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Reagent Friday: Di-isobutyl Aluminum

Hydride (DIBAL)
AUGUST 26, 2011 BY JAMES — 29 COMMENTS

In a blatant plug for the Reagent Guide, each Friday I profile a different reagent that is commonly
encountered in Org 1/ Org 2. Version 1.2 just got released, with a host of corrections and a new page
index.

DIBAL (Di-isobutyl aluminum hydride)

Also known as: DIBAL-H, DIBAH

What it’s used for: DIBAL is a strong, bulky reducing agent. It’s most useful for the reduction of
esters to aldehydes. Unlike lithium aluminum hydride, it will not reduce the aldehyde further if only
one equivalent is added. It will also reduce other carbonyl compounds such as amides, aldehydes,
ketones, and nitriles.

Similar to: LiAlH4, LiAl(Ot-Bu)3H

Like Lindlar’s catalyst, DIBAL is most notable for what it does not do. It reduces esters, but not to
alcohols – it stops at the aldehyde stage. Let’s have a look.

Keeping the temperature low (–70°C) tends to keep a lid on the reactivity here. So long as the
temperature is kept here for the duration of the experiment and only one equivalent of DIBAL is
added, the aldehyde is obtained.
In addition, DIBAL can do all the reductions that NaBH4 does, so ketones and aldehydes are reduced
to secondary and primary alcohols, respectively.

Finally, DIBAL will also do partial reductions of nitriles to imines. The imines are then hydrolyzed to
aldehydes upon addition of water. In this respect DIBAL again differs from LiAlH4, which will reduce
nitriles all the way to amines.

The mechanism for reduction by DIBAL is a little bit unusual compared to NaBH4. Whereas NaBH4 is
considered a “nucleophilic” reductant – that is, it delivers hydride (H-) directly to a carbonyl carbon,
DIBAL is an “electrophilic” reductant. That is, the first step in the reaction is coordination of a lone pair
from the carbonyl oxygen (a nucleophile) to the aluminum (electrophile). It is only after coordinating to
its carbonyl host that DIBAL delivers its hydride to the carbonyl carbon, resulting in formation of a
neutral hemiacetal intermediate that is stable at low temperatures. Quenching of the reaction then
breaks down the hemiacetal, resulting in isolation of the aldehyde. (“real life” disclaimer: this
reaction looks great on paper but can sometimes be difficult to achieve in practice).
The same mechanism is in effect in the reduction of nitriles to imines (and then on to aldehydes).
Coordination of the nitrile nitrogen to aluminum is followed by delivery of hydride, and from there,
addition of water leads to hydrolysis of the imine and subsequent isolation of the aldehyde.

P.S. You can read about the chemistry of DIBAL and more than 80 other reagents in undergraduate
organic chemistry in the “Organic Chemistry Reagent Guide”, available here as a downloadable PDF.

Related Posts:
Reagent Friday: LiAlH[Ot-Bu]3
Reagent Friday: Sodium Borohydride (NaBH4)
Reagent Friday: Lithium Di-isopropyl Amide (LDA)
Reagent Friday: Potassium t-butoxide [KOC(CH3)3]

FILED UNDER: ALDEHYDES, ESTERS, ORGANIC CHEMISTRY 2, ORGANIC REAGENTS

TAGGED WITH: BULKY, DIBAL, HYDRIDES, REAGENT FRIDAY, REAGENT GUIDE, REAGENTS APP, REDUCING AGENTS,
REDUCTION, STERIC HINDRANCE

Comments

azmanam says
AUGUST 26, 2011 AT 3:36 PM

re: real life disclaimer. And man those hydrolized aluminum salts are some of the nastiest
emulsions I’ve ever experienced!

According to my dissertation, my largest DIBAL-H reduction ran on 10.1 g (17.9 mmol) in 175 mL
CH2Cl2. The good news about this reaction for me are twofold. 1) The starting material is bright
crayon yellow and the product was colorless. 2) The reaction was instantaneous. It was like
titrating in DIBAL-H. Curiously, it always took 2 eq of DIBAL (still not quite sure why, only one
equiv of H- is incorporated), but as soon as the yellow disappeared, I was sure the reaction was at
100% conversion. Sure, I’d take a TLC just to be sure, and it was always complete.

Then quench the reaction with saturated aq. Rochelle’s salt (hm… TIL Rochelle was the city in
which it was discovered, not the name of the guy) to help break the Al emulsion. Our lab also
found empirically that diluting the CH2Cl2 reaction with a LOT of Et2O helped break the emulsion.
The bad news is you had to let this biphasic mixture stir vigorously for at least 90 min-2hr before
separating the layers. As long as enough Et2O was added, the emulsion broke down and
separation became very manageable if stirred long enough.

(In case you were wondering, 92% yield of the aldehyde with 93% recovery of the ‘other side’ of
the ester (it was a precious chiral auxiliary, and we wanted to reuse it!)

Reply

Jake says
JULY 14, 2015 AT 9:01 AM

I’ve done a few DIBAL reductions this year and often had trouble with them – in particular, if
your product is water soluble and loves the aqueous phase in a work-up (one can never quite
tell), then it’s an absolutely horrible to job to try and recover it from a saturated aqueous
phase full of Rochelle salts.

Somebody recommended to me that the Fieser work up followed by a filtration over Celite
should remove the Al salts emulsion just as well. I am probably going to use this method as a
first choice from now on, because trying to extract my product from Rochelle salts solution
caused me a lot of grief!

Also, having re-read this site properly, I will now always use H2O to quench my DIBAL
reductions of nitriles. I mistakenly used methanol earlier on and looking at the mechanism of
imine hydrolysis above, that might explain why I got a nasty mixture of crap when I quenched
 the imine with Methanol! Guess I can just pour the reaction on to water at 0 Celsius, rather
than quenching direct at -70.

Reply

James says
AUGUST 26, 2011 AT 5:30 PM

I personally was not able to obtain an aldehyde on the one occasion I tried DIBAL. Part of the
problem was likely the scale (<25 mg) and titre of the (old) DIBAL, as well as not choosing the
solvent well (should have used CH2Cl2 instead of ether). So I just re-oxidized the alcohol with
DMP and was done with it.
Aluminum salts are notorious for their bitching emulsions. For DIBAL I made sure to stir with
Rochelle's salt for a good long while. For LiAlH4 I always use the Fieser workup and filter off the
solid… no extraction required, thank goodness.

Reply

azmanam says
AUGUST 26, 2011 AT 7:35 PM

To be complete, I wasn’t reducing an ester, it was a thioimide. It was an (OH-protected) aldol

adduct utilizing a thiazolidinethione as a chiral auxiliary. We developed the conditions for
the aldol addition in our laboratory. Suffice it to say we did the diastereoselective aldol
addition a lot. Partial reduction of the thioimide to the aldehyde was a common next
transformation, so we always had a fresh bottle of DIBAL in the fridge. I reduced 5 different
thioimides this way who knows how many times as I ran through the synthetic scheme who
knows how many times.

The one time I did reduce an actual ester, it was on 0.7 g scale (2.4 mmol). 68% yield of
aldehyde, 30% yield of alcohol. Also reoxidized the alcohol with DMP back to the aldehyde in
63% (or 87% total from ester -> aldehdye) That reduction was following a Frater-Seebach
alkylation (which was a pain to run (-40 degC, 3 days), but a great reaction to have
experienced.

Reply

Martha says
AUGUST 4, 2013 AT 7:59 PM
Is it not DIBAH instead of DIBAL?

Reply

james says
AUGUST 4, 2013 AT 9:18 PM

It can be referred to as DIBAH, DIBAL, or DIBAL-H. Usually when discussing it amongst

themselves, organic chemists call it DIBAL because it rolls more easily off the tongue than
either of the other two.

Reply

Ricky says
AUGUST 15, 2013 AT 6:33 AM

Can we obtain alcohol from ketone, by DIBAH at –70°C? I know we can at room temperature, but
I don’t know if we can at –70°C. Any reference you have?

Reply

Tracy Phuong says

OCTOBER 22, 2013 AT 10:34 PM

can you demonstrate how hydrolysis occurs? im a little stuck

Reply

Dr. Pepper says

MARCH 14, 2017 AT 7:40 PM

Under the acidic conditions, convert the aluminum salt to the hemiacetal. Don’t worry,
students have this problem all the time because, well, they just do. When we grade quizzes,
students freak out when they see the hemiacetal under acid conditions and they are unable
to figure out what to do next. Then the students proceed to use OH- because remember in
student parlance, OH- is always available in acidic solution.

Reply
 Luke says
MARCH 3, 2014 AT 2:17 PM

I use 2,5-3,5 eq to reduce my esters to alcohols. So no, it doesn’t stop at aldehyde, it’s actually
more difficult to stop the reduction at aldehyde than to continue to alcohol.

Reply

ophir says
JUNE 19, 2014 AT 8:01 AM

thats because you use more then ONE eq.

Reply

Steve says
OCTOBER 20, 2014 AT 6:47 AM

Does your DIBAL acquire an extra carbon atom when it coordinates the oxygen?

Reply

James says
OCTOBER 22, 2014 AT 5:09 PM

Shoot. Yes, it does. Fixed

Reply

MRIDUL MISRA says

NOVEMBER 18, 2014 AT 11:47 AM
i used 6 year old DIBAL for opening up my isopropyldene ring itwas working fantastic but when i
used new Dibal it producing unusual reports does anyone feel any prb like this
what can be degraded product of DIBAL-H ?

Reply

Karthik says
NOVEMBER 29, 2014 AT 8:26 AM

Does this also reduce carboxylic acids?

Reply

ben says
JANUARY 16, 2015 AT 6:36 AM

You usually use a couple of eqivs of dibal to reduce ester to aldehyde not 1 eq as stated above.
The important thing is to keep the temp low [<-50] and quench at low temps (Ihave al3ways used
MeOH to quenchrather than water – water will freeze at this temp!)

Just using 1eq would not help anyway as the aldehyde is more facile to reduce than the ester.
Love the site and have learnt a lot from it so far :)

Reply

ben says
JANUARY 16, 2015 AT 6:40 AM

Dibal has another trick up its sleeve. If you have an a,b-unsat. ester or ketone, it can cleanly
reduce without affecting the double bond. Unlike NaBH4 or LAH.

Reply

Paul J. says
AUGUST 26, 2015 AT 9:32 AM
 Actualy, I have just used 2 eq. of DIBAL by accident in calculating and got 100% of alcohol
and not a trace of aldehyde, so I wouldnt be so hasty with more than 1 eq.

Reply

senthil says
FEBRUARY 27, 2015 AT 9:39 PM

Dibal h

Reply

YAgnik 003 says

JUNE 13, 2015 AT 1:28 AM

In the last step of preperation of aldehydes from alkyl nitrile, how ammonia(NH3) is formed – I
mean , where is an additional hydrogen proton (H+) available to form NH3? Thanks in advance.

Reply

James says
JUNE 15, 2015 AT 10:20 PM

It would come in the workup step when water is added. There’s excess water.

Reply

Keihann says
AUGUST 27, 2015 AT 12:09 PM

Hi,
I want to reduce an ester to an aldehyde.

I’ll try DIBAL at -78°C in DCM.

If it doesn’t work, I’ll do the reduction to alcohol then oxidize with PCC.

My questions :

1) I thought non polar solvent would make the reaction slower. Then should I use toluene instead
of DCM ?

2) If going to alcohol, why -78°C ? Can’t I do it at 0°C ?

And should I add the ester to the dibal or the opposite ?

3) Last question, if I go to aldehyde, can I quench with methanol ? Water will be frozen at -78°C.

Also, what do you think about the paper adding NaOtBu to Dibal to reduce to aldehyde at 0°C ?

Thanks a lot

Reply

James says
AUGUST 27, 2015 AT 2:21 PM

I’d look for a prep online where someone successfully reduced an ester to an aldehyde. For
example, if you go to the ACS Publications home page, search for “ester dibal reduction
aldehyde total synthesis ” . You’ll come up with some reputable papers with supporting
information. Use those conditions.
Follow this, for instance: http://pubs.acs.org/action/doSearch?
text1=baran+ester+reduction+aldehyde+dibal&field1=AllField

If you want the aldehyde, you MUST keep it at -78. A non polar solvent is ideal. Avoid
ethereal solvents (they tend to coordinate to the aluminum and this can affect reactivity),
DCM should be fine. Toluene can present solubility problems, but might be OK for you at -78.
If you are aiming for the alcohol, then warming is fine.

I haven’t come across the paper you mention at the end.

Reply

Sarah says
JANUARY 17, 2016 AT 10:06 AM

In the mechanism of Dibal reduction, from ester to aldehyde, we know that OCH3 is a bad leving
group but it still goes out. Plz explain how?? I have to explain this dibal mechanism in my seminar
Reply

James says
JANUARY 18, 2016 AT 6:01 PM

DIBAL reduction produces O(-) which itself is a strong base. The formation of the C-O double
bond along with expulsion of CH3O(-) is therefore not accompanied by a huge energy barrier.
CH3O(-) is not a great leaving group, but still a much better one than H(-) or most carbon-
based leaving groups.

Reply

Peyton says
OCTOBER 15, 2016 AT 2:16 PM

I was also wondering if DIBAL-H can be used to reduce carboxylic acids?! If it does, would the
product be an aldehyde like it is when we reduce an ester with DIBAL-H?

Reply

James says
APRIL 17, 2017 AT 5:40 PM

You’d really have to crank on it. It’s possible, but you’d have to use over 3 equivalents and
heat it up. It’s far superior to use LiAlH4 !

Reply

Tulasi ram says

APRIL 16, 2017 AT 12:43 PM

Did “dibal h ” reduce acid chlorides?

Reply
 James says
APRIL 17, 2017 AT 5:39 PM

Yes, it should give an aldehyde.

Reply

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