[OJM]

Hello,

I am currently synthesizing Tame (1,1,1-tris(amino-methyl)ethane) for my undergraduate research project.

I would greatly appreciate any advice from Inorganic & Organometallic chemist, or any who have experience working with azides. So Thank you in advance.

1,1,1-Tris(azido-methyl)ethane [10]:

A mixture of crude 1,1,1-(Benzenesulfonylchloride-methyl)ethane (50g) & NaN3 in Diethyleneglycol (170mL) is stirred and maintained under N2 @ 135° C for 16 hours. after cooling it is poured into water (340mL)

The resulting oil is collected and combined with diethyl ether (65mL) extract of the aqueous layer, and extracted with water.

The ethereal solution is is dried (Na2SO4), treated with charcoal, and evaporated.


Im trying to setup the apparatus in under a hood using N2 gas lines.

Thank you again for your time.

[Hunter2]

I am wondering how do you will come  from  1,1,1-(Benzenesulfonylchloride-methyl)ethane to 1,1,1-Tris(azido-methyl)ethane

I would assume Azid react with the -SO₂-Cl group.

[OJM]

Benzene sulfonylchloride is a tosyl group and a good leaving group. You are right.

[discodermolide]

You don't mention how much NaN₃ is used.

As you are making a tri-azido compound at 135°C what do you think may well happen here?

I don't see this as an undergraduate synthetic research project. So why do you need this compound?

[OJM]

I am synthesizing tame for my professor. I am well aware of the dangers of handling sodium azide.

^ 30.0 grams NaN3



After completing the azide substitution, the product in dry THF will be added slowly to a suspension of LiAlH4 (2Hr), then heated under reflux (18hr).-----> ***reduction of Polyazide to Polyamine

I specifically ask, How do i safely extract the resulting oil all while under the Nitrogen atmosphere.

I am a student in buffalo that has been working on this all semester.

Cheers

[discodermolide]

What is the yield of the azide reaction?
I ask because heating a tri-azide at 135°C may be a little unsafe.


If you have been working on this all summer then you should know how to do the extractions involved. And you should know the correct structures and their names as well.

[Hunter2]

 Iasked again Phe-SO₂Cl + NaN₃ => Phe-SO₂-N₃ + NaCl

But how do you will get 1,1,1-Tris(azido-methyl)ethane .

1,1,1-(Benzenesulfonylchloride-methyl)ethane is for me also not clear how this should look like.

[Dan]

1,1,1-(Benzenesulfonylchloride-methyl)ethane

Be careful with your nomenclature - this does not exist. I assume you mean 1,1,1-tris(benzenesulfonyloxymethyl)ethane (which does not contain any chlorine)?

This one:

Be very very careful heating this to 170 °C. Make sure that is absolutely necessary as it could explode quite spectacularly on that scale. You (or a colleague) could be maimed or killed. I'm no azidophobe, I have worked with them quite extensively over the last 8 years, but I would never attempt that procedure at that temperature on that scale. I am 99.9% certain there is no way the safety office here would allow anyone to set it up anyway. My advice would be to speak to the safety office at your institution before doing it.

[clarkstill]

Be very very careful heating this to 170 °C. Make sure that is absolutely necessary as it could explode quite spectacularly on that scale. You (or a colleague) could be maimed or killed. I'm no azidophobe, I have worked with them quite extensively over the last 8 years, but I would never attempt that procedure at that temperature on that scale. I am 99.9% certain there is no way the safety office here would allow anyone to set it up anyway. My advice would be to speak to the safety office at your institution before doing it.

I couldn't agree more; you absolutely should not do this reaction. If you're desperate to make the triamine you could try a triple Gabriel synthesis? Or benzylamine and then reduction of the benzyl group? Or even just excess ammonia?  Anyway you definitely should be not heating a molecule with 4 carbons and 9 nitrogens to 170C, neither should you be evaporating the product to dryness. If you're dead set on doing this reaction please let me know where in the world you are so I can arrange to be elsewhere.

[mjc123]

Tame 1,1,1-tris(aminomethyl)ethane? Sounds like pretty wild 1,1,1-tris(aminomethyl)ethane to me!

[OJM]

My apologies,

Dan is right it should be,

" I assume you mean 1,1,1-tris(benzenesulfonyloxymethyl)ethane (which does not contain any chlorine)?"

We haven't started the reaction yet but i could upload a picture of the apparatus.

TAME has already been synthesized 3 times at my school a decade ago.The temperature never exceeds 135° C.

[OJM]

Some modifications to the apparatus need to be made. a soxhlet thimble apparatus and dean stark apparatus will be added.

[Dan]

Some modifications to the apparatus need to be made. a soxhlet thimble apparatus and dean stark apparatus will be added.

I'd definitely add a blast shield as well if I had to do that experiment.

TAME has already been synthesized 3 times at my school a decade ago.The temperature never exceeds 135° C.

Just because it was done before a decade ago doesn't mean it's safe to do or is compatible with your school's current safety policies (which have probably tightened in the last 10 years).

You should consult with your safety officer(s) before doing the experiment to ascertain whether you can actually do it and, if you can, to make sure all reasonable precautions to minimize the risks are in place. This is probably a legal requirement. You could be in serious trouble (even if nobody is injured or if nothing goes wrong) if you are not operating according to health and safety law.

[OJM]

thanks Dan,

My professor has already consulted with the school safety office. I will be attempting a dry run to see if everything works first. I do have a blast shield but did not want to block the apparatus in the picture.

Ill post an update of the most current apparatus later today.

[Enthalpy]

Supposedly obvious for you all, but for my personal information:
- What prevents 30 batches with each 1g azide, instead of one batch with 30g?
- Could neopentane triol or trihalide react with ammonia to provide the triamine?

I just read (without understanding the implications) in Huntsmnn's brochure about ethyleneamines:

"Huntsman manufactures ethyleneamines by the ethylene dichloride/ammonia process. This process consists of the reaction of ethylene dichloride with ammonia, followed by neutralization with sodium hydroxide to produce a mixture of ethyleneamines and sodium chloride. The salt is removed from the amine mixture, and the individual amines are separated by fractional distillation."

They don't tell about the pressure, though.

Ill post an update of the most current apparatus later today.

OJM, is everything fine?