FriendlyFinger (Hive Bee)
05-28-03 11:46
No 436052
      Performic Oxidation of beta-Methylstyrene     

Hi there,
When adding Performic to isosafrole and mixing it's supposed to be orange. How about if adding to trans-beta-Methylstyrene? Because my stuff is clear after 24 hours. I'm doing it via Labtops "One and Only Performic"

Edit: I guess what I should really be asking, is can I get to P-2-P using B-Methylstyrene and the Buffered Performic the way it has been described for isosafrole?

Be joyful, though you've concided the facts!
 
 
 
 
    FriendlyFinger
(Hive Bee)
06-01-03 07:16
No 436916
      No, Buffered Performic didn't Perform on my...     

No, Buffered Performic didn't Perform on my B-Methylstyrene. Actually, it did but only on about 2% of the propenyl. 50g B-methylstyrene + DCM + 25g BiCarb stirred for 10 min. Tech 85-88% Formic + 30% H2O2 mixed and left for 1 hour at room temp then cooled to 0C

Driped in the performic over 10 min. Over half the volume was dripped and streamed in before I felt any heat happening. Reflux hung around for an hour then left stirring hard for 24 hours.

When stopped, both layers were crystal clear! Hydrolysed by preheating the organic to 80C, preheated 15% H2SO4 and poured that through the condenser and held at 75-80C for 2 hours. Stopped, cooled, 2 layers appeared. Top layer was the light yellow organic. Transfered to sep funnel, hit it with 60ml DCM, washed aqueous layer with 2X 20ml DCM. Combined, washed organic with 150ml 5% NaHCO3. Organic turned milky white. Washed with dH2O and got a terrible emulsion so added some NaCl and it cleared. Repeated the wash and the same thing happened then filtered through MgSO4 which cleared it up beautifully and distilled off DCM then I got back at least half of my unreacted B-Methylstyrene and after that about 2 ml Ketone. The rest was some viscous high boiling point oil.

Could it be bad H2O2? It sat in the fridge unopened for 7 months. Surley it can't decompose that quickly? Got B-Methylstyrene from Propiophenone and It came over at the right temp. Right on the nose and I'm impressed with the yield. What about the Formic. Technical no good?

Thanks,
FF

Be joyful, though you've concided the facts!
 
 
 
 
    LaBTop
(Daddy)
06-01-03 18:12
No 436996
      It should be possible to get P2P.     

See Post 96788 (Professor: "real question anyone please /trans-beta-methylstyrene", Chemicals & Equipment) and the yield is advertised as 93%.
H2O2 which is 7 month old should be checked (how to: Search), it is also important to know how much light has gotten to the bottle in that lifespan, a lot of light will decompose it quicker. There is a nice simple method to check the real percentage of H2O2 and its purity somewhere on the Hive.
Technical grade 85-88% Formic acid should be good enough, eventually check the real percentage also by titration with a base or compare its weight per ml to a table in literature.

You can repeat the procedure with fresh H2O2, and take samples at intervals to use TLC on, so you can see when the conversion peaks. Then you stop stirring and proceed to the next step.
Different starting materials could need shorter or longer stirring times, the data for a certain compound are only sure after someone did a series of real testruns, like you are doing now.
Stirr your propenylbenzene, DCM and sodiumbicarbonate a bit longer perhaps, or use sodiumcarbonate.
You could also try the Rhodium/Semtexium peracetic acid procedure instead of the buffered performic, less harsh, just a little longer.

Now put the word " propenylbenzene " in the FSE, you'll get 508 hits , the first 100 will already give you a days work to study, f.e.
Post 436456 (Aurelius: "Primary Carbon", Chemistry Discourse),
Post 322503 (hypo: "bps and mps of various propenyl and allylbenzenes", Methods Discourse), bps and mps of various propenyl and allylbenzenes
Post 431689 (FriendlyFinger: "Allylbenzene to propenylbenzene", Methods Discourse) your post on isomerization of allylbenzene.
Post 434529 (FriendlyFinger: "Thanks for the references, I understand it...", Methods Discourse):
this is your own post on how you made your trans-beta-methylstyrene. You stated there:
""eventually got about 40% visually of something ---Don't get me wrong I'm not unhappy with what I did. I just don't know what I'm doing here and there."" 
I hope you understand that your statement in this, your last post:
""Got B-Methylstyrene from Propiophenone and It came over at the right temp. Right on the nose and I'm impressed with the yield. ""
got me a bit worried about your obtained supposed trans-beta-methylstyrene. Or there must be a post from you about the same topic slipped through my event horizon since 21 May.

Now this answer costed me quite some time to establish, but I hope you don't see it as negative critics, just thinking in the blind, I'm not looking at a lot of chems as you do, so keep trying, this whole route should be feasible in quite good yield.
And setbacks are much more occuring than a straight one time result, so keep trying and asking. LT/

WISDOMwillWIN
 
 
 
 
    FriendlyFinger
(Hive Bee)
06-02-03 02:35
No 437083
      Labtop, thank you for your very positive ...     

Labtop, thank you for your very positive pro-active reply.  I can see you have the hall mark of  a good teacher. Very rare.

I am confident about having trans-beta-methylstyrene because since my last post when I first tried it, I repeated it several times. The part I felt uncomfortable with was dehydration of the alcohol but I got through that and then fractionally distilled to be sure I had B-Methylstyrene.

Yes I've seen the reference to that method quoted in the "Professor" link  before. It's posted on Rhodiums page under the heading "P2P from Propenylbenzenes", by T.A. Dal Cason et. al., Journal of Forensic Sciences 29(4), 1187-1208 (1984)

"By using a modification of Fujisawa and Deguchi's [2] synthesis of 3,4-methylenedioxybenzyl methyl ketone, the trans-beta-methylstyrene by-product of the previous reaction was also converted to P-2-P"
"The resulting solution was neutralized with aqueous base and extracted with CH2Cl2 to yield phenyl-2-propanone (93%)."

[2]Fujisawa and Deguchi, Journal of the Pharmaceutical Society of Japan, Vol, 74, No. 9, 1954 p. 975.


That's just a standard peformic isn't it? I've read quite a bit about the performic, Gyrogearloose, Bal, Ritter, yourself etc, the quarrel over NaHCO3 etc., black tar etc., stiring time, emulsion, low yield of the standard performic etc. etc. So I didn't feel that a claim of 93% yield was believable, actually I thought it was a typo and they really meant 93% Monoformyl glycol. Otherwise why wouldn't people be using this method for P-2-P, and talking lots about it? Hence my decision to go modified performic.

I'm only up to chapter 3 of my general chemistry book, so this is a lot for my depressed brain to comprehend, but I already know that when making MDP-2-P, a loss of yield happens in the hydrolysis step because the methylenedioxy bridge is sensitive to attack from H2SO[sub]4, but this wouldn't happen if using Trans- beta-methylstyrene as the starter, so the yield would be higher. Am I thinking right? There's only one way to find out and it's a lot of fun!

Regards,
FFlaugh

Be joyful, though you've concided the facts!
 
 
 
 
    LaBTop
(Daddy)
06-02-03 12:31
No 437187
      Review     

This post: Post 187637 (OChem: "When substituting GAA for Formic acid...", Chemistry Discourse),
and all of the posters remarks, you will get some valuable info there.

Another tiny problem perhaps: Dal Cason used the word "modification" of Fujisawa and Deguchi's standard performic oxidation which uses acetone, so what modification is meant here? One we don't know of? Anybody knows?

The 93% yield mentioned seems exagerated, normally you may be glad to get 72-75% yield, and first time runs end up usually more in the 55-65% yields. Or did he really talk only about the trans-beta-methylstyrene conversion when giving that yield of 93%??

You should also look for a post of Ritter last year, who told us to use a special distillation apparatus called Wiped Film Evaporator, which are used in organic chemistry to produce high purity products by evaporation, distillation or stripping. Thin film evaporation is required for viscous and/or heat sensitive products. In certain cases evaporation can proceed to a dry residue or to crystal formation.
http://www.albmolecular.com/features/tekreps/vol03/no23/
In this post he gives his ultimate procedure to obtain >80% yields in the performic oxidation.
Ask him in case you can't overcome your problems alone, he's a very saffy performic artist.smile

WISDOMwillWIN
 
 
 
 
    Rhodium
(Chief Bee)
06-02-03 16:10
No 437230
      Fujisawa/Deguchi original performic oxidation
(Rated as: excellent)
    

The Fujisawa/Deguchi performic oxidation appear in the following two CA citations - compare these originals with Dal Cason's modification:

Utilization of safrole as medical raw material. VI. New syntheses of 3,4-methylenedioxybenzyl methyl ketone.
Fujisawa, Toshiro; Deguchi, Yoshio.
Yakugaku Zasshi 74, 975-7 (1954), Chem. Abs 49:56727

Abstract

cf. C.A. 47, 3300a. A soln. of 34 g. 30% H2O2 and 150 g. 80% HCO2H was treated dropwise with 32.4 g. isosafrole in 120 ml. Me2CO below 40C, the mixt. stirred 2 hrs. and let stand overnight, and the HCO2H and Me2CO removed in vacuo to give 61 g. residue (I). 

I (30 g.) in 30 ml. MeOH and 180 g. 15% H2SO4 were heated 3 hrs., the mixt. cooled and extd. with Et2O, the ext. washed with water and 5% NaOH and distd. to give 10.3 g. (58%) 3,4-CH2O2C6H3CH2COMe (II), bp2 108-112C; oxime, mp. 85-8C; semicarbazone, mp. 162-3C.


Fujisawa, Toshiro; Okada, Mitsuzo; Deguchi, Yoshio.
Patent JP31008573 CA 52:66321  

Abstract

To a cooled mixt. of 34 g. 30% H2O2 and 150 g. HCO2H is dropped a mixt. of 32.4 g. isosafrole and 120 mL acetone below 40C, kept overnight, evapd. in vacuo, 60 mL MeOH and 360 g. 15% H2SO4 added, heated on H2O bath 3 hrs., cooled, extd. with ether or C6H6, and distd. in vacuo to afford 20.6 g. 3,4-methylenedioxybenzyl methyl ketone (I), bp2 108-20C. 

I (23 g.) and 65 g. HCONH2 is heated at 190C 5 hrs., cooled, 100 mL H2O2* added, extd. with C6H6, the ext. evapd., 8 mL MeOH and 75 mL 15% HCl added, heated on a H2O bath 2 hrs., alkalified with caustic alkali, the oil extd. with C6H6, and the ext. distd. in vacuo to afford 11.7 g. 3,4-methylenedioxyphenylisopropylamine (II), b5 122-7.


* A classical typo in the clandestine chemistry literature. It has also been reprinted in several other publications, for example M. V. Smith's "Psychedelic Chemistry". It should read "H2O" and not "H2O2"...
 
 
 
 
    Osmium
(Stoni's sexual toy)
06-03-03 16:53
No 437539
      > Driped in the performic over 10 min.     

> Driped in the performic over 10 min.

Sounds like you added it way too fast.

> Could it be bad H2O2? It sat in the fridge unopened for 7 months.

I have successfully used tech grade H2O2 which was stored at room temp for 2 years.

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com
 
 
 
 
    FriendlyFinger
(Hive Bee)
06-04-03 02:53
No 437673
      Yes I did drip to fast.     

Yes I did drip to fast. Too impatient because I wasn't seeing a reaction. I was just reading sopme of your old posts where you drip in without acetone.

I think Dal Carson does hint at what those " modifications" are. The difference that I see from the origional Fugisawa/Deguchi synth is;

1) After acetone/Propenyl is dripped in, "The acidic solution was refluxed"
 
2) "and, then, neutralized and extracted with CH2Cl2"



In the discussion after they say; "The NMR spectrum of a hydrolysis sample removed after 2 h shows P-2-P to already be a major component. After 3.5 h of hydrolysis, virtually the entire sample converted to P-2-P."


So if they really mean reflux, then that's at least 56C. How long for? Can I assume that side reactions will occur on  substrates other than Isosafrole as well if not kept below 40C. Also they infer a high yield for a 3.5hr hydrolysis.

I'll try it keeping below 40C and I'll try the buffered a few times.

Regards,
FF

Be joyful, though you've concided the facts!
 
 
 
 
    FriendlyFinger
(Hive Bee)
06-04-03 11:33
No 437743
      I will try and test my H 2 O 2 , but in the...     

I will try and test my H2O2, but in the meantime, I've just done the following using standard performic;

57.6g H2O2 and 254g Formic acid was combined and left at room temp for an hour then the fridge, then into a 1L flask with stirrer sitting in an ice bath. 40g B-methylstyrene was mixed with 170ml acetone in a dropping funnel and was dripped in over 25 minutes with temp easily staying under 26C.

Removed the ice bath straight away and watched the temp climb slowly up to 38C, then fall slowly 50 minutes after addition. Colour after 2 hours was slightly yellow. Stopped stirring and letting stand till tomorrow. Can't wait!

How does this sound so far? Is there any such thing as the correct temp range for this reaction other than staying under 40C? Thanks for all the interest.

Regards,
FF.

Be joyful, though you've concided the facts!
 
 
 
 
    Osmium
(Stoni's sexual toy)
06-04-03 13:30
No 437757
      I never ever said to add the shit fast, and I...     

I never ever said to add the shit fast, and I never said to cool the reaction flask too much too early.

Also, it sounds like you are a little confused about the whole reflux deal. When they talk about acidic reflux they mean the post-performic H2SO4 hydrolysis, not the actual performic reaction.

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com
 
 
 
 
    FriendlyFinger
(Hive Bee)
06-23-03 08:29
No 441872
      Yeah! I must be loosing my mind, reading too...     

Yeah! I must be loosing my mind, reading too many different posts without taking notes! Anyway, got a couple of grams of ketone from that abortion.

Tried the performic again with fresh B-methylstyrene, Formic and 35% H2O2 using Sodium Carbonate.

1) 72.3g 86% Formic acid (diluted from 99% AR stock) was combined with 43.8g 35% H2O2 and left at room temp for 1 hour then in fridge till 0C

2) Put 4.4g Na2CO3, 34.2g B-Methylstyrene and 173.3g DCM in a 500ml RBF and stired.

3) Dripped in the performic acid and kept the solution tempreture between 38C and 40C. Addition took 2 hours 20 minutes (Ha Ha Didn't screw up here!). After 5 hours temp was 28C (may have screwed up here?). Stirred for 24 Hours.

4) Poured solution into sep funnel, waited 1 hour. Tapped off organic layer and extracted aqueous layer with 20ml DCM. Washed Combined organic layer with 2 X 40ml dH 2O and poured in a 1L RBF with stir bar.

5) DCM was removed with vacuum and  the rest of the DCM was allowed to evaporate with the distillation head removed.

6) The glycol was heated to 80C then 260g 15% H2SO4 and 74g MeOH pre-heated, was added though the condenser and refluxed for 2 hours. Solution tempreture was 71C (feel bad here)

7) After 2 hours 100ml water was added and the flask cooled in a room temp bath, then a cold bath and transfered to a 500ml sep funnel. This time a very light yellow layer appeared at the bottom.

8) Extracted 3 X 40ml DCM, washed 2 X 75ml 5% Na2CO3 then 55ml brine, dried over MgSO4 and filtered in to a 250 RBF.

9) Removed DCM. A few drops of B-Methylstyrene came over at 43C and 4mm, then a few drops of ketone at 75C and 4 mm, then the rest at 135C at 4mm.

Can I assume that the high boiling point liquid (about 290C) was the unreacted glycol and that I can run it through the hydrolysis again and that it was the re-arrangement step that failed! 71C too low? Also, should the reaction tempreature of 36C-40C be kept for the full 24 hours or 6 hours or just for the addition?

Thanks again,
FF

Be joyful, though you've concided the facts!
 
 
 
 
    FriendlyFinger
(Hive Bee)
07-15-03 08:03
No 447345
      It's nice when perple answer your posts, but...
(Rated as: excellent)
    

It's nice when people answer your posts, but even more satisfying when you can answer your own.

The colour of the performix using B-Methylstyrene during reaction and stirring is grey/white. After stirring is complete and layers have separated, the bottom organic layer is clear and the top layer is frosty!

Hydrolysing with H2SO4 has not yet worked for me even at 80C, so this time I refluxed some of the glycol (distilled, 11.5g,) with 50ml benzene and 0.6g tosic acid using a Dean-Stark trap for 3 hours. Some effervesence was seen but died down very early on. Bugger-all water deposited and colour of the solution was the same.

After that, I went ahead and fractionally distilled under vacuum totally forgetting to neutralise and wash. Benzene came over first then water and with bath temp at 140-160C and pressure of 11 mbar came P2P at 88C. three quarters of the way through, the vacuum started dropping steadily and more water was seen in the condenser. Recovered 8.1g P2P and 2.1g tar remained.

The performic was run again with 79.4g B-Methylstyrene using NaCO3, addition took 3 hours at 39-40C, kept there for 6 hours and stirred for 24h total. Removed the DCM, then added 6.7g tosic acid. Recovered 50g P2P, at 96-99C , approx 16mm, bath temp 140-160C, Yield 55%. 26.2g tar left behind.

I won't do this again. Water was a major problem. Didn't have a cold trap. I'll try toluene instead of benzene and I'll also try heating the glycol with tosic without vacuum. I have a feeling that hydrolysing with 15% H2SO4 will work at higher tempretures.

The P2P aminated just fine with Osmiums Al/Hg. Snow white. Yield 85%. 50mg of the d-l made me horny all day and night. Just like it did in the 80's! 

Regards,
FF.
 
 
 
 
    Rhodium
(Chief Bee)
06-03-04 18:27
No 511241
      First Performic Oxidation of Isosafrole to MDP2P
(Rated as: good read)
    

This article has been abstracted/summarized in Post 437230 (Rhodium: "Fujisawa/Deguchi original performic oxidation", Methods Discourse)

Studies on the Utilization of Safrole as Medical Raw Material. VII.
New Syntheses of 3,4-Methylenedioxybenzyl Methyl Ketone.

Toshiro Fujisawa and Yoshio Deguchi
Yakugaku Zasshi, Vol. 74, No 9, 975-977 (1954) (../rhodium/pdf /mdp2p.fujisawa-deguchi.pdf)

Summary
Hydrogen peroxide solution was applied to isosafrole in formic acid and the oil thereby obtained, assumed to be isosafrole glycol ester, was submitted to hydrolysis and dehydration with sulfuric acid from which the objective 3,4-methylenedioxybenzyl methyl ketone was obtained in approx. 60% yield.

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