dwarfer (Hive Addict)
02-05-02 13:08
No 265591
      Didrex modification protocols if you will...  Bookmark   

Didrex, benzphetamine, futher described below, is easily made by the addition of benzyl chloride to d-desoxyphedrine, whatever that is, in the presence of sodium carbonate in non polar..

See [url]=http://patimg1.uspto.gov/.piw?docid=US002789138&SectionNum=1&IDKey=24483B99C9C4&HomeUrl=http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1%2526Sect2=HITOFF%2526d=PALL%2526p=1%2526u=/netahtml/srchnum.htm%2526r=1%2526f=G%2526l=50%2526s1='2,789,138'.WKU.%2526OS=PN/2,789,138%2526RS=PN/2,789,138[/url]


Now as it so happens, my evil neighbor Marvin has stumbled across a cache of this in the closet of his deceased great aunt Mergatroid, whose obesity problem is legend hereabouts: supposedly she was consuming prodigious quantities of the stuff to try to lose excess poundage, to no apparent effect..

Anyway, Marvin wants to know how to undo the benzyl chloride effect: he says he wants to have the pure desoxy-shit for some reason:

any help appreciated...

( I dida search for didrex afore doing this post: zero results
I'll 'research for benzphetamine: )


   Title: Benzphetamine. 
   CA name(s):
 (S)-N,.alpha.-Dimethyl-N-(phenylmethyl)benzeneethanamine; N-benzyl-N,.alpha.-dimethylphenethylamine;
   Molecular formula:  C17H21N
   Molecular weight:  239.36
   Composition:  C 85.31%, H 8.84%, N 5.85%. 
   Literature references:

 Prepd from d-desoxyephedrine:

  Heinzelman, Aspergren, U.S. pat. 2,789,138 (1957 to Upjohn).
   Properties:  Liquid.  bp0.02 127 deg.  nD19 1.5515.  Practically insol in water.  Sol in methanol, ethanol, ether, chloroform, acetone, benzene.
   Boiling point:  127
   Refraction:  1.5515
    Note:  This is a controlled substance (stimulant) listed in the U.S. Code of Federal Regulations, Title 21 Part 1308.13 (1995).

   Derivative:  Hydrochloride
   CAS Registry number:  [5411-22-3]
   Trade name(s):  Didrex (Upjohn),  Inapetyl (Upjohn).
   Molecular formula:  C17H21N.HCl
   Properties:    Crystals from ethyl acetate, mp 129-130 deg.  Dextrorotatory.  Sol in water, 95% ethanol.
   Melting point:  129-130

   THERAP CAT:  Anorexic. 

   Title: Methamphetamine. 
   CA name(s): 
methyl-.beta.-  phenylisopropylamine;
   Trade names(s):  Norodin (Endo). 
   Molecular formula:  C10H15N
   Molecular weight:  149.24
   Composition:  C 80.48%, H 10.13%, N 9.39%. 
    Note:  This is a controlled substance (stimulant) listed in the U.S. Code of Federal Regulations, Title 21 Part 1308.12 (1995).


(Hive Addict)
02-05-02 13:15
No 265593
      Re: Didrex modification protocols if you will...  Bookmark   

[No 239321]oops:
Catalytic hydrogenolysis on Pd/Pt under pressure, Rhodium says...

Hmm: wonder if it's worth the effort??

11-02-02 15:46
No 375837
      A possible solution.  Bookmark   

A Mild and Efficient Method for the N-Debenzylation of Aromatic Heterocycles

Haddach, A. A.;1 Kelleman, A.;2 Deaton-Rewolinski, M. V.1
1Agouron Pharmaceuticals, Inc., A Pfizer Company, Chemical Research & Development, 3565 General Atomics Court, San Diego, CA 92121, 2University of California, San Diego.
A procedure for the N-debenzylation of aromatic heterocycles was reported. The procedure involves preparation of solution of the substrate in DMSO (0.1 M) with KOtBu (7.0 equivalents), followed by bubbling oxygen through the solution until the starting material has been consumed. Examples of the substrates reported are N-benzyl -indoles, -imidazoles, -indazoles, pyrazoles benzimidazoles, and -carbazoles. Yields are reported to range from 82% to quantitative conversion. A proposed mechanism is shown in

Scheme 10.

Proposed Mechanism for N-Debenzylation


If it works I think this would give N-debenzylation without producing diastereomers or removing the methyl group in most cases.

Maybe isopropyl alcohol could replace the tert alcohol but I wouldn't bank on it.

It may chew on non amine or oxygen bound benzylic carbons too though so it may be a dud killing everything.