Synthesis of 3,4-methylendioxybenzylmethylketone from piperonal ...

William D.

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• Jul 23,

• #1

Step 1. PMK-glycidate.

1. Freshly prepared powdered sodium ethoxide (23 g.) was added during 4 hours to a stirred mixture of piperonal (50 g.) and ethyl a-bromopropionate (61 g.), cooled in ice-salt.
2. Stirring was continued overnight at room temperature and for 6 hours on the water-bath; ice-water was then added, and the mixture acidified with dilute acetic acid.
3. The glycide ester was extracted with ether, and ethereal solution washed with aqueous sodium carbonate and dried with sodium sulphate.
4. After removal of ether, the residue was distilled and collected between 70 *C and 200* at 20 mm.
5. Subsequent redistillation gave B-3,4-methylenedioxyphenyl-a-methylglycide ester (40 g.) b.p. 184-186*/14 mm (yield, 48%).


Step 2. 3,4-methylendioxyphenylacetone.

1. The ether (35 g.) was refluxed for 5 hours with a solution of sodium hydroxide (10 g.) in 90% aqueous alcohol (150 ml).
2. After removal of part of the alcohol by distillation, the residue was diluted with a large volume of water and extracted with ether, and with the addition of a trace of copper powder;
3. The liquid was then distilled slowly under reduced pressure in the presence of copper powder. Redistillation of the product gave 3,4-methylenedioxybenzylmethylketone (11,1 g.) b.p 154-156/11 mm. (yield, 44.5%). Last edited by a moderator: Jul 13,

William D.

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• #3

This synthesis of glycidat works, but for hydrolysis would better use hydrochloric acid. And bromopropionate can replace to chloropropionate.

C14

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• #30

hello one question please , the first step it is for pmk methyl glycidate or pmk ethyl glycidate,?? Thanks becouse in another forum ethyl glycidate and hier methyl

C14

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• #31

Hier say pmk ethyl glycidate now i am comfused

kawaii

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• #4

does this synthesis Works for pmk ethyl glycidate cas-16-7? It's much more complicated than pmk methyl glycidate

William D.

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• #5

Step 2 there is a route for this CAS. But I would use softer conditions when reactions with alkali (1eq of NaOH and low temp), if there is access to aqueous hydrochloric acid.

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William D.

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• #7

Methyl, ethyl, tert-butyl, isopropyl, etc ethers

ukises

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Montecristo

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• #8

Would Step 2 be good for converting the new PMK ethyl glycidate? Seems it needs saponification with sodium first, would this tek cover that with the NaOH reflux?
By 90% aqueous alcohol you mean 90% abv? not 90% aqueous?

btcboss

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• #9

Could be copper replaced by any other metal? Iron, Aluminum...?
Thanks.

William D.

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• #10

No. But you can use another route, with alkali and hydrochloric acid.

btcboss

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William D.

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• #12

It depends on what starting reagents you have. Do you have a piperonal? Last edited by a moderator: May 13,

realboss

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• #28

Man I have piperonal
Can I use bmk glycidate video
As a reference and use piperonal as a starting chemical and make pmk can you help man

btcboss

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btcboss

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• #14

Sorry ;-) Not final product new cas pmk oil to process

btcboss

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• #15

I can obtain the same cas in powder

William D.

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• #16

if it is a powder - for rearrangement needs only HCl acid and water (better that NaOH aq. soln only). If the liquid - needs NaOH and HCl desirable

William D.

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• #17

In general, you can do without metal, it is here more in the role of a catalyst.

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• #18

@William Dampier



So if reacting the powder "pmk ethyl glycidate" with HCL and water, it will convert to PMK or PMK glycidic acid?

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• #19

@William Dampier , the second part would be only applicable for the non ethyl pmk that we have now , right?