Epoxide Hydrolyzing

[hCiLdOdUeDn]

Hey there bees!

Hcildoduedn here wants to know if the quantity of epoxide is crucial with the quantity of 15% h2so4? In oxone write-up for hydrolyzing it says for 15g epoxide use 150mL 15% sulfuric acid and 25mL MeOH. If hcildoduedn added 20g epoxide with the same amount of hydrolyzing stuff will it still convert to mdp2p?

Thanks!
hcildoduedn

[Rhodium]

Yes, it should work all right.

[OB1KNoBee]

"Should" sounds a little leary there rhodium, but hey HcljfkhoxJC (spelling) please post your ketone results if it works.

OB1

[Rhodium]

Okay, you'll get a long response then:

Nothing is hurt by using a too high epoxide/acid ratio, the worst case scenario would be the unlikely event that there is too little acid in the mix to convert the epoxide in the usual time, and it might be recovered in the following distillation step as either epoxide or glycol. To make sure everything gets converted to the ketone as usual, extend the acid reflux time by 25%.

[hCiLdOdUeDn]

As soon as i get to my lab, i will do this. Ill just let it reflux for ~5hours or so instead. Results will be posted soon!
hcildoduedn

[sYnThOmAtIc]

Some article I read recnetly said they use 1% acid at room temp with stiring and get high 80% yield hydrolysis.

[Rhodium]

What article? The one with tosic acid in toluene?

[sYnThOmAtIc]

Yea p-Tosh BTW got a synth for that para-tolusulfonic acid?

[Vibrating_Lights]

I believe chromic was messing withthe tosoic for a while..  I don't know if he ever got any goo tosic though.  Swim once converted a whole lot of glycol  with a very minimal ammount of acid the acid was still 15% but the volume was greatly reduced.  I sorry i can't give any specifics .  This happened during one of swims month long valium binges. Lesson here benzos and cooking NOOOOOOOOOOOOOOOO GOOOOOOD.
\Vl_

[Chromic]

Go by Vogel's method as posted by Terbium in

Post 261199

(terbium: "Re: p-toluenesulfonic acid", Chemistry Discourse). Bring 3 molar eq toluene and 1 molar eq 95% sulfuric acid to a very light reflux in a flask equipped with a dean stark trap and a condenser with good stirring. Then slowly increase the heat... you'll produce a some nasty SO2 if you heat it too fast. Make sure to use a Dean Stark trap to isolate the water formed. Once I get mine, I'll have another run on making tosic acid and use it for rearrangement (this way I can also use it as an indicator of the progress of the conversion of the glycol in toluene, an idea that Ritter has privately mentioned)... I'm very hopeful about this route, especially with regard to rearranging asarone glycol.

[sYnThOmAtIc]

So is thiophene present in all toluene? So one should just fractionally distill toluene before reaction? 84c frm 111c seems good enough. Or better yet is p-tsoh like suspicous or anything? Seems more practical for SWIM to buy his right now as his resources are going toward LiI.

[Chromic]

Tosic acid isn't suspicious. I like to stick to OTC whenever I can.

[sYnThOmAtIc]

I agree! But I can no longer get toluene OTC anyway so why not just order it since the toluene would need to be ordered? Plus I don't like the idea of making so2 in my bathroom    . I want to be able and breathe for another ten years or so   .
Yes, That pic really is me!

[hCiLdOdUeDn]

Hey Bees!

Finished making epoxide see

Post 338466

(hCiLdOdUeDn: "Ok...here are the results..", Methods Discourse) and

Post 338527

(hCiLdOdUeDn: "^^^Too late. Ok, phew...SWIM is now finished!!!", Methods Discourse) for detailed writeup.

This is what SWIM did once he got his epoxide made. He added ~70ml of crude epoxide dissolved in 100mL ethanol with 450mL 15% h2so4, (note this is 25% less h2so4 than what is usually used) This was refluxed in a 1L FB Boiling Flask with reflux condensor and was put on a water bath for 5hours (instead of 3). The water bath was on a light boil.

Once finished the solution was poured into 1L seperatory funnel and there were two distinct layers. The bottom layer was a blood-red colored and way seperated off and kept. The top layer was extracted with 3x75mL DCM and the extracts were put with the first seperated layer. This left me with ~350mL of opaque reddish colored solution. The solvents were evaporated and SWIM was left with ~75mL deep red residue which was fairly fluid like. SWIM was jumping for joy at this point.

The 75mL deep red residue went through distillation in a simple vacuum distillation setup (boiling flask, still head, condensor, vacuum adapter, recieving flask) The first fraction that came over came over at 160C, this is suspected iso-safrole as SWIMS safrole comes over at ~145. This first fraction was clear and about 5mL worth and saved for future use. The second fraction came over at 190C and about 50mL came over then no more came over. SWIM was so nervous at that point as he did not want things to get screwed up so he stopped. This left SWIM with very light yellow clear liquid and very water like. The rest of the resiude was approx 10mL worth and simply discarded. Although maybe more could have came over this was good enough for SWIM. JUMPING FOR JOY!! SWIM cant wait for his first amination and crystallization.

So it works!! Ethanol as solvent & less h2so4. The BP for the second fraction is right so SWIM should have good KETONE.

THANKS BEES SOOOOOOOOO MUCH!!! 
hcildoduedn

[Chromic]

Why 5 hours?

[Wargasm]

I believe he is compensating for the reduced acid/epoxide ratio.
Personally, I don't like the idea of my epoxide staying in hot sulfuric any longer than it has to, but if it works...

Worker bees can leave
   Even drones can fly away
      The queen is their slave

[Flip]

I believe were all still waiting on Ritter's writeup where he performed the p-tosic hydrolysis in five minutes, neutralizing the acid with a high boiling tertiary amine (i'm pretty sure it's a commercial chem though) to prevent it from destroying the molecule at the end of the procedure.  That would be dank if I had a way of filtering those tosic crystals.

Flip
Conclusion /nm./: the place where you got tired of thinking.