https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2p.piperonal.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2p.piperonal.html)
has anyone figured out if the Pseudonitrosite reaction works for IsoSaffy or are the rumors of it being an exception correct?
Post 177886 (missing)
I think you might want to check out the thread starting with
"High yeilding iso-safrole to MDP2NP pseudonitrosite proceedure
by Antibody2 02/2001
Having had a few sucessful dreams synthing TMA2 from asarone and PMA from anethole via the pseudonitrosite route, antibody was delighted to find that iso-safrole suffers from none of the yeild limiting factors suffered by either asarone, which easily polymerizes during nitration or anethole whose pseudonitrosite is difficult to hydroylse in satifactory yeilds. In two consecutive reactions with iso-safrole near quantitaive yeilds of the pseudonitrosite were formed. This pseudonitrosite is also hardier during hydolysis. The hydrolysis method outlined below is gentler than that in common usage and was inspired by a Weiland ref that Uemura came-up with and a re-read of TSII.
Nitrosation of iso-safrole
A 2l rb flask is charged with 2.5M NaNO2 (173g ) in 250mls dH2O. The flask is placed an ice bath and the NaNO2 is dissolved with mag stirring. 0.5M freshly distilled [1] iso-safrole (89g) was dissolved in 900mls diethyl ether (distilled from zerostart starting fluid). This is added to the flask. A pressure equalized dropping funnel charged with 1.25M H2SO4 in 500mls dH2O is placed in the rb flask. a hose is attached to the top of the funnel leading out of doors. After contents had been allowed time to cool. the H2SO4 solution was dripped in over 6 hours with slow mag stirring, ice being replaced as necessary. Flask was then allowed to sit for an additional 9 hours while ice was allowed to melt. During this step, a 6-7cm layer of white spongy precipitate will form at the interface of the two layers.
The dropping funnel is removed, and the reaction mixture is stoppered, and shook vigourously, with care being taken not to break flask with mag stir bar [2]. The entire contents is gravity filtered using coffee filters and a 2l gasoline funnel. The etherial layer and the the aqueous layers are saved for later [3]. The filter cake is then scraped into a 2l beaker containing 1l dH2O and stirred with a spoon for a couple minutes. What will happen is all the NaSO4 will settle at the bottom, while all the pseudonitrosite will float in suspension. The water is decanted with the suspended pseudonitrosite from the NaSO4 which can be saved for other uses if desired.
The water layer with pseudonitrosites is vacuum filtered and washed with additional dH2O. The filter cake can then be washed 2X with EtOH or more expediently the filtercake is then dropped into a beaker containing 200mls EtOH nand stirred throughly, and then vacuum filtered.
Yeild 0.49M pseudonitrosite of iso-safrole 98% (127g) as white crunchy nuggets [4]
Hydrolysis of pseudonitrosite
A 2l beaker sitting in an ice bath is charged with mixture of 0.5M KOH (28g) dissolved in 700mls EtOH. When mixture has reached 10°C the pseudonitrosite is added portionwise over 10-15 minutes with care being taken not to allow temperature to exceed 20°c. The is mag stirred vigourously until all pseudonitrosite has gone into solution. While this is stirring prepare 500mls of 2M aqueous HCl (approx 105mls 31% HCl and 395mls dH2O) and refrigerate. When all the nitrosite is in solution it was vac filtered and the filtrate returned to the ice bath and one tray of ice-cubes is added and cooled to 5°C. Then as 500mls cold dH20 is added slowly the solutions goes from an umbra to an ochre color,the chilled dilute HCl solution is added as a tiny stream to the stirring solution over 5-10 minutes. During the addition the solution becomes cloudy and most of the ice melts. The entire mixture is poured into a 4l wine jug containing 2l dH2O. And the entire mixture is refrigerated for a couple hours. During which time the the entire jug will transform into bright yellow crystal matrix, and probably a brilliant yellow bottom oil layer, which is also the nitropropene in oil form. The crystals and solution are decanted from the oil layer and vac filtered, the filtercake is dissolved in 300-400mls boiling IPA to which the yellow oil layer is also added. Agitate until all is in solution then allow to cool slowly [5] to room temperature when it may be refrigerated for an additional hour to complete recrystalization. Then vac filter, wash filter cake with dH2O, and place in a stoppered filter flask charged with silica gel and attach to low vac (fridge compressor) overnight to desicate.
Yeild 0.36M 3,4 methylenedioxy-phenyl2nitropropene 73% (80g)
as bright yellow needles the texture of compressed glass wool insulation."
Followed by some discussion and notes, then kudos, and then minor tweaks.
:)
z
Post 177857 (https://www.thevespiary.org/talk/index.php?topic=10355.msg17785700#msg17785700)
(LaBTop: "Re: DETAILED METHODS for NON-CHEMISTS The Sequel !", Newbee Forum)http://www.pmf.ukim.edu.mk/PMF/Chemistry/reactions/akabori2.htm (http://www.pmf.ukim.edu.mk/PMF/Chemistry/reactions/akabori2.htm)
Uemura really thinks he posted some infos.
I was just asking because my evil twin had no probs at all with 8% KOH/EtOH. Had to stir and heat a bit, but it turned out fine. Rextallization gave translucent yellow needles..
z
https://www.thevespiary.org/rhodium/Rhodium/chemistry/isosafrole.txt (https://www.thevespiary.org/rhodium/Rhodium/chemistry/isosafrole.txt)
on Rhod's page, but there must be a more OTC/kitchen friendly way to go from (substituted)benzaldehyde to (substituted)propenylbenzene. Then you're plugged into the performic/peracetic/oxone route to ketone with no EtNO2.Post 178931 (missing)
(PolytheneSam: "PPA --> meth this easy?", Chemistry Discourse) Maybe there are other ways to hydrogenate the intermediate.