Antibody2
(Commodore "Mole Bouncer")
12-24-01 11:03
No 250280
      Complete synthesis of DMMDA-2 and DMMDMA-2
(Rated as: excellent)
 Bookmark   

My christmas gift to the hive, MUAW! luvs yas all.

iso-dillapiole

500mls of dillapiole [1] was refluxed with 10g of 85% KOH under medium vacuum for 11 hours, then transfered to a vacumm distillation rig and 450mls of iso-dillapiole was recovered at bp 145-146/6, it was recrystallized from an equivalent volume of boiling petroleum ether, yeilding 410g of clear 1-2cm prisims with MP of 38C [2].

2,3-Dimethoxy,4,5-Methylenedioxy-Phenyl-2-Propanone

337g 85% HCOOH is added to 206g H2O2 with stirring, then added dropwise to a stirred mixture of 300g isodillapiole,  811mls of DCM and 68g NaHCO3, which was stirred under light reflux for 24 hours, then allows to settle. The DCM layer was isolated and stripped of solvent on the water bath. The residue was stirred with 189g H2SO4 diluted to 15% with dH2O for 2hours at 80C. The organic layer was removed, and acid layer extracted with 100mls dcm. Which was pooled with organics and washed 1X w/NaHCO3, 1x w/dH2O and distilled [3]at at 151-156/6 C to yeild 230g of ketone [4].

2,3-Dimethoxy,4,5-Methylenedioxy-Methamphetamine-2.hydrogen cloride

14g of Al (Heavy duty Reynolds) was amalgamated in 400mls MeOH and 50mg Hg2Cl2, by heating to reflux. Flask was fitted with a refulx condenser and was then transferred to a cold stirrer, 18.3g ketone and 13.7g MeNO2 in 50mls MeOH were then added dropwise over 15 minutes [5]. The rxn was allopwed to stir overnight. 500mls 50% NaOH was slowly added, then extracted with 400mls toluene followed by a 150ml extraction. Pooled extracts, and washed with 2X w/ dH2O and 1X with brine, driied through MgSO4, and gassed yeilding 15.5g of DMMDMA-2[6] with a melting point of 147-148C [2].

Oxime of 2,3-Dimethoxy,4,5-Methylenedioxy-Phenyl-2-Propanone.

195g NaAc(H2O)3 was dissolved in 140mls dH2O with stirring, followed by addition of 725mls MeOH, 230g of the phenylacetone and 83g NH2OH.HCl, the stirred suspension was heated to reflux for 1.5hrs  on water bath then 350mls of cold dH2O was slowly poured down the condenser and rxn was allowed to cool to RT with vigourous stirring and then refrigerated and the precipitate vac filtered after 2-3 hours. The mass of the crude oxime was greater than the input of precursor ketone. Recrystallization of 55g crude from 100mls IPA yeilded 20g of white needles with a MP of 107-108C [2][7].

2,3-Dimethoxy,4,5-Methylenedioxy-Amphetamine-2,hydrogen cloride [8]

7g of oxime was dissolved in 150mls dry THF and poured over activated 10g HD reynolds Al [9] followed by 18g GAA. It was allowed to react with mag stirring at RT overnight. In morning rxn was basifiied with 50% NaOH, and top THF layer was seperated, and stripped of solvent under low vac. The residue was dissolved in a portion of 2M HCl with much shaking. This was basiied and extracted with 150mls toluene, which was also stripped of solvent under low vac on a water bath. The residue being taken up in 50mls acetone, and gassed with dry HCl yeilding 3.75g of the title compound with a MP of 178-180C

Footnotes

1) The dillapiole used was the residue of Indian Dill Seed Oil (Anethum sowa robx.) after d-Carvone had been removed for the flavouring industry. It was represented as being 90% dillapiole and was used as is, with no further purification.

2) Melting point apparatus in all experiments was a -15C-260C immersion thermometer taped to a 20ml testtube containing 1 mg of product. These were placed in a 100ml beaker filled with safflower oil and slowly heated on hotplate until product had melted.

3) smaller batchs of ketone had much lower yeilds (ca 50%) due to polymerization during distillation. Smoke entering the reciver was witnessed with oil bath temperatures as low as 190C. 185C was the highest bath temperature that did not result in massive polymerization. Bisulfite purification with amounts < 100mls might be prudent.

4) ketone reacted quantitativly with sodium metabisulfite. ketone tested via bisulfite adduct requiring  addition of EtOH, refrigeration and titration to crystallize.

5) this addition rate caused several runaways, requiring rxn to be cooled in ice water periodically.

6) crystals are extremely fine, and take some time to properly crystallize, initially the gassed solution appears as though there was H2O in the gas, the cloudiness disappears as amine crystallizes, leaving a water clear solution.

7) oxime that was produced in rxns lacking the H2O quench at the end, yeilded, white needles with the same MP.

8) attempts to optimize this rxn have failed, one attempt to reduce at reflux temp failed entirely as did a rxn using Al sheet.

9) prepared by amalgamation using Hg2Cl2 in refluxing 50%H20/MEOH, followed by MeOH wash  and a THF wash.

Appendix 1 molecular weights
and for all the bees who hate calculations, here are the molecular weights for most of the dillapiole derivatives you will encounter.

Dillapiole-228
iso-228
ketone-244
oxime-259
pseudonitrosite-319
nitropropene-288
amine-246
amine.HCl-282
methylamine.HCl-297

Appendix 2 bioassays

DMMDA-2

A bioassay was attempted last nite, before making the last couple posts, a wee taste test was done make sure that characteristic amphetamine taste was present,  so as not to make a fool of myself, it was definately present, although distinct from  dmmda there was some common ground in the taste. A much driier taste.

Anyways licked the finger eneough to be worried that a small dose 30mgs had been consumed, wasn't really meant to be bioassay, but on the way out the door , put another 60-70mgs in a a baggie just in case the 30mgs kicks in so there is enoeugh to evaluate the trip. Well sitting bored at this agm  start getting these warm muscle sensations, a bit like the onset of mdma the 1st time, excited we make a trip to the washroom and eat the maybe another 50mgs. go back and half an hour latter squirming in my seat, a really strong body stone starts tro set in , i find myself cracking huge grins and feeling a ot of empathyt for those at the meeting. Yet tyhere is no impairment thinking or external sensory. this feeling slowly tapers off after 3 hours the meeting lasted, and while receeding hit baseline and then bounced back up a few times breifly. At home later that evening a 50mg line was snorted, with no tangible effect.

At the height of this trip though, i was for 10-15 minutes concerned i had eaten way too much. All in all a slightly erratic trip. I would reccomend a much larger dose another time 120-180mgs. But keep in mind your lift off may be turbulent and alarming.

DMMDMA-2

120mgs were consumed, 45 minutes later, no activity is as yet apparent, an additional 120mgs were consumed. maybe 15 minutes later, we decide to smoke a joint. It kicked in while smoking the joint and then slowly tapered off over the next 2 hours, and was again re-activated by smoking another joint, with the effects disappearing with the pot buzz. It is for me a very mild drug, pleasant, a slight euphoria was apparent, thios stuff would be good for doing at work or in church maybe. There was no impairment of motor function or thought processes, just a mild buzz. This compound might be best described in the words Shulgin used to describe butylamines, he refered to them as emphogens. It may be that psychadelic activity is beyond the scope of this drug, or perhaps much larger doses 450-600mgs would be required for recreational use. One pitfall to be aware of, is that doses greater than 400mgs daily, are likely to cause the amphetamine psychosis that Shulgin cautions of in his PMA write-up.



Added March 3, 2002, after the departure of Antibody - see Post 276882 (Antibody2: "Wish him life!", The Couch)

2,3-MeO-4,5-MD-6-Br-Amphetamine.HCl (6-Bromo-DMMDA-2)

1.6g DMMDA-2.SO4 (5mmol)is dissolved in 150mls H2O. Then slowly basified with 25% NaOH. Xtract 3x 75mls DCM. Solvent stripped on water bath and residue was dissolved in 10ml HOAc and placed in an ice bath. 0.3ml Br2 dissolved in 4mls HOAc is added dropwise with stirring. Solution turns bright orange/gold. Ice bath is removed when rxn begins to freeze. Rxn allowed to stir for 2.5 hours during which time colour fades from bright orange to a golden to a yellow and then a light ochre precipitation turns entire rxn into a beige suspension, requiring a  5mls HOAc dilution.

Option 1) Rxn is extended with 150mls dH2O, and washed 1x with DCM, then basified with 25% NaOH and Xtracted 3x 75mls DCM. Xtracts pooled washed with a portion of H2o followed by brine, driied through MgSO4, and the striiped of solvent. The dark amber residue was dissolved in 10mls HOAc (the freebase was not soluble in acetone), the acetate salt visible in suspension. 31% HCl is dripped through MgSO4 into the amine solution until precipitation ofwhite crystals stops. Mixture is refridgerated and then vac filtered yeilding 0.5g of the hydrochloride salt.

Option 2) Skip the extension & concentrate on water bath, with med vac, cool to crystallize and elute repeatedly with acetone until washs were clear.  YIELD: 1.1g 6Br-DMMDA-2.HBr (2.7mmol)

Bioassay

40mgs - No discernable activity

90mgs - At 1.5 hours i find myself wondering how i am managing so well with some drudgery i would normally find it hard to stick to. I finished more than i set out to do. At 2 hours +1 here getting abit of that expanding head tiype sensation and hints of breathlessness, but pleasant as is the mild buzz that is becoming more and more apparent,  kind of a glowing satisfaction, with heitened awareness of white noise. 2.5 hours, +2 there is a lightness to my movement. Am in a warm space like being in bed on a cold morning, mellow and everything has sugar coating. 4 hours its pretty much gone now, didn't even notice it slipping away.

Antibody - thinking of you...wink
 
 
 
 
    SpicyBrown
(Hive Bee)
12-24-01 11:58
No 250288
      Re: Complete synthesis o DMMDA-2 and MDMMDA-2  Bookmark   

Excellent! Looks like an anhydrous Al/Hg was the key? Much appreciated, Antibody2. Any idea on dosages or effects of the DMMDMA-2?

SpicyBrown
 
 
 
 
    Antibody2
(Commodore "Mole Bouncer")
12-24-01 13:00
No 250295
      Bioassays  Bookmark   

hi spicy

i added the bioassays to the original post

There is one huge problem with my bioassays of these compounds, i suffer from an overwhelming addiction to much stronger amphetamines that are used several times weekly, i expect my tolerance to them, masks many of the effects of dmmmda-2 and dmmdma-2.

I would like to arrange some kind of bioassay in a more controlled environment using a much larger control group to draw results from. Unfortunately i don't know ANY amphetamine users to do so with. If anybee has any ideas how this type of testing could be performed anonymously, pm me.

also so far as i am aware, both of these substances are as of this writing STILL LEGAL!!!!!!
 
 
 
 
    unnilhexium
(Stranger)
12-24-01 21:25
No 250328
      Re: Bioassays  Bookmark   

Still legal where?  I thought all of those designer drug laws (USA) made pretty much anything with the phenethylamine or amphetamine structure illegal, if not approved for use in medicine, or elsewhere.

106
 
 
 
 
    ChemReack
(Hive Addict)
12-24-01 21:34
No 250329
      Re: Bioassays  Bookmark   

What makes you believe everything you read originates from the usa?

"Two is not a winner and three nobody remembers"
 
 
 
 
    sunlight
(Pioneer Researcher)
12-25-01 12:37
No 250414
      Re: Bioassays  Bookmark   

Unbelievably work, Antibody2 !!! You have touched the sky.
 
 
 
 
    Antibody2
(Commodore "Mole Bouncer")
12-26-01 10:15
No 250572
      Re: Bioassays  Bookmark   

smile thanx sunlight, now i can think about some skiing this winter, heh.
 
 
 
 
    unnilhexium
(Stranger)
12-26-01 20:22
No 250694
      Re: Bioassays  Bookmark   

Actually, I was just asking "where is it legal?"  More importantly, I didn't want any bees in more anal countries (like the U.S.) to manufacture and think that they wouldn't get in trouble if they were caught.  BTW, great post antibody, I just wanted to clarify that those compounds may be legal where you're from, but are probably still illegal for the majority of bees.

106
 
 
 
 
    Rhodium
(Chief Bee)
12-26-01 20:51
No 250698
      Re: Bioassays
(Rated as: good read)
 Bookmark   

This writeup is now available in an illustrated version at ../rhodium/chemistry /dmmdma-2.html
 
 
 
 
    Antibody2
(Commodore "Mole Bouncer")
12-26-01 21:40
No 250704
      Re: Bioassays  Bookmark   

[bold]smile[/bold]
 
 
 
 
    baalchemist
(Chef d'Equippe)
12-27-01 18:07
No 250853
      Re: Bioassays  Bookmark   

Shulgin seems to compare it to Mescaline in its effects. Thats sounds cool to me, I wonder if it'll make you grow a hump or not? I get nervous in unexplored ground, but hell its easy enough to make. I wonder what other oils can be run through the same exact protocol?

--------------------------------------------------------------------------------


GODISNOWHERE
 
 
 
 
    Rhodium
(Chief Bee)
12-27-01 19:02
No 250857
      Re: Bioassays  Bookmark   

All allyl- and propenylbenzenes are candidates for exactly this protocol. I think we should start with myristicin and apiole.
 
 
 
 
    Antibody2
(Commodore "Mole Bouncer")
12-27-01 21:45
No 250881
      Re: Bioassays  Bookmark   

been there already. experiments with parsley seed oil. the apiole oxime forms in lower yeilds than with either dillapiole, or safrole, but is very reducible by more conventional alcoholic Al/Hg rxns . Myristicin wasn't isolated in large enough yeilds to arrive at any conclusions, but intial experiments showed its oxime to be formed in yet lower yeilds in the same oximation rxn. Those precursers were abandoned in favour of the  much less expensive and suspect dillapiole.

both ketones were formed in good yeilds from buffered performic rxns.
 
 
 
 
    Rhodium
(Chief Bee)
12-28-01 00:03
No 250908
      Re: Bioassays  Bookmark   

Oh, you tease... Could we have the experimental details and physical data for these too?
 
 
 
 
    Rhodium
(Chief Bee)
01-08-02 01:38
No 253945
      Re: Bioassays
(Rated as: excellent)
 Bookmark   

Thanks goes out to Lone Deranger for sending me a picture of crystallized isodillapiole:

 
 
 
 
    SpicyBrown
(Hive Bee)
01-08-02 01:42
No 253947
      Re: Bioassays  Bookmark   

That is... Awesome. smile Thanks much!

SpicyBrown
 
 
 
 
    Antibody2
(Commodore "Mole Bouncer")
01-10-02 10:04
No 254833
      Re: Last waltz
(Rated as: excellent)
 Bookmark   

i know i know, but i felt the thread incomplete lacking the following

DMMDA-2.SO4[1] (MP 220C[2])
bioassay; dose 125mgs, duration 14+hrs.

For reasons i've yet to fathom, at 11:30PM last nite I decided to attempt a second bioassay of DMMDA-2.  What a sleeping giant it turned out to be. 
1 hour- nothing really apparent, might be a hint of something, an affinity for white noise perhaps.
1.5 hours - I give up waiting for something to happen, smoke a joint and go to bed, fall asleep dissapointted.
3 hours - I inexplicably awake, the simple act of stretching in bed is gratifiing, roll over on wife and have some of the most unbearably tactile sex i can remember. No love/empathy a purely hedonistic experience. Performance enhanced, no impairment whatsoever. Stamina extended, quik reload time.
4 hours - have given up on sleep now, sipping a glass of wine, realizing how very very high i am, but a high unquanitifiable by any criteria previously established, It has a very clean stimulant quality to it while the hint of something cerebral as well. None of the impairment one might experience on MDA, MDOH  or DMMDA. at all. completely dissimular
4.5 hours - have given up trying to read book and have become a spider, contected to every part of the house, my web, any time the a duct shrinks in a cold draft or a creak in the floor, it is transmitted to me, i feel it, it comes togather in a disjointed peice of jazz where the musician n hasn't made it apparent where he's going with the peice yet, but still you strain for the rythym. My elbows are itchy as is my scalp. I can feel the hint of brain tickles the way lsd can cause your cheek muscles to become tired from too much smiling, and i have attained a state  hyperawarness with a definite cerebral spin to it,  some psychadelic activity but just the promise not more. No impairemnt whatsoever of motor function or apparent ability too reason.
6 hours - we're on the downslope now, the cerebral aspect of the high is gone, which seems to empasize the stimulant aspect again. Insomnia persists throughout night.
9 hours - strong residual stimulant effect, when wife gives me my coffee and look in the face i again realize i'm reallly high or rather far from baseline. feels abit like a very strong caffeine buzz now without the mental irritability, but some pyhsical irritability  obvious, itchy.  slight rash on underside of lats where they intersect shoulder, irritated.
12hours - things are bit tinny now, but stimulant effect still there, itchy elbows and neck. i feel out of sorts, don't think i'm going to have a very productive day. I'm still twitching.

At this dose I've learned respect for the power of this amphetamine, nothing revelatory , but feel like we were at the psychadelic threshold for this substance. I think it would be more pronounced at 150mgs, but with the accompanying stimulant effect, not a dose to be undertaken lightly. Definately worthy of a second look. Scary thing is that a drug like this might evn have military applications. Overall i would describe the high as a hyperawareness. Benzedrine and meth users probably will enjoy this.

1) the sulfate was found to be a much easier salt to form than the hydrogen chloride salt, whose solubility in acetone and toluene seems very ph dependant.  Dmmda-2 freebase was dissolved in 2 volumes of acetone, another solution of 1drop H2SO4/ml acetone was prepared and added dropwise to freebase, there is the immediate precipitation of beige salt, which is filtered off periodically while acidifiing. N.B. over acidification will result in salt becoming acetone soluble, neccesitating an A/B extraction to remedy.

2) MP is in reality more of a decomposition point for the sulfate, discoloration was apparent at 204 deg C,  by 220 deg C entire sample had decomposed


there, done!
 
 
 
 
    Chromic
(Hive Addict)
03-05-02 20:28
No 277539
      We'll go a-waltzing
(Rated as: excellent)
 Bookmark   

I received this trip report by email by someone who received a sample of DMMDA-2 from ab2, I thought I'd post it for the enjoyment of the Hive:

dmmda-2
[T=0:00] I'm trying 70mg of DMMDA-2. The taste is bitter, but not unpleasant. I wonder what lays ahead of me.

[T=0:20] Something is on its way, a +/-.

[T=0:45] A detached light-headed feeling is noticed. Something might happen?

[T=1:00] Something is happening... my pulse is 90bpm while sitting down. The body effects are light and not really describable, it's rather pleasant.

[T=1:30] Nothing exciting. 20mg booster is decided on. My pulse is still 90bpm. I'm laughing more than usual, in a positive mood. There is a stimulant effect to it. Nothing else is noted.

[T=2:00] No psychedelic effects... pulse still elevated.

[T=3:00] Ahh! This is fun stuff! My tripping partner joins the space with 90mg.

[T=4:00] My girlfriend decides to take 70mg.

[T=8:30] My girlfriend mentions her skin feels hot, and slightly vibrating. Sleep doesn't seem to come easily as the material is very stimulating. Sleep is possible about ten hours after ingesting it.

Summary
Well, four of us tried the dmmda-2 material in total. All round good reviews. It takes about 3hrs to get fun, and there's no big hallucinogenic effect from it. The first 3hrs was annoying for my girlfriend as she noticed more intense anxiety than myself on the way up, and in retrospect it would have been ok to take the material earlier to get past some of its ugly beginning which she hated. Most people will be expected to tolerate it well. Take it early in the afternoon, about 3hrs before you're going to go out and do whatever you're doing that you want to enjoy, and you'll be in for a nice surprise when the effects hit.

There is no anorexia but there were some mild closed-eye visuals. The visuals were entertaining but not overwhelming, in that respect it was a ++ (plus two). There was some "strobing" to my visual field. Physically it was a plus one or plus two, none of it was uncomfortable and I don't see a problem if one wanted to take the dose to a slightly higher level (say 120mg).

Some people mentioned that they almost preferred the feeling of dmmda-2 to mdma as it lasted longer and gave a good energetic buzz. It certainly isn't as strong and the empathetic affects aren't interesting. There is no real hang over effect either. All in all, this drug is worthwhile doing, but is not anything mindblowing.
 
 
 
 
    Chromic
(Hive Addict)
03-05-02 20:31
No 277542
      "No thanx, I'd rather sit this one out"
(Rated as: excellent)
 Bookmark   

6-br-dmmda-2

[T+0:00] Particularly nasty bad taste (120mg in water)

[T+1:00] The material starts to come on, and was a pleasant dreamy feeling

T+1:30] The light-headed feeling becomes very annoying and starts to feel aweful. Nausea starts to kick in and vertigo becomes overwhelming. All there is do is lie down on the floor and wait for the material to subside. 50mg dimenhydrinate is taken to counter the nausea, but it does not stop the aweful vertigo.

[T+8:00] After lying on the floor for six and a half hours it starts to wear off.

The overall experience was a ++ mental as the material's effects were unmistakable, but not strong... unfortunately none of it was pleasant, no hallucinations, etc! The body load was a +++ physical, it was unmistakable and totally engaging, for the worse.
 
 
 
 
    Chromic
(Hive Addict)
03-05-02 20:34
No 277546
      DMMDMA-2
(Rated as: excellent)
 Bookmark   

DMMDMA-2
Only extremely light effects noted at 250mg of DMMDMA-2, even mixed with weed. Something similar to TMMA-2.
 
 
 
 
    foxy2
(Distinctive Doe)
04-08-02 00:20
No 294122
      original Shulgin Article
(Rated as: good read)
 Bookmark   

Psychotrophic phenylisopropylamines derived from apiole and dillapiole.    
Shulgin A T; Sargent T   
NATURE  (1967 Sep 30),  215(109),  1494-5.

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
 
 
 
 
    foxy2
(Distinctive Doe)
04-18-02 09:14
No 298704
      Lit Reference
(Rated as: excellent)
 Bookmark   

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. 

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
 
 
 
 
    Antibody2
(Rehabilitated)
04-18-02 16:59
No 298865
      hot damn foxy!  Bookmark   

hot damn foxy! cool just to make sure we are on the same page though could dihydroxydillapiole be described as 2,3-hydroxy4,5-Methylenedioxyallybenzene?
 
 
 
 
    foxy2
(Distinctive Doe)
04-19-02 09:40
No 299136
      sadly nope  Bookmark   

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
(Hive Bee)
04-19-02 10:08
No 299145
      Outstanding!!!! :-D :-D :-D :-D This dude knows ...  Bookmark   

Outstanding!!!! laughlaughlaughlaugh

This dude knows the art of growing crystals ...
 
 
 
 
    Chromic
(Hive Addict)
06-26-02 11:20
No 325707
      Corrections to appendix 1  Bookmark   

The molecular weights in Appendix 1 are all slightly off. The url ../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
(Rehabilitated)
06-26-02 16:57
No 325803
      maybe you could correct my MWs for dillapiole ...  Bookmark   

maybe you could correct my MWs for dillapiole aldehyde, nitrostyrene and PEA while you at it?laugh

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?wink
 
 
 
 
    Chromic
(Hive Addict)
06-29-02 13:36
No 326917
      MWs  Bookmark   

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
(Bee without a Title)
08-24-02 16:01
No 348662
      2,3-dimethoxy-4,5-methylenedioxyphenylethylamine
(Rated as: excellent)
 Bookmark   

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
(Chief Bee)
09-02-02 09:07
No 351828
      2,3-MeO-4,5-MD-PEA  Bookmark   

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...