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Topic: Substitution/addition with an aromatic hydrocarbon  (Read 4260 times)

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Scutum

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Substitution/addition with an aromatic hydrocarbon
« on: November 30, 2005, 02:46:39 PM »
Hi there =)
Well, my class is currently dealing with arenes (and their reactions), we've got some homework and I need help >.<

Actually, I have solved the main synthesis task, which, if I am correct, leads to azulene.
The latter reacts with a few other substances, yet I don't know how :(

1) Azulene reacts with tert-butanol, catalysed by an acid, in a substitution reaction to F.

2) With an alkali organyl or a Grignard reagent azulene reacts in an
addition reaction to form  a salt. This, after an aqueous preparation and oxidation with tetrachloro-para-benzo-quinone, becomes a respective alkyl substituted derivative of azulene.
Two different products (isomers) are possible. The first (G) emerges from the usage of methyllithium, the second (H)  from the usage of triphenylmethyllithium.

3) Also compounds of transition metal of azulene are synthesisable. If azulene reacts  with LiAlH4  and  Iron(II)-chloride, a red compound I is formed in the form of multiple stereoisomers.
Via careful hydrogenation of the isomers a single orange compound of J is formed with the empirical formula C20H26Fe.

My homework is to draw the chemical structure of F, G and H, as well as to draw all isomers of I and the chemical structure of J. But since I don't feel confident about the reactions or the products ??? , I can't do it  :(

I would be deeply grateful if you helped me  :-\

Offline AWK

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Re:Substitution/addition with an aromatic hydrocarbon
« Reply #1 on: December 01, 2005, 07:56:57 AM »
for:
3)
see:M.R.Churchill, J.Wormald (1969) Inorg.Chem.,8,716
AWK

Scutum

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Re:Substitution/addition with an aromatic hydrocarbon
« Reply #2 on: December 01, 2005, 01:17:00 PM »
Many thanks for your quick help :)
But unfortunatelly there's only one copy of that book at the library of my university, which is borrowed till the end of month (*doh*, but already ordered ;)).
Still I found another book about additions and subsitutions of arenes, which I know understand a bit better. Yet I'm still not sure about the products, I've tried it anew but they somehow don't look quiet right to me :S
Would you be so kind to post your findings here? Otherwise I don't know how to solve this riddle till next week *g*
However, thanks again ^^

Offline AWK

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Re:Substitution/addition with an aromatic hydrocarbon
« Reply #3 on: December 02, 2005, 02:09:51 AM »
Plot of complex attached. Note, this is 4,6'-dimer
« Last Edit: December 02, 2005, 02:12:51 AM by AWK »
AWK

Scutum

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Re:Substitution/addition with an aromatic hydrocarbon
« Reply #4 on: December 03, 2005, 01:10:56 PM »
Wow, that looks cool 0_o
Thanks a lot :)

Yet I have another question, since your compound has only 16 H atoms, this is one of the stereoisomers of I, right?
Well, I was wondering whether the other isomeres are just slightly shifted versions of this one?
Btw. is it also possible, that the Fe is located either in the 5- or the 7-ring complex and after the hydration (since arenes cannot (AFAIK) be hydrated) only in the 7-ring part of azulene? (If Fe would become ironhydrid (FEH4) the formula C20H26Fe would be fitting)
F, I think is a tert-butyl substituent on azulene (with dehydration of water) on C 6.
« Last Edit: December 03, 2005, 01:24:35 PM by Scutum »

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