Author Topic: Benzyl Chloride (Read 596 times)

Douchermann · « **on:** February 02, 2009, 05:10:27 AM »

Benzyl chloride is the monochloride of the three possible side chain chlorinated toluenes. This means, it's toluene, but instead of C6H5CH3 it's C6H5CH2Cl, where as benzal chloride and benzotrichloride are C6H5CHCl2 and C6H5CCl3 respectively. It is quite useful, and is moderately easy to produce, however cleanup is not fun at all. Clean-up isn't exactly difficult, until you get to the point where you can no longer see. Thats right, benzyl chloride is a lachrymator, and a powerful one at that. In the presence of water, it hydrolyzes to benzyl alcohol and hydrochloric acid, so it's clear why it burns your water saturated eye so bad. The burn is quite disorienting too, so during cleanup, or anytime you are exposed to the vapors, wear the proper protection (full face mask or sealed goggles. It is also very unhealthy to breathe in the vapors, as your lungs are mostly water as well. Fortunately, the lachrymatory effects are only temporary and cause no permanent damage. I cannot say the same for inhalation however. It is generated by the photocatalyzed free-radical chlorination of toluene, with a slight change. Instead of involving anhydrous chlorine gas, I nixed the chlorine gas all together and went for a much more friendly alternative.

3C6H5CH3 + C3Cl3N3O3 ----> 3C6H5CH2Cl + C3H3N3O3

Into a 1000ml flask, pour 600ml of toluene followed by a few drips of concentrated hydrochloric acid. This will impregnate some toluene with a small amount of hydrogen chloride, which is necessary to initially kick off the reaction. Set the flask up for reflux with a thermometer in the second neck, and a plain stopper in the third, and begin heating on an oil bath. Remove the glass UV filter from your halogen lamp, and get it as close as possible to the flask. Set up a fan to blow air across the flask, at a moderate to high rate. This is because you will be opening the flask fairly often, and when you have a 600watt halogen lamp next to a flask spewing boiling toluene vapors, there WILL be a fire. I started a fire my first time doing this. However, a fan will completely negate the chance of a fire.

Once the toluene has started warming up, measure out 90g of trichloroisocyanuric acid (TCCA). Add a small amount of the TCCA to the hot toluene and close the flask back up. Note, you can not add the TCCA through the condensor. The coils will form condensation and the TCCA will stick to this. Not only will you lose TCCA, but it's also a pain in the ass to clean. It must be added through the only unused neck. Repeat the small additions until all 90g has been used up. This should take 30 min to 1hr to complete and the boiling toluene should be milky white, due to precipitated cyanuric acid. Remove heat and let it cool down

As soon as the mixture is decently cool, it should be a clear liquid (varying from water white to yellow) above a white precipitate. Filter off the precipitate, which is cyanuric acid. It is almost necessary to use vacuum filtration here, otherwise it will take the rise and fall of three succesive galaxies to complete filtration. Rinse 3 portions of toluene through this. Read the notes at the bottom for suggested uses of the cyanuric acid on the filter paper. Add your filtered solution to a distillation apparatus and begin simple distilation. At first you will collect a very large amount of toluene which can be reused. approximately 500ml, read notes below for purification. Then, switch flasks and collect the portion coming over at 175-185C. This is relatively pure benzyl chloride. Redistil with a fractioning column, collection the portion between 178-182C for pure benzyl chloride. Theoretical yeild = 147g (134ml). Mine was 106g (72%) but I spilled a lot of TCCA.

Cleanup:

All flasks that came in contact with benzyl chloride should be treated with a hot 5% sodium hydroxide solution. This will hydrolyze all benzyl chloride into benzyl alcohol and sodium chloride. Afterwhich, soap and water will clean the equipment completely. Cyanuric acid can be removed by treating with dilute sodium hydroxide solutions, and excess TCCA treated with dilute hydrochloric acid.

Notes:

The cyanuric acid can be used to prepare sodium cyanide. Reacting sodium cyanide and benzyl chloride will give benzyl cyanide, a useful reagent.

The toluene distilled off should be well shaken with sodium bicarbonate until it registers neutral. It is then dried using magnesium sulfate or calcium chloride. It can be filtered and used directly from this to produce more benzyl chloride. However for anything else it should be redistilled, collecting fractions between 108-112C.

Vesp · « **Reply #1 on:** March 24, 2009, 11:53:52 PM »

Quote

The toluene distilled off should be well shaken with sodium bicarbonate until it registers neutral. It is then dried using magnesium sulfate or calcium chloride. It can be filtered and used directly from this to produce more benzyl chloride. However for anything else it should be redistilled, collecting fractions between 108-112C.

If it is going to be reused to make more benzyl chloride, why do you need it to register neutral? can't you just use it as is?

Sedit · « **Reply #2 on:** April 03, 2009, 07:22:27 PM »

I would think because if there is BnCl still present one would want to rid it before handling it anymore. BnCl can be a bitch to deal with and where as Iv never had a face full and worked with ventilation your eyes will still feel as though they have sand in them from even the smallest exposure.

Douchermann · « **Reply #3 on:** April 10, 2009, 09:03:24 PM »

That was actually poor wording on my part.

The toluene distilled off should be well shaken with sodium bicarbonate until it registers neutral. It is then dried using magnesium sulfate or calcium chloride. It can be filtered and used directly from this to produce more benzyl chloride. However for anything else it should be redistilled, collecting fractions between 108-112C.

It meant to say:

The toluene distilled off should be well shaken with sodium bicarbonate until it registers neutral. It is then dried using magnesium sulfate, or calcium chloride, and redistilled collecting fractions between 108-112C. However, if it is to be used again for producing more benzyl chloride, it can be used directly, without neutralization.

Reaminator · « **Reply #4 on:** April 28, 2009, 08:32:06 PM »

What is the point in adding a "few drips of concentrated hydrochloric acid"?

It does not make much sense to add an acid and water given the side chain chlorination is a radical chain reaction. Moisture would only promote ring chlorination by forming electrophilic chlorine species, and HCl would get consumed by TCCA anyway while unnecessarily forming Cl2. The N-Cl bond in TCCA is just as easily homolyticaly cleaved as the Cl-Cl in chlorine, maybe even easier (bond energy of N-Cl is about 200kJ/mol vs. 239kJ/mol for Cl-Cl, see http://butane.chem.uiuc.edu/cyerkes/Chem104ACSpring2009/Genchemref/bondenergies.html). After all, during the radical side chain bromination of toluenes with N-bromosuccinimide (NBS) one does not add any HBr.

In the original published method for the side chain chlorination of toluene with TCCA (JOC,56, 1970, 719-722) they do not add any hydrochloric acid (BTW, why didn't you cite that paper?). Instead of using dibenzoyl peroxide as radical initiator like they did you can just use a halogen lamp like you did (which is known to work much better for side chain chlorinations of toluene when compared to Bz2O2).

Also, how much was the cca. 160°C fraction corresponding to o- and p-chlorotoluenes?

Douchermann · « **Reply #5 on:** April 28, 2009, 09:16:26 PM »

If there is nothing to initiate the reaction, it will do nothing, then spontaneously react at an unexpected time. Vesp has seen personal accounts of this, and it makes a terrible mess (and is quite violent). The HCl is added to initiate the reaction. If using toluene recycled from benzyl chloride production, the addition is unnecessary (unless it is purified heavily). As for the fractions, the fractional column I owned did not last long, and unfortunately was never used during distillations. There were never sharply defined fractions, but distillate was collected from 108C up to 175C in a very linear temperature increase. Any distillate between 160-175C couldn't be more than 10-15ml. This was simply recycled for producing more benzyl chloride, so I don't know how much of the side-chlorinated products were produced, however yield of benzyl chloride has always been above 70% so I can't imagine it was much.

Sedit · « **Reply #6 on:** April 28, 2009, 09:27:52 PM »

I can validate this runaway reaction also. I use Ca(OCl)2 which causes the same occurance if HCl isn't added to add some free chlorine to initiate the reaction. If no HCl is added when it reaches the BP of toluene then the reaction startes and will quickly runaway producing temperatures exceeding 300 degreess F in a matter of 20 seconds or so cracking many forms of glass that are not Borosilicate. Not to mention from the excess heat you will have side reactions and worst of all free BzCl in the air if your not careful.

Where as I agree that it is not needed I feel it is something that one should add if they would like to have any control over the reaction what so ever.

Reaminator · « **Reply #7 on:** April 29, 2009, 08:01:37 PM »

Quote from: Douchermann on April 28, 2009, 09:16:26 PM

If there is nothing to initiate the reaction, it will do nothing, then spontaneously react at an unexpected time.

A runaway is normal since you were attempting to do the reaction at a temperature about 30°C higher than the one reported in the literature. CCl4 boils at 77°C while toluene at 111°C. You shouldn't have made such drastic modifications to the original procedure.

Quote

The HCl is added to initiate the reaction.

I don't understand this logic. How can HCl initiate a radical chlorination? On the other hand it is known that it will initiate the electrophilic chlorination. But your desired product was benzyl chloride and not the chlorotoluenes.
Again, like I said, I just find it unusual and counterintuitive to contaminate the reaction mixture with water and HCl. The rate of electrophilic chlorination of toluene is slow with Cl2 even at elevated temperatures, but in the presence of moisture or protic solvents toluene is rapidly chlorinated at the ring positions. Therefore the addition of HCl(aq) which reacts with TCCA to form Cl2 is extremely weird if the desired compound is the product of radical rather than electrophilic chlorination.
In my experience, refluxing TCCA in excess toluene/water mixture gives a complex mixture of product, which after extraction and rotavaping consists of:

o-Chlorotoluene ( 5.4 )
p-Chlorotoluene ( 2.8 )
Benzyl chloride ( 1.4 )
4-Chlorobenzyl chloride ( 1.3 )
4-Chlorobenzyl chloride ( 1.0 )

The ratio of products is in the parenthesis (normalized toward the lowest component) and is estimated from proton NMR spectra. The goal was electrophilic chlorination of the ring and the radical chlorination of the benzylic position came as an (unpleasant) surprise.
As you see, the presence of large amount of water leads to the electrophilic mechanism prevailing. In your case where there was just a little water present you should obtain more benzylic chlorination products than chlorotoluenes, but still... Another experiment where a mild acid, acetic acid, was added to the same reaction mixture and this allowed to stir in dark for a couple of days at room temperature, lead only to electrophilic chlorination (no benzylic chlorination was observed). Therefore even with such a mild acid like acetic one gets the same result as did Juenge et in the previously mentioned JOC paper where they used aqueous H2SO4 or AlCl3.
As a side note… Allylic chlorination with TCCA was first reported already in the seminal paper by Ziegler et all (Liebigs Ann. Chem., 551, 1942, 80–119), the guy from which this radical halogenations of allylic and benzylic positions using haloimides got its name. They chlorinated cyclohexene and obtained 3-chlorocyclohexene in 29% yield (NCS, which is less electrophilic than TCCA and thus less prone for side reactions, of course gave better yields on this substrate). Obviously they added no acid, just the radical initiator.

Quote

As for the fractions, the fractional column I owned did not last long, and unfortunately was never used during distillations. There were never sharply defined fractions, but distillate was collected from 108C up to 175C in a very linear temperature increase. Any distillate between 160-175C couldn't be more than 10-15ml. This was simply recycled for producing more benzyl chloride, so I don't know how much of the side-chlorinated products were produced, however yield of benzyl chloride has always been above 70% so I can't imagine it was much.

So you are essentially giving us the yield of the mixture of chlorinated products? There is absolutely no way you could have got any separation between the benzyl chloride and the chlorotoluenes without fractionation trough a distillation column. Compounds with such close bp simply do not separate with only 1 theoretical plate distillation. Don't get me wrong, I like your experimental efforts and this is supposed to be constructive criticism, but I simply can not trust your word that you obtained pure benzyl chloride just for one simple reason: you present no convincing analytical evidence. From what we know you could have something like a 50:50 mixture of benzyl chloride and chlorotoluenes. The bp interval would still be more or less like the one you reported. I think it is very important that when you do a modification of a published method you also independently confirm you obtained the same product by analytical evidence or derivatization.

Douchermann · « **Reply #8 on:** April 29, 2009, 08:46:54 PM »

I'm curious, have you ever attempted this method? How about the published method, have you ever attempted that? As for the carbon tetrachloride solvent, that defeats the purpose of being OTC. Also, chlorine forms free radicals under UV light, which I specifically stated is used in this procedure. You may call it a modification to the procedure, I call it an improvement; it was designed around the ability to buy the materials OTC. I can make one trip to the hardware store and have enough chemicals to produce a couple liters of benzyl chloride. The shipping alone on carbon tetrachloride would cost as much as the hardware trip including gas and a beverage. The amount of water used in almost insignificant

It was you that also stated the chlorotoluenes boil around 160C, whereas I didn't take product until 175C, which also redistilled starting at 178C. When did I ever say I included all of the chlorotoluenes?

Reaminator · « **Reply #9 on:** April 29, 2009, 10:46:14 PM »

Quote from: Douchermann on April 29, 2009, 08:46:54 PM

I'm curious, have you ever attempted this method? How about the published method, have you ever attempted that?

No, if I need benzyl chloride I just buy it. It is too cheap to bother with. The goal in my experiments was not radical but electrophilic chlorination instead.

Quote

As for the carbon tetrachloride solvent, that defeats the purpose of being OTC.

Who said you need CCl4? Toluene is a liquid so you don't need a solvent for it. In the JOC paper they used CCl4 just to have controlled reaction parameters rather than have the substrate in excess (it was a reactivity study, not preparative reaction optimization). CCl4 is the most common solvent for radical halogenations, but you don't need it when you can just use a large excess of a liquid substrate. You do have to control the temperature by other means though, like using a thermostated bath, for example.

Quote

Also, chlorine forms free radicals under UV light, which I specifically stated is used in this procedure. You may call it a modification to the procedure, I call it an improvement; it was designed around the ability to buy the materials OTC.

Are you insinuating that it was your idea to use light instead of dibenzoyl peroxide? This is a general method of the benzylic halogenations and the Wohl-Ziegler reaction. You would know this if you would bother to add literature references to your posts. There are literally hundreds of examples in the literature where a mercury lamp or other source of UV to near-UV is used, even plain wolfram lamp works. Also, the UV light does not even go deep enough in the reaction medium to be of much relevance. It is mainly the near-UV and visible light that gives useful homolytic cleavage of N-X and X-X bonds. You could at least check the review in Kirk?Othmer Encyclopedia where there is a whole chapter dedicated to toluene chlorination. In the industrial processes visible light that has a better penetration is used (cca. 500 nm).

Quote

It was you that also stated the chlorotoluenes boil around 160C, whereas I didn't take product until 175C, which also redistilled starting at 178C. When did I ever say I included all of the chlorotoluenes?

Before, I interpreted your work as if you were fractionating your products. It wasn't till your previous reply that I realized you never separated the chlorotoluenes from your product. A mixture of chlorotoluenes and benzyl chloride can not be separated without a very efficient distillation column. That you did not start to collect your product until 175°C does not mean that you were collecting benzyl chloride (mixtures do not boil at the bp of the lowest boiling component!). Unless there is contious liquid/gas equilibration on a long enough column, you can not say which component is distilling from the temperature of the vapours. For example, try distilling water from glycerol and you will see how the temperature of the distillate has little to do with the 100°C bp of water. You should definitively read upon the theory behind distillation, fractionation and liquid/gas equilibriums (Henry's and Raoult's laws). Distillation without a column is not even considered as a separation technique in chemistry unless the difference in boiling points between the components is more than 100K. Simply distilling compounds with the difference of less than 20K gives no separation whatsoever, and I can tell you this from experience. With your distillation you removed most of the toluene and most of the dichlorinated side products, but the question of yield and purity still remains open.

Vesp · « **Reply #10 on:** April 30, 2009, 01:01:25 AM »

Quote

No, if I need benzyl chloride I just buy it. It is too cheap to bother with. The goal in my experiments was not radical but electrophilic chlorination instead.

This is a benzyl chlorde thread, not a chlorotoluene thread. Feel free to make a chlorotoluene thread though since that seems to be what you are interested in.

HCl is not only consumed, but it is also produced in the reaction. The added HCl is to initiate the reaction. chlorine and toluene can produce benzyl chloride and hydrogen chloride. The hydrogen chloride continues to produce chlorine from the TCCA.

Douchermann wasn't claiming to have invented chlorination using UV light.

Don't let this get out of control in discussion. I don't want any flame wars.

Douchermann · « **Reply #11 on:** April 30, 2009, 04:15:29 AM »

I can't imagine I'm making a typo on my part, but I can not see where you keep finding these claims that you think I'm making?

Quote from: Reaminator on April 29, 2009, 10:46:14 PM

Are you insinuating that it was your idea to use light instead of dibenzoyl peroxide? This is a general method of the benzylic halogenations and the Wohl-Ziegler reaction. You would know this if you would bother to add literature references to your posts.

I would never make an outrageous claim such as that. I was merely responding to this:

Quote from: Reaminator on April 29, 2009, 08:01:37 PM

Therefore the addition of HCl(aq) which reacts with TCCA to form Cl2 is extremely weird if the desired compound is the product of radical rather than electrophilic chlorination.

So I responded with this:

Quote from: Douchermann on April 29, 2009, 08:46:54 PM

chlorine forms free radicals under UV light, which I specifically stated is used in this procedure.

On a similar note
This is what you said:

Quote from: Reaminator on April 29, 2009, 08:01:37 PM

A runaway is normal since you were attempting to do the reaction at a temperature about 30°C higher than the one reported in the literature. CCl4 boils at 77°C while toluene at 111°C. You shouldn't have made such drastic modifications to the original procedure.

So I responded with this:

Quote from: Douchermann on April 29, 2009, 08:46:54 PM

As for the carbon tetrachloride solvent, that defeats the purpose of being OTC.

And you came back with this:

Quote from: Reaminator on April 29, 2009, 10:46:14 PM

Who said you need CCl4? Toluene is a liquid so you don't need a solvent for it. In the JOC paper they used CCl4 just to have controlled reaction parameters rather than have the substrate in excess (it was a reactivity study, not preparative reaction optimization). CCl4 is the most common solvent for radical halogenations, but you don't need it when you can just use a large excess of a liquid substrate. You do have to control the temperature by other means though, like using a thermostated bath, for example.

99% of the benzyl chloride I produce is immediately turned into other, more useful products with purification methods more fitting to my current set-up/budget, such as benzaldehyde or benzyl cyanide. Using my benzaldehyde synthesis (via sommelet) I routinely obtain yeilds >75%, which is quite close to what is claimed in research papers and patents IIRC. This is the ultimate reason I assume my benzyl chloride to be of sufficiently high purity. You are right, there could be side chlorinated products in there, but they would be small percentages of the final product. If I were to attempt a synthesis such as benzyl piperazine, I would consider fractional distillation of the benzyl chloride before hand, but when being turned directly into benzaldehyde, it is simply not worth my time.

Frankly, I don't quote research papers for the simple reason that I don't need to prove something works while I'm proving that it works. If I were theorizing, I might quote some examples as to why I think a method might work, but when I'm posting success, I see it pointless.

The majority of this argument has just been about us criticizing eachother on what we say, and has very little actual scientific realization or collaboration in it. I understand the points you are making, don't take me wrong, however if I was concerned with ACS purity standards, I would have made the effort to buy the benzyl chloride. I also don't claim that the first distillation is pure, but I did mention to fractionate the benzyl chloride after the bulk distillation.

Vesp · « **Reply #12 on:** April 30, 2009, 11:18:46 PM »

being slightly off topic, the benzaldehyde produced from this benzyl chloride would still contain the small amounts of chlorotoluenes. I think an easy way of purifying at least the benzaldehyde would be with a bisulfite adduct. I could be wrong though and should really look more into it.

Douchermann · « **Reply #13 on:** May 01, 2009, 01:59:01 AM »

Good point, I forgot chlorotoluenes can be steam distilled.

Happyman · « **Reply #14 on:** June 27, 2009, 04:06:50 AM »

Since I would probably have to get trichloroisocyanuric acid at a chemical supplier I would much rather go on the apparent benzyl alcohol & HCl reaction. Does anyone anything about this reaction? And how would I go about extracting benyl alcohol from an OTC source like mouthwash?

Douchermann · « **Reply #15 on:** June 27, 2009, 06:56:31 AM »

Haha mouthwash is about 1% or less benzyl alcohol. Go to any hardware store and into the pool section and you can find it.

Vesp · « **Reply #16 on:** June 27, 2009, 07:11:55 AM »

Yeah TCCA is a very common chlorine source for pools.

Bubbling chlorine gas in at a slow rate is also supposed to work IIRC.

Happyman · « **Reply #17 on:** June 28, 2009, 11:08:53 PM »

One percent! I thought they had to order ingredients from Greatest to Least?! Oh well.... However with straight mouthwash a colorless liquid did magically precipitate. This happened in small quantities but if more spontaneously generates I'll certainly post pictures.

Vesp · « **Reply #18 on:** June 29, 2009, 01:47:43 AM »

I fell for that listing as well, is it perhaps in alphabetical order like mine was?

Sedit · « **Reply #19 on:** June 29, 2009, 02:28:30 AM »

No need for mouthwash if you want OTC BnOH look at Old Spice. It is something along the lines of 30-40% BnOH. I found this out after dumping 3 bottles of it down the drain because my daughter took a bath in it.

The big bottle I have here is 125ml so at 30% your looking at 37.5 ml of BnOH or 39.15 grams of Benzylalcohol. If your hard up I guess you could do it. Sure beats 1% mouthwash

Vesp · « **Reply #20 on:** June 29, 2009, 04:44:04 AM »

What is Old Spice? The cologne?
Do you know the other chemicals in it as well?

Sedit · « **Reply #21 on:** June 29, 2009, 04:53:38 AM »

Yeh the cologne.

Ethanol/SD Alcohol 40
Benzyl alcohol
Water
Fragrance(s)/perfume(s)

OTC Benzyl alcohol.
http://whatsinproducts.com/search_ingredients_result.php?chemicalId=142&PHPSESSID=5259

2bfrank · « **Reply #22 on:** July 02, 2009, 05:12:12 AM »

Quote from: Vesp on June 27, 2009, 07:11:55 AM

Yeah TCCA is a very common chlorine source for pools.

Bubbling chlorine gas in at a slow rate is also supposed to work IIRC.

Pool shops also can have oxone, potassium peroxymonosulfate, which was very much a surprise. It is a non-chlorine oxidiser with lots of uses.

2bfrank · « **Reply #23 on:** August 15, 2009, 02:49:22 AM »

Electrochemical chlorination of toluene in two phase electrolysis.

Been meaning to include what looks like a pretty user friendly prep of 2 phase oxidation of toluene to Benzyl chloride and the additional generation of minute amount of chlorotoluenes and overall looks might good. Obviously, well at least with respect to one other paper, that confirms the potential for 2 phase electrochemical, this set up could indeed be used for other type reactions that go through a typical free radical chain reaction pathway. This procedure is very applicable to the formation of Chloroform, and appears to have some good overall scope. I will dig up that 2 phase chloroform prep, as it is of interest and may be handy for a member here
One potential issue, is this paper using chloroform as the solvent that the toluene is added for the hydrocarbon phase and uses aquarius sodium chloride the other phase . I see that their would be no issue of using a cell with just toluene, for the hydrocarbon phase of this said reaction and separation obtained by the b.p differences, of toluene and benzyl chloride

2b

Sedit · « **Reply #24 on:** August 15, 2009, 03:00:46 AM »

I have not read the paper yet(Recently anyhow) but there could be a problem when using neat toluene because the solvent may be in place to prevent formation of benzal chlorides or possibly aid the mediation in the formation of benzyl chloride instead of the ring substitued product.

Chloroform is no real problem for the home chemist to synthesis other then the large bulk of the reaction. See the chloroform theed in other
chemistry.

[edit]

After a quick review what does every one think about Pb electrodes as instead of Pd electrodes? Other then them I would be all set to perform this quick experiment after a little cleaning and polarizing my cell.

2bfrank · « **Reply #25 on:** August 15, 2009, 03:05:57 AM »

yeah, didn't consider that, but chloroform aint such a hurdle, and can easily be obtained by for starters a 2 phase electro prep, and the known ones all over the place. THis paper albeit that one issue, looks pretty good, and it was sort of obvious, and on the cards but a paper is handy, etc...

Vesp · « **Reply #26 on:** August 15, 2009, 03:45:32 AM »

Very interesting! I bet graphite electrodes would work with out much of a problem, I don't know about lead. Just something that doesn't react with the chlorine being formed, so essentially whatever works in a chlorate/hypochlorite cell.

It seems the function of the chloroform is to simply sink the toluene. That means that other solvents that will not interfere could be used. Possibly tetrachloroethylene, which is more OTC then chloroform, could be used as well if it didn't react.

Sedit · « **Reply #27 on:** August 15, 2009, 03:51:45 AM »

No need for anything fancy as DCM is always there as a nice little backup. That will be my first choice here and it shares many properties with Chloroform as well. Temperature controle will be a bitch and I may just have to cut down to a really long cell run and cut the ampers down to something like 500ma without strong external cooling.

Vesp · « **Reply #28 on:** August 15, 2009, 04:01:38 AM »

Well, then it will float. I think this could cause problems - such as the Cl2 floating up and dissolving into the organic layer..but perhaps that won't matter. It just seems weird that they would go through the effort to keep it on the bottom using chloroform if it doesn't have some other use.

Sedit · « **Reply #29 on:** August 15, 2009, 04:03:21 AM »

?HUH?

DCM is a bottom puller Vesp. Not much different the Chloroform at all.

[edit]
hey cool look if you put 4? marks in a row it creates that lil confused face.

Vesp · « **Reply #30 on:** August 15, 2009, 04:06:51 AM »

Oh shit you are right. WTF am I thinking.
Ha, I dunno I must have been thinking of ethyl acetate or some other solvent. It has been a while since I've messed with it, as if that isn't obvious.

2bfrank · « **Reply #31 on:** August 17, 2009, 09:34:04 AM »

I rechon DCM would be fine, but could possibly compete, as the very same sort of conditions use DCM to produce CHCl3... if memory serves me correct... I think Ill try both and see what occurs... and the graphite as youve suggested should be okay. I am not that up with electostuff, but kind of like it..and think I have read, or heard that carbon can sort of replace the electrode in the paper... similiar over potential or something.
tomorrow is the day for this for me..Ill try and find that DCM>CHCl3 2 phase prep.. I am going to have to sort my files, and perhaps take the offer to put them up to share...

2b

lugh · « **Reply #32 on:** August 17, 2009, 12:12:19 PM »

Toluene and benzyl chloride form an azeotrope, which can be separated using azeotropic distillation by adding isopropanol to form the lower boiling point azeotrope with toluene

The toluene-isopropanol can be separated by adding water, the isopropanol-water mixture can be separated using sodium chloride

2bfrank · « **Reply #33 on:** August 18, 2009, 12:42:59 AM »

Thats good to hear about. I have avoided this, and lack experience, but if adding a determined amount of isopropanol to the mix, and this holding the toluene, and can be simply distilled of, well its good news indeed.
Less work perhaps, all the better, ill check out these b.p's of these azeotropes, Thanks lugh indeed..

ps.. Benzyl acetate prep, electro.. Didn't know where to post it.. Similiar to Mn3+ > the honey. Apologies if already posted.

POSEIDON · « **Reply #34 on:** September 06, 2009, 07:21:33 PM »

hey swip found this in orgsyn check out

lugh · « **Reply #35 on:** September 27, 2009, 05:32:55 PM »

The isopropanol-toluene azeotrope boils at around 80 degrees Centrigrade at STP, and contains at least 50% isopropanol unless one lowers the pressure down to aboout 20 mm Hg

One can use methanol in the same manner, but since the methanol-toluene azeotrope contains less toluene than the isopropanol-toluene azeotrope it's best to use isopropanol

no1uno · « **Reply #36 on:** September 28, 2009, 11:26:49 AM »

Quote from: Sedit on June 29, 2009, 02:28:30 AM

No need for mouthwash if you want OTC BnOH look at Old Spice. It is something along the lines of 30-40% BnOH. I found this out after dumping 3 bottles of it down the drain because my daughter took a bath in it.

The big bottle I have here is 125ml so at 30% your looking at 37.5 ml of BnOH or 39.15 grams of Benzylalcohol. If your hard up I guess you could do it. Sure beats 1% mouthwash

Or even better (probably also cheaper) Benzyl Benzoate is in most (if not all) chemists/pharmacies for Scabies/Head lice treatment (avg seems to be around 25% emulsion - in about 200mL packs [approx $9-10], so what, 50g of the ester/pack [1 mol of the ester = 212.2g = 0.236 mol/pack], hydrolysis of which would give 0.24mol of both Benzyl alcohol [25.5g]and benzoic acid [28.8g - yeah I know, it don't add up, think about the extra OH before you post;)])...

It is also available for Horses, so vet supply shops should stock it in far larger qty's for a cheaper price / L.

Author Topic: Benzyl Chloride (Read 596 times)

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