8-bromo-4-(2-aminopropyl)benzodifuran synth q?

timnickbear · Tue Jun 28, 2005 4:28 am

This (1-(8-bromobenzo[1,2-b;4,5-b']difuran-4-yl)-2-aminopropane gives no real synth write up besides this:
http://pubs.acs.org/isubscribe/journals/jmcmar/44/i06/figures/jm000491yh00001.html
Swim would like to know what chems are involved and what type of equipment.

ApprenticeCook · DILLIGAF

The diagram tells you down the bottom, rxn schemes.

Starting from -->
2,2'-(1,4-phenylenebis(oxy))diethanol is placed in pyridine (C5H5N) where thionyl chloride (SOCl2) is added. The product is extracted with dichloromethane (CH2Cl2) to obtain 88% yield. This step may require some low heating and venting of formed vapours of SO2 and HCl.
The DCM is evaporated and the product is solvated in glacial acetic acid (AcOH), ZnCl2 and Bromine in glacial acetic acid are added to perform this step giving 91% product. This step may require some heating.
The product is then extracted from the DCM solvent and placed into Tetrahydrofuran (THF) where magnesium dust is added and heated to initiate the cyclic formation. (Im not to sure about this last one)

Whats this stuff for anyway?
As for equiptment, you would need a suitable vented space, several flasks or big beakers, a hotplate/stirrer combo plate and maybe a steam distillation setup if you want to purify the product that much between steps.

-AC

Star-light · Blacklight bulb

spicybrown · Wed Jun 29, 2005 6:36 am

Here's the synthesis from the paper (I could provide the PDF if there's a convenient way..). This isn't the easiest synthesis around...

--
1,4-Bis(2-chloroethoxy)benzene ( Cool

.23 A mixture of 50
g (0.455 mol) of hydroquinone, 196 g (1.37 mol) of 1-bromo-2-
chloroethane, 190 g (1.37 mol) of finely powdered anhydrous
potassium carbonate, and 300 mL of acetone was stirred and
heated at reflux under N2 for 24 h. Acetone and excess
dihaloethane were removed in vacuo, and the residue was
partitioned between Et2O and H2O. The Et2O phase was
extracted three times with 4 M NaOH, dried with anhydrous
MgSO4, and filtered. Solvent was removed in vacuo, yielding
33.7 g (32%) of a white solid with a 1H-NMR spectrum identical
with that reported in ref 23.
1,4-Bis(2-chloroethoxy)-2,5-dibromobenzene (9). To a
stirred suspension of 1.0 g (4.26 mmol) of the bis-ether 8 in
20 mL of CCl4 was added 12 mg (0.21 mmol) of Fe granules.
Bromine (1.50 g, 9.37 mmol) in 5 mL of CCl4 was added
dropwise, and the reaction mixture was stirred for 4.5 h at
room temperature. The mixture was washed twice with H2O,
dried with MgSO4, and filtered. The solvent was removed in
vacuo, yielding 1.54 g (92%) of an off-white solid. An analytical
sample was recrystallized from EtOH: mp 119 °C; 1H NMR
(CDCl3) ä 3.83 (t, 4, ArOCH2CH2Cl, J ) 6 Hz), 4.23 (t, 4,
ArOCH2CH2Cl, J ) 6 Hz), 7.15 (s, 2, ArH).
2,3,6,7-Tetrahydrobenzo[1,2-b:4,5-b¢]difuran (10).21 A
solution of 10 g (25.4 mmol) of the dibromo bis-ether 9 in 250
mL of dry THF was placed in a N2 atmosphere and cooled to
0 °C. A solution of 2.5 M n-butyllithium in hexanes (21.4 mL,
2.1 equiv) was added very quickly (addition time: 7 s) to the
rapidly stirred solution using a syringe with a large gauge
needle. (Fast addition of n-BuLi is critical. An otherwise
identical run in which this reagent was added over 40 s
resulted in a 25% reduction in yield.) The reaction mixture
was stirred for 10 min, and solvent was removed in vacuo. The
residue was partitioned between Et2O and H2O, and the
organic phase was dried with MgSO4 and filtered. The
resulting solution was evaporated in vacuo until crystallization
occurred. The crystals were filtered off, the filtrate was again
evaporated, and a second crop of crystals was collected. After
executing this procedure a third time, a total of 3.30 g (80%)
of off-white crystals was obtained. Recrystallization from ether
gave fluffy white crystals: mp 155-156 °C (lit.21 mp 153 °C);
1H NMR (CDCl3) ä 3.13 (t, 4, ArOCH2CH2, J ) 8.5 Hz), 4.52
(t, 4, ArOCH2CH2, J ) 8.5 Hz), 6.63 (s, 2, ArH); CIMS m/z
163 (M + 1).
4-Formyl-2,3,6,7-tetrahydrobenzo[1,2-b:4,5-b¢]difuran
(11). A solution of 3.0 g (0.019 mol) of the tetrahydrobenzodifuran
10 in 100 mL of dry CH2Cl2 was stirred under N2
and cooled over an ice bath. Tin(IV) chloride (2.81 mL, 0.024
mol) was added to the solution, and the mixture was stirred
for 5 min. Dichloromethyl methyl ether (1.67 mL, 0.019 mol)
in 5 mL of CH2Cl2 was then introduced into the mixture
dropwise over a 5 min period. After the mixture had stirred
for 30 min, the reaction was quenched by the addition of 50
mL of ice-H2O, and the layers were separated. The aqueous
phase was extracted with 2 30 mL of CH2Cl2, and the organic
fractions were combined. The organic extract was washed with
3 N HCl (3 100 mL), 100 mL of H2O, and 100 mL of brine,
dried over MgSO4, and filtered through a pad of Celite and
silica gel. Removal of solvent under reduced pressure and
drying under high vacuum gave 2.9 g (82%) of a yellow oil that
spontaneously crystallized upon standing. The solid was
recrystallized from chloroform-hexane to yield 2.51 g (71%)
of pure product 11 as light yellow crystals: mp 86-87 °C; 1H
NMR (CDCl3) ä 3.20 (td, 2, ArOCH2CH2, J ) 8.6 Hz, 1.1 Hz),
3.45 (t, 2, ArOCH2CH2, J ) 8.8 Hz), 4.60 (t, 2, ArOCH2CH2, J
) 8.8 Hz), 4.70 (t, 2, ArOCH2CH2, J ) 8.8 Hz), 6.80 (s, 1, ArH),
10.25 (s, 1, ArCHO); CIMS m/z 191 (M + 1), Anal. (C11H10O3)
C, H.
4-(2-Nitro-1-propenyl)-2,3,6,7-tetrahydrobenzo[1,2-b:
4,5-b¢]difuran (12). The aldehyde 11 (2.3 g, 0.012 mol) and
ammonium acetate (0.93 g, 0.012 mol) were dissolved in 10
mL of nitroethane and stirred under a nitrogen atmosphere
at 90 °C for 15 h. The volatiles were removed in vacuo, and
the residue was taken up in ether-ethyl acetate and washed
with 3 50 mL of 3 M HCl, 3 50 mL of 5% NaHCO3, and
50 mL of brine. The organic phase was dried over MgSO4 and
filtered through Celite-silica gel, and the solvent was removed
under reduced pressure to yield a thick red oil. The oil was
purified on the Chromatotron (4 mm silica plate, CH2Cl2) to
give 1.74 g (60%) of the desired product 12 as an orange oil.
The oil was crystallized from methanol to give yellow-orange
crystals: mp 94 °C; 1H NMR (CDCl3) ä 2.24 (s, 3, CH3), 3.10
(t, 2, ArOCH2CH2, J ) 8.6 Hz), 3.20 (t, 2, ArOCH2CH2, J )
8.7 Hz), 4.60 (t, 4, ArOCH2CH2, J ) 8.6 Hz), 6.73 (s, 1, ArH),
7.80 (s, 1, ArCHdC); CIMS m/z 248 (M + 1), 230, 191. Anal.
(C13H13NO4) C, H, N.
--

From there, reduction by LAH (standard conditions) gave the amphetamine. Sorry about the formatting, there's only so much I can stand doing manually. Smile

-SpicyBrown

mk-1 · Wed Jun 29, 2005 4:16 pm

these compounds (none that i know of yet anyway) are not more potent then LSD.
the brominated saturated dragonfly compound is active at +-800mcg
and the aromatic one is active at 400mcg, but really u need at least 600-800 to make it interesting. Also the more you take, the longer it stays...

joe_aldehyde · huxleys associate

mk-1, i'd would say, thats "almost" as potent as LSD. have you ever tried them? i think the synthesis is a bit lengthy, so it has to be real fun in order to make it worth synthing.

Star-light · Blacklight bulb

timnickbear · Thu Jun 30, 2005 3:11 am

What is this substance like? There isn't a trip report done by anyone that I believe thus far that I have seen. Is this chem like mescaline or more like a strong 2c?

radio879dmt · Sun Jul 03, 2005 2:02 pm

Bromo-dragonfly is available, well they had it on their web site but its off now (probably from all the attention lately), SWIM has 750mcg on the way here, from what i'm reading (there is some info on forums like bluelight.nu, not much yet though) there is actual blotter going around in the U.S. that has 100mcg of it per dose, and it takes a good 3-4 hours to get going, and the more of a dose you take the longer it lasts.

Also a post from a guy who took 1mg, "lost contact with reality" and "not recommended to do again". SWIM might start with 150mcg myself. Been hearing 100-200mcg a dose is good, but there's just not that much info yet (but there will be since a lot of people on these other forums have been shipped some of this stuff).

Also that one vendor isn't the only one, i know at least two more have it (although i only know of one) - and one of them plans to get "a few more of the dragonfly's" (I really hope one of them is a methyl version..)