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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: strider on June 13, 2006, 06:14:14 AM

Title: Converting Ethyl bromide into Methane
Post by: strider on June 13, 2006, 06:14:14 AM
hi, i was wondering as to how can Ethyl bromide be converted into Methane. I'm all puzzled  ???
Title: Re: Converting Ethyl bromide into Methane
Post by: Dan on June 13, 2006, 06:41:34 AM
here's an idea.

1. Eliminate HBr to give ethene
2. Ozonolysis to give formaldehyde
3. NaBH4 to give methanol
4. TsCl to give MeOTs
5. LiAlH4 to give methane

It's a bit long though, so there is probably an easier way...
Title: Re: Converting Ethyl bromide into Methane
Post by: strider on June 13, 2006, 06:47:36 AM
thanks man, u saved me much time  :) if u somehow manage to find an easier way to carry the conversion please do let me know  :-*
Title: Re: Converting Ethyl bromide into Methane
Post by: Dan on June 13, 2006, 06:49:58 AM
sorry, i meant formaldehyde, not acetone, I have corrected it...
Title: Re: Converting Ethyl bromide into Methane
Post by: Dan on June 13, 2006, 06:53:05 AM
Actually, from formaldehyde you could do W-K reduction, Mozingo reduction, or Clemmenson reduction. That's more obvious and has fewer steps...
Title: Re: Converting Ethyl bromide into Methane
Post by: strider on June 13, 2006, 07:12:21 AM
hmmm...cant we just convert ethyl bromide into ethane and then through thermal cracking obtain methane. If so, what would be the exact chemical reaction.. :-\
Title: Re: Converting Ethyl bromide into Methane
Post by: Dan on June 13, 2006, 07:22:56 AM
I don't know enough about cracking to answer that confidently, but I don't think you can crack ethane into two methane (not enough H).

To get ethane from ethyl bromide, you could use Bu3SnH with AIBN initiator (this is a radical reaction).

I think the best bet is to get to formaldehyde and then reduce with Wolff-kischner, Mozingo or Clemmenson.
Title: Re: Converting Ethyl bromide into Methane
Post by: strider on June 13, 2006, 07:31:10 AM
yup, ure right. Thanks for helping me out  :)
Title: Re: Converting Ethyl bromide into Methane
Post by: lavoisier on June 13, 2006, 01:05:17 PM
There's in fact a simpler way (in terms of chemistry involved and reagents used), even though nobody would ever use it to make methane, I guess.

EtBr + LiOH --> EtOH + LiBr
EtOH + KMnO4 --> CH3COOH
CH3COOH + NaOH --> CH3COONa + H2O
CH3COONa --> CH4 + CO2

I remember reading somewhere that acetates are the only simple fatty acid salts undergoing decarboxylation on heating.
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 13, 2006, 01:25:51 PM
And what happen with your Na, where H coming from  ???
I suggest the path to H3CCOOH and after that:
2CH3COOH + Ag2O--> 2CH3COO:-Ag+
CH3COO:-Ag+  + Br2 --> CH3Br (Borodin reaction)
CH3Br + Mg--> CH3MgBr (Grignard)
CH3MgBr + H2O or alcohol --> CH4...
Also from acetic acid-->bromacetic acid-->nitromethane-->Me-NH3-->Hoffman elimination-->CH4
Do you think bromacetic acid may thermally decompose to CH3Br?
Thats what i can suggest now :)
Title: Re: Converting Ethyl bromide into Methane
Post by: lavoisier on June 13, 2006, 01:53:18 PM
And what happen with your Na, where H coming from ???

J. March, Advanced Organic Chemistry, 4th edition Wiley Interscience, page 627:

"An exception is acetic acid, which as the acetate, heated with base, gives good yields of methane".

But I have no idea of the mechanism.

In either way, this would be the most expensive methane on Earth!
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 13, 2006, 02:13:02 PM
Heating with base is another thing :) Here we are discussing only possible on blank sheet synthesis with about no practical cost. But its always useful to think about how can prepare some compound from others in the lab as we all know how rich Sigma&Aldrich are from the same kind of thinking :))
Title: Re: Converting Ethyl bromide into Methane
Post by: lavoisier on June 13, 2006, 03:15:56 PM
HP,

apparently the fact that they use a 'base' tells you something more about how it works and where this 'H' comes from. Could you please explain it to everybody? Thanks
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 13, 2006, 03:48:40 PM
I am not sure but may be so:
CH3COONa + NaOH heat--> CH4 + Na2CO3
So H comes from OH from sodium hydroxyde...
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 13, 2006, 03:56:32 PM
Oh, yes this is the so known method of Duma: heating sodium salt carboxylic acid with melted NaOH.
Another similar method is the Kolbe method for electrolysis sodium salt carbo acid in water solution...
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 14, 2006, 03:20:10 PM
One more aproach with industrial hint:
C2H5-Br + Mg--> C2H5MgBr
C2H5MgBr + C2H5Br--> C4H10 (butan)
Butan gas is industrially oxidized to acetic acid with Co catalyst, at T=150C and 55atm presure:
C4H10 + O2 --> 2CH3COOH
Then using Kolbe or Duma methods or Borodin-Grignard you may transfer acetic acid to methane...
Title: Re: Converting Ethyl bromide into Methane
Post by: swati on June 15, 2006, 05:25:05 PM
 :D  I think another method that can be used is :

1.)   Elimination of HBr from C2H5Br  to form  H2C=CH2
2.)   Ozonolysis of H2C=CH2 to form formaldehyde  HCHO
3.)   reduction of HCHO with HI in presence of red phosphorus to give CH4

         
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 16, 2006, 03:01:12 PM
Can you explain us the mechanism reaction CH2O + HI with red P to CH4?
Its really posible to obtain ethylen fron EtBr by dehydrobromination at heat and some basic catalyst or by dehydrobromination with ethanolic KOH at mild conditions. Then ethylene may be transformed  to acetic acid by industrial Wacker proces..
Title: Re: Converting Ethyl bromide into Methane
Post by: swati on June 16, 2006, 05:04:34 PM
Can you explain us the mechanism reaction CH2O + HI with red P to CH4?
Its really posible to obtain ethylen fron EtBr by dehydrobromination at heat and some basic catalyst or by dehydrobromination with ethanolic KOH at mild conditions. Then ethylene may be transformed to acetic acid by industrial Wacker proces..

 :-\  Sorry but I dont know its mechanism .
 :)  The only thing I know about it is that on heating an aldehyde or a ketone with HI in presence of red P at 150 oC , it is reduced to corresponding alkane .


                                                 Red  P
                     HCHO + 4HI  -------------------->  CH4 + H2O + 2I2
                                                  150 oC
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 17, 2006, 04:57:43 AM
Yah it seems possible as HI is known reductive compound. But i think the formed elemental I2 will react with red P to PI3 which can hydrolyze with H2O to H3PO3 or H3PO4 and 3HI regenerated..Again at 150C HI can be farely god reductive agent similar to nascent H generators used at Clemenson reduction for example :)
Title: Re: Converting Ethyl bromide into Methane
Post by: HP on June 17, 2006, 05:25:58 AM
Also possible Wolf-Kishner reduction of CH2O with hydrazine:
CH2O + H2N-NH2 --> CH2=N-NH2 + NaOH --> CH4 + N2
Title: Re: Converting Ethyl bromide into Methane
Post by: Alberto_Kravina on June 17, 2006, 08:28:40 AM
My idea:

1.)C2H5Br -----> H2C=CH2 + HBr
2.)H2C=CH2 ------- Ozonolysis -----> CH2O
3.)CH2O -------LiAlH4---> CH3OH
4.)CH3OH + HCl -----> CH3Cl + H2O
5.)CH3Cl + Mg -----Grignard reaction ---> CH3MgCl
6.)CH3MgCl + H2O --------> CH4 + MgClOH