Sciencemadness Discussion Board

Prins reaction to form a 1,3-Diol from an Alkene and Methanal

Thaekross - 28-7-2015 at 05:54

I would like to know the conditions and practice of using the Prins reaction to form a 1,3-Diol, specifically 1,3-Propanediol. Although I am interested in this reaction, if anyone knows of a simpler way of obtaining this compound, I would gladly accept any information.

Thank you for all helpful advice in advance.

[Edited on 28-7-2015 by Thaekross]

j_sum1 - 28-7-2015 at 07:14

http://www.ebay.com/itm/1-3-Propanediol-Trimethylene-glycol-...

Or

http://www.sciencemadness.org/talk/viewthread.php?tid=11283#...
http://www.sciencemadness.org/talk/viewthread.php?tid=16264

?


[Edited on 28-7-2015 by j_sum1]

Thaekross - 28-7-2015 at 14:10

Thanks for the response, but.... I don't have access to expensive palladium or rhodium catalysts and I don't think that using (and preparing) a cobalt catalyst ( e.g. Cobalt tetracarbonyl hydride) will be easier than the the conditioning of a Prins reaction.

The buying option IS there, but violates my personal rule of only using things I can buy in town. Otherwise, I would've just bought Mg metal for Grignard reagents instead :)

Furthermore; Unless you have knowledge of an antifreeze that contains 1,3-propanediol rather than (or alongside of) 1,2-propanediol (β-propylene glycol and α-propylene glycol, respectively) please don't mention antifreeze.

[Edited on 28-7-2015 by Thaekross]

Thaekross - 28-7-2015 at 22:41

Bump.

Sorry, looking forward to performing this reaction xD

CuReUS - 29-7-2015 at 00:41

Quote: Originally posted by Thaekross  
I would like to know the conditions and practice of using the Prins reaction to form a 1,3-Diol, specifically 1,3-Propanediol.

there is a book in the SM library called "excuse me sir,would you like to buy a kilo of isopropyl bromide ? " by gergel.In that book,he discusses the prins reaction.but I am afraid it is not very detailed.
Quote: Originally posted by Thaekross  

Otherwise, I would've just bought Mg metal for Grignard reagents instead :)

I am guessing you want to make cyclopropane,If so,then you could try some other method,like decarboxylation of cyclopropane carboxylic acid
you should be able to find references for making that,because Perkin did a lot of research on strained alicyclic compounds.
also,Wiki says that propan,1,3 diol can be found in wood paint

[Edited on 29-7-2015 by CuReUS]

Thaekross - 29-7-2015 at 03:07

A substituted chloropropane.
(didn't see the error I made 'till now)

I am trying to make N substituted chloropropylamines. As far as I can tell, experimentation with the Prins reaction is the easiest way to do so, at least from a reagent standpoint.

[Edited on 29-7-2015 by Thaekross]

Thaekross - 31-7-2015 at 03:15

:o

The Prins reaction: Help me

Thaekross - 1-8-2015 at 07:06

I would like to discuss the Prins reaction. (Note to staff: Please find out what the Prins reaction is before moving this topic from organic chem. Thank you)
What I would like to know is if anyone has performed this reaction, found any accessible literature on this reaction, or knows enough about it to help with working out reaction conditions to use this reaction to produce a 1,3-diol.
I would specifically like to use this organic reaction to produce 1,3-propanediol from ethene and methanal in the presence of sulphuric acid and water.

This part of this post is dedicated to "Scientific Discourse".
Protonation of methanal is preformed by a protic acid to produce an oxonium cation (Specifically an oxocarbenium cation) and resonance removing electrons from the carbon to stabilize the oxygen (thus forming a carbocation), ethene is introduced and electrophilic addition is carried out between the carbocation and alkene. After this, how can I ensure that the formed oxo-carbenium ion is reacted with water at the ionic (carbocatonic) carbon rather than another electrophilic reaction with the nearest saturated carbon to form another double-bond? What conditions would be required?

I hope this is up to the standards of Lord Nicodem. :o

[Edited on 1-8-2015 by Thaekross]

CuReUS - 1-8-2015 at 09:40

calm down thaeky,why did you start another thread for the same topic ?
Quote:
Note to staff: Please find out what the Prins reaction is before moving this topic from organic chem. Thank you

before advising the staff,pls read the forum rules.It clearly states that questions without appropriate background info will be put into the "beginning" section.

in your original post,you told me you wanted to make an N-substituted chloropropane. Suppose you want 3-chloropropanamine.
how are you going to make that from 1,3 dichloropropane ?
the only way I can think of is reacting acrylonitrile with HCl and then reducing the CN to amine.(but you would have to choose the right reducing agent,one that doesn't remove halogens).Could Pd black be used ?
Quote:
I hope this is up to the standards of Lord Nicodem.

sorry to say,but this is not even near nicodem's standard. from the day I joined SM,I have been struggling to reach his standards.10 months and 400 posts later,I have ( hopefully) reached one-millionth of his standard.

[Edited on 1-8-2015 by CuReUS]

Thaekross - 1-8-2015 at 17:26

Sorry, I just wish for this topic to stay in organic.... I don't see a lack of scientific discourse, nor any info that Nicodem even knows what discourse means.

"It is not about language or content, it is about discourse" -Nicodem.

Discourse, noun: Written or spoken communication or debate.


ANYWHO, I was going to use HCl gas to chloronate the 1,3-Propanediol to 3-chloropropanol then adding a substituted amine to form a 3-aminopropan-1-ol and further react with more HCl gas to form a 3-chloropropanamine hydrochloride.
Inspired by www.youtube.com/watch?v=bKiXxoRZ_VQ.

CuReUS - 2-8-2015 at 07:21

I liked the video on the synthesis of chloroethanol.I suppose it would work similarly(although there was no chance of an elimination reaction while using ethylene glycol).
but I don't understand why you find it so difficult to find a reference.see the wiki page and try to get the chemical abstracts info on the reaction.Chemical Abstracts 13, 3155 1919 (if you find it,post it in this thread);)

I found this though http://pubs.acs.org/doi/abs/10.1021/cr60160a004 ,also from wiki.It should be of some use.
I hope you have a reference for the amination,that's going to be the difficult part,keeping in mind the moodiness and the madness of the amine nucleophile :D
prins wiki - https://en.wikipedia.org/wiki/Prins_reaction

[Edited on 2-8-2015 by CuReUS]

gdflp - 2-8-2015 at 07:53

Nicodem's been here just a bit longer than you have, I think he has a better idea of what belongs where. Just as a general rule, posts in the Organic section should be thoroughly researched, you shouldn't expect others to search for information for you. Including several references goes a long way.

For example, an OrgSyn search turns up details on the Prins reaction using styrene as the substrate : http://www.orgsyn.org/demo.aspx?prep=CV4P0786 Using higher reaction temperatures favors the diol as the main product instead of the acetal.

Searching JACS turns up Chem. Rev., 1952, 51 (3), pp 505–555 http://pubs.acs.org/doi/abs/10.1021/cr60160a004
as well as many articles on the subject of the mechanism such as
J. Org. Chem., 1968, 33 (5), pp 1873–1876 http://pubs.acs.org/doi/abs/10.1021/jo01269a037 and
J. Org. Chem., 1962, 27 (9), pp 2971–2975 http://pubs.acs.org/doi/abs/10.1021/jo01056a001

The Prins reaction with ethylene or propylene is not going to be very efficient though, yields will be quite low as described in J. Chem. Soc., 1948, 89-93 http://pubs.rsc.org/en/Content/ArticleLanding/1948/JR/jr9480...

Edit: Here is an OrgSyn procedure for the preparation of 3-chloro-1-propanol(trimethylene chlorohydrin) http://www.orgsyn.org/demo.aspx?prep=CV1P0533

To replace the halogen with a nitrogen, if your target is a primary amine, the Delépine reaction may be amenable. Here is an example OrgSyn procedure using the Delépine reaction on a similar substrate http://www.orgsyn.org/demo.aspx?prep=cv5p0121

[Edited on 8-3-2015 by gdflp]

Nicodem - 2-8-2015 at 23:53

Quote: Originally posted by Thaekross  
This part of this post is dedicated to "Scientific Discourse".
Protonation of methanal is preformed by a protic acid to produce an oxonium cation (Specifically an oxocarbenium cation) and resonance removing electrons from the carbon to stabilize the oxygen (thus forming a carbocation), ethene is introduced and electrophilic addition is carried out between the carbocation and alkene. After this, how can I ensure that the formed oxo-carbenium ion is reacted with water at the ionic (carbocatonic) carbon rather than another electrophilic reaction with the nearest saturated carbon to form another double-bond? What conditions would be required?

I hope this is up to the standards of Lord Nicodem. :o

That is not written in a scientific discourse. What you wrote is considered pedagogical discourse (may also be called beginner's discourse by some).
Quote:
Sorry, I just wish for this topic to stay in organic.... I don't see a lack of scientific discourse, nor any info that Nicodem even knows what discourse means.

"It is not about language or content, it is about discourse" -Nicodem.

Discourse, noun: Written or spoken communication or debate.


If you are unfamiliar with worldwide used Latin scientific terms, see definition 5 from Merriam-Webster which is suitable when the word "discourse" is preceded by an adjective (as in "scientific discourse"): a mode of organizing knowledge, ideas, or experience that is rooted in language and its concrete contexts (as history or institutions) <critical discourse>

I don't expect you to study Foucalt's works on discourse, or go to any depth at all in this regard, but it is obvious that if you don't even know what scientific discourse is, or how to master it, then you should limit your topics to Beginnings section only. Using common sense should be enough to comprehend why. After all Organic chemistry is not only an art, it is also a science.

The first google hit on "scientific discourse" gives a good description for you to read:
http://www.wisegeek.com/what-is-scientific-discourse.htm

And like I told you in my private message, from which you quoted without my consent, read the forum guidelines for more information (it is terribly obvious you did not read them).

For examples of scientific discourse see the two posts above. Even the post by CuReUS applies scientific discourse, regardless if it is stylistically and grammatically very different to gdflp's post. As I already told you, scientific discourse is not measured by the language, style or any such thing. Instead, like any other ideological tool, it has to do with intent and method.

CuReUS - 3-8-2015 at 04:35

Quote: Originally posted by gdflp  

The Prins reaction with ethene is not going to be very efficient though, yields will be quite low as described in J. Chem. Soc., 1948, 89-93

I couldn't read the paper(having trouble with my internet),but I am guessing the yield is bad since ethene being a gas will have trouble mixing with the other reagents.that can be fixed,can't it ?
Quote:
To replace the halogen with a nitrogen, if your target is a primary amine, the Delépine reaction may be amenable

he said he wanted to put a substituted amine.Also won't dehydration be a side reaction in the second step of the delepine reaction(refluxing in HCl) ?
nicodem or gdflp,could one of you post that chemical abstracts info that I asked thaeky to find,I wanted to read that,but I couldn't find it.

Nicodem - 3-8-2015 at 06:44

Quote: Originally posted by CuReUS  
I couldn't read the paper(having trouble with my internet),but I am guessing the yield is bad since ethene being a gas will have trouble mixing with the other reagents.that can be fixed,can't it ?

Ethylene should be sufficiently soluble in acetic acid. Propylene is likely not much more soluble and its reaction worked fine for them. Unlike propylene, ethylene cannot undergo the ene reaction mechanism and is also terribly nonreactive compared to styrenes where the addition can result in the formation of a well stabilized carbocations. I would say that the results from that article are surprising, as in surprising that the reaction actually gave sizable amounts of the diacetate at all. It is actually so surprising that I would be tempted considering a termolecular mechanism.
The yields of the experiment described in the article cannot be calculated since they do not report the amount of the propane diacetate obtained after the fractionation, but the impression is that it is completely useless as a preparative reaction. It is only certain that the yield based on trioxane (0.183 mol) as the limiting reagent was more than 2.3% as they mention characterization by degradation of a 2 g sample. It was also not more than 26% as they report the crude mixture of products before the fractionation having the mass of 23 g. Given one of the main isolated products was CH2(OAc)2 and some other unidentified higher boiling compound, the actual yield of the 1,3-propane diacetate is probably in the range of 3-10%, which is surprisingly high.

Quote:
nicodem or gdflp,could one of you post that chemical abstracts info that I asked thaeky to find,I wanted to read that,but I couldn't find it.

The CA13:3155 leads to some irrelevant abstract of some report of certain magnetic materials. It is probably a typo or a mistake in the Wiki review.

Thaekross - 3-8-2015 at 09:47

Aaaahhh, I looked at many definitions without seeing that. But I highly doubt I'l ever write in a more "Scientificly organised" manor. I am sorry, Nicodem, but providing apt information for the parts I didn't understand, would have been helpful (Not complaining).

Back to the Science!
Thank you for the new references gdflp; The second to last reference especially. Alas, I cannot get access to ACS Pubs, they always require money for 48 hours of access to the paper, which is why I am having trouble with finding literature :P I did look for a few days before coming here.

The dioxane paper was interesting, I would have to have a slight excess of Sulphuric acid, or so I understand. Very interesting reaction IMO.

[Edited on 3-8-2015 by Thaekross]