal is dissolved. Filter the solution to get rid of the Pd/C (of course it can be reused). Maybe you have to dilute the solution a little before filtering.
Add a huge amount of HCl until your solution is strongly acidic, now you obtain of mixture of KCl (or NaCl), AlCl3 and your desired hydrocinnamic acid. Separate the product as suitable (filter the acid off and wash it or extract it with ether or DCM). Purify it in a suitable way. Yield was in my case approx. 80% if I remember correctly.

Vogelzang - 9-12-2009 at 17:46


Look at the bottom of column 8 in US patent 4206139

http://www.google.com/patents?hl=en

Vogelzang - 16-2-2012 at 17:43

Quote: Originally posted by Vogelzang  
Ber 1914 pages 71-72 German to English translation.

Alpha, beta- hydrocinnamic acid

The hydrogenation was carried out according to Paal-Skita. The cinnamic acid was just neutralized with alkali, after addition of several cubic centimeters of colloidal palladium solution hydrogen under 1 atm. pressure was led in, until a probe (in Soda solution) of permanganate was no longer reduced. Both forms of the cinnamic acid gave the same hydro derivative.

The hydro acid forms beautiful, white, surface rich crystals, which when recrystallized from gasoline melt at 137-138°. After further recrystallization the melting point sank to 132°, whereby from the prisms broad, white needles were obtained. After further recrystallizations we found the melting point always to be 130-131.5°. The substance was already soft before this.

Reduction with sodium amalgam. In the cold or at room temperature the sodium amalgam had over all no effect on the dimethylcinnamic acid. Although, 1 g of the acid could be fully reduced with 3 % amalgam through long warming and shaking on a water bath, whereby 50 times excess of amalgam was necessary. The hydro acid melted at 137-138° and was certainly identical with that described above, although the melting point after recrystallization was not undertaken.


Correction:

The title should be Alpha, beta-dimethyl hydrocinnamic acid

clearly_not_atara - 3-6-2022 at 09:17

Isopropanol can be used as the hydrogen donor at atmospheric pressure with finely divided nickel for a wide variety of alkenes. Cinnamic acid is not tested in the attached paper, but the Introduction reviews similar work, and notes particularly:

"Despite the attractiveness of the combination Ni/i-PrOH, only two reports describe its application to the transfer hydrogenation of olefins. In the first one, Raney nickel (10–50 wt % of total substrate) was used under reflux, showing high conversions for cinnamates and cyclic olefins and low conversions for acyclic olefins.9 In the second report, activated metallic nickel, prepared by thermal decomposition of in situ generated nickel diisopropoxide in boiling 2-propanol, was more effective in the reduction of non-functionalised and non-activated olefins (10–30 mol % Ni, 95–100 °C).10"

The free acid might be esterified (or insoluble) under the conditions, but the ester works great.

Attachment: alonso2009.pdf (653kB)
This file has been downloaded 262 times