reissert indole synt

[flipper]

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_xrvg.gif" title="View this image">

What can you bees tell me about this reaction?

[Rhodium]

What do you want to know?

[flipper]

Everything ofcourse! How it works. How to perform it. The yields. The difficulties and the tips and tricks. The whole list.
Is it recomended, is it crap. Some examples are also welcome
Some literature as well and some ref's.
That's all        
ThanX

[PrimoPyro]

I can tell you that a reference for this very specific reaction would be Heterocyclic Compounds 3, 18 (1962). Maybe you could go look that up to find out such details as yields, availability, etc.

Chemfinder and Rhodium would also be helpful to you, especially combined with TFSE. These would tell you that NaOEt for example is sodium ethoxide. Alkoxides are somewhat newly charted territory for clandestine synthesis, and it can be difficult to acquire them elsewhere. Not to say they are impossible to make, no no; I'm just saying it is something you could become aware of.

ortho-nitrotoluene? How is that made, other than the oxidation of toluidine? Perhaps I can search as well.  

                                                    PrimoPyro
The Water Will Be Your Only Mirror

[terbium]

Just buy the indole. It is readily available and not expensive. If you can't even buy indole then you are certainly not going to be able to buy the other chemicals that you would need to make it into something interesting.

[flipper]

This also looks cool.
Some info would be welcome.

Scheme 1
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_zkfw.gif" title="View this image">

Many other syntheses of indole compounds have been reported. An efficient synthesis of indole (1) and its derivative beginning with lithiation at the methyl group of o-tolylisocyanide (37) follows

Back to the subject.

Scheme 2
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_g6zy.gif" title="View this image">
Condensation of an o-nitrotoluene with oxalic ester, reduction to the amine, and cyclization to the indole
A. Reissert, Ber. 30, 1030 (1897).

W. O. Kermack et al., J. Chem. Soc. 119, 1602 (1921); P. C. Julian et al., Heterocyclic Compounds 3, 18 (1962); J. G. Cannon et al., J. Med. Chem. 24, 238 (1981).

Scheme3
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_rdls.gif" title="View this image">

The Reissert indole synthesis is a convenient method for the synthesis of indole and indoles substituted in the benzene ring. In this method, o-nitrophenylpyruvic acid (35) [prepared from o-nitrotoluene (33) and diethyl oxalate (34)] is reductively cyclized to indole-2-carboxylic acid (36), which readily decarboxylates:

If you can't read it here is the link

Synthesis of indoles

(http://www.unb.br/iq/labpesq/qo/olv/olv/about.htm)

What I don't understand is that Scheme 3 which suposed to be a reissert indole synt, looks different the scheme 2. They use in scheme 3 NH3 and Fe2+. Whats the bloody deal over hear. Could somebody explain

Terbium, ofcourse I could buy indole or whatever. But that ain't no fun. I also can buy MDP2P in China but what fun would that be. I like to sweat.

[Rhodium]

I guess that Fe²⁺ as well as Zn can be used for the reduction/ring closure step...

[flipper]

But isn't Fe2+ an oxidator and Zn a reductor?

[Rhodium]

No, both are reducing agents. Fe²⁺ wants to become  Fe³⁺ and Zn wants to become  Zn²⁺ so both will themselves be oxidized, therefore reducing whatever they are in contact with. I have also seen a variation of this synth with Fe metal instead.

[flipper]

Cool. I love it.

One little question. That little triangle above the arrow for the means heat isn't it? If not what does it means? And even a more little question. Are the ratios correct or do I still have to calculate the one and other. How much electrons does the second step needs and what about solvents. Do I need to dissolve something. Sorry but I learn more and more everyday thanks to the hive and I'm very gratefull for that.  
ThanXTC  

[bucockey]

the triangle means heat...

[Rhodium]

You probably need to look up a synthesis (in the library) using this method to find out the optimum ratios of reducing agent. On the pages where you found the graphics, you have good examples.

[flipper]

I've got this from Organic syntheses.

ETHYL INDOLE-2-CARBOXYLATE (CV 5, 567)

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_wgn6.gif" title="View this image">

indole-2-carboxylate link

(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0567)

Looks cool

From Organic Syntheses, CV 3, 479

The authors recommend the method of Reissert,12 which involves condensation of o-nitrotoluene with ethyl oxalate, followed by reduction to indole-2-carboxylic acid and decarboxylation of the latter.

Link

(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0479)

So I went searching and this synthesis supposed to match like the indole synthesis via Reissert but I don't see the connection.

4-NITROINDOLE (Organic Syntheses, CV 8, 493)

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_oikk.gif" title="View this image">

Link

(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv8p0493)

Again I ask. What can you tell me about these syntheses? And can they help me with that bloody Reissert Synt

Some Bonus info:

ETHYL OXALATE (Organic Syntheses, CV 1, 261)

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000268709-file_8vyo.gif" title="View this image">

link

(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0261)

You've gotta love me.

[Rhodium]

Flipper: I am really confused now. Exactly what information do you need, and what are your intended use for it? It would help very much if you would begin telling us that.

Have you looked up the references supplied above yet, whatever you want to know - it should be in there.

[flipper]

I wanna know the ratios and the best conditions to perform the reissert reaction. And my library doesn't have those books. I have to go to the library of the university but they have an idiotly high membership price and I doubt that they let me in. So I had hoped somebody knows something.
I will buy a university library membership soon but before that time I try to get my info by asking it in this topic.
And I thought i sended some usefull info. But anyway Thanks and sorry for my vaque writing and my stubborness.  

(I still wanna know the ratios and conditions so if anybody knows the answer he can send it to the topic or to my PM.)
You've gotta love me.

[Rhodium]

Ok. Use the patent search engine at

http://patft.uspto.gov/netahtml/search-bool.html

and search for "reissert" or a combination of the names of the reactants. There should be a few patents using this reaction...