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Author: Subject: bitter almond benzaldehyde
paccman278
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sad.gif posted on 2-12-2004 at 04:51
bitter almond benzaldehyde


anyone ever xtract benzaldehyde from bitter almond extract? swip has been searching the net for a week now and cant find a bulk amount of the almond, any one know a name of a brand or company that has it in bulk. swip knows how to make it from oxidation of toluene but is looking for a less time consuming way. thanks for saving swip from yet another headache
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[*] posted on 2-12-2004 at 08:45


Benzaldehyde is a list I chemical and watched. If you cannot get oil of bitter almonds locally OTC, I wouldnt recommend to order it from anywhere.

The purification depends on
- the oil, often alcohol and other stuff is added
- what you need it for, different reactions demand different grades of purity, or tolerate certain impurities or not.




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[*] posted on 2-12-2004 at 09:21


I agree with Organikum. You shouldn't try to order "bitter almond oil" or any pure (high %) benzaldehyde product which is sometimes marketed as an "almond" product from anyone, as it is indeed closely watched.

However some retail bottles of synthetic "bitter almond extract" for food flavoring from one of those not-quite-third-world countries contain upwards of 30% benzaldehyde. +water&alcohol
Seperation would be simply by distillation.

YMMV

[Edited on 10-18-2006 by Polverone]
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[*] posted on 2-12-2004 at 15:19


Order cassia(cinnamon) oil instead, refluxing cassia oil with a solution of potassium carbonate gives benzaldehyde in fairly high yields. US Patent 4,716,249 gives this procedure:



EXAMPLE II

Preparation of Natural Cinnamaldehyde and Natural Benzaldehyde

Reaction: ##STR47##

Into a three neck flask equipped with stirrer, thermometer and reflux condenser is placed 10 grams of cassia oil and 100 ml of a 3% aqueous sodium carbonate solution. Boiling chips are added and a water-washed stream of nitrogen is passed over the reaction mass to help prevent oxidation of the formed benzaldehyde. The mixture is heated to reflux and refluxed for a period of 7 hours (100.degree. C.). The resulting material contains 70% benzaldehyde and 30% cinnamaldehyde.



There is another US patent, 4,673,766, which gives a similar procedure that uses cassia oil. I got those two patents from the hive, which is unfortunately down :(. Search the net for "cassia oil" and "bulk" and you should find what you're looking for. I found a supplier where I can get 2 L for about $50 which should yield around 1 - 1.5 L of benzaldehyde. As far as almond oil goes, I wouldn't try it, and the crappy 1 oz of bitter almond oil at the grocery store containing around 20% benzaldehyde for $2.00 is a rip-off . You could also look into synthesizing it by MnO2 oxidation of toluene, and hydrolysis of benzal chloride, which can be easily synthesized.

[Edited on 2-12-2004 by Mendeleev]




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[*] posted on 3-12-2004 at 02:04


yeah swip thought so, he knew benzaldehyde was a list 1, here in so. cal you could buy the bitter almond but not by the bulk although he found a few companies that sell it by the gal. benzalhyde content unknown. swip will go back to the oxidation of tolu. just got tired of chlorine. thanks guys
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Mendeleev
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[*] posted on 29-12-2004 at 20:05


You know what, fuck the DEA, benzaldehyde is restricted, but they can't regulate an essential oil in my opinion. At least I don't think bitter almond oil would actually be considered a LIST 1 chemical since it isn't pure benzaldehyde. So even if it is watched, they can't do anything about it legally. If they get on you about it you can tell them to piss off since it isn't a chem supplier but an aromatherapy store.

[Edited on 30-12-2004 by Mendeleev]




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[*] posted on 29-12-2004 at 21:47


Well if you want to play russian roulette, go right ahead and order a truckload of the stuff.

You can tell the DEA to go fuck all you want, right up untill they decide to show up at your door at 5am.

Of course ordering a reasonably small quantity of "synthetic almond extract" is rather unlikely to provoke such a response, but it's worth being aware that its possible for you to be put on a watch list.

You need to ask yourself - is it worth the risk? Perhaps.
But they're sneaky bastards.
They can and they do regulate anything they want.
See the recent busts involving controlled delivery of certian other essential oils.

The days of mailordering gallons of potential drug precursors without serious threat of problems are over and I'm not afraid to say so.

[Edited on 30-12-2004 by Thermal]
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Mendeleev
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[*] posted on 29-12-2004 at 22:07


What recent busts involving controlled delivery of oils? And anyway they have no legal grounds to do anything. They can watch all they like, they can't do shit because bitter almond oil does not appear in any of their scheduling actions.

EDIT: I happen to be russian ;).

[Edited on 30-12-2004 by Mendeleev]




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[*] posted on 29-12-2004 at 22:57


Benzyl alcohol is sold by the gallon as a solvent for artists and bookbinders artwork restorers , and it should be easy enough to convert to benzaldeyde , probably more cheaply than an essential oil . IIRC , either HCl or Cl can convert the alcohol to the chloride and then that reacted with hexamine gives the aldehyde . Damn , is this place turning into a dope cookers convention ????;):D
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Mendeleev
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[*] posted on 30-12-2004 at 08:56


Yeah, when the hive went down they all fled here. Benzaldehyde is not really a dope chemical exclusively. It's kind of sad it's a list I it's got so many other uses.



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[*] posted on 25-1-2005 at 23:54
the "lazy-ghetto" way


I wanted a small amount of benzaldehyde to try making bisulfite adduct with. So I grabbed from the kitchen a bottle containing "water, 36% alcohol, and benzaldehyde" (the usual artificial flavoring stuff) and saturated some of the liquid with table salt in a large test tube. Then I extracted by shaking it several times with unrefined automotive starting fluid and pipetting off the top layer. This top layer gave a thick mass of white, flocculent adduct when shaken with an alcoholic bisulfite solution made according to Vogel and left to stand for several minutes. Yield of adduct was not determined by weighing because I did not want to dry it. Half the portion of adduct was filtered then while still wet shaken with sodium carbonate solution in a smaller test tube to give a visibly distinct and heavenly-smelling layer of benzaldehyde on top of the aqueous solution. If you're not interested in the behavior of bisulfite adducts, the starting fluid can simply be evaporated away to give fairly pure benzaldehyde, though if done in open air you may well lose much of the aldehyde to oxidation.

This would be a very expensive way to get benzaldehyde if you rely on the usual supermarket flavorings, but I've seen inexpensive containers of up to 300 ml artificial almond flavor at stores that target restaurant-scale customers. And of course the small Lorann Oils containers of pure benzaldehyde ("almond oil";) are also available OTC at specialty cake/candy places. If you need more than 100 grams or so, though, I think the cassia oil method looks much more attractive.




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conducter
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[*] posted on 7-10-2006 at 01:40


hey polverone, swim had been wondering the exact same way to extract the aldehyde from local grocery store artificial almond extract.

If swim didnt want to distill and didnt care about yields, would there be a way to evap the ether without overoxidizing the benzaldehyde? Maybe on very low heat and as soon as the ether is gone wash the benzaldehyde with water/sodium carbonate solution and then store in sealed container?

Also there is a very popular site, not an auctioning site that is selling Lorann Gourmet Brand Bitter Almond Artificial Flavouring, now from what ive read this should be highly concentrated Benzaldehyde and with a wash should be usable as is?

[Edited on 7-10-2006 by conducter]
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[*] posted on 7-10-2006 at 10:23


None of this 'swim' business here, please. I would guess the fastest way to remove ether would be under vacuum, and with that you shouldn't need any heat. If you did want to heat, maybe a small amount of BHT preservative or hydroquinone would minimize oxidation. Lorann bitter almond flavor oil is pure benzaldehyde.



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[*] posted on 7-10-2006 at 17:30


I often order essential oils from a wholesaler out of the pacific northwest, because I make soap to sell at local farmers markets and art shows. Only legitamate oils, mind you, but noticed their policy on oils like brazilian sassafrass and bitter oil of almonds required one to fill out a DEA form, stating the use, expected amount used in a year, and a copy of the formula(e) one expects to use, along with name, address, business license number, and social security number. Too bad, because I noticed most if not all of their oils (legit or no) could be ordered in 5 gallon buckets, or larger, and their prices were VERY reasonable. This is a wholesale operation. They also carry olearesin of black pepper, also reasonably priced, and no DEA form required for that one, as of yet. I wanted to order some oleoresin of black pepper to try to isolate piperine, to try to potentiate my asthma medication, because I'm fucking tired of gasping for air, and extracting from peppercorns is a pain in the neck. But I digress. The moral is, if it's a list 1, don't even think of buying it, if you're into the shady side of the law, which assume most of you aren't. If you're crafty, you can find small amounts of what you're looking for, with no suspicion. good luck.



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[*] posted on 8-10-2006 at 08:43


the Baking Almond flavour around here has also some plant oil in it, what would you say would be the best way to get it out there?

The method described by polverone sounds very good, but i fear the diethylether would also dissolve the oil ... or wouldn't it?

Maybe one should distill the benzaldehyde?
Or where is it more soluble in - in the nonpolar plant oil or in ethanol?
i'd like to avoid distilling if possible.

Thanks for any hint!
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[*] posted on 8-10-2006 at 23:28


I don't think you'd have decent results with anything other than distillation.
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[*] posted on 8-10-2006 at 23:56


Quote:
Originally posted by dr. nick
the Baking Almond flavour around here has also some plant oil in it, what would you say would be the best way to get it out there?

The method described by polverone sounds very good, but i fear the diethylether would also dissolve the oil ... or wouldn't it?

Maybe one should distill the benzaldehyde?
Or where is it more soluble in - in the nonpolar plant oil or in ethanol?
i'd like to avoid distilling if possible.

Thanks for any hint!



It would take the plant oil, but that is left behind in the bisulfite addition product step.

At some point you are likely going to need to distill, depending on what is done to the benzaldyhed after isolation and what other compounds are in the source material.

Quote:

Originally posted by conducter
If swim didnt want to distill and didnt care about yields, would there be a way to evap the ether without overoxidizing the benzaldehyde? Maybe on very low heat and as soon as the ether is gone wash the benzaldehyde with water/sodium carbonate solution and then store in sealed container?


Better to extract while still in ether solution, evap in a distillation type setup to recover the ether and reduce the fire and other health risks. Flush the apparatus with CO2 or other oxygen free gas before heating, ditto for the bottle after filling.

Note that it's not going to take a high temperature to evaporate the ether, use a waterbath and hot plate or immersion heater. non-borosilicate glass can be used.
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[*] posted on 9-10-2006 at 09:09


Hm, i see - so best will probably be to destill the whole almond flavor?. I guess i'd sacrifice a bottle and mix with Ethanol, just to see what happens but i think it won't help much ...

Seems the Almond flavor here does only contain plant oil and benzaldehyd, so how about oxydation when distilling that?

Thanks for the hints!

***edit:

oops, before i forget - when buying aethereous oil of bitter almond - how to get rid of the cyanide?

[Edited on 9-10-2006 by dr. nick]
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[*] posted on 16-10-2006 at 16:33


I'm curious, what is the use for benzaldehyde that the DEA doesn't like?

I'm guessing to make Ph-CH2-CH(-NH-CH3)-CH3 but it isn't obvious to me how that would work.
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[*] posted on 17-10-2006 at 17:37


Methyl benzyl ketone primarily. But that's not something that's preferred to be discusssed here.

Edit: Yea I meant the nitropropene directly -> ketone

[Edited on 18-10-2006 by Thermal]
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[*] posted on 17-10-2006 at 17:55


How is methyl benzyl ketone made from benzaldehyde? I'd think benzyl chloride ( -> benzyl cyanide -> phenylacetic acid) would be more useful for this.
Or do you mean by making phenyl-2-nitropropene and then converting this into the ketone?

In Europe, at least in Germany, benzaldehyde can be obtained from chemical suppliers without any problems (non-watched, non-controlled). It even is really cheap. Synthesis of Benzaldehyde is not a topic in german forums, as anyone can buy it.
Benzaldehyde is nice for simple and fun organic syntheses, like mandelic acid (requires NaCN though), benzoin (also requires NaCN), cinnamic aldehyde and cinnamic acid. Also beta-nitrostyrene (with nitromethane), this forms nice crystals from petroleum ether and has an interesting smell. Benzaldehyde is great for beginners in organic chemistry, as so many things can be made with it.

[Edited on 18-10-2006 by garage chemist]




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[*] posted on 17-10-2006 at 18:59


Quote:
Originally posted by garage chemist
In Europe, at least in Germany, benzaldehyde can be obtained from chemical suppliers without any problems (non-watched, non-controlled). It even is really cheap. Synthesis of Benzaldehyde is not a topic in german forums, as anyone can buy it.
[Edited on 18-10-2006 by garage chemist]


You do realize that you suck don't you? :P

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[*] posted on 17-10-2006 at 19:25


I don't understand the problem anyway, benzyl alcohol can be easily obtained from photography suppliers, which can be neatly oxidised to lovely aldehyde with K2Cr2O7. Did it, and works wonderfully well!

Even if you don't have benzylalcohol, just oxidise toluene... there are threads on this. Ok this may not be a 'just do' effort...its a bit more difficult I suppose.




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[*] posted on 18-10-2006 at 00:11


Quote:
Originally posted by chemoleo
I don't understand the problem anyway, benzyl alcohol can be easily obtained from photography suppliers, which can be neatly oxidised to lovely aldehyde with K2Cr2O7. Did it, and works wonderfully well!

Did you isolate and determine the yield? K2Cr2O7 is inconveniently bulky considering its available oxygen, even if oxygen went 100% to producing aldehyde.




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[*] posted on 18-10-2006 at 01:21


In another thread (sec. alcohol -> ketone) we recently talked about the FeBr3 catalyzed H2O2 oxidation of benzyl alcohols to benzaldehydes in over 80% yield. TCCA/KBr in DCM can also be employed for the oxidation of benzyl alcohol.
I also must say that benzyl alcohol is the best precursor to benzaldehyde you can get, much better than toluene.
I even think it would be worthwhile to make benzyl chloride from toluene, hydrolyze this to benzyl alcohol and oxidise it.
How is the availability of benzyl alcohol in the US?




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