To a solution of the ketone in 300 ml IPA was added a solution of 25,3 g methylamine hydrochloride in 30 ml water followed by dropwise addition of 15 g NaOH dissolved in 40 ml water during 10 minutes while stirring the mixture violently.Ketone(slightly blue tone) used was MDP2P from benzo wacker oxidation. methylamine hcl used was reagent grade, IPA used was 99.7% reagent grade, H2O used was distilled water. NaOH used was reagent grade.
After all the addition, while stirring, the color was noticed as orange.
When the addition was complete the mixture was stirred for another hour at room temperature.A solution of 5,5 g sodium borohydride in 20 ml water containing 25 mg NaOH was then added dropwise over 30 minutes while the mixture was stirred violently.They were all reagent grade.
The 5,5 g sodium borohydride in 20 ml water containing 25 mg NaOH solution was prepared just 20min before the addition, and it was very concentrated.
A mistake was the addition was done in less than 15 minutes.
The stirring was violent, but after completion, the solution seemed to have a layer of oil in the middle that could stir easily and another layer on the outer part wouldn't move at all, gel like..... tried to increase the speed of overhead stirrer until the whole gel would stir, violently.
When addition was complete the stirring was continued for two hours.ok, how to define violently? SWIM tried not to splash the solution out of the 3 neck RBF(2 neck covered) while stirring with maximum rpm but there were still some part dropping here and there. wasn't that violent?(SWIM's a peace lover, thus this was classified as violent under SWIM:))
When the stirring stopped, there were 2 layers observed, in the dream. on top was a dark color thought to be oil, below was thought to be aqeous layer.
The residual borohydride was destroyed by addition of diluted hydrochloric acid (1:5 conc hydrochloric acid:water) until gas evolution ceased and pH 3 was reached.The diluted muriatic acid was added in portions(stirred the solution to make sure the aqeous and oil layers would be acidic), till gas evolution ceased and pH3 was reached, using pH paper to test the acidity. The amount of muriatic acid(37%) used was about 350ml.
The alcohol was removed by distillation in a rotovapThe IPA distilled under simple distillation, would the be any significant here? SWIM assume there isn't. But who knows, rotovap might give some magic touch that simple distillation wouldn't have?
After distillation(stopped the distillation just at the point of 100C), there were 2 layers present, the top dark layer was now in small volume only. SWIM did not measure them, does it really matter? If yes, SWIM will dream again to report the volume.
and the aqueous solution diluted with 100 ml water, extracted once with 50 ml toluene, made strongly alkaline with 25% aq. NaOH and then extracted with 2x50 ml toluene. SWIM dreamt that in the previous step, acid addition, a lot of water(about 400ml) was already added. so SWIM did not "dilute" the solution. The temperature of the solution was about 70C and toluene was added to extract the solution, dark color toluene solution was obtained. Added NaOH solution(the solution became milky) and tested with pH paper till the solution became alkaline, extracted with toluene 2 times.
The combined alkaline extracts was dried over MgSO4 and the solvent removed by distillation.since there will be distillation of solvent, which BP is at 110C, SWIM did not dry the extracts over MgSO4, anyway, SWIM did not have any MgSO4, but only some silica gel. The solvent was removed, under atm pressure, simple distillation.
After distillation(stopped at temp 130C), some brown salt/crystal was present. the dark color solution was poured out for next step, the salt was kept aside, let's call them brown salt for SWIM's sake, as SWIM really could not identify what were they. The closest SWIM could think was methylamine.hcl as the weight was about 20g. COuld it be the MDMA? no, SWIM did not take them..... SWIM did not ask anyone to try as well. So swim could just stare at them interrogating with acetone, boiling IPA and they just did not give in. SWIM held them at the fridge, now, until they reveal their identification, they will not get released from SWIM's [medline]prison[/medline] fridge.
The residual oil was dissolved in 200 ml EtOACreagent grade was used, merck to be sure. CAS number checked, expiry date checked, seal checked, tatse, emm... not checked(SWIM got his own "spirit", so ok)
and 5N HCl/IPA was added in portions until pH 5 was reached. Several times the acid addition had to be stopped and the formed crystals removed by filtration.the HCL/IPA was dried using silica gel. pH5 was reached easily. crystals isolated by vacuum filtration. a bit brown, dried them in oven.
The salt was then recrystallised in IPA.oh no, SWIM now suspected all these are out there to tease SWIM, THEY just would not dissolve in boiling IPA. How could SWIM recrystallise?
OMG, help, what are they?
SWIM then washed them with acetone and they looked white, SWIM and FOAF was so dumb, tried the unidentified salt(tested not like shit but very salty), oh no..... up to 1 g or 2, there was no effect noted till 2 hours later. the last dose SWIM took was more than a month ago, so there should be minor effect noted even with 40mg dosage.
What can these junk be? surely not sodium borohydride as the amount weighed to be more than 10g.
Can any bee, or almighty Barium help SWIM to spot what was the problem, please? What is the critical thing(s) to note in this reaction?
ps: This was the second dream SWIM have about this reaction, both yileded 0% MDMA. Does it matter w/w or molecular % in this case?