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			Discussions on aminomercuration of safrole
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		A Synthesis of MDMA from Safrole by Aminomercuration

			   by Zbyszek Szczesny (ziggi@polbox.com) 
					     July, 1997

According to my experience I would suggest a different method of MDMA synthesis 
- in my opinion simpler than what I see on the web. The biggest advantage of my
"developement" is that all processes are conducted in aqueous solution under 
mild conditions instead of in organic solvents, reducing the risk of fire or 
explosion. In fact, you need some toluene at the very end - to extract the final 
amine - but this is normal and brings no difficulties. Reduction with sodium 
borohydride is very elegant but pH control is a must with the buffer used for it. 

Yield is very good - total over 90%. Because aminomercuration is a very simple 
and mild reaction it should present no difficulties for an experienced chemist, 
but since mercury is very poisonous I will not give all the details to the broad 
public. I believe collegues with a chemical background will know how to perform 
these reactions correctly. I strongly recommend against anyone without training 
in chemistry performing these reactions. It could result in serious injury or 
poisoning. 

Scheme:
=======

Step 1: A Markovnikov-order aminomercuration. 

	Safrole ==> Intermediate 2-Methylamino 1-mercuric salt


Step 2: Reduction with sodium borohydride, producing 
        elemental mercury which is easily removed. 

	Intermediate salt => MDMA + Hg

References:

1. Lattes, Perie; C.R. Acad. Sci., Ser. C 262, 1591 (1966). 
2. Tetrahedron Lett. 5165 (1967). 
3. Backval, Akermark; J. Organomet. Chem. 78, 177 (1974). 
4. Gasc, Perie, Lattes; Tetrahedron 34, 1943 (1978). 
5. Barluenga, Villanana, Yus; Synthesis 375 (1981). 
6. Koziara, Olejniczak, Osowska, Zwierzak; Synthesis 918 (1982). 

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Further Notes, Jan 98

1. As most of you probably know oxidation of alkenes with mercure II salts is one 
   of the most important ways leading to relative alcohols. Please notice that 
   this reaction called 'oxymercuration' has the following properties: 

	* high yield 
      * 100% Markovnikov orientation 
      * in some cases there are some organomercure byproducts occuring 

2. Most popular oxymercurations are in fact 'hydroxymercurations' what means that 
   the reacting compounds are: alkene, mercure II salt (usualy mercuric acetate) 
   and water used as a reactive solvent. 

3. But if water is replaced with alcohol the resulting product is corresponding 
   ether. The reaction goes well with primary or secondary alcohols but when a 
   tertiary alcohol is used the mercure salt must be highly reactive mercuric 
   trifluoroacetate. 

4. If the oxymercuration is carried out in a presence of a hydroperoxide instead 
   of water (or alcohol), the product (after demercuration with NaBH4) is an alkyl
   peroxide(-> peroxymercuration). 

5. The latest example is the best to explain aminomercuration idea. Who is 
   interested may look into: 
      
	* Ballard & Bloodworth, J. Chem. Soc. C 945 (1971) 
      * Bloodworth & Loveitt, J. Chem. Soc., Perkin Trans. 1 1031 (1977) 
      * Bloodworth & Courtneidge, J. Chem. Soc., Perkin Trans. 1 3258 (1981) 
      * Bloodworth & Courtneidge, J. Chem. Soc., Perkin Trans. 1 1807 (1982) 
      * Sokolov & Reutov, J. Org. Chem. USSR 5, 168 (1969) 
      * Schmitz, Reiche, Brede, J. Prakt. Chem. 312, 30 (1970) 
   
   I said it is a good idea because the reagent is not the solvent in this case!

6. It is necessary to comment the problem of mercuric organocompounds which may 
   occure when the aminomercuration is carried out with aromatic compounds (like
   safrol undoubtly is...). I would say there is not many things to worry about 
   in this point. Typical way of cleaning the final product (the amine) is a 
   measure good enough to avoid any significant mercuric pollution: extraction 
   with ether, steam distillation, fractional vacum distillation, cristallisation 
   of the sulfate from isopropanole. 

7. It is important to remember that the necessary supplementary solvent used 
   when oxymercuration (or aminomercuration) is carried out is THF!

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Aminomercuration-demercuration Discourse at the Hive:

ReFlux:

So the subject of hypothetical Aminomercuration-demercuration of our
favourite olefin safrole has been widely discusssed on this board. I'd now
like to get to some specifics, so here are a few questions that are on my
mind:

1. What is the ideal solvent for this reaction? Most journal refs call for
THF, but the problem with THF is its perpensity for formation of explosive
peroxides upon distilling that can make it go BOOM! Also, it is relativley
expensive. How about 1,2-Dichloroethane (DCE) or methylene chloride (DCM)?
Factors to consider are solubility of Safrole in the solvent, solubility of
the Amine source in the solvent, and non-reactivity of the solvent.

2. For creation of secondary aminated product (MDMA) what form should the
amine source (MeNH2) be in? The journal refs call for it to be used in aq.
solution, but can a solution of the hydrochloride salt (MeNH2.HCL) be used
somehow?

3. For creation of primary aminated product (MDA) what amine source can be
used? Ammonum Acetate is not very soluble in THF or DCE, however, this
should only slow down the speed of the creation of the organomercurial
complex. More important to consider is will the formed complex dissolve in
these solvents? What other sources for NH3 can be used? Perhaps aq.
ammonium?

4. What species of Mercury II salt should be used? Mercuric Acetate is
widely used in oxymercuration reactions, but is less reactive than Mercuric
Nitrate or Chlorate. It appears that speed of reactivity with amine source
to form organomercurial complex is the only main issue, and as such, can
the acetate salt be used with MeNH2?

5. What is the best procedure for issolation of the resulting amines
(MDA/MDMA)? It is important to carefully issolate the product from the rxn.
mix so as to avoid any possible mercury contamination. Are standard solvent
extractions, acid-base washings enough?

6. How to issolate pontential anti-Markownikoff aminated product? According
to some journal refs, though most of the product from these rxns will
proceed with Markownikoff addition of the amine, some anti-addition
products can occur. How can these be seperated/issolated from the product ?

The refs that I have looked into for researching this method are:
J Org Chem Vol 44, 20. Pg. 3581 (1979) Tett Vol 40, 7. Pg. 1199 (1984)

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Labrat:

ReFlux, a while ago I got interested in that specific reaction too. I did a
little reading and would like to share my thoughts with you:

1)THF is probably the best solvent you can get. If you want to substitute,
why don't you use diethyl ether? That's an ether too. I wouldn't use
chlorinated hydrocarbons like DCM or DCE, cuz they might react with the
Hg-salt. Distilling THF is not a problem if you throw in some reducing
agent to take care of the peroxides, and then distilling.

2)I've asked the same questions as you a while back. Ziggy answered to me,
that you have to use methylamine freebase.

3)For primary amines, why don't you use benzylamine. You'll make the
N-benzylamine, which can be split off by hydrogenation with Pd/C. This
aminomercuration is actually suited better to make secondary amines, like
MDMA.

4)After the aminomercuration, you'll pour in some NaOH solution to make the
mixture basic, then reduction with NaBH4. This'll reduce the Hg2+ to Hg(l).
Mercury isn't soluble in water, so you can separate the layers. I guess
acid-base extraction are sufficient to prevent mercury-contamination.

5)This bothered me too, until I read in PIHKAL, that the anti-Markovnivkov
product, 1(3,4-methylenedioxyphenyl)-3-propylmethylamine, is a known under
the name GAMMA and is an active compound. So why bother removing it?

I hope I've helped you a little with this. This is a very interesting
reaction, so if you find anything good, keep me posted OK? 

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Reflux:

I REALLY like your benzyl-substituted amine idea, (Check out my new post: A
substitute for MeNH2 in various Synths.) although I think you meant Aniline
for MDA as Benzylamine gives MDMA.

As for the anti-markownikoff product, GAMMA is the MDA anti-addition
product (gamma-3,4-methylendioxy-phenylproplyamine), and though it is
active, it didn't seem to have a desirable effect (see PIHKAL). Any info on
the MDMA anti-product? In any case I think we should think of ways to
remove them.

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Labrat:

Reflux: no, I didn't mean aniline, I did mean benzylamine. Hydrogenation
with Pd-C is known to split off benzyl groups, just check out the
literature to remove benzyl groups from benzyl alcohols. What GAMMA is
gamma-3,4-methylendioxy-phenylproplyamine, not the methylamine? Damn, my
mistake. But I still think it's active. And I would just use it as is.
Otherwise you'll be forced to use chromatography to separate the
anti-Markovnikoff from the Markovnikoff compound. Ziggy is indeed the guy
who posted the aminomercuration method for MDMA.

I've done some reading too. I've read the JOC 44:3580('79) again and found
some interesting leads.

It's stated that:"In all cases, rapid formation of amine-mercury complexes
was observed prior to addition of olefin". Hmm, what would happen if one
would try aqueous MeNH2 here? Will there be formation of amine-mercury
complex? If there is, one could use aqueous methylamine. You probably have
to use Hg(ClO4)2 instead of Hg(NO3)2. They also state:"We have observed
that the aminomercuration can be performed in aqueous or anhydrous
THF...this means hydroxide ion does not compete successfully with
ethylamine as a nucleophile for the intermediate mercurinium ion or a
direct addition of amine-mercury complex is involved". Hmm, I'm guessing
that you could probably use aqeous methylamine solution.

Then I also read another good article:

Chem.Het.Compounds. 11:4('75)

This is actually about INTRAMOLECULAR not intermolecular aminomercuration,
but they give some properties of the reaction:

- nature of the anion on Hg is important

 HgCl2 > Hg(OAc)2 > Hg(NO3)2 = Hg(ClO4)2

-the reaction has an IONIC character:

first a pi-complex between the olefin and the mercury salt is formed, then
the amine adds to give the Markovnikoff addition product

-reduction with NaBH4 has an radical OR an ionic mechanism. If the
mechanism is ionic, then during the reduction aziridinium ion is formed,
which explains the presence of the two isomeric amines.

Remember when reading this article, that intramolecular aminomercuration is
a lot easier to accomplish then intermolecular aminomercuration and that
with intermolecular aminomercuration more hydroxymercuration occurs.

Well, that's it for today. I'm gonna find some more refs on this very
interesting reaction and would like to communicate with you on it. 

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Reflux:

Labrat- I'm confused now. Aniline HAS a benzyl group doesn't it? (just one
less methyl group before the amine when compared to Benzylamine) Or is a
Benzyl group the benzene ring plus a single methyl (essentially a toluene
less one H)? Please clarify.

As to rxns. w/ aq. MeNH2, I too believe that it would work fine. In J Org
Chem Vol 44, 20. Pg. 3581 (1979) they used aq. EtNH2 w/
m-methoxyallylbenzene & Hg(ClO4)2 and produced then ethylaminated product
in high yields (87%)

Can one make an aq. MeNH2 sol'n from MeNH2.HCL? If it were to be disolved
in H20, and then the sol'n basified w/ NaOH, would that not result in MeNH2
(g) which would stay disolved in the H20 plus NaCL?

I'll continue digging ... I look forward to further discussion with you on
this topic.

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Labrat:

Reflux, aniline is phenylamine, benzylamine is like toluene with an -NH2
group substituted for a -H! Basic chemistry me boy!

Using aqueous methylamine is indeed a very viable option, although you have
to heat the mercury salt/aqueous MeNH2 mixture to 60 C to expedite
formation of the amine-mercury complexes. If the Labrat remembers correct,
the bp of an 40% aqueous solution is about 50 C (correct?). I wonder if
refluxing the amine-mercury mixture will take care of the complex
formation. Have any thoughts on this?

Making aqueous methylamine is easy! Just put your MeNH2.HCl in a flask,
attach a distillation setup to it and fill a dropping funnel with 50%
aqueous NaOH. Now slowly drip the alkalic solution on the salt to create
MeNH2 gas. Now bubble the gas into a water mixture until it has gained the
proper amount of weight to get aqueous MeNH2! You could neutralise it as
you described, but you'll have NaCl contamination. I don't know what this
will do to the yield.

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i previously posted a lot of ref and notes from ziggy on the rxn on this
board. elf has posted attempts with aminomercuration but with the MeNH HCl
salt which is definitely bad. I noticed that in one of the major ref for
this rxn in JOC uses ethylamine as one of their variable amines and in
methods they mention that it is used as a 70% solution (but i dont remember
if it was aqueous of alcoholic) but this example made me think that aq
methylamine would work. question is: is 40% enough and will much be lost
during reflux. ziggys suggestions to over come this problem was doing rxn
in a presurized container of sorts.

i think this rxn has a lot of potential, someone just has to ave the balls
to dream about it a few times to perfect a procedure. my guess is that HgAc
and HgNO3 salts will work, and that HgNO3 and Hgperchloriate would be best
(based on the articles i have read-they seem to use these the most)

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Reflux:

I don't think that the % of Aq. sol'n of the amine (ethyl-methyl) is that
important. 70% aq. EtNH2 & 40% aq. MeNH2 are standard concentrations and
that is probably why the JOC paper used the 70% soln.

As for the heating of reaction mix to 60-65 degrees C to "speed up the
formation of the intermediate organomercurials", I believe that here again
the researchers in the JOC paper chose this temp as it just below the BP of
THF (66 C). The paper did not call for refluxing the mix, but simple
stirred heating.

The paper also indicates that "In all cases, rapid formation of
amine-mercurcy complexes was observed prior to the addition of the olefin
substrate. The rate of aminomercuration proved to be a sensitive function
of the mercuric salt employed."

This indicates to me that there is no need for any refluxing or
pressurized/sealed reaction vessels. The amine source is converted almost
immediately into an amine-mercury complex which is dissolved in the THF.
Simply add the 40% aq. methylamine to the stirring Mercuric salt in THF
soln. Then add the Safrole, heat to say 60 C, and leave stirring for
prolonged period of time (72 to 96 hrs.) until all of the safrole is
converted to an organomercurial intermediate.

As for the species of Mercuric salt used, only dreaming will tell! As far
as I can tell, Hg(NO3)2 would be ideal, but Hg(OAC)2 is easier to aquire.
Also, no need to worry about the hyrdated state of your HG salt
(mono-hydrate, tri-hydrate etc.) Use whatever type is easiest/cheapest to
aquire and then adjust the amount used in reaction so that it is used in
the correct molar ratios.

Just a few more musings...will continue the search!

PS Labrat-I found the BP of 40% Aq. Methylamine at 48 C. Looked it up in
Acros catalog.

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Labrat:

ReFlux, thanx for the comments. It's good to discuss this with a fellow
chemist, cuz it seems we agree on a lot of things here. So we should
definitely use 40% aqueous methylamine and we don't have to heat it to
reflux (but I think it's better to speed up the complex formation).

I think that when using aqueous methylamine it's better to use Hg(ClO4)2
then Hg(NO3)2 and you can definitely forget Hg(OAc)2. That anion is very
important for the course of the reaction. That anion is the nucleophile
that has to compete with hydroxide and methylamine nucleophiles, so you'd
better choose the right anion. It's easy to prepare those salts from HgO,
just by dissolving this mercuryoxide in e.g. perchloric acid you'll end up
with Hg(ClO4)2. I'll try to find the intricate details for this. 

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Reflux:

In Tet. Vol. 40,7 (1984) pg. 1199-1204 they discuss reversibility in
aminomercuration. They found that aminomerc. w/ Mercury(II) Acetate is an
irreversible process while w/ Mercury (II) salts derived from strong acids
(Hydrochloric, Nitric, Perchlorate etc) it is reversible. Could this pose a
problem? The only main differnce is the rate of the rxn. which I think
would be fine with acetate salt. Nucleophility (sp?) is not an issue as
hydroxy mercuration never occurs even with very weak nucleophilic amines
and mercuric acetate. However, yeilds can be affected by weaker salts,
though I wonder if that is because the reactions just aren't given enough
time to complete?

In Tet. Vol 34 (1978) pg. 1943-1950 they discuss using a catalytic amount
of concentrated (70%) perchloric acid sol'n w/ mercury (II) acetate which
results in greater yields and much accelerated reaction time. My french
really sucks, so If yours is any better maybe you could look up this ref.
as it has a lot of info on the process and mechanisms of aminomercuration.

Also, won't using a strong acid based salt will result in highly acidic
conditions in the reaction mix after aminomercuration is complete? The
anion will turn the aq. sol. acidic will it not, which could damage the
methylenedioxy ring structure, no?

Just a few more thoughts for us to ponder, though I really think many of
these issues would be resolved with a little dreaming!

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Reflux:

Just one more point, I don't see the point in having a 2.67X molar excess
of amine to mercury salt as suggested by the JOC ref. Since in the first
part of the reaction, there is a near immediate formation of
organomercurial complex (before addition of the olefin) then what is the
point in having all that highly nucleophilic (as in the case of MeNH2)
excess amine floating around in the reaction mix.

I would suggest equimolar or if not then just a slight excess of amine
(1.1X maybe? relative to the mercury salt), while still maintaining the
excess of mercury salt relative to olefin ratio (1.5X). What are your thoughts?

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Reflux:

Labrat-On a related note, how about using an aq. Ammonia sol'n for
hypothetically creating MDA in this reaction. Any thoughts?

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Labrat:

ReFlux - sorry it took a while to answer this, but my computer got fucked.
I tried to post the answers Friday, but no good. I'll try it again today:

>Tet. Vol 34 (1978) pg. 1943-1950

This is a real goldmine! I'll translate the most important things for you:

They used 15 molar excess of water compared to the amine and got NO
oxymercuration products!

They added the olefin to a aniline/Hg-Ac mixture in dry THF, then added
water. They obtained uniquely aminomercurations compounds. When they added
water to Hg-Ac in THF, then added the amine, the oxymercuration products
were obtained. This means it's important to have the amine in the mix
BEFORE the alkene is added.

Mercury has a greater affinity for nitrogen (N) then for oxygen (O). In the
reaction conditions used, there is competition between two nucleophiles:
the amine and water. Since no oxymercuration product was found, they
concluded amines are better and stronger nucleophiles then water.

Aminomercuration is a compromise between the nucleophilicity of the amine
and the weak stability of the amino-mercury complex. There's always complex
formation, that's why you have to use at least 4 moles of amine to 1 moles
of Hg-salt. In the case of intermolecular aminomercuration the stability of
the complex formed between the amine and the mercury salt plays a dominant
role in determining the rate of the reaction. In reactions with strongly
basic amines (like ammonia, methylamine) a reaction time of several days is
necessary to get a decent yield.

The absence of a reversible binding of the complex mercury salt-olefin
makes nucleophilic attack on the carbon atom possible even for weak
nucleophiles.

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Labrat:

Now onto the questions:

>Also, won't using a strong acid based salt will result in highly acidic
conditions in the reaction mix after aminomercuration is complete? The
anion will turn the aq. sol. acidic will it not, which could damage the
methylenedioxy ring structure, no?

=>No! The salt of a strong acid is by definition a very weak base! Theory
me boy!

>I would suggest equimolar or if not then just a slight excess of amine
(1.1X maybe? relative to the mercury salt), while still maintaining the
excess of mercury salt relative to olefin ratio (1.5X). What are your
thoughts?

=>In Tet 34:1943('78) they're talking about complex formation between the
amine and the Hg-salt is a competing reaction with complex formation of the
Hg-salt with the alkene. With aniline, two molecules of aniline complex
with one molecule of Hg-salt. I don't know whether more basic amines like
ammonia will complex with even more amines per Hg-salt. This means the
excess amine IS NECESSARY. Otherwise the reaction will be slowed down.

>On a related note, how about using an aq. Ammonia sol'n for hypothetically
creating MDA in this reaction.

=>Great idea! That way you won't have to go through all that trouble making
aqueous methylamine. I guess it'll work. Otherwise, bubble dry NH3 into a
mixture of dry THF and a mercury salt, drip in the alkene. If an insoluble
complex forms, add a little perchloric acid and watch it dissolve. The
water in the mix is used to make the amine-mercury complex less stable. Lr/

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Labrat:

I've done a little literature searching on aminomercuration and found some
more refs:

Synth.Comm.26:4279-88 and 1507-16('96)

=>Here they're talking about creating an mercurinium ion between mercury
and the olefin, which is trapped with a nucleophile, like amines. So no
direct addition of the amine-mercury complex to the double bond as
mentioned in JOC 44:3580('79)

J.Organomet.Chem. 78:177-84('74)

=>not so interesting, dealing mainly with the stereochemistry of
aminomercuration

TL 51:5165-8('67) + C.R. 262:1591('66)

=>using NaBH4 instead of LAH produces less anti-Markownikoff compound.

Synthesis 375('81) + 919('82)

=>reduction and deaminomercuration are always competitive processes
=>use of dichloroethane as a solvent for the aminomercuration reaction

JOC 37:3069('72)

=>not worth looking up, just mentioning it.

Well, this'll keep you busy for a while. Lr/

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Reflux:

I understand exactly what you mean about the excess of amine needed, since
more than one amine complexes per mercury, even though only one gets added
on, and since all the complex formation is at the begininng, excess of
amine is required.

Now, as to the anion of the mercuric salt, I'm a little confused (picture
ReFlux scratching his head!) If, for example, Mercuric Perchlorate is used;
when it is dissolved in H20:THF sol'n. you have mercury ions and
perchlorate ions, correct? Now when the amine is added and it complexes
with the mercury, what happens to the perchlorate ions?

I too have faith in the Aq. NH3 route and wish to use it as a test bed for
initial dreaming about this reaction. (No sense in wasting hypothetical
MeNH3 on working out the bugs in our system, cause even in dreams, MeNH3 is
hard to get!!)

I'll check out the synthesis and synth. comm. refs that you posted. They
both seem very interesting! You know I've been looking for an alternative
to THF for this reaction from the begining!

Also, do you have any info on solubility of MeNH3 and ammonia in THF/DCE? 
Ideas on where to look?
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Labrat:

ReFlux - I've read the article you mentioned:
Tetrahedron 40:1199-1204('84)

And I guess you're right what the reversibility of the aminomercuration
concerns: if you use the mercury salt of a strong acid, the
aminomercuration is reversible.

The authors in this article mention the contradictory results of Perie and
Lattes(BSCF 583('70) and Griffith et al (JOC 44:3580('79) concerning the
rate of aminomercuration with use of the various mercury-II-salts. I'd
follow the instructions of Griffith et al, since they've tried it on
allylbenzenes.

The authors state that: "..aminomercuration is reversible only when the
mercury(II)salt derives from a strong acid. By the contrary the
aminomercuration of olefins with mercury(II)acetate has been found an
irreversible process which only leads to the kinetically controlled
products." It's very worthwhile to consider using mercury-II-acetate.
You'll have to expect a reaction time of several days/weeks to get a decent
yield of product. Refluxing will speed up the process.

In the article I read that: "The rate of aminomercuration increases with
the ionic character of the mercury salt and the polarity of the solvent,
but the extent to which the deaminomercuration takes place largely depends
on temperature and reaction time"

Hmmm, I wonder, what if we used mercury(II)acetate in combination with a
little perchloric acid as done in Tetrahedron 34:1943-50('78)?? Probably
the aminomercuration will proceed with a faster rate and higher yield.
Well, let's do it then!

I'm very curious what will happen if somebody used the above mentioned
protocol to brew some MDA. It's probably best to use dry ammonia for
starters, you can always add a little perchloric acid (or water) if a
insoluble complex precipitates. I'd certainly consider using
mercury(II)acetate, since this gives irreversible aminomercuration.

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Osmium posted 11-04-98 06:04 AM CT (US)         

2-acetamidohexane [N-(2-hexyl)acetamid]

To a ice-cooled solution of 64.8g (0.20mol) of Hg(NO3)2 in 100ml MeCN 
16.8g (0.20mol) of 1-hexene are slowly added keeping the temp below 30°C. 
The clear yellow solution is stirred for 1hr at RT. With ice-cooling 200ml 
3N NaOH are added, followed by a solution of 3.80g (0.10mol) of NaBH4 in 
200ml 3N NaOH. Again stir for another hour. Decant the aq/organic layer 
leaving the elemental Hg behind, saturate the aq. layer with NaCl and 
extract with Et2O (2*100ml). The extracts are dried with Na2SO4, the 
solvent removed and the residue distilled. 22.8g (80%) amide, bp (1.6 torr) 
93-96°C.

Ref: JACS 91, 5647 (1969)

Hydrolysis (use the crude amide):

20.0g (0.14mol) of the above amide, 15.7g (0.28mol) KOH in 25ml H2O and 
62.5 ml ethyleneglycol are refluxed for 24 hours with good stirring. After 
cooling to RT extract with ether (3*100ml), back-extract the amine with 
3*100ml 2N HCl. From the ether 3.08g of unconverted amide are obtained.
The acidic aq. extracts are basified with 30g NaOH and the amine is 
extracted with ether (2*150ml). The extract is dried with K2CO3, the ether 
evaporated and the crude amine is distilled. 7.50g (53%, 62% considering 
the unreacted amide), bp 114-116°C. 

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