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The Beckmann rearrangement, named after the German chemistErnst Otto Beckmann(1853
1923), is anacid-catalyzedrearrangementof anoximeto anamide.[1][2][3]
Cyclic oximes yield
lactams.
This example reaction[4]
starting withcyclohexanone,forming thereaction intermediatecyclohexanone oxime and resulting incaprolactamis one of the most important applications of
the Beckmann rearrangement, as caprolactam is the feedstock in the production ofNylon 6.
The Beckmann solutionconsists ofacetic acid,hydrochloric acidandacetic anhydride,and was
widely used to catalyze the rearrangement. Other acids, such assulfuric acidorpolyphosphoric
acid,can also be used.sulfuric acidis the most commonly used acid for commercial lactamproduction due to its formation of an ammonium sulfate by-product when neutralized with
ammonia.Ammonium sulfateis a common agriculturalfertilizerproviding nitrogen and sulfur.
Contents
Reaction mechanism
Thereaction mechanismof the Beckmann rearrangement is in general believed to consist of analkylmigration with expulsion of the hydroxyl group to form anitrilium ionfollowed by
hydrolysis:
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In one study,[5]the mechanism is establishedin silicotaking into account the presence ofsolventmolecules and substituents. The rearrangement of acetone oxime in the Beckmann solution
involves three acetic acid molecules and one proton (present as anoxonium ion). In thetransition
stateleading to the iminium ion (-complex), the methyl group migrates to the nitrogen atom inaconcerted reactionand the hydroxyl group is expulsed. The oxygen atom in the hydroxyl group
is stabilized by the three acetic acid molecules. In the next step the electrophilic carbon atom in
the nitrilium ion is attacked by water and the proton is donated back to acetic acid. In the
transition state leading to the N-methyl acetimidic acid, the water oxygen atom is coordinated to4 other atoms. In the third step, an isomerization step protonates the nitrogen atom leading to the
amide.
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The same computation with ahydroxoniumion and 6 molecules of water has the same result,
but, when the migrating substituent is phenyl in the reaction of acetophenone oxime withprotonated acetic acid, the mechanism favors the formation of an intermediate three-membered
-complex. This -complex is again not found in the H3O+(H2O)6.
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With the cyclohexanone-oxime, the relief ofring strainresults in a third reaction mechanism,
leading directly to the protonated caprolactam in a single concerted step without the intermediate
formation of a -complex or -complex.
Cyanuric chloride assisted Beckmann reaction
Beckmann reaction is known to be catalyzed bycyanuric chlorideandzinc chlorideco-catalyst.For example, cyclododecanone can be converted to the correspondinglactam,amonomerfor the
production ofNylon 12.[6][7]
Thereaction mechanismfor this reaction is based on acatalytic cyclewith cyanuric chloride
activating thehydroxylgroup via anucleophilic aromatic substitution.The reaction product isdislodged and replaced by new reactant via an intermediateMeisenheimer complex.
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Beckmann fragmentation
When the oxime has aquaternary carbon atomin an anti position to the hydroxyl group afragmentation occurs forming anitrile:
The fluorine donor in this fragmentation reaction is diethylaminosulfur trifluoride (DAST):[8]
SemmlerWolff reaction
The oxime ofcyclohexenonewith acid formsanilinein a dehydrationaromatizationreactioncalled the SemmlerWolff reactionor Wolff aromatization
[9][10][11][12]
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Fries rearrangementFrom Wikipedia, the free encyclopedia
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The Fries rearrangement, named for the German chemistKarl Theophil Fries,is arearrangement reactionof aphenylesterto ahydroxyarylketonebycatalysisofLewisacids.
[1][2][3][4]
It involves migration of anacylgroup ofphenyl estertobenzenering. The reaction isortho andpara selectiveand one of the two products can be favoured by changing reaction conditions, such
astemperatureandsolvent.
Contents
Mechanism
Despite many efforts a definitivereaction mechanismfor the Fries rearrangement is not
available. Evidence for inter- andintramolecularmechanisms have been obtained by so-calledcross-experiments with mixed reactants. Reaction progress is not dependent onsolventor
substrate.A widely accepted mechanism involves acarbocationintermediate.
In the first reaction step aLewis acidfor instancealuminium chlorideAlCl
3co-ordinates to thecarbonyloxygen atom of theacylgroup. This oxygen atom is moreelectron
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oxylhttp://en.wikipedia.org/wiki/Esterhttp://en.wikipedia.org/wiki/Phenylhttp://en.wikipedia.org/wiki/Rearrangement_reactionhttp://en.wikipedia.org/wiki/Karl_Theophil_Frieshttp://en.wikipedia.org/wiki/Fries_rearrangement#p-searchhttp://en.wikipedia.org/wiki/Fries_rearrangement#mw-navigation5/20/2018 The Beckmann Rearrangement
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rich than thephenolicoxygen atom and is the preferredLewis base.This interactionpolarizesthe
bondbetween the acyl residue and the phenolic oxygen atom and the aluminium chloride group
rearranges to the phenolic oxygen atom. This generates a freeacyliumcarbocationwhich reactsin a classicalelectrophilic aromatic substitutionwith the aromatic ring. The abstracted proton is
released ashydrochloric acidwhere the chlorine is derived from aluminium chloride. The
orientation of the substitution reaction is temperature dependent. A low reaction temperaturefavorspara substitutionand with high temperatures theorthoproduct prevails, this can berationalised as exhibiting classicThermodynamic versus kinetic reaction controlas the ortho
product can form a more stable bidentate complex with the Aluminium.[5]
Formation of the ortho
product is also favoured in non-polar solvents; as the solvent polarity increases, the ratio of thepara product also increases.
[6]
Scope
Phenolsreact toestersbut do not react to hydroxyarylketones with acylhalogen compounds
underFriedel-Crafts acylationreaction conditions and therefore this reaction is of industrial
importance for the synthesis of hydroxyarylketones which are important intermediates forseveral pharmaceutics such asparacetamolandsalbutamol.As an alternative toaluminium
chloride,otherLewis acidssuch asboron trifluorideandbismuthtriflateor strong protic acids
such ashydrogen fluorideandmethanesulfonic acidcan also be used. In order to avoid the use ofthese corrosive and environmentally unfriendlycatalystsaltogether research into alternative
heterogeneouscatalysts is actively pursued.
Limits
In all instances onlyesterscan be used with stable acyl components that can withstand the harsh
conditions of the Fries rearrangement. If the aromatic or the acyl component is heavilysubstituted then thechemical yieldwill drop due tostericconstraints. Deactivating meta-directing groups on the benzene group will also have an adverse effect as can be expected for a
FriedelCrafts acylation.
Photo-Fries rearrangement
In addition to the ordinary thermal phenyl ester reaction a so-calledphotochemicalPhoto-Fries
rearrangementexists[7]
that involves aradicalreaction mechanism.This reaction is also
possible with deactivatingsubstituentson the aromatic group. Because the yields are low this
procedure is not used in commercial production. However, photo-Fries rearrangement may occur
naturally, for example when a plastic bottle made of polyethylene terephthalate (PET) is exposedto the sun, particular to UV light at a wavelength of about 310 nm, if the plastic has been heated
to 40 degrees Celsius or above (as might occur in a car with windows closed on a hot summer
day). In this case, photolysis of the ester groups would lead to leaching of phthalate from theplastic.
[8]
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note-8http://en.wikipedia.org/wiki/Fries_rearrangement#cite_note-8http://en.wikipedia.org/wiki/Substituenthttp://en.wikipedia.org/wiki/Reaction_mechanismhttp://en.wikipedia.org/wiki/Radical_%28chemistry%29http://en.wikipedia.org/wiki/Fries_rearrangement#cite_note-7http://en.wikipedia.org/wiki/Photochemistryhttp://en.wikipedia.org/wiki/Friedel-Crafts_reactionhttp://en.wikipedia.org/wiki/Steric_hindrancehttp://en.wikipedia.org/wiki/Chemical_yieldhttp://en.wikipedia.org/wiki/Esterhttp://en.wikipedia.org/wiki/Heterogeneous_catalysishttp://en.wikipedia.org/wiki/Catalysthttp://en.wikipedia.org/wiki/Methanesulfonic_acidhttp://en.wikipedia.org/wiki/Hydrogen_fluoridehttp://en.wikipedia.org/wiki/Triflatehttp://en.wikipedia.org/wiki/Bismuthhttp://en.wikipedia.org/wiki/Boron_trifluoridehttp://en.wikipedia.org/wiki/Lewis_acidhttp://en.wikipedia.org/wiki/Aluminium_chloridehttp://en.wikipedia.org/wiki/Aluminium_chloridehttp://en.wikipedia.org/wiki/Salbutamolhttp://en.wikipedia.org/wiki/Paracetamolhttp://en.wikipedia.org/wiki/Friedel-Crafts_acylationhttp://en.wikipedia.org/wiki/Esterhttp://en.wikipedia.org/wiki/Phenolhttp://en.wikipedia.org/wiki/Fries_rearrangement#cite_note-6http://en.wikipedia.org/wiki/Fries_rearrangement#cite_note-5http://en.wikipedia.org/wiki/Thermodynamic_versus_kinetic_reaction_controlhttp://en.wikipedia.org/wiki/Arene_substitution_patternshttp://en.wikipedia.org/wiki/Arene_substitution_patternshttp://en.wikipedia.org/wiki/Hydrochloric_acidhttp://en.wikipedia.org/wiki/Electrophilic_aromatic_substitutionhttp://en.wikipedia.org/wiki/Carbocationhttp://en.wikipedia.org/wiki/Acyliumhttp://en.wikipedia.org/wiki/Covalent_bondhttp://en.wikipedia.org/wiki/Chemical_polarityhttp://en.wikipedia.org/wiki/Lewis_basehttp://en.wikipedia.org/wiki/Phenol5/20/2018 The Beckmann Rearrangement
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Benzidine(trivial name), also called 4,4'-diaminobiphenyl(systematic name), is the solidorganic compoundwith theformula(C6H4NH2)2. Thisaromaticamineis a component of a test
forcyanideand also in theproductionofdyes.Benzidine has been linked tobladderand
pancreatic cancer.[1]
Since August 2010 benzidine dyes are included in the EPA's List ofChemicals of Concern.
[2]
Contents
Synthesis and propertiesBenzidine is prepared in a two step process fromnitrobenzene.First, the nitrobenzene is
converted to 1,2-diphenylhydrazine, usually using iron powder as the reducing agent. Treatmentof this hydrazine with mineral acids induces arearrangement reactionto 4,4'-benzidine. Smaller
amounts of other isomers are also formed.[3]
The benzidine rearrangement, which proceeds
intramolecularly, is a classicmechanisticpuzzle inorganic chemistry.[4]
The conversion is described as a [5,5]sigmatropic reaction.[5][6]
In terms of its physical properties, 4,4'-benzidine is poorly soluble in cold water but can berecrystallized from hot water, where it crystallises as the monohydrate. It is dibasic, the
deprotonated species hasKavalues of 9.3 1010
and 5.6 1011
. Its solutions react withoxidizing agents to give deeply coloured quinone-related derivatives.
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Applications
As with some otheraromatic aminessuch as2-Naphthylamine,benzidine has been significantly
withdrawn from use in most industries because it is so carcinogenic.
In the past, benzidine was used to test forblood.Anenzymein blood causes the oxidation ofbenzidine to a distinctivelyblue-coloured derivative.
The test forcyaniderelies on similar reactivity.
Such applications have largely been replaced by methods usingphenolphthalein/hydrogen
peroxideandluminol.
he pinacol rearrangementor pinacolpinacolone rearrangementis a method for converting a
1,2-diolto acarbonylcompound inorganic chemistry.This1,2-rearrangementtakes place underacidic conditions. The name of the reaction comes from the rearrangement ofpinacolto
pinacolone.
This reaction was first described byWilhelm Rudolph Fittigin 1860.[1]
Contents
An overview of mechanism(discussion)
In the course of thisorganic reaction,protonation of one of theOH groups occurs and acarbocationis formed. If both theOH groups are not alike, then the one which yields a more
stable carbocation participates in the reaction. Subsequently, analkylgroup from the adjacentcarbon migrates to the carbocation center. The driving force for this rearrangement step is
believed to be the relative stability of the resultant oxonium ion, which has complete octet
configuration at all centers (as opposed to the preceding carbocation). The migration of alkylgroups in this reaction occurs in accordance with their usualmigratory aptitude,i.e.Aryl>>>>
hydride>Phenyl> tertiary carbocation (if formed by migration) > secondary carbocation (if
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formed by migration) > methyl cation . The conclusion which group stabilizes carbocation more
effectively is migrated
Stereochemistry of the rearrangement
In cyclic systems, the reaction presents more features of interest. In these reactions, thestereochemistryof the diol plays a crucial role in deciding the major product. An alkyl group
which is situated trans- to the leavingOH group alone may migrate. If otherwise, ring
expansion occurs, i.e. the ring carbon itself migrates to the carbocation centre. This reveals
another interesting feature of the reaction, viz. that it is largely concerted. There appears to be aconnection between the migration origin and migration terminus throughout the reaction.
Moreover, if the migrating alkyl group has a chiral center as its key atom, the configuration atthis center is retainedeven after migration takes place.
HistoryAlthough Fittig first published about the pinacol rearrangement,it was not Fittig butAleksandr
Butlerovwho correctly identified the reaction products involved.[2]
In a 1859 publicationWilhelm Rudolph Fittigdescribed the reaction ofacetonewithpotassium
metal...[3]
Fittig wrongly assumed amolecular formulaof (C3H3O)nfor acetone, the result of along standing atomic weight debate finally settled at theKarlsruhe Congressin 1860. He also
wrongly believed acetone to be an alcohol which he hoped to prove by forming a metal alkoxide
salt. The reaction product he obtained instead he called paraceton which he believed to be an
acetonedimer.In his second publication in 1860 he reacted paraceton withsulfuric acid(the
actual pinacol rearrangement).
Again Fittig was unable to assign a molecular structure to the reaction product which he assumed
to be another isomer or a polymer. Contemporary chemists who had already adapted to the new
atomic weight reality did not fare better. One of them,Charles Friedel,believed the reactionproduct to be theepoxidetetramethylethylene oxide[4]
in analogy with reactions ofethylene
glycol.Finally Butlerov in 1873 came up with the correct structures after he independently
synthesised the compound trimethylacetic acid which Friedel had obtained earlier by oxidizingwith adichromate.
[5]
Some of the problems during the determination of the structure are because carbon skeletal
rearrangements were unknown at that time and therefore the new concept had to be found.
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Butlerov theory allowed the structure of carbon atoms in the molecule to rearrange and with this
concept a structure for pinacolone could be found.
Hofmann rearrangement
From Wikipedia, the free encyclopedia
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The Hofmann rearrangementis theorganicreaction of a primaryamideto a primaryamine
with one fewercarbonatom.[1][2][3]
The reaction is named after its discoverer:August Wilhelm von Hofmann.This reaction is alsosometimes called the Hofmann degradationor the Harmon Process, and should not beconfused with theHofmann elimination.
Contents
Mechanism
The reaction ofbrominewithsodium hydroxideformssodiumhypobromitein situ,which
transforms the primary amide into an intermediateisocyanate.The intermediate isocyanate ishydrolyzed to a primary amine, giving offcarbon dioxide.
Variations
Several reagents can substitute for bromine.N-Bromosuccinimideand1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU)can effect a Hofmann rearrangement. In the following
example, the intermediate isocyanate is trapped bymethanol,forming acarbamate.[4]
http://en.wikipedia.org/wiki/Hofmann_rearrangement#mw-navigationhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#mw-navigationhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#mw-navigationhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#p-searchhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#p-searchhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#p-searchhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Amidehttp://en.wikipedia.org/wiki/Amidehttp://en.wikipedia.org/wiki/Amidehttp://en.wikipedia.org/wiki/Aminehttp://en.wikipedia.org/wiki/Aminehttp://en.wikipedia.org/wiki/Aminehttp://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-1http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-1http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-3http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-3http://en.wikipedia.org/wiki/August_Wilhelm_von_Hofmannhttp://en.wikipedia.org/wiki/August_Wilhelm_von_Hofmannhttp://en.wikipedia.org/wiki/August_Wilhelm_von_Hofmannhttp://en.wikipedia.org/wiki/Hofmann_eliminationhttp://en.wikipedia.org/wiki/Hofmann_eliminationhttp://en.wikipedia.org/wiki/Hofmann_eliminationhttp://en.wikipedia.org/wiki/Brominehttp://en.wikipedia.org/wiki/Brominehttp://en.wikipedia.org/wiki/Brominehttp://en.wikipedia.org/wiki/Sodium_hydroxidehttp://en.wikipedia.org/wiki/Sodium_hydroxidehttp://en.wikipedia.org/wiki/Sodium_hydroxidehttp://en.wikipedia.org/wiki/Sodiumhttp://en.wikipedia.org/wiki/Sodiumhttp://en.wikipedia.org/wiki/Hypobromitehttp://en.wikipedia.org/wiki/Hypobromitehttp://en.wikipedia.org/wiki/In_situhttp://en.wikipedia.org/wiki/In_situhttp://en.wikipedia.org/wiki/In_situhttp://en.wikipedia.org/wiki/Isocyanatehttp://en.wikipedia.org/wiki/Isocyanatehttp://en.wikipedia.org/wiki/Isocyanatehttp://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/N-Bromosuccinimidehttp://en.wikipedia.org/wiki/N-Bromosuccinimidehttp://en.wikipedia.org/wiki/N-Bromosuccinimidehttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/Carbamatehttp://en.wikipedia.org/wiki/Carbamatehttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-4http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-4http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-4http://en.wikipedia.org/wiki/File:Hoffmann_rearrangement_mechanism.svghttp://en.wikipedia.org/wiki/File:Hofmann_Rearrangement_Scheme.pnghttp://en.wikipedia.org/wiki/File:Hoffmann_rearrangement_mechanism.svghttp://en.wikipedia.org/wiki/File:Hofmann_Rearrangement_Scheme.pnghttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-4http://en.wikipedia.org/wiki/Carbamatehttp://en.wikipedia.org/wiki/Methanolhttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/1,8-Diazabicycloundec-7-enehttp://en.wikipedia.org/wiki/N-Bromosuccinimidehttp://en.wikipedia.org/wiki/Carbon_dioxidehttp://en.wikipedia.org/wiki/Isocyanatehttp://en.wikipedia.org/wiki/In_situhttp://en.wikipedia.org/wiki/Hypobromitehttp://en.wikipedia.org/wiki/Sodiumhttp://en.wikipedia.org/wiki/Sodium_hydroxidehttp://en.wikipedia.org/wiki/Brominehttp://en.wikipedia.org/wiki/Hofmann_eliminationhttp://en.wikipedia.org/wiki/August_Wilhelm_von_Hofmannhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-3http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-1http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-1http://en.wikipedia.org/wiki/Carbonhttp://en.wikipedia.org/wiki/Aminehttp://en.wikipedia.org/wiki/Amidehttp://en.wikipedia.org/wiki/Organic_chemistryhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#p-searchhttp://en.wikipedia.org/wiki/Hofmann_rearrangement#mw-navigation5/20/2018 The Beckmann Rearrangement
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In a similar fashion, the intermediate isocyanate can be trapped bytert-butanol,yielding thet-butoxycarbonyl(Boc)-protected amine.
A mild alternative to bromine is also(bis(trifluoroacetoxy)iodo)benzene.[5]
http://en.wikipedia.org/wiki/Tert-butanolhttp://en.wikipedia.org/wiki/Tert-butanolhttp://en.wikipedia.org/wiki/Tert-butanolhttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/%28bis%28trifluoroacetoxy%29iodo%29benzenehttp://en.wikipedia.org/wiki/%28bis%28trifluoroacetoxy%29iodo%29benzenehttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-5http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-5http://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-5http://en.wikipedia.org/wiki/File:Hoffmann_Rearrangement_NBS.pnghttp://en.wikipedia.org/wiki/Hofmann_rearrangement#cite_note-5http://en.wikipedia.org/wiki/%28bis%28trifluoroacetoxy%29iodo%29benzenehttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/Di-tert-butyl_dicarbonatehttp://en.wikipedia.org/wiki/Tert-butanol