Author Topic: cl2 + koh + iso = mdp2p  (Read 11663 times)

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jacob019

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cl2 + koh + iso = mdp2p
« on: September 25, 2001, 09:32:00 PM »
In the folowing text from the book of ecstacy is it necessary to extract with benzene or could one just distill

Piperonylacetone from the Dichloro Derivative of Isosafrole
Yuki[37] reports on piperonylacetone from 1-(3,4-methylenedioxyphenyl)dichloropropane and KOH.
Chlorine and the other halogens react readily with double bonds (like the one of isosafrole's) to form dichloro compounds in solvents inert to the halogens. The most commonly used solvents are CH2Cl2 (methylene chloride), CHCl3 (chloroform), and CCl4 (carbon tetrachloride). Running a stream of chlorine in a solution of isosafrole in one of these solvents from a cylinder or chlorine generator (see misc. chemicals chapter) will produce the appropriate dichloro compound. Use of bromine will generate the dibromo compound which could be used in place of the dichloro compound. Bromine reacts quickly in carbon tetrachloride. It is bromine in carbon tetrachloride that is used as a test for double bonds since the solution is clear red and the red color disappears as the bromine reacts. Chlorine will react slower. If water is present, a chlorohydrin will be formed which would probably react similarly to give the ketone. Experiment is king.




23.2 g (0.1 mole) of 1-(3,4-methylenedioxyphenyl)-1,2-dichloropropane is refluxed for 10hrs with 75g of 15% KOH (potassium hydroxide) solution. The mixture is cooled extracted with benzene. The benzene is removed in vacuum and the residue distilled to yield approximately 15.2 g of piperonylacetone (bp 149-151°C/10 mmHg). 85% yield from the dichloro compound.

Rhodium

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Re: cl2 + koh + iso = mdp2p
« Reply #1 on: September 25, 2001, 11:23:00 PM »
Extract with any non-polar solvent (like DCM, toluene, ether etc) but don't skip the step.

jacob019

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Re: cl2 + koh + iso = mdp2p
« Reply #2 on: October 03, 2001, 06:41:00 PM »
So let me see if I got this procedure right.
I searched the hive for a while, but couldn't find anything.
1. Mix isosafrole with DCM (50%/50%?)
2. Pump chlorine gas through the solution. (How much, how long?)
3. Distill off DCM. (is that sufficient or do I need to distill out the dichloro compound)
4. Take remaining dichloro compound and reflux for 10hrs with 75g of 15% KOH solution. (Could NaOH be used?, same concentration?)
5. Extract remaining solution with DCM. (How much should I use?)
6. Distill off DCM.
7. Distill MDP2P under vacuum.

This procedure looks great to me, because even though yeilds are small all I need to get from safrole to MDP2P in large amounts is KOH, DCM, and a Chlorine generator.

Oh and one more question, is the dichloro compound stable enough to store for long periods of time at room temperature.  That would be great because I could store it and be one easy step away from MDP2P.

Once I have the procedure and dream a bit, I'll post the results.

sunlight

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Re: cl2 + koh + iso = mdp2p
« Reply #3 on: October 04, 2001, 04:22:00 AM »
I would be fine, I'm asked myself if it's better than performic.

cilliersb

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Re: cl2 + koh + iso = mdp2p
« Reply #4 on: October 04, 2001, 01:56:00 PM »
Here's an idea

Setup your glassware for distillation. Add to the distilling flask a volume of 48% HBr. Add an equimolar amount of H2O2 to a pressure eq. addition funnel and fit this to the distilling flask. Take your IsoSassy and disolve in equal vol DCM. Place this in the recieving flask and place the recieving flask in an ice salt water bath on a magnetic stirrer.

While stirring the Iso in the reciever flask drip some (not much) of the H2O2 into the 48%HBr and bring your distilling flask to 59C and keep it there. Make sure that your condenser is efficiently cooled with ice water!!

Bromine should start distilling over as it is formed and drip onto the Iso. Control the rate of addition by controlling the rate at which H2O2 is added.

I'm not too sure how heat sensitive this reaction is, but it's probably a good idea to not let the Iso mix go above 25C.

I know, the bromine is very volatile and will interfere with your visual access to the reaction mix. I would also suggest a good mask or at least good ventilation or a fume cubby.

You'll probably need about a 20% excess of H2O2 and HBr beacuse of Bromine's solubility in water.

Dr. Hallucinator out. 8)

Agent_Smith

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Re: cl2 + koh + iso = mdp2p
« Reply #5 on: October 04, 2001, 02:04:00 PM »
cillers, that seems to me like a god synth for tar.  Doesn't iso brominate in the presence of Br2 just like safrole does?


blah blah blah something clever blah blah blah

jacob019

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Re: cl2 + koh + iso = mdp2p
« Reply #6 on: October 04, 2001, 04:33:00 PM »
Tdoesn't do much for me, because I'm not having anyluck getting HBr or H2O2 above 15% (food grade).  I could setup a bromine generator like in Agent_Smith's famous post for the glassless MDA with mothballs,  but that just changes chlorine to bromine, and doesn't really answer any of my questions.

cilliersb

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Re: cl2 + koh + iso = mdp2p
« Reply #7 on: October 05, 2001, 11:01:00 AM »
Agent, the way I understand it, with safrole the double bond is in the wrong place and it brominates incorrectly.

According to the first post (no refs??) the dibromo should form which makes sense if you look at the structure of Isosaf.

I'll do a nano and report back.

Lem2

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Re: cl2 + koh + iso = mdp2p
« Reply #8 on: October 08, 2001, 11:38:00 PM »
would anyone know if this would theoretically work on asarone?

Rhodium

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Re: cl2 + koh + iso = mdp2p
« Reply #9 on: October 08, 2001, 11:44:00 PM »
It would theoretically work on asarone if it does with isosafrole.

IudexK2

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Re: cl2 + koh + iso = mdp2p
« Reply #10 on: October 08, 2001, 11:49:00 PM »
I don't see why not  ;D

jacob019

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Re: cl2 + koh + iso = mdp2p
« Reply #11 on: October 09, 2001, 01:58:00 AM »
The original text says bromine would work.  I know from Agent_Smiths post that reacting safrole with HBr produces bromosafrole would reacting isosafrole with HBr produce dibromosafrole?  Could the rest of the procedure be done the same?  I still need imput on my original procedure.

IudexK2

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Re: cl2 + koh + iso = mdp2p
« Reply #12 on: October 09, 2001, 10:15:00 AM »
Reacting isosafrole with HBr would not produce dibromosafrole. The Q is, would reacting isosafrole wioth Br2 really produce a dibromosafrole that when refluxed w/KOH would give MDP2P?  ;D  Some wise bee please confirm or unconfirm this.

Many thankx,
IudexK

Osmium

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Re: cl2 + koh + iso = mdp2p
« Reply #13 on: October 09, 2001, 12:11:00 PM »
> would reacting isosafrole wioth Br2 really produce a
> dibromosafrole that when refluxed w/KOH would give MDP2P?

Yes of course.

cilliersb

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Re: cl2 + koh + iso = mdp2p
« Reply #14 on: October 09, 2001, 02:27:00 PM »
This is kinda how I understand the literature too Os, now all we have to do is work out ratios / temps (Very cold    -10C to 10C Max)

A higher temp in the reaction / reciever flask (distill setup as mentioned before) would interfere with the bromine staying liquid and also probably favour side reactions and probably tar formation as mentioned by Agent Smith earlier.

I can't see why a normal Ice / Salt bath won't work perfectly fine.

48%HBr costs nothing and so does H2O2. Maybe some testing in this field is called for!! let's see what a nano (5g Iso) brings to the table.

The only thing that bothers me is that bromination of the ring may take place too, touch wood!

Will report back later.

Rhodium

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Re: cl2 + koh + iso = mdp2p
« Reply #15 on: October 09, 2001, 02:29:00 PM »
Osmium: I see the source of confusion here. We should probably call the reaction product between isosafrole and bromine "dibromoisosafrole" so that it is not confused with the dibromosafrole produced when adding bromine to safrole.

cilliersb

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Re: cl2 + koh + iso = mdp2p
« Reply #16 on: October 09, 2001, 02:53:00 PM »
I agree Rhodium, they are far from being the same and definitely not interchangeable.

Do you think that this reaction has much potential? To me that 85% eild of MDP2P with 15% KOH looks very attractive. All we need to do is make sure the formation of the DiHalo compound comes over in good eild.

How would you suggest getting the Dibromo comp out of the DCM / Br2?

IudexK2

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Re: cl2 + koh + iso = mdp2p
« Reply #17 on: October 09, 2001, 02:56:00 PM »
How about washing w/thiosulphate etc. to remove Br2, then w/dH2O, then dry DCM layer, remove DCM by distillation, and distil dibromoisosafrole under vacuum, or just use as is and do purification on ketone?

cilliersb

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Re: cl2 + koh + iso = mdp2p
« Reply #18 on: October 09, 2001, 03:09:00 PM »
How about several washes with normal dH2O? with Bromine's solubility in water, three to four dH2O washes should remove Br2 enough to just distill off DCM and then pull the ketone over at the pump.

Remeber that Br2 should not be in large excess to begin with. If you use the right ratios and cooling there should be very little free Br2 in there after the reaction.

I do think that the Br2 need to be removed completely before distillation beacuse higher temps with Br2 in the mix will surely screw up the product.

Any idea if the H2O washes will work anyone? ;)

Osmium

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Re: cl2 + koh + iso = mdp2p
« Reply #19 on: October 09, 2001, 04:06:00 PM »
I wouldn't bother isolating the dibromo compound at all. Simply evap the DCM and proceed with the KOH reflux.