Author Topic: Urushibara (Read 258 times)

2bfrank · « **on:** September 01, 2009, 09:10:41 AM »

I am assuming that Reference includes presenting them.. This is an old one, yet I have not seen it around, hence thought out of interest I would present.

1. Novel reductions of various organics using ppt Nickel and water..
2. Nickel catalyzed reductions of aryl halides with zinc powder and ethanol
3. Redox reaction between organic compounds, nickel and primary alcohols

Hope these are of at least some interest..

2b

Mr.Murphy · « **Reply #1 on:** September 01, 2009, 01:15:52 PM »

Quote from: 2bfrank

Hope these are of at least some interest..

I can assure you: They are indeed! Thx for sharing those refs!

Vesp · « **Reply #2 on:** September 01, 2009, 01:16:03 PM »

Yes I'm sure there is an interest in these, thank you for providing them.

2bfrank · « **Reply #3 on:** September 01, 2009, 02:29:04 PM »

Good, I got 2 more on Urushibara, but on another computer elsewhere, and will post when I can.. ..

2b

Mr.Murphy · « **Reply #4 on:** September 01, 2009, 03:18:27 PM »

Always keep 'em coming!

2bfrank · « **Reply #5 on:** September 02, 2009, 05:16:46 AM »

Gladly,, I suppose due to the fact that much has been discussed/presented, and not wanting to rehash, etc, plus a reasont past ramblings on chem nonscense, I get a bit reserved. But fuck that, HANG ON That sound to right

Perhpas Ill go with, well fuck that, lifes short, and if it helps the cause, etc

IMHO though, that arylhalide hydrogenolysis which also states benzylchloride > toluene 53% and bibenzyl 36% or close, and in half an hour, so if a molecule had a halide in a secondary position, and had some steric hinderance issues that could make coupling difficult, is somewhat of interest.. perhaps that is not thought out, but did cross my mind....theoretically.

2b

poisoninthestain · « **Reply #6 on:** September 03, 2009, 09:44:39 PM »

Nice! For those looking for nickel metal in the US I bought some 100% nickel tacks for about $1-3 a pack from CVS/Rite Aid. Probably weighs ~10g as ppt. Not the most economical means but better than nothing.

Vesp · « **Reply #7 on:** September 03, 2009, 10:54:25 PM »

Are you sure it is pure Ni?
Does it stick to a magnet?

Sedit · « **Reply #8 on:** September 03, 2009, 11:04:20 PM »

I have read about this quite a few times and am still a bit confused as to its nature. As I understand it after reading the text Nickle chloride is precipitated as Nickle with the use of Zinc or Aluminum and then dryed correct.

Has anyone ever checked to see if A soluble nickle salt such as Nickle nitrate or acetate in MeOH/Substrate with the addition of Zinc will precipitate the Nickle and effect the reduction all at once?

I have half a mind to attempt this on nitromethane but due to the fact that Nitromethane can be reduced with relative ease to many other substrates it may not give me the information I desire. If anyone else has an idea of what else I could attempt to reduce to test it please speak up. As it stands the most over the counter material I could test this on would be Styrene at the moment.

I suppose I could be way off base here but it seems feesible in my eyes.

[EDIT]

Duh Nevermind. That is exactly what they are discussing in the third paper 2b linked.
What I did not expect was there proposed mechanism of the formation of HNi(EtO) before it reacted with Zinc and precipitated the nickle. It appears that NiBr is soluble in MeOH but does anyone have data on the solubility of the various salts of Nickle in MeOH or quite possible the use of Glacial Acetic acid.

poisoninthestain · « **Reply #9 on:** September 04, 2009, 02:42:32 AM »

Quote from: Vesp on September 03, 2009, 10:54:25 PM

Are you sure it is pure Ni?
Does it stick to a magnet?

I'm not 100% sure it's all nickel but I have no reason to believe it's mixed with something else. It was advertised as "nickel tacks". I haven't used them for anything as of yet. I sorta just bought 'em in case I ever needed some nickel since they sorta stood out. I went downstairs and got a fridge magnetic after I read your question.

The tacks stick very hard to the magnet from what I observed.

poisoninthestain · « **Reply #10 on:** September 07, 2009, 06:55:47 PM »

Sedit-Since I'm having trouble sending pics through PM I figured I'd post here.

no1uno · « **Reply #11 on:** September 26, 2009, 02:00:47 PM »

Here are a bunch of articles on these catalysts - one in particular appears to be claiming that the precipitated Nickel is capable of CTH of Nitriles, simply by refluxing them in water.... That and the U-Ni is capable of reducing acetophenone to ethylbenzene....

Seems kinda fucking interesting

Sedit · « **Reply #12 on:** September 26, 2009, 02:54:53 PM »

I merged this with the existing Urushibara threed

~Sedit

Quote

acetophenone to ethylbenzene....

No shit? Any chance it will work with other benzylic carbonyl compounds? I would think it proceeds thru the alcohol which opens even more options for the use of this. Im still looking for pure nickle to start playing around with this. I could not find those tacks poison.

Thanks for the articals No1uno, I will see they get put to god use.

lugh · « **Reply #13 on:** September 27, 2009, 03:40:34 AM »

The french paper retrieved long ago for Rhodium stated:

1) alpha,beta-Unsaturated acids (reduction to the saturated acid).

Malic, crotonic, oleic, and cinnamic acid have been respectively
transformed in succinic, butyric, stearic and phenylpropionic acids.

2) Aldehydes and Ketones

Formaldehyde, salicylaldehyde and vanillin has been reduced to methanol,
salicylalcohol and vanillic alcohol. Salicylaldehyde forms an insoluble
complex with nickel in ammoniacal solutions (4), its reduction has been
furnished in the presence of potassium carbonate. The
beta-keto-substituted phenylpyruvic and benzoylpropionic acid has been
transformed to phenylacetic acid and gamma-phenylbutyrolactone
respectively.

3) Oximes/Isonitrosoketones

Ketoximes are reduced to the primary amine. 2-Phenethylamine and
Phenylisopropylamine has been obtained from phenylacetaldoxime and
phenylacetoxime, respectively. The isonitrosoketones are reduced to
amino-alcohols (Pyrazines are not formed as a by-product in this
reduction, for example in the reduction of alpha-isonitrosoacetophenone to
beta-phenylethanolamine)

4) Nitriles

Benzyl cyanide is hydrogenated in aqueous alcohol to phenethylamine, and
ethyl-2-amino-4-cyano-5-pyrimidine furnishes first the orangish red
complex describes by M. Delépine (5), then the corresponding diamine.

5) Nitro Derivatives

p-Nitrobenzoic acid is hydrogenated smoothly to p-aminobenzoic acid.

6) Direct reductive amination of ketones to amines in the presence of
ammonia.

If the usual reaction mixture is mixed with anhydrous alcohol to increase
the solubility of the ketone to be reacted, one obtains with a
satisfactory yield, in certain cases, the corresponding primary amine.
Cyclohexanone, in particular, furnishes in these conditions 60-70% of
primary cyclohexylamine. Phenylacetone and b-naphtanone have been
transformed equally in amphetamine and beta-naphtanamine.

Conclusions

The examples that we have just quoted show the properties of the
zinc-nickel couple. The simple preparation and the facile conditions of
employment shows that this couple warrants further investigation.

Antoncho was able to produce cyclohexylamine following this procedure so it's definitely of extreme interest

no1uno · « **Reply #14 on:** September 27, 2009, 09:42:22 AM »

Couple more, must make a list of what I actually have already posted

no1uno · « **Reply #15 on:** October 10, 2009, 05:25:59 AM »

A CTH using Urushibara type Ni catalysts on Nitroarenes

Baba_McKensey · « **Reply #16 on:** November 26, 2009, 02:16:21 PM »

There's more in the Urushibara related folder here:

http://www.4shared.com/dir/2038202/e41cdcd7/sharing.html

Sedit · « **Reply #17 on:** November 18, 2011, 02:29:34 AM »

All the downloads are labeled Index.php....

Can someone please upload the third paper please or figure out what the hell is up with the downloads on the forum.

dream0n · « **Reply #18 on:** November 18, 2011, 02:38:26 AM »

Third in the OP ?
--Attached--
http://uploaded.to/file/62e56ugi

Author Topic: Urushibara (Read 258 times)

2bfrank

Urushibara

Mr.Murphy

Re: Urushibara

Vesp

Re: Urushibara

2bfrank

Re: Urushibara

Mr.Murphy

Re: Urushibara

2bfrank

Re: Urushibara

poisoninthestain

Re: Urushibara

Vesp

Re: Urushibara

Sedit

Re: Urushibara

poisoninthestain

Re: Urushibara

poisoninthestain

Re: Urushibara

no1uno

Urushibara Nickel Catalysts

Sedit

Re: Urushibara

lugh

Re: Urushibara

no1uno

Re: Urushibara

no1uno

Re: Urushibara

Baba_McKensey

Re: Urushibara

Sedit

Re: Urushibara

dream0n

Re: Urushibara