Reduction of carboxylic acids & esters to alkane

[Bandil]

Hi!

Just found an interesting article i would like to read:

From advance organic chemistry by Jerry March, 4. ed. pp.1214:

9-43:

         (C5H5)TiCl2
RCOOR'----------->RCH3 + R'OH

"The reagent titanocene dichloride reduces carboxylic esters and acid in a different manner from that of 0-81, 9-40, or 9-42. The product are the alkane RCH3 and the alcohol R'OH. The mechanism probably involves an alkene intermediate

The reference to this is: van Tamelen; Gladys J. Am. Chem. Soc. 1974, 96, 5290.

Does anyone have access to this article? It would be really nice to read it, as titandodecene is not super expensive(if the yeilds are half descent that is).

Regards
Bandil

[Aurelius]

Yes, but it appears to react with air.  "rigorously" excluding oxygen?  not exactly kitchen chem, but interesting none-the-less.

[Bandil]

It doesn't seem like a totally evil chemical like LAH, bromine or DMS according to chemfinder. LAH is also quite sensitive to moisture etc, but that is still used on the kitchentable by many folks... Maybe it's just the authors being overly carefull

I think this compound deserves it's go at some tryptophan. Always hated the oxygens on that compound and think they deserve to be removed ASAP!!!

[Prometheuz]

It actually seems to be a relatively benign chemical, at least compared to LAH and Br₂. Interesting. But I could imagine that stuff would be rather expensive.

Datasheet

(http://ntp-server.niehs.nih.gov/htdocs/CHEM_H&S/NTP_Chem1/Radian1271-19-8.html)

[Bandil]

It says here:

      This chemical is sensitive to exposure to moisture [058,062,269,275].
 It is stable in dry air Post 062 (not existing).  UV spectrophotometric stability screening
 indicates that solutions of this chemical in 95% ethanol are stable for less
 than two hours (RAD).  Fresh solutions should be prepared before each use.

So, as prometheus says, it looks like playdough compared to other chemicals.

It's quite soluble in DMSO(100 mL/mL). Could it be preferable to do the reductions in DMSO over benzene?

Does anyone have an compentent estimate of the yeilds if some rouge bandit where to use it on tryptophan or 5-HTP?

Regards
Bandil