Author Topic: Complete synthesis of DMMDA-2 and DMMDMA-2  (Read 7761 times)

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foxy2

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original Shulgin Article
« Reply #20 on: April 08, 2002, 12:20:00 AM »
Psychotrophic phenylisopropylamines derived from apiole and dillapiole.    
Shulgin A T; Sargent T   
NATURE  (1967 Sep 30),  215(109),  1494-5.

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foxy2

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Lit Reference
« Reply #21 on: April 18, 2002, 09:14:00 AM »
Some new transformations of dillapiol.   
Barnes, Roderick A.; Koketsu, Midori.   
An. Acad. Bras. Cienc.  (1992),  64(4),  353-9. 
Abstract
A new source of dillapiol has made possible further study of its reactions.  The migration of the double bond to form isodillapiol produced mainly the trans isomer.  The cis isomer not previously isolated was obtained by gas chromatog. and found to be a liq.  Bromination under conditions which lead to an abnormal dibromide in he case of safrol, produced only the known dillapiol tribromide.  The chloromethylation under mild conditions gave in addn. to the expected product, 4-chloromethyl-6,7-dimethoxy-5-(2-propenyl)1,3-benzodioxole, a large amt. of methylenebis(6,7-dimethoxy-5-(2-propenyl)-1,3-benzodioxole.  Two minor products 7,8-dimethoxy-5-methyl-cyclopenta[e]-1,3-benzodioxole and 4,5-dimethoxy-7-methyl-6-(2-propenyl)-1,3-benzodioxole probably resulted from redn. and reductive cyclization of the intermediate hydroxymethyl deriv.  The acetylation to yield 1-(6,7-dimethyoxy-5-(2-propenyl)-1,3-benzodioxol-4-yl)ethanone proceeded in low yield due to other reactions under acid conditions used.  Further treatment with HCl yielded 1-(6-methyl-4-methoxy-6,7-dihydrofuro[2,3-f]-1,3-benzodioxol-8-yl)ethanone.  Birch redn. gave a single product, 3,4-dimethoxy-5-(2-propenyl)phenol.  These studies produced new derivs. of dillapiol except for the tribromide.

Isolation of dillapiole
The leaves of Piper aduncum L. (50kg, partly dry) were steam distilled to yeild a dry oil weighing 738g, containing 88% dillapiole.  Fractional distillation of 448g of crude oil gave 9 fractions and a total of 325 g pure dillapiole, b.p. 173-174C (20 mm).

Isomerization of Dillapiole(I)
A solution of I (3 g) in butanol (30 ml) containing KOH (2.7 g) was stirred and heated at reflux temp. in a flask attached to a Dean-Starke water trap.  After 4 hours the reaction mix was washed with water and the butanol removed under vacuum to leave 2.8 g (94%) of a mixture which upon GC analysis showed two components in the ratio 85:15.  Upon cooling to 0C the major component crystallized and after recrystallization from hexane had m.p. 42-43C (trans-dillapiole).  The minor component (cis) did not crystallize even after several months.

4-bromo-5-(2,3-dibromopropyl)-6,7-dimethoxy-1,3-benzodioxole(VI)
A solution of I (1.1g, 0.005 moles) in t-butanol (15 ml) was treated with a solution of bromine (1.6g, 0.01 moles) in t-butanol (15 ml) at room temp.  Upon standing the product crystallized and after recrystallization from MeOH there was obtained 1.86 g (82%) of (VI) with a m.p. 108-109C.  This same reaction using 1,2-dichloroethane followed by evap. of solvent and recrystallization gave (VI) in almost quantitative yeild.
Reaction with 2 Eq of NBS in water at 35C gave an oil from which VI was obtained 34% by crystalliation from MeOH.

Birch Reduction of dillapiole
A solution of dillapiole (10g) in ethanol (50ml) was added to liq. ammonia (300ml) and subsequently sodium (3 g) in small pieces was added gradually with stirring.  The reaction mix was stirred for 30min after Na had dissolved and then ammonium chloride (7 g) was added and the ammonia allowed to evaporate at room temp. for 24 hours.  The residue was treated with cold water, acidifyed, and extracted with ether.  The ether solution was washed with 3% KOH solution and ether evaporated to leave 0.7g of neutral product.
Acidification of the alkaline solution, extraction with ether and evaporation of the solvent left a solid, 7.23g (83%) which could bee recrystallized from ethanol-water, m.p. 71-72C. 
They analyze the NMR and conclude the product is 2,3-dimethoxy-5-hydroxy-allylbenzene, but they don't say it with alot of conviction.  Its definately a pure product based on the tight melting point.

Hmmm, A route to 2,3,5-trimethoxy-4-Br-amphetamines??


Photon-induced reactions:  part V - photochemical and chemical oxidation products of dillapiole and isodillapiole.
Walia, S.; Dureja, P.; Mukerjee, S. K.       
Indian J. Chem., Sect. B (1985), 24B(2), 147-50.

Abstract
Photometabolites of dillapiole (I), obtained by irradiating I in MeOH were identified as isodillapiole, dihydrodillapiole, 1-cyclopropyl-2,3-dimethoxy-4,5-methylenedioxybenzene, dillaldehyde and 2 new MeOH adducts II (R = CH2CHMeOMe, CHEtOMe).  Isodillapiole under the same conditions furnishes II and dillaldehyde.  Dye-sensitized photooxidn. of I gives dillaldehyde, dillapional, and dihydroxydillapiole.  For comparison, KMnO4 oxidn. of I was also investigated in detail. 

Oxidation of isodillapiole with KMnO4/MgSO4
Isodilapiole (4.4 g) when oxidised with KMnO4 (6.3 g)/MgSO4 (4.8 g) in acetone at 0C afforded dillaldehyde in 80% yeild allong with dihydroxyisodillapiole and dillapionic acid in traces.

Derivatives of methylenedioxybenzene.  XXVII.  Synthesis of allyldimethoxy(methylenedioxy) benzenes.
Dallacker, Franz.
Chem. Ber.  (1969),  102(8),  2663-76.
Journal  written in German. CAN 71:90987
Abstract
Treatment of 2-methoxy-3,4-methylenedioxybenzaldehyde with HCO2H and H2O2 gave 2-methoxy-3,4-methylenedioxyphenol, which reacted with H2C:-CHCH2Br to give 2-methoxy-1-allyloxy-3,4-methylenedioxy-benzene.  The latter gave upon heating 2-methoxy-3,4-methylenedioxy-6-allylphenol which was methylated to give 2,3-dimethoxy-4,5-methylenedioxy-1-allylbenzene (dill apiole).  Also synthesized were 2,5-dimethoxy-3,4-methylenedioxy-1-allylbenzene (parsley apiole) and 4,6-dimethoxy-2,3-methylenedioxy-, 2,6-dimethoxy-3,4-methylenedioxy-, 5,6-dimethoxy-2,3-methylenedioxy-, and 4,5-dimethoxy-2,3-methylenedioxy-1-allylbenzene. 

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Antibody2

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hot damn foxy!
« Reply #22 on: April 18, 2002, 04:59:00 PM »
hot damn foxy!  8)  just to make sure we are on the same page though could dihydroxydillapiole be described as 2,3-hydroxy4,5-Methylenedioxyallybenzene?

foxy2

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sadly nope
« Reply #23 on: April 19, 2002, 09:40:00 AM »
Sorry AB
They are talking about the diol from the allyl side chain, not demethylating the aromatic ring.

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

malvaxman

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Outstanding!!!! :-D :-D :-D :-D This dude knows ...
« Reply #24 on: April 19, 2002, 10:08:00 AM »
Outstanding!!!!  ;D  ;D  ;D  ;D

This dude knows the art of growing crystals ...

Chromic

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Corrections to appendix 1
« Reply #25 on: June 26, 2002, 11:20:00 AM »
The molecular weights in Appendix 1 are all slightly off. The url

https://www.thevespiary.org/rhodium/Rhodium/chemistry/dmmdma-2.html

could use these additions/changes:

Appendix 1
isodillapiole - 222.24
isodillapiole epoxide - 238.24
isodillapiole glycol - 256.26
isodillapiole ketone (DMMDP2P-2) - 238.24
isodillapiole ketoxime - 253.26
isodillapiole pseudonitrosite - 298.25
isodillapiole nitropropene - 267.24
isodillapiole amine (DMMDA-2) - 239.27
isodillapiole amine hydrochloride (DMMDA-2.HCl) - 275.73
isodillapiole methylamine (DMMDMA-2) - 253.20
isodillapiole methylamine hydrochloride (DMMDMA-2.HCl) - 289.66

(not: Dillapiole-228, iso-228, ketone-244, oxime-259, pseudonitrosite-319, nitropropene-288, amine-246, amine.HCl-282 and methylamine.HCl-297)

I've also made similar listings for all other essential oils of interest. If it would be useful, I could post them elsewhere.

Antibody2

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maybe you could correct my MWs for dillapiole ...
« Reply #26 on: June 26, 2002, 04:57:00 PM »
maybe you could correct my MWs for dillapiole aldehyde, nitrostyrene and PEA while you at it? ;D

2,3-dimethoxy,4,5-methylenedioxy-benzaldehyde = 216
2,3-dimethoxy,4,5-methylenedioxy-betanitrostyrene = 259
haven't actually bothered to take a stab at the PEA freebase, HCl or H2SO4 yet . . .

did i ever mention i hate math? ;)

Chromic

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MWs
« Reply #27 on: June 29, 2002, 01:36:00 PM »
210.19g/mol for 2,3-dimethoxy-4,5-methylenedioxybenzaldehyde
253.21g/mol for 2,3-dimethoxy-4,5-methylenedioxy-beta-nitrostyrene
225.25g/mol for 2,3-dimethoxy-4,5-methylenedioxyphenylethylamine
261.71g/mol for 2,3-dimethoxy-4,5-methylenedioxyphenylethylamine hydrochloride

This seemed to take me forever... but I believe the answers are right.

The sulfate salt is a bit weird, it depends if you have the sulfate or the hemisulfate. I'll leave that up to you. Basically you just add 98.08g/mol, then one or two freebase MWs.

Antibody2

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2,3-dimethoxy-4,5-methylenedioxyphenylethylamine
« Reply #28 on: August 24, 2002, 04:01:00 PM »
i never bothered posting a formal write-up for this one as it was inactive at 175mgs but it was made via

Uemura's KMnO4 oxidation of isodillapiole (yeild 51%) > Rhodium's NaOH catalyzed Condensation w/ MeNO2 and in MeOH (yeild 82%) > reduction with Sunlights Zn/HCl (yeild 25%, but rxn was not allowed to run to completion, ca 50% of Zn remained - higher yeilds could be anticipated with longer rxn time), then gassed with dry HCl.

sorry no MPs. the substance didn't seem to merit the effort lacking any activity at 175mgs, thought i'd post this to save other bees the effort

Rhodium

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2,3-MeO-4,5-MD-PEA
« Reply #29 on: September 02, 2002, 09:07:00 AM »
Antibody: Excellent information! I am just as interested in cataloging inactive compounds as active ones, as both types maps out the psychedelic landscape - just knowing what's active paints no sharp boundaries...