Author Topic: Phenyl Ethyl Alcohol (Read 601 times)

pawan · « **on:** September 23, 2009, 08:05:40 AM »

I am looking for a different & simple route for manufacturing of this chemical.
I know Styrene oxide route & Ethylene oxide route in Mg chlorobenzene (prepared by Grignard reaction of chlorobenzene with Mg). Both of them give low yield.

So can anyone discuss any simpler route.

Goldmember · « **Reply #1 on:** September 23, 2009, 10:37:42 AM »

Not a synthesis, but perhaps certain rose isolates... Rosewater etc. Some contain more than others.

What do you plan on doing with it if you dont mind me asking?

zzhuchila_clocker · « **Reply #2 on:** September 23, 2009, 07:14:59 PM »

i think that yield is not the main issue if the starting materials are cheap. Low yield in case of styrene route is better then the same yield in ethylene oxide-gringard route which is more for laboratory rather then industry.
Do you want to manufacture it in industrial scale, or laboratory scale?

Moriarty · « **Reply #3 on:** September 25, 2009, 05:35:31 AM »

I know what I'd do with 2-phenylethanol but I don't mess with speed. That's just me. Hey, it's very cheap and easy to just buy the stuff. It's like $50 a kilogram.

"Saturated primary alcohols are readily oxidized to aldehydes, which in turn further oxidized to monocarboxylic acids having the same number of carbon atoms.

R.CH2OH---> R.CHO---> R.CO2H

The reaction is frequently effected using alkaline potassium permangamate solution (e.g. Expt. 5.122). Aqueous sodium dichromate/sulphuric acid mixtures may be used, but yields are not always satisfactory because the attendant production of applicable amounts esters...."

-Vogel, The Textbook of Practical Organic Chemistry, 5th Edition, p. 667.

You probably don't even need a reflux condenser as the boiling point of phenylacetaldehyde is ~193C.

chemchem · « **Reply #4 on:** October 05, 2009, 11:52:40 PM »

I looked into this before but it was to get phenylacetaldehyde (phen ethyl aldehyde). I hope the aldehyde isnt used for meth because I broke down and ordered it.

Its one of the main constituents in rose water, I'm pretty sure it smells like roses. I tried a DCM extraction of rose water bought at the store but got nothing out of it. The literature showed a DCM extraction getting the alcohol, along with many others. Not the best route.

I looked into it pretty hard, using scifinder and other programs that search journal articles for structures, can't recall anything I thought was promising.

You can look into fragrance and essential oil places, if you're a company you're golden, I couldn't find any suppliers.

no1uno · « **Reply #5 on:** October 06, 2009, 01:14:32 AM »

The odour of the aldehyde is floral, wouldn't describe it as roses but (fucking horrible, medicine, floral - way too fucking sickly actually)

There is a paper on Syntheses with Styrene oxide where it is the main product of some hydrolysis of the epoxide (the aldehyde I mean), reduction of that - CTH using an alcohol and Urushibara catalysts (reflux in ethanol seems ideal) should give the phenylethanol.

Naf1 · « **Reply #6 on:** October 07, 2009, 12:27:49 AM »

"R.CH2OH---> R.CHO---> R.CO2H"

Dont know about everyone else, but that reads R-CH2OH--->Benzaldehyde----> Benzoic acid. Now unless someone has a synth for phenylacetaldehyde from benzoic acid, it aint happening! It would be useful if someone found a selective oxidation that stopped at benzaldehyde....

@pawan; How about producing phenylacetic acid from phenylalanine as per;
OXIDATION OF SOME ?-HYDROXY-ACIDS WITH LEAD TETRA-ACETATE
http://www.journalarchive.jst.go.jp/english/jnlabstract_en.php?cdjournal=bcsj1926&cdvol=9&noissue=1&startpage=8

Then hydrogenation with Raney's nickel to produce 2-phenylethanol as per;
US Patent 4064186 - Hydrogenation of styrene oxide to produce 2-phenylethanol
http://www.patentstorm.us/patents/4064186/description.html

I think that would be somewhat easier than some of the procedures I have seen so far. Except for the pressure needed for hydrogenation, maybe using a different (easier) reduction of phenylacetaldehyde to 2-phenylethanol?

Moriarty · « **Reply #7 on:** October 07, 2009, 04:36:21 AM »

Um, well the thing about quoting a reference is that you have to quote it just as it appears in the text

. Understand that "R" doesn't necessary stand for benzene. We are talking about 2-phenylethanol. In this case, "R" stands for C6H6.CH2. We are concentrating on the 2-carbon on 2-phenylethanol (C6H6.CH2.CHOH) which will become phenylacetic acid under the condition quoted in Vogel's, 5th.

Are there oxidation agents that stop at the aldehyde, yeah, that and some practices that can isolate them as well prior to further oxidation. One that comes to mind is the classic pyridinium chlorochromate (PCC). It's just complex of chromium trioxide with pyridine and HCl. Also, I think NaOCl oxidizes to the aldehyde but these aren't our goals, or at least I don't think that's what the poster was asking?

Naf1 · « **Reply #8 on:** October 07, 2009, 05:03:34 AM »

I am sorry Moriarty, I was somehow under the impression that the R was referring to a benzyl group. oopps. And looking back you were referring to what you would do with 2-phenylethanol, ohh I remember I saw the chart and thought you were proposing to make 2-phenylethanol via that not phenylacetic acid, sorry! I will read properly in future!

Moriarty · « **Reply #9 on:** October 07, 2009, 07:32:54 PM »

No worries

! This thread is sort of all over the place to begin with, as in, we kind of all hijacked it. The original poster was looking for a phenyl ethyl alcohol synth. I think we all know what he was after so we started putting out ideas but who knows, he might have just wanted to know how to make 2-phenylethanol so he could make the corresponding ethyl bromide with fentanyl analogues on his mind

.

chemchem · « **Reply #10 on:** October 14, 2009, 10:58:44 PM »

I am back to being interested in phenyl ethyl alcohol after my source turned out to be fake

I was really looking for phenethyl aldehyde (phenylacetaldehyde) but no one carries it because of meth.

I'll start looking up some other synthes for it, I thought I could replace it with phenyl acetone but I just found out thats controlled too because of cooks!

Also, I'm not sure I would convert the alcohol to the bromide for fent, maybe oxidize and then react.

My method of extracting with DCM from rose water probably failed because the rose water was probably fake. Who knows... well I guess I could find out.
You would need to separate the other alcohols from the extract though, I think fractional distillation would work but some compounds have bp's very very close to each other.
This is what a paper has to say "The dichloromethane extract of rose water showed higher contents of
2-phenethyl alcohol and lower contents of citronellol, nerol, geraniol, and linalool, as compared with a lower content of
2-phenethyl alcohol and a higher content of citronellol, nerol, geraniol, and linalool in redistilled rose water at higher
temperature and atmospheric pressure, respectively"

Since they are terpenoids wouldn't it be possible to do a polymerization reaction?

I think the best route (unless a good synth is found) is a Cl2CH2 extraction of rose water and then separation, either distill or the polymerization. I dont know though, would chromatography work?

Naf1 · « **Reply #11 on:** October 14, 2009, 11:21:26 PM »

"I am back to being interested in phenyl ethyl alcohol after my source turned out to be fake"

So I am not the only sucker in the international chem trade

Seems to be more and more nowadays (anyone want to swap fake sources? lol).

"I was really looking for phenethyl aldehyde (phenylacetaldehyde) but no one carries it because of meth."

Smart man! I hate to repeat myself, but....
In the link below, phenylalanine can be stirred with nitrous acid (sodium nitrite + HCl). To prepare phenyllactic acid, which can be oxidized to phenylacetaldehyde with lead tetraacetate (red lead oxide + acetic acid). All cheap and easily acquired reagents all OTC. Nitrous acid is prepared by treating sodium nitrite with a mineral acid, the red lead oxide is cheap. The only bad point is the 58% yields of phenylacetaldehyde, also treating the phenylalanine with nitrous acid should be done with careful stirring (not shaking them together)
OXIDATION OF SOME a-HYDROXY-ACIDS WITH LEAD TETRA-ACETATE
http://www.journalarchive.jst.go.jp/english/jnlabstract_en.php?cdjournal=bcsj1926&cdvol=9&noissue=1&startpage=8

chemchem · « **Reply #12 on:** October 15, 2009, 03:25:02 AM »

Quote from: Naf1 on October 14, 2009, 11:21:26 PM

So I am not the only sucker in the international chem trade

Actually, it was a US based company.

And yes, we should swap fake sources so people know who is a scam. Are we allowed to list scammers?

I appreciate the article, I must have went through scifinder for hours with out finding anything good.

I hate how meth cooks ruin it for us chemists that just want personal quantities of material

edit: Just wanted to say that the synth above is the best I've read, and then you would just reduce for the alcohol. The starting materials are easy to obtain and won't raise any eyebrows. The yield is low but the material isn't too bad. The most difficult part is the distillation. I don't think many people would have access to a controlled vacuum. Maybe there is another way? Acid base wash?

Locked · « **Reply #13 on:** October 15, 2009, 07:22:00 PM »

Quote from: Moriarty on September 25, 2009, 05:35:31 AM

"Saturated primary alcohols are readily oxidized to aldehydes, which in turn further oxidized to monocarboxylic acids having the same number of carbon atoms.
R.CH2OH---> R.CHO---> R.CO2H
The reaction is frequently effected using alkaline potassium permangamate solution (e.g. Expt. 5.122). Aqueous sodium dichromate/sulphuric acid mixtures may be used, but yields are not always satisfactory because the attendant production of applicable amounts esters...."
-Vogel, The Textbook of Practical Organic Chemistry, 5th Edition, p. 667.

SWIM tried that exact thing with Phenylethanol and potassium permanganate twice and made a ton of beautiful crappy benzoic acid before digging a little deeper and finding that potassium permanganate cleaves the chain down to benzoic acid, whether you started with phenylethyl or phenylpropanol or whatever as long as the first carbon has a free hydrogen or something. The aldehyde works, the alcohol doesn't, at least not with KMnO4. It was done cold and alkaline.

Sorry I don't remember where the info came from. I really wanted it to work.

Sodium Bichromate gets it done with reverse addition from the smell test, but the reaction wasn't worked up due to not knowing the smell of PAA and expecting a bad smelling post reaction mix. Live and learn.

Sedit · « **Reply #14 on:** October 15, 2009, 07:38:51 PM »

Are you sure that what you had was benzoic acid? I find cleavage unlikely and if you can provide a reference for the mechanism of this cleavage it would be great. It seems far more likely however that you found alot of Phenylacetic acid crystals and tossed them thinking they where BnOOH.

chemchem · « **Reply #15 on:** October 15, 2009, 09:19:36 PM »

Quote from: disposable stirbar on October 15, 2009, 07:22:00 PM

Quote from: Moriarty on September 25, 2009, 05:35:31 AM
"Saturated primary alcohols are readily oxidized to aldehydes, which in turn further oxidized to monocarboxylic acids having the same number of carbon atoms.
R.CH2OH---> R.CHO---> R.CO2H
The reaction is frequently effected using alkaline potassium permangamate solution (e.g. Expt. 5.122). Aqueous sodium dichromate/sulphuric acid mixtures may be used, but yields are not always satisfactory because the attendant production of applicable amounts esters...."
-Vogel, The Textbook of Practical Organic Chemistry, 5th Edition, p. 667.

SWIM tried that exact thing with Phenylethanol and potassium permanganate twice and made a ton of beautiful crappy benzoic acid before digging a little deeper and finding that potassium permanganate cleaves the chain down to benzoic acid, whether you started with phenylethyl or phenylpropanol or whatever as long as the first carbon has a free hydrogen or something. The aldehyde works, the alcohol doesn't, at least not with KMnO4. It was done cold and alkaline.

Sorry I don't remember where the info came from. I really wanted it to work.

Sodium Bichromate gets it done with reverse addition from the smell test, but the reaction wasn't worked up due to not knowing the smell of PAA and expecting a bad smelling post reaction mix. Live and learn.

I'm not sure what you mean. You were trying to oxidize phenethyl alcohol to the aldyhyde and you're saying it was cleaved?
There are also many different ways to do oxidations, especially with primary alcohols. Swern comes to mind.

May I ask how you obtained phenyl ethanol?

Locked · « **Reply #16 on:** October 16, 2009, 04:55:08 AM »

Sure you can ask where I got it. I also wont tell you. It was diversion and had its assay.

The crystals were benzoic acid. The hotwater wash/recrystallization and their MP were what first got me, that and their smell. Oh, and wikipedia has the mp way off. It is less than PAA, not more. The crystals also look different and there are examples online.

The oxidative goal was phenylacetic acid.

I will try to find the info. It was something about a free hydrogen on the carbon next to the phenyl ring and oxidative cleavage. I dug deep after two failures on an easy oxidation. Like I typed, I read all the same "It is super easy to oxidize primary alcohols to carboxylic acids with KMnO4" stuff and all of them are not using phenylethanol. I used cold alkali technique. It was not a hot reflux that would be sure to oxidativly cleave the chain.

I was sort of hoping one of you library wonderkids could have put some more info out there so I could understand it better. I am not trying to steer you away from the hot ticket. I am just trying to help someone not to waste time/money/resources.

The info was probably buried in one of those google book previews. I know it wasn't a real reference or I would have written the journal down on my to look at list.

All of the things you see online are showing the oxidation by KMnO4 of the aldehyde, not the alcohol, and where is a real ref? I would like to hear from anyone that has actually done this.

Prove me wrong. Please. I have 18L of the shit and a grip of KMnO4. But without some real compelling, as in refs backing the KMnO4 oxidation of 2-phenylethanol to phenyl acetic acid, it isn't getting another thought.

Now the dripping addition to refluxing sodium dichromate/sulfuric is another story... Standard "reverse addition" tech.

Acetic acid bacteria might also be the hot ticket to a greener lab. Anyone got those refs? They are using 2-phenylethanol and making PAA with batch reactors and bacteria.

Sedit · « **Reply #17 on:** October 16, 2009, 05:11:44 AM »

Quote

I am not trying to steer you away from the hot ticket. I am just trying to help someone not to waste time/money/resources.

No if you are 100% sure(and non the less at this point) that it is greatly helpful to us all so thank you because I had simular thoughts of KMnO4 on this reaction. Is there any way that you could reperform the experment even on a mm scale and do a small writeup on how it goes?

Goldmember · « **Reply #18 on:** October 16, 2009, 06:49:16 AM »

Yes,permanganate will afford Benzoic acid.This is why I asked my initial question,as Ive not seen or found and easy otc oxidation of the alcohol. Dichromate etc, although not that hard to aquire is still not what Id concider otc.

On a side note, Phenylacetaldehyde.
I know I keep pumping this one,but how about

1) Styrene monomer,Acetone,TCCA to form the chlorohydrin(Courtesy of Smuv from S.M)]
http://jbcs.sbq.org.br/jbcs/2002/v13_n5/27.pdf

2) Phenylacetaldehyde = Chlorohydrin passed over inert catalyst in quartz tube @ 500c
http://v3.espacenet.com/publicationDetails/originalDocument?CC=US&NR=2397412A&KC=A&FT=D&date=19460326&DB=EPODOC&locale=en_gb

Every time I mention this or something simular somewhere it becomes a thread stopper....literally!
Does this seem hard? Am I missing something? Am I a Lepor?

Locked · « **Reply #19 on:** October 16, 2009, 02:51:29 PM »

http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THB-49204NB-3&_user=10&_rdoc=1&_fmt=&_orig=search&_sort=d&_docanchor=&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=dbc12d6700b669bd8e3eb092ff861535

You want otc? Just a quick trip to Home "batch reactor" Depot and you are on your way. Time and large volumes, but the sweetness of it! Just think of the stories you can tell at the next burning man!

Author Topic: Phenyl Ethyl Alcohol (Read 601 times)

pawan

Phenyl Ethyl Alcohol

Goldmember

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zzhuchila_clocker

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Moriarty

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chemchem

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no1uno

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chemchem

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Sedit

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chemchem

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