raffike (Hive Addict)
02-23-03 14:26
No 411059
      Question about performic  Bookmark   

Does anything bad happens when little more(1/5-1/4 v/v more than buffered performic writeup says) H2O2 is added to rx mix.Raf mixed 125 grams of isosafrole with 350 mls of DCM and added 40 gms of NaHCO3 and stirred with overhead.Started adding mix of 150 mls of 85% HCOOH and 120 grams of 35% H2O2.When halfway thru adding performic mix,raf accidentally turned variac to full power and stirrer went mad,1/5 of the rx mix jumped out and started eating plastic.Raf cleaned mess up and added slowly rest of the performic mix to now reduced volume of rx mix.Rx itself goes like it should.Help appriciated

For those about to synth,we salute you
 
 
 
 
    lugh
(Moderator)
02-23-03 15:36
No 411084
      Exothermia  Bookmark   

Yields have been known to bee lower when the temperature gets to high, much more useful info can bee found by



laugh
 
 
 
 
    raffike
(Hive Addict)
02-23-03 15:45
No 411085
      Temperature didn't go over 40 C since DCM was...  Bookmark   

Temperature didn't go over 40 C since DCM was used as solvent,just little more H2O2 was used,that was the reason of this topic.Temperature wasn't problem.

EDIT:Just discovered a possible security problem.Lugh's UTFSE gif's on the net is shown thru HIVE proxy but reply mail i got contained non-proxylated image address that goes like http://www...utfseredani.gif
Administrators might want to fix that.

For those about to synth,we salute you
 
 
 
 
    raffike
(Hive Addict)
02-23-03 16:18
No 411090
      One more question,does raf have to scale down...  Bookmark   

One more question,does raf have to scale down that amount of 15% H2SO4 when he starts that hydrolysis or is amount not importnant as long as it's concentration stays same(15%).I'm not sure in that amount of iso that stayed in that flask.He started with 125 grams of iso,maybe 100 stayd in that flask after some jumped out,not sure.This situation hasn't been covered in TFSE,AFAIK.

EDIT:
PS i did found something on TFSE,somebody said using slight excess of performic got nice yields,he didn't mention how slight excess.I think raf should be fine,he doesn't scale down that amount of 15% needed for hydrolysis as slight excess of it shouldn't make no harm.Second opinion is always appriciated though...

For those about to synth,we salute you
 
 
 
 
    Stonium
(Employee Supervisor)
02-23-03 22:37
No 411170
      Uhm...  Bookmark   

Thank you for pointing that out, raffike...and for your discretion in doing so. smile
 
 
 
 
    GC_MS
(Hive Addict)
02-24-03 00:12
No 411216
      peracid  Bookmark   

If you are worried about the temperature of your reaction mixture when applying a peracid oxidation method, then you can do the following:
*) Add the peracid dropwise over an extended amount of time, like e.g. 2-3 hours. Just extend the total reaction time a little bit.
*) Put the reaction mixture in an ice bath. No need to refresh the ice, allow it to melt. The exothermic reaction only occurs during the beginning of the reaction, and is completely finished after a couple of hours.

Concerning the sulfuric acid: don't increase the concentration. Keep in mind that sulfuric acid stimulates polymerization of your compounds and will yield you the legendary "black tar".

Hoping your reaction will end well and results in a nice and educationally enriched trip wink

Abusus non tollit usum
 
 
 
 
    raffike
(Hive Addict)
02-24-03 07:57
No 411381
      16 hour stir is over.2 layers formed.Bottom...  Bookmark   

16 hour stir is over.2 layers formed.Bottom layer is kinda dark orange but clear.Upper is supposed to be water/performic.Will sepp lower layer off and see what 15% H2SO4 hydrolysis says @ 80 C and exactly for 2 hours like Ritter advised.So far so good...smile

PS: GC_MS,thanks for trying to help but he didn't meant to raise the concentration of H2SO4 in hydrolysis mix but rather was concerned if too much of that 15% mix would do any harm?It's probably my bad english...laugh

For those about to synth,we salute you
 
 
 
 
    raffike
(Hive Addict)
02-25-03 20:13
No 411496
      Hive was off for some time but lot has ...  Bookmark   

Hive was off for some time but lot has happened in between.So raf did hydrolsysis with 15% sulfuric and 80C for 2 hours.Sepped off and tried to distill.@ 10 mm 150 degrees by C 40 mls came over and then temp went to 180 and something that solidified in condenser also started to came over,probably glycol,seems like 2 hours isn't enough,will go 3 next time.Redistilled ketone and got 36.5 grams of it.Aminated with Al/Hg and got 18 grams of white MDMA,not bad for raffike's very first Al/Hg with MDP2P.18 grams of MDMA from 200 mls of safrole doesn't sound too good but raf made lots of mistakes he won't do next time.Raf has never tried MDMA so he doesn't know what to expect,wonder what it would be like... smile

For those about to synth,we salute you
 
 
 
 
    GC_MS
02-25-03 20:56
      condensed
(Rated as: misinforming)
 Bookmark   
 
 
 
    raffike
(Hive Addict)
02-25-03 21:21
No 411529
      Hmmm,wonder where did these come from.  Bookmark   

Hmmm,wonder where did these come from.

For those about to synth,we salute you
 
 
 
 
    GC_MS
(Hive Addict)
02-25-03 21:45
No 411538
      It's normal  Bookmark   

It's normal... There is a handful of side reactions that makes they are present. Just to name one possibility: acid catalyzed cyclialkylation. In acid environments, diisosafrole (an indane) can be formed by the addition of one molecule isosafrole to another one. Another form of polymerization is photo-induced dimerization, which will yield a dimere different from diisosafrole. Etc etc. Think about it... no side-reactions would have given you 99% yield ;)

Abusus non tollit usum
 
 
 
 
    Rhodium
(Chief Bee)
02-26-03 03:51
No 411732
      It is very likely the glycol
(Rated as: excellent)
 Bookmark   

Isosafrole glycol definitely solidifies in the condenser upon distillation, and is common as a second fraction after MDP2P (as a yellowish gel) if the preceding H2SO4 was incomplete. Just collect it and re-subject it to H2SO4 rearrangement.

1-benzo[1,3]dioxol-5-yl-propane-1,2-diol (Isosafrole glycol); physical data:

mp 102C, bp 205C/12mmHg1
mp 101-102C2

[1] Gazz.Chim.Ital.; 42 I, 36 (1912)
[2] Chem Ber 36, 3580 (1903)
 
 
 
 
    abacus
(Hive Bee)
02-26-03 09:23
No 411862
      What the ?????  Bookmark   

If the mp of isosafrole glycol really is 102DegC, then someone please explain to me, why is it that my professor has heated the post performic reaction isosafrole glycol/DCM mixture to well over 100DegC to remove all DCM and then stored the orange coloured glycol in the fridge for days (many times), and it has never gone solid, ever ???????

Then hydrolysis with 15% H2SO4 for 3 hours at 90DegC, ketone distilled and then animated via al/hg with no problems whatsoever?????

EDit:  Am I missing something somewhere?????

Abacus
 
 
 
 
    GC_MS
(Hive Addict)
02-26-03 10:54
No 411879
      Polymerization  Bookmark   

Polymerization:

- Post 409525 (Rhodium: "Why asarone cannot be oxidized with peracids", Methods Discourse)
- Friedel-Crafts and related reactions, GA Olah. II, Part 2: Alkylation and related reactions. Interscience publishers 1964. p 944-977. Of possible further interest [478: A Mueller, M Meszaros, A Karczag-Wilhelms. Ber 87 (1958) 1761]
- Photodimerization: DB Saxena & SK Mukerjee, Photooxidation of beta-asarone. Indian J Chem 24B (1985) 683-684. A load of articles can be found for other phenylpropenyl substances, especially anethole.

Or where you thinking I was pulling it from my ***? :P

Abusus non tollit usum
 
 
 
 
    baalchemist
(Chef d'Equippe)
02-26-03 13:05
No 411906
      That solidified leftover crap in the flask...  Bookmark   

That solidified leftover crap in the flask after a ketone distillation is often 'referred to' or 'assumed to be' a polymerized by-product of the ketone distilled. Baal took some of that solidified-tar/? and found that it liquifies around 100c, as does the glycol. So on a hunch, this hot, syrupy stuff was diluted with some MeoH and ran thru some 15%H2SO4 for 2 hours@80c. This was extracted with DCM, H2O/bicarb washed a few times,DCM was rotovapped off leaving behind a dark colored,liquid @ roomtemp. It smells like dirty ketone, and does'nt freeze, but still havent distilled yet to see what specific fractions are present in there. It definately has become a different substance than what was started with(slightly melted some plastic on contact). More investigation into mystery substance soon to follow. If this turns out to be legit ketone, then that would certainly explain what that crap actually is(not assumed) that somebees complain about cleaning from the flask afterwards. Wishful thinking maybe, but it certainly got Baals curiosity going. More to follow........

    GODISNOWHERE
Shoot Narcs, Not Drugs
 
 
 
 
    Rhodium
(Chief Bee)
02-27-03 02:56
No 412118
      isosafrole glycol
(Rated as: excellent)
 Bookmark   

abacus: That is probably because the main product from the performic oxidation is not the plain glycol, but isosafrole glycol monoformate (formic acid ester of the glycol), see Post 250865 (Ritter: "buffered performic -> monoformyl glycol", Chemistry Discourse). The reason that free glycol is the solid that collects in the reciever is likely due to the following reasons:

* The isosafrole glycol monoformate is thermally decomposed to the glycol during distillation
* Isosafrole glycol is less reactive than isosafrole glycol monoformate in the H2SO4 rearrangement, thus this compound is the one that is predominantly found unreacted after an incomplete H2SO4 rearrangement, see Post 99146 (Ritter: "isosafrole glycol less reactive than its formate", Chemistry Discourse).

GC_MS: I do not doubt that polymerization occurs, but I do not think that these products will distill in the range observed for the glycol in a relatively pure form, as well as solidify in the condenser just like predicted for the glycol.

I am very interested in your references, particularly the Ind. J. Chem article, could you post it? The Berichte article I can fetch myself, and I have the "Friedel-Crafts and related reactions" book series on the attic, so I can get that tomorrow.
 
 
 
 
    GC_MS
(Hive Addict)
02-27-03 12:13
No 412228
      Ind J Chem  Bookmark   


GC_MS: I do not doubt that polymerization occurs, but I do not think that these products will distill in the range observed for the glycol in a relatively pure form, as well as solidify in the condenser just like predicted for the glycol.
I am very interested in your references, particularly the Ind. J. Chem article, could you post it? The Berichte article I can fetch myself, and I have the "Friedel-Crafts and related reactions" book series on the attic, so I can get that tomorrow.




You can get some polymers distilled over, although I made the mistake to assume that every newbee can pull a 0.1 mmHg "vacuum" by a snap of the finger.
The Friedel-Crafts related indanes are interesting, since it seems they are found in plants as well. I only know of one such indane been discovered up till today, but I wouldn't be surprised if similar compounds would be present in essential oils with a high propenylbenzene content (eg anise and sassafras oil). Reference: DB Saxena, Phenyl indane from Acorus calamus. Phytochemistry 25(2) (1986) 553-556. It really is nothing more then the indane arising from a condensation between 2 molecules of asaron.


Abusus non tollit usum
 
 
 
 
    madprosr
(Hive Bee)
02-27-03 17:29
No 412280
      tlc or color changes?  Bookmark   

i believe tlc would be the best way to check if all your glycol is consumed...

but swim doesn't have plates yet, so he is wondering if he should be looking for a change from orange juice color to more of a pink/red to indicate that the h2so4 hydrolysis is done.

he has been stirring (on high) some glycol from 65g iso with 360g 15% h2so4 at 60C for almost 4 hours now, and it's still orange juice colored. hardly a hint of pink.

will let you know how it works out... tfse had nothing on "ketone h2so4 color" or "ketone h2so4 orange"

that glycol contamination sure does suck, eh bro?
 
 
 
 
    raffike
(Hive Addict)
02-27-03 20:53
No 412342
      Well i knew that glycol isn't good in Al/Hg so  Bookmark   

Well i knew that glycol isn't good in Al/Hg so i redistilled ketone and didn't let temperature over 160 @ 10 mm

For those about to synth,we salute you
 
 
 
 
    madprosr
(Hive Bee)
02-27-03 22:17
No 412367
      bad idea, swim hydrolized for 6h until the mix  Bookmark   

bad idea, swim hydrolized for 6h until the mix finally took on a slightly more red-orange look. this was after a buffered performic ala Detailed Methods btw.
he used bicarb, 92% formic, and 35% h2o2 that he assumed had degraded to about 30% over 5 months. is his h2o2 too old? perhaps there was a touch of AlOH present. yes, next time he will take a freezing point on the h2o2, doh!

anyway, he cooled the soln on an icebath then poured out some really sticky orange-red ketone. he had thought it would turn red-brown when hydrolized too much, telling him to stop. but there was only a little bit of brown in the ketone which washed out easily with bicarb. for some reason, it seems to him he still has the dread glycol contamination even after such a long hydrolysis. unless the extended hydrolysis created other sticky contaminants?

at least the tone dissolved in ~220ml dcm, allowing him to wash with 3x 50ml saturated bicarb.

swim's going to try freezing out the sticky stuff and pouring off the dcm+ketone. dang it.

swim has a slow stirrer (vortex maybe 3/4" across in a 500ml rb) and he skipped MeOH in the hydrolysis, factors which could require more time. he was willing to sacrafice yields in order to make sure he converted all that damn glycol. but it didn't work.
 
 
 
 
    raffike
(Hive Addict)
02-27-03 22:49
No 412371
      I posted some diagrams(if it's the right word...  Bookmark   

I posted some diagrams(if it's the right word for that) some time ago,oh here they are...
Post 385218 (raffike: "Also make sure your H2O2 is actually 35%.", Methods Discourse)
Measuring density @ room temp would be more accurate,it worked fine for me.My 5 year old H2O2 was still 35%,it was stored in cold and dark.

For those about to synth,we salute you
 
 
 
 
    madprosr
(Hive Bee)
02-28-03 13:55
No 412535
      swim just can't seem to get it right.  Bookmark   

swim just can't seem to get it right.

he distilled the still-orange over-hydrolized ketone through a 30mm column packed fairly tightly with steel wool. from 65g iso swim gets 8.1g ketone starting at 90C, peaking at 102C, then slowly climbing up to 105C. he was trying to use a lower vacuum, but was having a hard time (3 hours wasted) trying to get the column to heat up without having to boil the ketone too vigorously. so swim pushed slightly distended o-ring on his pump he uses to reduce vacuum back into place, and in seconds the ketone starts coming at 100C.

swim knew something was wrong when the temp didn't hold at 102C, but he kept collecting until he saw that new drops of ketone were leaving a snakey translucent 'string' in the oil which dissolved slowly.

he has seen this before as an early indicator of glycol contamination.
fortunately he cut the fraction after just a few sticky drops and the ketone does not become viscous when cold. maybe it will actually aminate well!

so swim distilled the next fraction coming at 114C, it's about 7-8g of orange oil. gotta be glycol. the rest is apparently burnt/polymerized crud.

at this point swim can't understand how there is glycol left after a 6h hydrolysis. please can someone explain this? this is swim's 3rd bad performic in a row.

it worked textbook-style once, all the glycol turned from orange to light red after 3 hours hydrolysis. swim distilled the tone with no column from 120-122C exactly, leaving only burnt stuff in the distillation flask, 75% m/m yield.

now swim can't duplicate this reaction. he tried another 3h glycol hydrolysis  using MeOH, but then distilled the ketone through a column at 100C instead of no column at 120. he got sticky shit.

the only thing different is the h2o2 has sat 3 more months at room temp.
could this somehow influenece the ratio of glycol to monoformyl glycol making the hydrolysis more difficult? swim thinks it should only result in more unconverted iso, but he'll check the h2o2 density eventually anyway...

he can't keep fucking up this reaction- thinking about trying some straight epoxide made with oxone at neutral pH. but the performic has the (potentially) high yields and the small volumes, it's so sexy...

one other thing, swim had more powerful stirring when he did the good hydrolysis. then he burned out the heating element, so now he has another hotplate with less powerful stirring. it still creates a vortex, but could this be IT? the reason for these problems?
 
 
 
 
    madprosr
(Hive Bee)
03-02-03 03:17
No 412917
      44% w/w on ketone reduction- fukkin glycol  Bookmark   

the 8.1g ketone distilled from 90-106C was dripped into a directly-scaled Osmium MeNH2/al/hg utilizing small square MeNH2 crystals extracted from nh4cl with IPA, crystalized, then dcm-washed. swim used 4g Al, 9g MeNH2.hcl freebased with NaOH solution before addition. solution was homogenous and at pH 9 (bit of extra NaOH) after 6 hours, basified to pH 12, extracted 3x 50ml toluene. washed 3x 50ml brine, dried over 7g MgSO4.1h2o, and gassed 3.6g mdma.hcl

after the ketone was distilled, 8.9g of slightly sticky when cold yellowish oil was collected peaking at 114C.

the rest of his 65g batch of iso turned into super-sticky brown sludge. eww...

swim is thinking it has to be insufficient stirring. his 75% m/m performic was done on an IKA Labortechnik hotplate/stirrer which no longer heats. the last three bad performics were hydrolized with a Marec Thermodyne 3.
to the glycol from 65g iso in a 500ml rb flask, swim added 360g 15% h2so4, and stirred with the Marec on max with a 1/2" octagonal stir bar, creating a vortex 3/4" across and perhaps 1" deep.

it was held at 60C for 6h, until swim realized that the orange color was never going away completely, turning a sweet red-brown, it was just going to stay orange as it burned.

any advise on this hydrolysis would be enormously appreciated.
how can swim have glycol contamination after such an excessive hydrolysis?

swim is going to try an oxone epoxidation followed by hydrolizing on the IKA stirrer, pulling the waterbath out occasionally to heat it up.
that or he could try to rig a mechanical stirrer for hydrolysis, he has a small AC motor rated at 2000 rpm, is this about right? where to find a sheet of teflon?

"one way or another, sooner or later, this darkness has got to give" -the dead
 
 
 
 
    abacus
(Hive Bee)
03-02-03 06:48
No 412951
      Use more 15% H2SO4  Bookmark   

Am I the only one so far to realise you are not using enough 15% H2SO4, double the amount you are using and forget the remark that you can use half IMHO

Abacus
 
 
 
 
    madprosr
(Hive Bee)
03-02-03 09:59
No 412989
      many bees have had success with 90g 15% h2so4...  Bookmark   

many bees have had success with 90g 15% h2so4 per 100mmol isosafrole used in the performic. swim shared this success. then he switched stirrers.

if using 180g 15% h2so4 and 60ml MeOH can make up for slow stirring speed, that would be wonderful.

can anyone confirm or deny this conjecture?

swim is going to use his IKA stirrer for an oxone run, then 'hydrolize' with 120g 15% h2so4 per 100mmol iso and 45ml MeOH just as chromic wrote. hopefully he will have good new data soon for his bee brothers.

you tell me, how deep is your vortex when you convert epoxide/glycol?
 
 
 
 
    Rhodium
(Chief Bee)
03-02-03 12:02
No 413024
      Layer mixing & PTC  Bookmark   

It is not so much the depth of the vortex that is important, it is rather a question if you are stirring the solution hard enough to whip it into an emulsion, where no layers or even large droplets are visible. Make sure you evaporate off any DCM or other non-polars that may be left in your organics, or the layers will not mix as good.

Something I have always wondered is if the addition of 0.01-0.05% of a tetrabutylammonium bromide (or other relatively hydrophilic PTC) wouldn't increase the yields and/or shorten the reaction time in this step. It would be very nice if someone could try that out on a smaller (100 mmol) scale.
 
 
 
 
    raffike
(Hive Addict)
03-02-03 12:08
No 413025
      Rh: What do you define as large(i mean ...  Bookmark   

Rh:
What do you define as large(i mean droplets) when it comes to hydrolysis w/H2SO4?Raf used overhead to stir hydrolysis mix(made out of electric drill and variac) and did see small droplets or bubbles or whatever you call em.Rad also had some DCM in his mix.

For those about to synth,we salute you
 
 
 
 
    Rhodium
(Chief Bee)
03-02-03 12:16
No 413027
      how large is large  Bookmark   

I think I would define "large" as a few millimeters in this case. If your droplets are 1-2 mm you are fine. Mayber bigger is ok too, but 10 mm is definitely too much.
 
 
 
 
    raffike
(Hive Addict)
03-02-03 12:19
No 413028
      Oh,mine were 0,5-1 mm or so in dia.No problem...  Bookmark   

Oh,mine were 0,5-1 mm or so in dia.No problem in that case,thanx.

For those about to synth,we salute you
 
 
 
 
    SiLiCoN7
(Hive Bee)
03-02-03 16:49
No 413060
      You should try the oxone method!!!  Bookmark   

The Oxone route works great and has been scaled to the size you are talking about. Works with about 70% yields and OTC!!!!


the 21st of the 12th 2012......
 
 
 
 
    hCiLdOdUeDn
(Hive Addict)
03-02-03 18:38
No 413092
      Swim has always consistenly gotten 50% yield...  Bookmark   

Swim has always consistenly gotten 50% yield from distilled isosafrole to distilled ketone with the oxone method.

Chemistry is hard to learn, but its worth it.
 
 
 
 
    madprosr
(Hive Bee)
03-03-03 02:24
No 413213
      silicon, do you vacuum distill the epoxide?  Bookmark   

silicon, do you vacuum distill the epoxide? i think VL was talking about this.

in swim's last 3 h2so4 rearrangements, he set the Thermodyne 3 on high, using a 1/2" octagonal stirbar in either a 250ml or 500ml flask.
he saw no droplets bigger than .5mm, pretty much a uniform orange soup.

swim is going to give the oxone a whirl, just as soon he gets some dcm out of a paste-stripper with MeOH,toluene,acetone. the dang big orange store tricked him when they gave him an msds claiming 80% dcm, 10% MeOH, ethanolamine. it was from 1999; no longer correct. gotta h2o wash the dcm and redistil apparently...
 
 
 
 
    abacus
(Hive Bee)
03-03-03 02:36
No 413214
      Rhodiums right  Bookmark   

Rhodiums correct re stirring.

Firstly, remove the condenser for a couple minutes to let any residual DCM boil away,

Then stirring should be strong enough so that there shouldn't be any layers forming on the bottom of the flask and you can notice small droplets swirling around the flask at about 1 revolution per second.

Normally such droplets are about 1mm or less with good stirring then after 2 hours at around 90DegC, stop stirring and a brown ketone layer will settle on the bottom of the flask.

 
 
 
 
    SiLiCoN7
(Hive Bee)
03-07-03 12:38
No 414542
      Explanation....  Bookmark   

Err, what SWIM ment was 70% iso to epoxide...

55% from distiled iso to distilled ketone has been known and that was with H2SO4 rearragnment.
No real need to distill epoxide for 'purity' only for thermal rearrangment.


the 21st of the 12th 2012......
 
 
 
 
    wacko_reaco
(Hive Bee)
03-13-03 00:09
No 416285
      ptc trial  Bookmark   

Rhodium,
My mother happens to have some of the PTC you mentioned but has no experience whatsoever with PTC's. What would be the workup after the hydrolysis to break the emulsion, is it simply extraction into non-polar? Also what proportion of PTC shall she use (as a w/w for glycol).

 

wacka wacka wacka
 
 
 
 
    madprosr
(Hive Bee)
03-15-03 09:31
No 417223
      it was bad peroxide  Bookmark   

swim got some fresh 35% peroxide, ran a Na2CO3 buffered performic, and got 99% yield of monoformyl glycol (stripped solvent under high vac, stopping when formic smell was noted), then 75% yield of ketone after a 3h rearrangement.

an MeNH2/al/hg yielded 80% w/w of the hcl salt.

is it possible that the monoformyl glycol rearranges more easily than the glycol? i know rhodium's faq shows the glycol as an intermediate, is it really?
 
 
 
 
    Rhodium
(Chief Bee)
03-15-03 17:32
No 417311
      The formyl ester activates the glycol  Bookmark   

Yes, that's true - see Post 99146 (Ritter: "isosafrole glycol less reactive than its formate", Chemistry Discourse).

The glycol need not to be a "true" intermediate in the rearrangement, even though at least part of the formylglycol is hydrolyzed to the free glycol in the course of the reaction. The reaction diagram in my Peracid Review is just a simplified schematic outline to illustrate that both the formyl glycol and the free glycol are rearranged by H2SO4 to MDP2P.
 
 
 
 
    Promethium
(Stranger)
04-02-03 03:05
No 423183
      Indan-5-carbaldehyde in a plant  Bookmark   

GC_MS mentioned that indanes are natural substances found in plants. Actually, even the very desirable indan-5-carbaldehyde (I5A) can be found in a plant called Ammomum medium: Ind J Chem Sect B, 27, 1988, 660-661. The article reports the synthesis of I5A via Vilsmeier (POCl3/DMF) benzannulation from 1-allylcyclopentanol, which is easily accessible from cyclopentanone and allyl bromide via Grignard or Barbier reaction. The yield, however, is disappointing.

The new Hitlers are wearing Stars and Stripes