Lets try this again. I've been working on the One Pot Reaction from alpha-methyl-1,3-benzodioxole-5-propanal to the corresponding amide using these two refs:

1) J. Org. Chem. 2003, 68, 1158-1160

2) Tetrahedron Letters 42 (2001) 1103–1105

Although i tried tweeking it a little using more OTC solvents than THF and only 13% ammonia.

akcom suggested using hydroxylamine HCL in DMSO to achieve the same result. ( Could you re-post about that? )

If anyone ever ran this your input would be appreciated.

@NaBH4 from the previous post:  I need the H2O2 to oxidize the nitrile intermediary. The purpose isnt to add an amine group but to obtain the amide in order to run Hoffman on it and obtain the honey with on less Carbon atom.

Cheers

sorry to piss on your earlier thread i like that idea though.
like to see it in action just keep it under the table, it's no secret you can use AMBP to make mda but once yeilds get higher and it becomes more practical watch what happens.




Those kind of words aint helping here jon, synonyms and chemical names would greatly help the cause of laying low for as long as reality would allow.

Lol bit harsh on poor old slash got his thread axed! Nice work there slash u will fit in much better over here than our last home which is completely empty for some reason..

yes i agree, how can we get that ref up without it being traced to someone.. i would like to see it

Since you have those refs handy, could you attach a PDF for the benefit of us who lack journal access?

Representative Procedure for Transformation of Aldehydes into Amides: A solution of appropriate aldehyde (1a-j, 5 mmol) and iodine (5.5 mmol) in ammonia water (30 mL of 28% solution) and THF (5 mL) was stirred at room temperature for 1 h. The dark solution became colorless at the end of reaction. Aqueous H2O2 (3 mL of 35% solution) was then added dropwise. The reaction mixture was stirred for 2-4 h and extracted with CH2Cl2. The organic phase was washed with brine, dried (Na2- SO4), and concentrated in vacuo. The residue was rinsed with hexane/EtOAc (1:3) to give a pure amide product (3a-j, 81- 98% yields). Amides 3a-j are characterized by their physical and spectral properties that are consistent with known com- pounds (see Supporting Information).

You can all see why i was interested in this. Easily scalable, no heat, nothing. Just mix and enjoy. Sedit says I2 is a bit of a turnoff in today's weather. I wasnt aware of this.  Im not from the States and have access to it... ( plus you dont need tons of it. More or less 1g of Iodine per gram of Aldehyde).

@ Hypnos: Keep digging

@Akcom:   You talked about a way using DMSO and Hydroxylamine HCL. I found a reference doing just that but using a Pd Catalyst. Did you forget to mention the use of the catalyst or did i find some other ref?

I2 acts as an oxidiser in the transformation; it is possible to use a combination of KI and an external oxidant such as tert-butylhydroperoxide:

http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THS-4VKXBXN-3&_user=10&_coverDate=05%2F06%2F2009&_rdoc=1&_fmt=high&_orig=gateway&_origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1697021442&_rerunOrigin=google&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=9d86015bcc1c9acb90ea65a8a79638c9&searchtype=a

or diiodohydantoin:

http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THR-4NWCD8B-5&_user=10&_coverDate=08%2F20%2F2007&_rdoc=1&_fmt=high&_orig=gateway&_origin=gateway&_sort=d&_docanchor=&view=c&_searchStrId=1697020622&_rerunOrigin=google&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=ad7cb0cda3a72966b228b8656516f427&searchtype=a

The use of hydroxylamine and a Beckmann rearrangement has also been discussed, but I'm sure we're all well aware of that. One thing of note: you don't oxidize a nitrile to an amide, you hydrolyse it. Oxidizing a nitrile produces a nitrile oxide, which, while interesting and potentially useful in the synthesis of e.g. muscimol, is kind of useless here.

Thing is for this to get anywhere someone's going to have to actually get hold of the stuff at some point... even though the spooks might not be aware of it yet it's still not going to be easy.

@ WizardX: Lol thanks but i said THF should NOT dissolve iodine easily as iodine is non polar and THF is.

@Atara: I am getting my hands on it! I am just BEING TOO MUCH OF A RETARD to properly dissolve the Iodine. Thus my previous post. Did you check the ref i posted? it seems a lot less complicated than using convoluted chemicals such as tertbutylhydroperoxide..

Twodogs presented this method with the Beckman Rearregement, this is somewhat of a try to improve this with a high yielding one step OTC from the aldehyde to the amide instead of going through the trouble of isolating the aldoxime.

You are right though I2 acts as an oxidizer here... I went back to the ref and checked the mechanism again. I had forgot about that. I've been trying to wrap my head around this and now i'm going in circles you see ^^.

So i cant just use I- since i need the oxidative properties of I2. I dont get it though. How the hell can they dissolve Iodine ( I2) in 28% ammonia solution with THF as a Cosolvent. Everything is Polar! They dont give any hint to the use of KI and i dont think the formation of I3- would be of any help as it is less oxidative than I2 ( increased oxidation number)

Any thoughts? Because all i get is clogged up I2 swirling in my flask.. so depressing

I'm thinking of giving it a try with acetone as cosolvent. Conversion of nitrile compounds to their corresponding amides has been reported in acetone so that step should be fine. And it should help dissolve iodine.

As a solvent. http://en.wikipedia.org/wiki/Tetrahydrofuran#As_a_solvent

The other main application of THF is as an industrial solvent for PVC and in varnishes.[6] It is an aprotic solvent with a dielectric constant of 7.6. It is a moderately polar solvent and can dissolve a wide range of nonpolar and polar chemical compounds.[7] THF is water-miscible, and can form solid clathrate hydrate structures with water at low temperatures.[8]

you know i completly forgot about that alpha carbon