Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  2  
Author: Subject: Indole Synthesis
Waffles SS
Fighter
*****




Posts: 931
Registered: 7-12-2009
Member Is Offline


[*] posted on 22-12-2009 at 09:53


My believe isnot murder of relatives and killing,..or anotherthing,please finish it.
I just love chemistry nothing else.
View user's profile View All Posts By User
ScienceSquirrel
Super Moderator
*******




Posts: 1863
Registered: 18-6-2008
Location: Brittany
Member Is Offline

Mood: Dogs are pets but cats are little furry humans with four feet and self determination! :(

[*] posted on 22-12-2009 at 10:42


Really you would be better off just buying it as it is readily available.
Otherwise the way to go is via some of the routes in the discussion section in the preparation below, assuming that you don't have an autoclave handy :)

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV5...

[Edited on 22-12-2009 by ScienceSquirrel]
View user's profile View All Posts By User
Polverone
Now celebrating 17 years of madness
*********




Posts: 3148
Registered: 19-5-2002
Location: The Sunny Pacific Northwest
Member Is Offline

Mood: No Mood

[*] posted on 22-12-2009 at 10:52


Quote: Originally posted by Waffles SS  
My believe isnot murder of relatives and killing,..or anotherthing,please finish it.
I just love chemistry nothing else.


I have done you a favor by renaming your account so that any future technical questions of yours can be discussed without distraction.




PGP Key and corresponding e-mail address
View user's profile Visit user's homepage View All Posts By User
Satan
Hazard to Others
***




Posts: 126
Registered: 1-5-2009
Member Is Offline

Mood: No Mood

[*] posted on 22-12-2009 at 12:32


Quote: Originally posted by not_important  

The Fischer synthesis can be used to directly produce IIA and IBA or simple derivatives of them, without going through indole in an intermediate step.


For what derivatives of indole this reaction will also work? Or in other words, wich functional groups would not interfere with normal progres of Fischer synthesis?



[Edited on 22-12-2009 by Satan]
View user's profile View All Posts By User
sonogashira
International Hazard
*****




Posts: 555
Registered: 10-9-2006
Member Is Offline

Mood: No Mood

[*] posted on 22-12-2009 at 12:37


It is acid-catalysed reaction, so anything resistant to decoposition by acid (amines, carboxylic acids etc.) is ok I think.

[And maybe, if 'WaffenSS' is changed, 'Satan' is as big a enemy?! Or the only enemy, to some! Hehe!]

[Edited on 22-12-2009 by sonogashira]
View user's profile View All Posts By User
ChrisWhewell
Hazard to Self
**




Posts: 66
Registered: 22-12-2009
Location: Austin
Member Is Offline

Mood: No Mood

[*] posted on 22-12-2009 at 19:35


What do you intend to do with indole ?
View user's profile Visit user's homepage View All Posts By User
hector2000
Hazard to Others
***




Posts: 127
Registered: 22-8-2006
Member Is Offline

Mood: Cool

[*] posted on 24-12-2009 at 01:14


Quote: Originally posted by Waffles SS  
I have problem with Fischer indole synthesis For making IAA.
@Nicodem said this reaction need special condition and he suggest Phenylhydrazone+Pyruvic acid but i need more detail about it.
Anyone can send refrence or instruction about that?


here you are
us2,701,250
process of producing indole3-acetic acid by fischer method

Attachment: US2701250.pdf (237kB)
This file has been downloaded 587 times





Chemistry=Chem+ is+ Try
View user's profile View All Posts By User
Satan
Hazard to Others
***




Posts: 126
Registered: 1-5-2009
Member Is Offline

Mood: No Mood

[*] posted on 24-12-2009 at 11:04


Another document about IAA:


Attachment: Synthesis.Indoleacetic.Acids.Glutamine.pdf (279kB)
This file has been downloaded 932 times
View user's profile View All Posts By User
JohnWW
International Hazard
*****




Posts: 2849
Registered: 27-7-2004
Location: New Zealand
Member Is Offline

Mood: No Mood

[*] posted on 24-12-2009 at 11:52


That reminds, me, "Satan": how do Satanists celebrate Christmas? With horns, hooves, a pointed tail, the wings of a bat, goatee beard, red scaly skin, smelling of sulfur (or of selenium or tellurium or polonium, or of indole, if you like), and going around dressed in red tights and brandishing a pitchfork, it must be rather difficult.

Another indole derivative is the purple dye "Tyrian purple", used to dye the robes of Roman Emperors and patricians, originally obtained from two species of whelk, originally called Murex brandaris and Murex trunculus, which are the older names for Haustellum brandaris and Hexaplex trunculus, found in the Mediterranean, in what was a very smelly and costly operation; see http://en.wikipedia.org/wiki/Tyrian_purple . Fortunately the stuff can now be made synthetically. It is 6, 6'-dibromoindigo, a double-bonded dimer of indole via the 5-membered rings, on which there are also keto groups, and there are Br atoms on the aromatic rings.

There is also the important dye indigo, also a substituted dimer via the 5-membered rings of indole, see http://en.wikipedia.org/wiki/Indigo_dye . It was originally obtained from the indigo plant, and is now produced synthetically in large amounts, although not via indole itself.

[Edited on 25-12-09 by JohnWW]
View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 24-12-2009 at 12:04


US 3790596 METHOD OF PRODUCING INDOLE AND SUBSTITUTION PRODUCTS OF THE SAME
acetaldehyde phenylhydrazone -> indole

US 3847937 PROCESS FOR THE PREPARATION OF INDOLES
diphenylaminoethane (from aniline and acetaldehyde) -> indole

Also found during the search:
US 2159167 Alcoholic beverage of reduced inebriating capacity


pyruvic acid:
http://www.sciencemadness.org/talk/viewthread.php?tid=8481


[Edited on 24-12-2009 by Vogelzang]

[Edited on 24-12-2009 by Vogelzang]
View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 24-12-2009 at 12:09



US 1891057 Production of indole and derivatives thereof

US 2086805 Purification of the isatins

US 2307244 Production of indoles
Page 1 column 1 lines 10+:
It has been proposed to produce indole from indigo by a preliminary reduction with tin and hydrochloric acid followed by destructive reduction with zinc dust at distillation
temperatures. It has also been proposed to produce indole by the distillation of indigo with the aluminum powder at red heat.

US 2365966 Production of indole -> in German Patent No. 260,327 it, is
disclosed that indole may be formed by heating an aqueous solution of indoxyl
and an alkali metal hydroxide in an autoclave to a temperature above 200' C.

US 1657869 Process for producing indigo white

US 1721319 Zn+2NaHSO3=2H+ZnSO3+Na2SO3 ; can be used to reduce indigo to indigo white

US 2130878 Leucoindigo

US 2159930 Preparation of leuco-indigo

US 1588960 Indigo dyestuff
shows structures of indole, indoxyl, isatin, etc.

US 2017120 Production of discharge effects
Page 1 column 2 lines12+:
The zinc compounds of leuco vat dyestuffs have been found particularly convenient for
application in accordance with the present invention, but other insoluble metal compounds may be utilized if desired, for example compounds with cadmium, aluminium, tin, lead or iron. These insoluble metal compounds of leuco vat dyestuffs are conveniently prepared by interaction between the alkali metal salts of the leuco compounds and appropriate metal salts, preferably such as are water-soluble. For instance, the dyestuff in question may be vatted with sodium hyrosulphite or other
reducing agent and just sufficient caustic alkali to yield a solution of the
leuco compound. The solution thus obtained, if desired after filtration,
may be treated with an aqueous solution of the appropriate metal salt, for
example a concentrated solution of zinc chloride, whereby the desired metal
compound of the leuco vat dyestuff may be precipitated.

US 3118724 Processes for reduction of organic substances with alkali-metal borohydrides in the presence of catalysts

US 5350425 Method of reducing vat dyes and the process of dyeing fabrics therein
column 1 lines 49+
Typically, sodium dithionite has been employed to reduce the dyes to
their leuco form, as is shown U.S. Pat. No. 3,798,172. Sodium dithionite
decomposes rapidly in the presence or absence of air; therefore, large, excess
quantities of this compound are used to reduce all of the dye and to maintain
the dye in is soluble leuco form. Regrettably, the use of sodium dithionite
raises ecological concerns.
column 1 lines 64+
Another reducing agent that has received some attention is
thiourea dioxide in an alkaline solution. However, thiourea dioxide is a
strong reducing agent, and therefore tends to over reduce the vat dye. When
reducing indigo overreduction is readily apparent by the smell of fecal
material which is present when indole (the overreduction product) is in the
reaction.
indigo -> leucoindigo using Al, NaOH & H2O column 7, several examples columns 8 and 9

US 2872482 Process of making thiourea dioxide
Column 1
Thiourea dioxide has heretofore been prepared by the oxidation of thiourea by the use of hydrogen peroxide.

US 2150921 Manufacture of imino-amino-methane-sulphinic acid
oxidation of thiourea by the use of hydrogen peroxide

US 2164930 Process for reducing vat dyestuffs
use of thiourea dioxide for reducing vat dyes

View user's profile View All Posts By User
unome
Hazard to Others
***




Posts: 134
Registered: 17-10-2009
Member Is Offline

Mood: No Mood

[*] posted on 24-12-2009 at 13:45


Attached find a review of the Fischer Indole synthesis.

View user's profile View All Posts By User
Waffles SS
Fighter
*****




Posts: 931
Registered: 7-12-2009
Member Is Offline


[*] posted on 24-12-2009 at 14:24


Thanks @VogelZang and Hector,
@JohnWW now i am Waffles SS,this remind you another thing again?
View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 25-12-2009 at 06:46


Ye Ol' zinc dust distillation to remove oxygen atoms.

Indole chemistry began to develop with the study of the dye indigo. Indigo can be converted to isatin and then to oxindole. Then, in 1866, Adolf von Baeyer reduced oxindole to indole using zinc dust.[2] In 1869, he proposed a formula for indole (left).[3]

2. Baeyer, A. (1866). "Ueber die Reduction aromatischer Verbindungen mittelst Zinkstaub". Ann. 140: 295. doi:10.1002/jlac.18661400306.

3. Baeyer, A.; Emmerling, A. (1869). "Synthese des Indols". Chemische Berichte 2: 679. doi:10.1002/cber.186900201268.

http://en.wikipedia.org/wiki/Indole

[Edited on 25-12-2009 by Vogelzang]
View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 25-12-2009 at 06:57


This discusses the production of indole from pyrrole (page 629).

http://books.google.com/books?id=MAA5AAAAIAAJ&pg=RA1-PA6...

[Edited on 25-12-2009 by Vogelzang]
View user's profile View All Posts By User
Satan
Hazard to Others
***




Posts: 126
Registered: 1-5-2009
Member Is Offline

Mood: No Mood

[*] posted on 25-12-2009 at 14:40


How would react hydrazone, made from condensation of 4-methoxyphenylhydrazine and acetaldehyde? There are two possible reaction products, 5-methoxyindole and 6-methoxyindole. My true question is: how to predict how substitiued phenylhydrazones would cyclicyze?

From 5-methoxyindole, melatonin can be made, it would be interesting synthesis of human hormone.
View user's profile View All Posts By User
sonogashira
International Hazard
*****




Posts: 555
Registered: 10-9-2006
Member Is Offline

Mood: No Mood

[*] posted on 26-12-2009 at 02:47


Quote: Originally posted by Satan  
From 5-methoxyindole, melatonin can be made, it would be interesting synthesis of human hormone.


If it is your interest there is this thread by a person now-departed from this site, God bless him :) Lot of good alternative methods and (maybe!) even the one you have an interest in...
http://www.sciencemadness.org/talk/viewthread.php?tid=10120



[Edited on 26-12-2009 by sonogashira]
View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 27-12-2009 at 13:22


US patents which disclose processes for producing indoles from phenylhydrazones: 4965369, 5229413, 2995566, 1866956, 2057948, 2068800, 3557142.

View user's profile View All Posts By User
Vogelzang
Banned





Posts: 662
Registered: 26-4-2008
Member Is Offline

Mood: No Mood

[*] posted on 27-12-2009 at 13:54


Another US patent on IAA 2701251.

US patents on anilines + glycols -> indoles: 4436916, 4436917, 4443615, 4456760, 4473698, 4474969, 4476310, 4659841, 4727161, 4732654, 4831158, 4937353, 5175308, 4404063 (with indole separation).

An interesting tryptamine process: US 5037845
View user's profile View All Posts By User
unome
Hazard to Others
***




Posts: 134
Registered: 17-10-2009
Member Is Offline

Mood: No Mood

[*] posted on 8-1-2010 at 00:20


Damn, I thought my attachment attached, obviously not here tis again...

B. Robinson, The Fischer Indole Synthesis, Chem. Rev., 1963, 63 (4), pp 373–401 (DOI: 10.1021/cr60224a003)
View user's profile View All Posts By User
Rattata2
Harmless
*




Posts: 35
Registered: 22-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 14-1-2010 at 18:02


I like this idea:

React benzaldehyde with nitroethane forming a beta-nitrostyrene. Nitrate this with HNO3 - this should nitrate mostly ortho-. Follow by heating with iron turnings to form indole.
View user's profile View All Posts By User
unome
Hazard to Others
***




Posts: 134
Registered: 17-10-2009
Member Is Offline

Mood: No Mood

[*] posted on 14-1-2010 at 22:57


Why aren't the attachments working?

There should be 4 attached here NOW:mad:



Attachment: VanOrder.Lindwall.Chem.Review.Indole.pdf (306kB)
This file has been downloaded 1161 times

Attachment: Bidylo.Yurovskaya.Synthesis.Tryptamines.Latent.AminoButanal.Review.pdf (835kB)
This file has been downloaded 7202 times

Attachment: indole.synth.review.1994-99.pdf (791kB)
This file has been downloaded 2230 times

Attachment: Improved.Synthesis.DMT.Psilocin.pdf (1.4MB)
This file has been downloaded 859 times


[Edited on 15-1-2010 by unome]
View user's profile View All Posts By User
Rattata2
Harmless
*




Posts: 35
Registered: 22-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 31-1-2010 at 06:14


Whoops I meant nitrom*ethane in the previous post. My bad, makes things easier eh? :p

Anyways, I found this recently which to me looks like an exciting method of indole synthesis: http://www.sciencedirect.com/science?_ob=ArticleURL&_udi...

I can't access the paper myself (anyone who can if you wanna upload it thatd be great) but the abstract says wonders..it's a fischer indole synthesis using pyruvic acid as the ketone, under microwave irradiation (with ZnCl2 as a catalyst.) This would first form indole-2-carboxylic acid as an intermediate which would then be decarboxylated to yield indole. Apparently in a microwave, this whole procedure can be done in a one-pot synthesis :)

Not sure if the PCl5 is really required for this (it isn't for classical fischer indole synthesis is it?), but I do believe the reaction is supposed to take place in acidic conditions. Anyways hope this turns out useful to someone :)
View user's profile View All Posts By User
IPN
Hazard to Others
***




Posts: 156
Registered: 31-5-2003
Location: Finland
Member Is Offline

Mood: oxidized

[*] posted on 31-1-2010 at 06:43


Here is the full paper. :)



Attachment: A new and efficient one-pot synthesis of indoles.pdf (95kB)
This file has been downloaded 2299 times

View user's profile View All Posts By User
Waffles SS
Fighter
*****




Posts: 931
Registered: 7-12-2009
Member Is Offline


[*] posted on 31-1-2010 at 09:19


One funny question:
May we use kitchen microwave oven for microwave irradiation step?
View user's profile View All Posts By User
 Pages:  1  2  

  Go To Top