Sciencemadness Discussion Board

2-chloroethanol

Picric-A - 30-7-2009 at 15:59

I have read about many ways to produce this compound, some look more simple than others.
2-chloroethanol is very usefull in organic synthsis. My intended use of this compound is in the synthesis of tetracaine, a potent yet disused ester type local anasthetic derived from 4-ABA.
Here i will list the methods i have found and if anyone has any comments to make on their reliability, yield ect. please comment.

1)2-Chloroethanol is produced by treating ethylene with hypochlorous acid:
CH2=CH2 + HOCl → HOCH2CH2Cl
(source- wikipedia)

2) bubbling a mixture of carbon dioxide and ethene through a suspension of bleaching powder (calcium hypochlorite) in water)
(source- 'Organic Chemistry' by P.J.DURRANT)

3) bubbling hydrogen chloride through ethylene glycol at 100deg.C. This formed water and 2-chloroethanol. at higher temps. ethane dichloride is formed.
(source- 'Organic Chemistry' by P.J.DURRANT)

So as you can tell 1 and 2 both rely on the action of hypochlorous acid on ethene, number 2 is just one of the many methods of perfomring number one,

I am most interested in number two however. both reagents, HCl and glycol are cheap and the prodedure seems simple.
The book says that HCl should just be bubbled through the glycol at 100deg.C and doesnt mention anything else. Because this reaction produces water i am guessing if conc sulphuric is added to this mix it will make it react quicker however my guess is the reason the reaction should be kept at 100deg.C is to boil off the water as it is formed. This however poses the problem of the 2-chloroethanol having a b.p. of around 120deg.C so msot of your product will boil off with the water. Can this problem be solved by refluxing the mix and adding conc sulphuric? this reaction would then resemble an esterification reaction between the glycol and HCl.


not_important - 30-7-2009 at 16:27

Adding H2SO4 will promote the formation of 1,4-dioxane with a boiling point of 101 C.

You should be able to distill both water and 2-chloroethanol off, they're both products so removing them from the reaction mix is not harmful to yields. You can fractionate them later to get the 2-chloroethanol.

BTW - 2-chloroethanol is fairly toxic and considered a carcinogen.

Methods 1 & 3 work, no idea as to how well 2 does.

Picric-A - 30-7-2009 at 16:32

Well if you are saying 1 works, two must work. 2 is simply forming the HOCl in situe by the reaction between Ca(ClO) and CO2 according to;
CO2 + H2O --> H2CO3
H2CO3 + Ca(ClO) --> 2HClO + CaCO3

garage chemist - 30-7-2009 at 18:09

Ethene and HOCl (from bleaching powder and CO2) will give a dilute aqueous solution of 2-chloroethanol. Isolating the pure substance from this is impossible via distillation, as it forms an azeotrope with water that also has a boiling point close to 100°C, IIRC.

The ethylene glycol/HCl method would be better suited to produce a relatively concentrated product.
One would bubble HCl gas into glycol at 100°C in a distillation setup until the glycol has disappeared. The distillate is then fractionated.
Don't add H2SO4 to this, it will make dioxane, as already said. The water of reaction will be found in the product, but it isn't much as you'll see if you calculate the stochiometry.

There is another method described in Vanino, Handbuch der präparativen Chemie Band 2 from 1937, that is refluxing ethylene glycol with disulfur dichloride for 3-4 days.
The reaction mix is diluted with ether, filtered from byproduct sulfur, shaken with moist K2CO3, dried with dry K2CO3 and fractionated to obtain the ethylene chlorohydrin. 100g glycol and 250g S2Cl2 give about 100g chlorohydrin.
This procedure has the great advantage to give an anhydrous product in relatively good yield, which is worth the long refluxing IMO if one is after the pure compound.

Another method is to simultaneously bubble chlorine and ethylene into stirred cold water.
Since chlorine in water dissociates to HOCl and HCl, this is similar to the bleach method.
Only dilute solutions of chlorohydrin can be obtained this way (maximum 14-15%) since already at 8% chlorohydrin, the side reaction of chlorine addition to ethylene giving 1,2-dichloroethane becomes noticeable and becomes the main reaction once a separate phase of 1,2-dichloroethane has been formed.

An interesting method of isolating the chlorohydrin from its aqueous solution is given: the solution is saturated with anhydrous sodium sulfate at 32°C, decanted from any indissolved solid, left to cool without disturbing it and then a seed crystal of sodium sulfate decahydrate is added. The supersaturated sodium sulfate solution crystallizes and the chlorohydrin separates as an oily phase on top of it. It is decanted, dried with Na2SO4 and rectified to give pure chlorohydrin.

Ethylene chlorohydrin is of special interest because of its use as a lab precursor to ethylene oxide- just add it to cold concentrated KOH solution.

[Edited on 31-7-2009 by garage chemist]

ammonium isocyanate - 30-7-2009 at 19:26

The classic synthesis of propylene oxide proceeds via a propylene chlorohydrin intermediate. It can be produced by bubbling chlorine and propylene gas through an aqeous solution of a metal hydroxide. I'm not sure what the reaction conditions or yields are, but I plan on trying it soon. The yeilds I assume are relatively high since it is the main method used in industry. According to garage chemist, the same method would produce the ethylene chlorohydrin intermediate. I imagine that performing an analogous reaction to the one I plan on attempting, using instead ethylene at elevated temperature, and collecting the epoxide as it boils over (which would probably be pretty concentrated, even if it does form a low-boiling allotrope with water, due to the large differences in polarity and boiling points) would allow for the production of relatively concentrated ethylene chlorohydrin by gassing with HCl.

It would be a roundabout method of production, but it might be worth a try.

Filemon - 31-7-2009 at 11:43

The reduction chloroacetaldehyde with Fe + HCl, 1:2 (chloroacetaldehyde: Fe). The iron proportion should be minimum because it also reduces halogens. Although it may reduce selective because the aldehydes or ketones are much more reactive.

http://www.orgsyn.org/orgsyn/pdfs/CV1P0304.pdf

[Edited on 31-7-2009 by Filemon]

Picric-A - 31-7-2009 at 13:27

@GC- your method of refluxing disulphur dichloride and glycol looks extremly tempting!
should you be refluxing the DSDC or the glycol for this?
Also, yes this is rather cheapskateish but do you rekon leaving a mix of DSDC and glycol to stand for a week will still work? the only thing i dont like about this procedure is the fact i would be wasting a hell of a lot of electricity/gas doing this. the reflux water isnt a problem becuase i have a recirculating pump.

DJF90 - 31-7-2009 at 15:38

You would heat to reflux. It doesnt matter which component is boiling; if you heat it to the higher bp then the lower bp component will escape through the top of the condensor

Magpie - 31-7-2009 at 16:03

In refluxing you are just boiling the mixture and condensing the vapors. The boiling point will be whatever it is for the system you have and depend on the proportions of the mutually soluble components. The vapor will also be a mix of these mutually soluble components and condense completely assuming the condenser temp and residence time in the condenser are adequate.

len1 - 31-7-2009 at 16:33

@entropy - do you have a full version of that article - I dont seem to be able to get it? thanks

[Edited on 1-8-2009 by len1]

entropy51 - 31-7-2009 at 16:45

Quote: Originally posted by len1  
@entropy - do you have a full version of that article - I dont seem to be able to get it? thanks

[Edited on 1-8-2009 by len1]


Well, I'm getting a little reluctant to post articles due to the animosity here, but for you, OK.



On second thought, since you have downloaded the article, I am removing it because of the sulfur mustard prep it contains.

[Edited on 1-8-2009 by entropy51]

[Edited on 1-8-2009 by entropy51]

len1 - 31-7-2009 at 17:03

Thank you very much. I must admit I have been feeling the same way.

setback - 31-7-2009 at 19:44

Quote: Originally posted by entropy51  
Quote: Originally posted by len1  
@entropy - do you have a full version of that article - I dont seem to be able to get it? thanks

[Edited on 1-8-2009 by len1]


Well, I'm getting a little reluctant to post articles due to the animosity here, but for you, OK.



On second thought, since you have downloaded the article, I am removing it because of the sulfur mustard prep it contains.

[Edited on 1-8-2009 by entropy51]

[Edited on 1-8-2009 by entropy51]


I don't blame people for not liking you.

len1 - 31-7-2009 at 19:58

Why this attack? Entropy did me a favour by posting an article. This is what he and I were talking about, I guess nothing you can do, this thing will happen its a public place.

ergoamide - 31-7-2009 at 20:51

The reaction between ethylene oxide and HCl is a very quick and complete reaction by all accounts in organic chemistry books. It proceeds very rapidly even at -30C.

Polverone - 31-7-2009 at 22:59

Good grief, the Gomberg paper is in the public domain by now. Here's a copy from Google Books, in case anyone following this thread was disappointed by the ninja editing:

http://www.sciencemadness.org/scipics/refs/gomberg_chlorohyd...

garuda - 1-8-2009 at 01:18

Notwithstanding the public domain ststus of the Gomberg paper, the fact remains that the topic is not mustard gas but 2-chloroethanol (ethylene chlorohydrin).

When Saddam Hussein was prevented from importing thiodiglycol to feed Chemical Ali's mustard plants, they switched to 2-chloroethanol and made their own thiodiglycol a la Gomberg.

A lot of people were injured, blinded, killed and who knows how many more will suffer delayed carcinomas because sulfur mustard is a potent carcinogen.

So do not call entropy's actions "mimja editing". instead consider the abject irresponsility of your own actions, polverone, and allow entropy51 to see to his own karma as best he can. I applaud his self-restrainst. What does the preparation of a compound that crosslinks the strands of DNA and prevents replication and repair, have to do with amateur chemistry?

It would have been better to extract the chlorohydrin info from the paper and publish only that.

Anyway Gomberg is obsolete for either product.

entropy51 - 1-8-2009 at 08:04

Fine, Polverone. Now if some young kid actually manages to make a gram of sulfur mustard and blind himself it will not be on my conscience. Any member of the public can now easily access a fairly explicit recipe, as I realized after I posted. I was focused on the chloroethanol aspect and didn't think about the rest of the paper. My mistake, and I admit it. Once I realized my mistake I tried to mitigate my error.

Being in the public domain is not the same as easily located.

See hubris.

Polverone - 1-8-2009 at 09:45

I have edited the paper to omit the last 4 pages which detail the mustard preparation. The bulk of the paper does deal with chlorohydrin preparation, and in detail that is likely to be useful to amateurs such as the thread starter who may not have ready access to ethylene oxide or modern chlorination reagents. The halogenohydrins are hazardous but versatile synthetic intermediates. The Gomberg reference was a fine addition to the thread as it illustrates how to produce ethylene chlorohydrin and gives a template for experimentation that would be useful as a starting point for working with other alkenes. The same paper is referenced by numerous later academics and the Kirk-Othmer encyclopedia of chemical technology on the topic of chlorohydrins so you were in more than respectable company to suggest it.

If your conscience will bother you when you share information about potentially hazardous reactions, please think twice before posting. Sharing and then withdrawing valuable information really rubs me the wrong way. It's the reason we have a time limit on editing posts.

JohnWW - 1-8-2009 at 10:05

But what is the point of such censorship, when any fool bent on death and destruction could simply Google for the phrase "sulfur OR sulphur mustard", and get the same information that way? This search string throws up 79,200 results to choose from, including (on refining by adding Gomberg to the search string, which reduces the number of results to only 38) the entire 1919 JACS paper (and what appears to be a patent by him) by Moses Gomberg (which fortunately came out a few months too late for the stuff to be used in the Great War/Whore)? As with its analog "nitrogen mustard" (249,000 Google results, but also of use as a chemotherapy drug for cancer), the structural relationship to 2-chloroethanol and the consequent synthetic possibilities would be obvious to any competent organic chemist.

(BTW Moses Gomberg was the same organic chemist who, around 1900, endeavored to prepare as many highly phenyl-substituted hydrocarbons as possible, using especially Grignard reactions, along with metal reductions. When trying to prepare hexaphenylethane, he discovered the intensely yellow colored triphenylmethyl carbocation and triphenylmethyl free radical instead, in which the positive charge and unpaired electron are resonance-delocalized over the whole structure, see http://en.wikipedia.org/wiki/Triphenylmethyl_radical and http://en.wikipedia.org/wiki/Triphenylmethanol )

[Edited on 2-8-09 by JohnWW]

entropy51 - 1-8-2009 at 10:43

Quote: Originally posted by Polverone  
I have edited the paper to omit the last 4 pages which detail the mustard preparation. The bulk of the paper does deal with chlorohydrin preparation, and in detail that is likely to be useful to amateurs such as the thread starter who may not have ready access to ethylene oxide or modern chlorination reagents. The halogenohydrins are hazardous but versatile synthetic intermediates. The Gomberg reference was a fine addition to the thread as it illustrates how to produce ethylene chlorohydrin and gives a template for experimentation that would be useful as a starting point for working with other alkenes. The same paper is referenced by numerous later academics and the Kirk-Othmer encyclopedia of chemical technology on the topic of chlorohydrins so you were in more than respectable company to suggest it..


Thank you for editing, I should have done that. I agree that it is a valuable paper with respect to the chlorohydrin part.
Quote: Originally posted by Polverone  
If your conscience will bother you when you share information about potentially hazardous reactions, please think twice before posting. Sharing and then withdrawing valuable information really rubs me the wrong way. It's the reason we have a time limit on editing posts.


I will try to do better the next time. But I was within my rights to edit within your time limit.

I wish you would get so indignant when one of your moderators deletes one of my posts as when I delete one myself.

entropy51 - 1-8-2009 at 10:51

Quote: Originally posted by JohnWW  
1919 JACS paper by Moses Gomberg (which fortunately came out a few months too late for the stuff to be used in the Great War/Whore)?


I hope your knowledge of chemistry is better than your knowledge of history.:P Mustard was the most used chem agent in the Great War, Gomberg just wasn't allowed to publish until after the war ended.

The Gomberg paper did not come up in the first 1000 hits when I googled those terms. EDIT: OK, so you modified it to search for Gomberg. Anybody who knew about the Gomberg paper didn't learn anything new. But the kewls wouldn't have known about Gomberg's paper, would they? As I said, public domain is not the same as easy to find.

[Edited on 1-8-2009 by entropy51]

[Edited on 1-8-2009 by entropy51]

len1 - 1-8-2009 at 19:01

Does one really think that with the many examples of kewls doing complicated experiments here, we will soon have someone post a successful mustard synthesis on a process that took the UK and France 18 months to get going, opearating in overdrive, without considering cost? I doubt anyone will even get to the chlorohydrin. 99% of posts end with just an exchange of refereces (which is fine), but often theres a pretence that the poster actually needs the ref for something practical, which never gets done.
Quote:
I wish you would get so indignant when one of your moderators deletes one of my posts as when I delete one myself.



Agree. Reminds me of the church in the 1800's, if the state takes your life, thats as it should be because nothing happens against God's will, but if you take your own life, thats a crime against God.


PS Since the deleted method is completely unsuitable for kewls, and moreover would be very hard for them to understand, which is unfair, may I propose this far simpler method which a dilitant can actually do (and pictures of what to aim for)

http://en.wikipedia.org/wiki/Mustard_gas

May I particularly recommend method 1? I know from my professional experience that anyone who is going to pass their second year organic can generate the two immediate precursors. The last step, although I have not myself done, but have read on, generates lots of colloidal sulphur which was a sticking point for the Allies. But who cares if you are going to maim yourself.

[Edited on 2-8-2009 by len1]

Picric-A - 2-8-2009 at 15:21

Slightly off topic but can one react 2-Aminoethanol with acylating agents like ethyl chloride to produce diethylaminoethanol?
thanks,

Nicodem - 2-8-2009 at 23:55

Ethyl chloride is not an acylating agent.
You can't just stop the alkylation of aminoethanol at the stage of diethylaminoethanol so the yield might be somewhat low, but in principle it is preparatively possible. Though nobody would ever use ethyl chloride for that - using rational reagents you get rational results, but with irrational reagents it's anyone's guess.
Check the literature for details.

Picric-A - 3-8-2009 at 02:06

I have looked this reaction up and noted i need ethyl iodide/bromide, not chloride.
I have one question though which remains unanswered. Surely you can choose what product to obtain by varying the ratios of the product, so for every mole of 2-aminoethanol use 2 moles of ethyl bromide... is there a problem with this?

According to the properties;
Mono;
Density 0.91
Melting point -6 ºC
Boiling point 167 ºC
Refractive index 1.439-1.441
Flash point 78 ºC
Water solubility miscible

Di;
Density 0.884
Melting point -70 ºC
Boiling point 161 ºC
Refractive index 1.44-1.442
Flash point 51.5 ºC
Water solubility soluble

the monoethylaminoethanol can be frozen out, like with the mononitrotoluenes, yielding pure diethylaminoethanol.



[Edited on 3-8-2009 by Picric-A]

garage chemist - 3-8-2009 at 07:15

The alkylation will go to the quaternary ammonium salt as well. You will inevitably get a mix of ethanolamine, N-ethylethanolamine, N,N-diethylethanolamine and N,N,N-triethylethanolammonium salt, along with alkali halide byproduct.
Freezing out is useless as a separation method here. Such mixes are generally fractionated. And this one is going to be hard.

If you're so interested in 2-chloroethanol that you made a thread about it, then make this compound and prepare ethylene oxide from it. Then react it with diethylamine. N,N-diethylethanolamine is the only product of this reaction if you keep diethylamine in excess (introduce the EO into diethylamine in a solvent). This is how to do it.

Make the diethylamine from ethyl halide (2 mol) and ammonia (1 mol) in presence of 2 mol NaOH. Again, you get a mix of ammonia, ethylamine, diethylamine and triethylamine if you basify the mix afterwards and distill everything that boils below 100°C.
Now, the catch is that the boiling points of the three ethylamines are far enough apart to make fractionation relatively simple. You will have no problem obtaining a sufficient amount of diethylamine this way.
And triethylamine contamination in your diethylamine is not of any concern, since EO doesn't react with it.

If you wanted to do a really good job with the diethylamine isolation, you could do the Hinsberg separation, which allows quantitative separation of short-chain alkylamines without any fractional distillation or crystallization whatsoever.



cal - 11-8-2012 at 09:44

This compound 2-chloroethanol can also be used to make Diethanolamine via ethylene oxide:
Quote: Originally posted by garuda  
Notwithstanding the public domain ststus of the Gomberg paper, the fact remains that the topic is not mustard gas but 2-chloroethanol (ethylene chlorohydrin).

When Saddam Hussein was prevented from importing thiodiglycol to feed Chemical Ali's mustard plants, they switched to 2-chloroethanol and made their own thiodiglycol a la Gomberg.

A lot of people were injured, blinded, killed and who knows how many more will suffer delayed carcinomas because sulfur mustard is a potent carcinogen.

So do not call entropy's actions "mimja editing". instead consider the abject irresponsility of your own actions, polverone, and allow entropy51 to see to his own karma as best he can. I applaud his self-restrainst. What does the preparation of a compound that crosslinks the strands of DNA and prevents replication and repair, have to do with amateur chemistry?

It would have been better to extract the chlorohydrin info from the paper and publish only that.

Anyway Gomberg is obsolete for either product.

Dr.Q - 30-6-2013 at 05:19

So i tried to make chloroethanol from bubling HCl gas through etyleneglycol at 100 'C.
The system that i had set up was pretty much like in the pic.






In the left flask HCl was generated by H2SO4+NaCl(solution) . In the middle flask there is pure etylene glycol.

Now here is the problem. Everytime i try bubling , it vacuums etylene glycol to HCl generator. I cant fix it. Because of it vacums i cant efficently bubling the gas.

Why it vacums , what could be the problem ?


[Edited on 30-6-2013 by Myeou]

[Edited on 30-6-2013 by Myeou]

[Edited on 30-6-2013 by Myeou]

Nicodem - 30-6-2013 at 11:46

Quote: Originally posted by Myeou  
Now here is the problem. Everytime i try bubling , it vacuums etylene glycol to HCl generator. I cant fix it. Because of it vacums i cant efficently bubling the gas.

Why it vacums , what could be the problem ?

HCl is extremelly rapidly and exothermically absorbed in ethylene glycol, so it is not possible to avoid suck-backs if you introduce it bellow the surface. On the other hand, there is no need to do that. Just introduce it above the surface. It will be equally well absorbed, but without the suck-back problem. Though, you need to use a stirrer, like a magnetic one. With bubbling you also get the mixture agitation, but if you introduce a gas from above the surface, you need to use a stirrer to compensate. Once the air is purged out of the system, the absorption is just as effective.

Be careful with chloroethanol. Genotoxic substances should be treated with great care even when there is no definitive evidence of carcinogenicity, especially if they are as toxic as chloroethanol. Also, beware that treating chloroethanol with bases produces the volatile, carcinogenic and very toxic ethylene oxide.

sonogashira - 30-6-2013 at 14:24

You could add an in-line non-return valve where you have the rubber connector.

Agricola - 1-11-2013 at 12:51

For a preparation of 2-chloroethanol (ethylene chlorohydrin) from hydrogen chloride and ethylene glycol, see the attached paper by Ladenburg. The document is in German, use Google Translator if necessary.

The procedure is analogous to the one below, in English:

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1...

For a volumetric determination of 2-chloroethanol, see the paper by Uhrig, in English.

Attachment: chlorohydrin_ladenburg1883.pdf (155kB)
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Attachment: chlorohydrin_uhrig1946.pdf (156kB)
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PHILOU Zrealone - 6-11-2013 at 12:47

I have long time ago thought about this because following me chloroethanol is a must have organic reagent/chemical.

There are in fact two options to get to chloroethanol... the first one everybody thinks about; and the second one by thinking in a reversal fashion.

1°) HCl + HO-CH2-CH2-OH --ZnCl2--> Cl-CH2-CH2-OH + Cl-CH2-CH2-Cl + H2O

2°) Cl-CH2-CH2-Cl + NaOH --H2O--> Cl-CH2-CH2-OH + HO-CH2-CH2-OH + NaCl

Then separation by fractionnal distillation thanks to the fact BP glycol >> BP chloroethanol >> BP dichlorethane

Thanks to fractionnal distillation and both reaction the theorical yield of chloroethanol can be set very close to 100%.

[Edited on 6-11-2013 by PHILOU Zrealone]

Agricola - 6-11-2013 at 14:53

PHILOU Zrealone, the second reaction will make a mess.

When you are mixing the reagents, one will be in excess. If an excess of NaOH is present, you will have mostly ethylene glycol. You can keep NaOH always in excess and get a good yield of ethylene glycol if your reaction conditions don't turn the ephemeral ethylene chlorohydrin intermediate into ethylene oxide before it turns into ethylene glycol.

If an excess of 1,2-dichloroethane is present, when the amount of ethylene chlorohydrin becomes considerable, yet still small, then some of the NaOH will eat some of the ethylene chlorohydrin and form ethylene glycol, thus preventing the accumulation of ethylene chlorohydrin. Adding more NaOH will just make a chemical soup of 1,2-dichloroethane, ethylene glycol, and ethylene chlorohydrin. Reaction conditions may also turn some of the ethylene chlorohydrin into ethylene oxide.

The heat of the distillation will help the CH2-OH negative oxygens react with the CH2-Cl positive carbons, replacing the latter's chlorines. This will go on and on creating a chemical monster. Separation by another method before distillation would be necessary to get a low yield of ethylene chlorohydrin.

The standard procedure is Ladenburg's. There is also another one, more economical on a technical scale, by Gomberg, based on the reaction of chlorine and ethylene in water.

Last but not least, there is another way to make ethylene chlorohydrin, shown on Vanino's Handbuch, available on S. C. Wack's Media Fire folder. It uses S2Cl2 and ethylene glycol and is easy to carry out (shake two liquids then apply heat). It is analogous to the procedure employed by Morley. For the preparation of S2Cl2 see Vanino's Handbuch or Biltz's Laboratory Methods, also on S. C. Wack's Media Fire folder.

Attached to this message is a print version of the Organic Syntheses preparation analogous to Ladenburg's, and the papers by Gomberg and Morley.

[Edited on 6-11-2013 by Agricola]

Attachment: chlorohydrin_gomberg1919.pdf (1.2MB)
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chlorohydrin_ladenburg1883.pdf

byko3y - 17-5-2015 at 08:05

German:
Die bekannten Methoden zur Darstellung von Chlorhydrinen liefern theils mangelhafte Ausbeuten, theils sind sie unbequem in der Ausführung, oder sie geben, wie die Methode von Carius mittelst Glycol und Chlorschwefel, meist ein unreines schwefelhaltiges Produkt.
Das folgende Verfahren, das sich in meinem Laboratorium bei der Darstellung von Chlorhydrinen vielfach bewährt hat, ist eine Modifikation der von Wurtz in seiner berühmten Abhandlung über die Glycole angegebenen Methode. Ich werde sie hier für die Gewinnung von Aethylenchlorhydrin beschreiben. Herr Dr. Berend hat dieselbe auch zur Darstellung von Trimethylenchlorhydrin verwerten können, worüber er später selbst berichten wird.
Glycol wird in einem Destillationsapparat auf 118°C erhitzt und gleichzeitig ein langsamer Strom trockner Salzsäure hindurchgeleitet. Das gebildete Wasser und Glycolchlorhydrin destilliren ab und werden in tubulirten Vorlagen aufgefangen. Nach und nach wird die Temperatur des Bades bis etwa 160°C gesteigert, wo dann bis auf einen unbedentenden Rückstand die angewandte Glycolmenge vollständig zerlegt wird. Bei der Verarbeitung von 100g Glycol sind etwa 16 Stunden nöthig.
Das Destillationsprodukt wird mit dem 2-3 fachen Volum Aether versetzt und durch Kaliumcarbonat zunächst von vorhandener Salzsäure befreit. Dann wird die ätherische Lösung abgesaugt und über frisch geschmolzenem Kaliumcarbonat vollständig getrocknet. Zwei Destillationen liefern ein reines zwischen 128°C und 131°C siedendes Produkt und zwar etwa 60 pCt. der theoretischen Ausbeute.

English:
The known methods for the preparation of chlorohydrins deliver partly poor yields, and partly they are uncomfortable in the execution, or specify how the method of Carius means Glycol and sulfur chloride, usually an impure sulfur-containing product.
The following procedure, which has proved in my laboratory in the preparation of chlorohydrins often, is a modification of in his famous treatise given by Wurtz on glycols method. I'll describe them here for the recovery of ethylene chlorohydrin. Dr. Berend has the same also can use to display Trimethylenchlorhydrin what he will tell himself later.
Glycol is heated in a distillation apparatus to 118°C while passing a slow flow of dry hydrochloric acid. The water and Glycol chlorhydrin formed from distil and are collected in tubulated templates. Gradually, the temperature of the bath is increased to about 160°C, which then except for a dent without end residue of glycol which is used completely dismantled. When processing 100g glycol are about 16 hours necessary.
The distillation product is mixed with 2-3 times its volume of ether and first freed by potassium of existing hydrochloric acid. Then the ethereal solution is aspirated and completely dried over freshly melted potassium. Two distillations deliver a pure between 128 ° C and 131 ° C boiling product and that about 60 per cent. of the theoretical yield.