Author Topic: Alternative possibilities from styrene?  (Read 345 times)

Goldmember

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Alternative possibilities from styrene?
« on: April 01, 2013, 06:28:30 AM »
Hi all, Excuse the cross post from another board. I realised Id get a more forthright response here after posting.

IMHO The Willgerodt in all of its unworldly manifestations belongs nowhere but the bowells of hell, and that dimisyl idea seems feasable in microgram theory, but Im not convinced through practice.

In saying that Im still quite interested in styrene as a starting block. Im short of time at the mo, and still getting my head around some of this, so please excuse any glaring mistruths. Ill keep it brief, but Ill post refs/pics experimental detail as I sort/find it. Consider this a short overview into which Ill insert refs as I go.
This is what Ive come to so far, and would appreciate any feedback from more knowledgeable dreamers.

What Im aiming at is routes from Cyclopropanated styrene derivatives. (Phenylcyclopropane being the intermediate when cinnamaldehyde is subjected to treatment with Hydrazine hydrate without base).

Now Styrene can be reacted with various reagents to form said cyclopropane.

1: Diazomethane derivatives catalysed  by metal ligands.
2: Zinc-Copper and Dihalomethane.(Simmons-Smith reaction).
3: Iron Pyrorphins/insitu diazo complexs etc
And the list goes on. But nothing stands out as being either OTC or amature friendly.

On the other hand we have the option of another somewhat more indirect route which will also open up some more possibilities.
That being  dichlorocarbene addition to styrene to form the geminal dihalide followed by dehalogenation  and thermal/base catalysed isomerisation  of the gem-dihalide to yield a mix of propenyl/ally benzene.

So first we would need to generate Dichlorocarbene.This can be done OTC with:
1: Carbon tetrachloride and magnesium under PTC or Ultrasound conditions.
2: Chloroform and Hydroxide under similar conditions.(Better)
This carbene will add to styrene insitu resulting in the formation of 1,1-dichloro-2-phenylcyclopropane.

Next to unselectively dehalogenate we can use.
1:Zinc dust in methanol/water
2:Dithionite in H20
3: Lithium or Sodium in Alcohol
4: Alkali metal in NH3 (for the SnBers)
This will yield straight Phenylcyclopropane. As mentioned above moderate temperature thermal rearangent of the cyclopropane yields our desires alkenes.
Alternatively base catalysed and you are vitually picking up at the end phase of the Wolf-kishner on cinnamaldehyde,yielding the same.

O.K so in a nutshell here we have :

1)Haloform + Base (PTC/ultrasound) -> Dihalocarbene + Styrene -> Dihalophenylcyclopropane.
2)Zinc/MeOH + Dihalophenylcyclopropane -> Phenylcyclopropane.
3) Phenylcycloppropane + Heat/base ->allyl/propenyl benzene(predominantly propenylbenzene).

Thats all good and well I suppose, but Im wondering if we can get a little bit trickier.

I.e Idea number :-

1) Hot Basic hydrolysis of the gem-dihalide should yield 2-Phenylpropionic acid sodium salt, which can then be halogenated, substituted to amide then Hoffman to amine.
2) React with Alkoxide to form an alkyl ester ,substitute to amide, Hoffman etc.
3) Dehalogenate as above, then react with PdCl2 to give a mix of phenylacetone/propiophenone.
4)Oxidative isomerisation by other means (Hg salts etc) to give mixed ketones.
5) Selective reductive dehalogenation (Dithionite) and subsequent ring opening of the monohalide to the desired Haloalkane. (This one interest me the most obviously. And this is where most of the conflicting info is found.) Depending on slight variations in method, reports described conflict as to which carbon cleavage will take place at.
Tthings I need to look into further:
6) Hydrolysis of the dihalide to Cyclic ketone and what can be done .
7) Amination of the monohalide and what can be done.
8) Alkyl cyclopropanes. Cyclopropyl carboxylates. and the Dakin rearangement.

Thats it for now.  Unless Im totally trippin ballz, you can see this could open up many possibilites.
Please discuss/ shoot me down in flames.

Again Ill post refs for each step, as they are located/fullfilled by the good folk who do such kind work.

phaseolus

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Re: Alternative possibilities from styrene?
« Reply #1 on: April 01, 2013, 07:19:30 AM »
Interesting research here.

Even though it's hardly practical, styrene can be ozonolyzed to benzaldehyde, from which there are a good half dozen viable routes to ketone.

Goldmember

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Re: Alternative possibilities from styrene?
« Reply #2 on: April 01, 2013, 11:36:41 AM »
C`mon bro, If we are talking practicality, 3-4 of those options beat the shit out of anything starting from  benzaldehyde.
Especially if you consider permanganate/Ozonolysis of styrene as a first step.

No offense, I like what you post very much, but what is so hard about Chloroform,sodium hydroxide, oxone etc vs nitroethane, BV oxidation,propionates etc?
That is if you consider route one,ie via the alkene,I put forth.
If you look at the possibility of selective ring opening of the monohalide, you are talking 3 simple steps styrene to amine.

Which part would you consider impractical?

It will make more sense when I post refs, fancy pictures etc.

Edit: ah maybe I did my usual jump the gun not realising you are calling the ozonolysis of styrene impractical. Maybe not? English being my first language and all....

Cheers, appreciate the input. Keep it comming please.

P.S you should clear your inbox at the-collective. What is going on with that Lugh/Wiz?

« Last Edit: April 01, 2013, 11:42:29 AM by Goldmember »

phaseolus

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Re: Alternative possibilities from styrene?
« Reply #3 on: April 02, 2013, 02:14:36 AM »
C`mon bro, If we are talking practicality, 3-4 of those options beat the shit out of anything starting from  benzaldehyde.
Especially if you consider permanganate/Ozonolysis of styrene as a first step.

No offense, I like what you post very much, but what is so hard about Chloroform,sodium hydroxide, oxone etc vs nitroethane, BV oxidation,propionates etc?
That is if you consider route one,ie via the alkene,I put forth.

Sorry I realize I didn't communicate clearly there. I was referring to ozonolysis as being impractical. "Even though it's hardly practical, styrene can be ozonolyzed to benzaldehyde." I only said that statement in the spirit of "alternative possibilities from styrene" to cover all bases (you mentioned Willgerodt and dimsyl). Definitely removing one carbon from the chain is a step in the wrong direction, especially when there's a functional group (alkene) at the end ready to be exploited.

atara

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Re: Alternative possibilities from styrene?
« Reply #4 on: April 03, 2013, 07:21:34 PM »
Styrene epoxide should alkylate ethyl acetate under Claisen reaction conditions (EtOH / NaOEt), correct?

Hydrolysis of the reaction product gives P1Pol-3-carboxylic acid. Oxidizing the alcohol to a ketone gives, after a spontaneous decarboxylation (beta-keto acid), P2P.

That's three (or four) steps to P2P -- epoxidation, alkylation (+hydrolysis), oxidation. Mostly familiar reactions, too.

EDIT: No, the alcohol ends up on the benzylic carbon instead of the phenethyl carbon. Might be able to work with that, though.
« Last Edit: April 03, 2013, 07:43:53 PM by atara »

phaseolus

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Re: Alternative possibilities from styrene?
« Reply #5 on: April 05, 2013, 12:01:04 PM »
It would seem to me that Claisen condensation of phenylacetaldehyde with ethyl acetate would give alpha-acetylphenylacetaldehyde upon acidic workup.

fishinabottle

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Re: Alternative possibilities from styrene?
« Reply #6 on: April 27, 2013, 02:44:43 PM »
It would seem to me that Claisen condensation of phenylacetaldehyde with ethyl acetate would give alpha-acetylphenylacetaldehyde upon acidic workup.
From Phenylacetaldehyde it is just one Grignard to Tweeker-heaven, but nobody has presented a working method to get it. Not pipedreams or articles but something working in our world. All trials failed.
Thats the problem.

Afraid of the Grignard? Bwiti did them without any glassware on the kitchentable, successfully.

/ORG

Balkan Bonehead

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Re: Alternative possibilities from styrene?
« Reply #7 on: April 28, 2013, 09:36:21 PM »
This looks feasible: http://127.0.0.1/talk/index.php/topic,1330.msg22206.html

Basically it is simple addition of chlorine across the double bond to form 1,2 dichloroethylbenzene, then stirring with aqueous alkali to dehydrohalogenate to alpha-chlorostyrene, then chlorination across the double bond a second time to yield trichloroethylbenzene. This is hydrolyzed in hot ethanolic NaOH to form phenylacetate (refs in thread).

fishinabottle

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Re: Alternative possibilities from styrene?
« Reply #8 on: May 02, 2013, 02:16:23 PM »
There was this chinese patent where triple chlorination of styrene and transformation of the product to PAA in situ was claimed as far one could decipher.
lugh might still have it, I lost it with all the rest.

/ORG

PS: All halogenations of styrene are very difficult if not done in the gasphase at 175°C+ IIRC as polymerisation is almost impossible to prevent.
There is even an article about this named like "is it possible to halogenate styrene if not in the gasphase"
I will try to find it again.
btw. The answer was "Yes, but....."

So everything what deals with halogen and styrene in one pot is inherently bound to make plastic except you know a trick or two, or are a wonder-chemist like jon, or are chinese.  ;)

/ORG
« Last Edit: May 02, 2013, 02:21:33 PM by fishinabottle »

lugh

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Re: Alternative possibilities from styrene?
« Reply #9 on: May 02, 2013, 07:30:04 PM »
Quote
lugh might still have it, I lost it with all the rest.

This thread seems to bee on point:

https://the-collective.ws/forum/index.php?topic=21881

 8)



Chemistry is our Covalent Bond

Balkan Bonehead

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Re: Alternative possibilities from styrene?
« Reply #10 on: May 03, 2013, 12:17:43 AM »
There was this chinese patent where triple chlorination of styrene and transformation of the product to PAA in situ was claimed as far one could decipher.
lugh might still have it, I lost it with all the rest.

/ORG

PS: All halogenations of styrene are very difficult if not done in the gasphase at 175°C+ IIRC as polymerisation is almost impossible to prevent.
There is even an article about this named like "is it possible to halogenate styrene if not in the gasphase"
I will try to find it again.
btw. The answer was "Yes, but....."

So everything what deals with halogen and styrene in one pot is inherently bound to make plastic except you know a trick or two, or are a wonder-chemist like jon, or are chinese.  ;)

/ORG

The chlorine adds across the double bond, thus is not a free-radical reaction and proceeds in the cold. Obviously, high temps plus radical initiator would turn styrene to plastic, but what I am proposing avoids this. I have collected a number of references on this reaction, not all of them Chinese (see posted threads). Berthelot mentions chlorine addition as "one of the characteristic reactions of styrene" (The Reactions of Monomeric Styrenes).
« Last Edit: May 03, 2013, 12:20:04 AM by Balkan Bonehead »

fishinabottle

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Re: Alternative possibilities from styrene?
« Reply #11 on: May 03, 2013, 09:56:51 AM »
There was this chinese patent where triple chlorination of styrene and transformation of the product to PAA in situ was claimed as far one could decipher.
lugh might still have it, I lost it with all the rest.

/ORG

PS: All halogenations of styrene are very difficult if not done in the gasphase at 175°C+ IIRC as polymerisation is almost impossible to prevent.
There is even an article about this named like "is it possible to halogenate styrene if not in the gasphase"
I will try to find it again.
btw. The answer was "Yes, but....."

So everything what deals with halogen and styrene in one pot is inherently bound to make plastic except you know a trick or two, or are a wonder-chemist like jon, or are chinese.  ;)

/ORG

The chlorine adds across the double bond, thus is not a free-radical reaction and proceeds in the cold. Obviously, high temps plus radical initiator would turn styrene to plastic, but what I am proposing avoids this. I have collected a number of references on this reaction, not all of them Chinese (see posted threads). Berthelot mentions chlorine addition as "one of the characteristic reactions of styrene" (The Reactions of Monomeric Styrenes).
The named "Reactions of Monomeric Styrenes" is not new, I read it so long ago I have already forgotten most of it...
Whatever, the last time I bought some polystyrene resin it contained a tin can of styrene some fiberglass and a tube of benzoylperoxide. Mix at RT and it will make the polystyrene you dont have much time hurry up! That was about what was written on the box and really it did.
What makes me fucking damn sure that radical initiators initiate polymerisation already at RT and below. And not just this, because of the intriguing prospect to make PAA from styrene quite easily I tried it several times in different configurations with different additives and different prayers and the only result is that I am now an expert in inducing polymerisation and I know that watching styrene polymerize beats watching paint dry all the time for being much faster.

Believe me, I am the first to jump up and start dancing anybody comes up with a working solution which does not include dilution beyond anything what makes volumetrically sense as its no solution but a joke if you have one ml styrene in onehundred ml solvent.
Industry does it in the gasphase, to hot, no problem for them. Give me a doable setup to do the same and bingo.

"Balkan Bonehead" gave me a good laugh, congrats! You make it round the world pretty fast dont you? From Australia to the Balkan with how many, one, two stops? If you are who I think you are then you owe me a ph-meter. Talk is cheap, that was never  more true...
 ;D

/ORG

Goldmember

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Re: Alternative possibilities from styrene?
« Reply #12 on: May 03, 2013, 11:46:03 AM »
Id prefer to forget about all of those reactions ending at PAA/Phenylacetaldehyde etc. These are well known and nothing new. Should they have been attempted it would soon be realised that they dont forgive the amature experimentalist...

Look at this molecule--> http://www.chemicalbook.com/ChemicalProductProperty_EN_CB12346477.htm  and tell me how to open that ring,and upon which carbon,without cleavage of the halide. Either that or open the ring and exchange with methylamine at the same time :)
Or at least suggest some non-exhausted search term.
Arriving here seems to be quite straight forward on paper. Dehydrohalogenation(with zinc or Hv) and thermal rearangment results in allyl/propenybenzene in more than adequate yield considering every other known route. This idea  I have the recipes for, but doing the whole shebang onepot seems a lot more arttractive if possible.


Cmon you mechanism guru`s, show your stuff here! I certainly aint no chemist, so fire away please.
 Im not shy of being schooled so long as its something I should not have read already in a 1st year chem-grad textbook, to which I say stick to your fucking paperback chemistry.

Balkan Bonehead

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Re: Alternative possibilities from styrene?
« Reply #13 on: May 03, 2013, 06:44:40 PM »
The named "Reactions of Monomeric Styrenes" is not new, I read it so long ago I have already forgotten most of it...
Whatever, the last time I bought some polystyrene resin it contained a tin can of styrene some fiberglass and a tube of benzoylperoxide. Mix at RT and it will make the polystyrene you dont have much time hurry up! That was about what was written on the box and really it did.
What makes me fucking damn sure that radical initiators initiate polymerisation already at RT and below. And not just this, because of the intriguing prospect to make PAA from styrene quite easily I tried it several times in different configurations with different additives and different prayers and the only result is that I am now an expert in inducing polymerisation and I know that watching styrene polymerize beats watching paint dry all the time for being much faster.

Forget radical initiation. Just forget it! I never said anything about radical initiation, except to point out that the addition of chlorine to a double bond is not a radical reaction. Perhaps this resource will be useful to you: http://chemwiki.ucdavis.edu/Organic_Chemistry/Hydrocarbons/Alkenes/Electrophilic_Addition_of_Halogens_to_Alkenes

Quote
"Balkan Bonehead" gave me a good laugh, congrats! You make it round the world pretty fast dont you? From Australia to the Balkan with how many, one, two stops? If you are who I think you are then you owe me a ph-meter. Talk is cheap, that was never  more true...
 ;D

/ORG

I have no idea if I am who you think I am or not. I should tell you that I have never been to Australia and do not own a pH meter, borrowed or otherwise.  ;D

Doc B

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Re: Alternative possibilities from styrene?
« Reply #14 on: May 05, 2013, 05:04:10 PM »
Oh shit, I still haven't sent that! Sorry Orgy, I've been distracted but am a different bonehead. :D

fishinabottle

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Re: Alternative possibilities from styrene?
« Reply #15 on: May 08, 2013, 08:23:06 AM »
The named "Reactions of Monomeric Styrenes" is not new, I read it so long ago I have already forgotten most of it...
Whatever, the last time I bought some polystyrene resin it contained a tin can of styrene some fiberglass and a tube of benzoylperoxide. Mix at RT and it will make the polystyrene you dont have much time hurry up! That was about what was written on the box and really it did.
What makes me fucking damn sure that radical initiators initiate polymerisation already at RT and below. And not just this, because of the intriguing prospect to make PAA from styrene quite easily I tried it several times in different configurations with different additives and different prayers and the only result is that I am now an expert in inducing polymerisation and I know that watching styrene polymerize beats watching paint dry all the time for being much faster.

Forget radical initiation. Just forget it! I never said anything about radical initiation, except to point out that the addition of chlorine to a double bond is not a radical reaction. Perhaps this resource will be useful to you: http://chemwiki.ucdavis.edu/Organic_Chemistry/Hydrocarbons/Alkenes/Electrophilic_Addition_of_Halogens_to_Alkenes

Quote
"Balkan Bonehead" gave me a good laugh, congrats! You make it round the world pretty fast dont you? From Australia to the Balkan with how many, one, two stops? If you are who I think you are then you owe me a ph-meter. Talk is cheap, that was never  more true...
 ;D

/ORG

I have no idea if I am who you think I am or not. I should tell you that I have never been to Australia and do not own a pH meter, borrowed or otherwise.  ;D

First my apologies for the mistaken identity, and second a humble question:
Did you ever try to chlorinate styrene?
It is interesting.
For sure.
I did.

So you have wiki-waki-wuki-pedia and I have tried it several times several ways.

Now you try it and show me how it is done.
I still would love it.


come on
talk is cheap
/ORG

Wizard X

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Re: Alternative possibilities from styrene?
« Reply #16 on: May 10, 2013, 06:27:11 AM »
Albert Einstein - "Great ideas often receive violent opposition from mediocre minds."

Balkan Bonehead

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Re: Alternative possibilities from styrene?
« Reply #17 on: May 11, 2013, 11:06:36 PM »
First my apologies for the mistaken identity, and second a humble question:
Did you ever try to chlorinate styrene?
It is interesting.
For sure.
I did.

No, I have never personally chlorinated styrene, but I have read the writeups of people who have, in the literature. What were the conditions of your styrene chlorination attempt(s) (temperature, solvent, additives, rate of chlorine addition, etc.)?