Catlisis

Curs201516

PROBLEMESUNITAT1

4rtcurs
GrauQumica

1. Themostimportant(andalsothemostexpensive)grapefruitaromacompoundisthebicyclicterpenenootkatone.Itis
manufacturedbyoxidationofvalencene,whichisextractedfromValenciaoranges.Nextfigureshowstworoutesfor
thisoxidation,astoichiometricreactionusingchromiumtrioxide,andacatalyticalternativeusingsodiumhypochlorite
(bleach)inthepresenceof1mol%osmiumtetraoxidecatalyst:

(a) Comparetheatomeconomybetweenthetworeactionsaccordingto:
(b)CalculatetheEfactorsvaluesforbothoptions.
(c)GiventhatbothCrOandOsO4areequallytoxic,estimatetheQvaluesinbothcases,andexplainwhichoption
youfavorandwhy.

2.

The classic synthesis of hydroquinone starts with aniline, and uses stoichiometric MnO2, sulfuric acid, and iron,
accordingtothefollowingreactions(equationsarenotbalanced);
O

NH2
+ MnO2 + H2SO4
O

+ (NH4)2SO4 + MnSO4 + H2O

O

+ Fe + H2O

OH
+ FeO

O
OH

(a) Calculatetheatomeconomyforthisprocess
(b)Anilineitselfismadebynitrationofbenzenetonitrobenzene,followedbyhydrogenation.Usingtheprinciples
ofgreenchemistry,drawaschemeforanewprocessformakinghydroquinone,startingdirectlyfrombenzene
(feelfreetoinventanycatalystsyouneed).
(c) Search on the Internet for information on the Upjohn hydroquinone process, and compare that with your
synthesisroute.WhataretheadvantagesoftheUpjohnprocessandofyoursynthesiscomparedtotheclassic
route?Arethereanydisadvantages?

3.

Fluorescentlightbulbscontainmercury,whichisreleasedintotheenvironmentwhenthebulbsaredisposedofin
landfills.Incandescent(regular)lightbulbscontainnomercury,andsodisposalisnotaproblem.However,regular
bulbsusemoreelectricitythanfluorescentones,whichmeansburningmorecoalatthepowerstation,andburning
coalalsoreleasesmercuryintotheenvironment.Atypicalfluorescentbulbconsumes11Wandburnsfor5000h,
whileatypicalincandescentoneconsumes75Wandburnsfor1000h.
(a)Constructtwolifecyclecharts,oneforfluorescentlightbulbsandoneforincandescentlightbulbs.
(b)Assumingthatcoalcontainstypically20ppmmercuryimpurities,whichtypeoflightbulbisbetter,fluorescentor
incandescent,fortheenvironment?
Hint:Ifyoudonotfindabettervalue,considerthattheefficiencyofpowerplantthatgenerateselectricityburning
coalis30%

4.

The asymmetric hydrogenation of aryl ketones is an important step in the synthesis of many pharmaceutical
intermediates.BlaserandcoworkersshowedthatRucomplexeswithFecyclopentadienyl.sandwichcomplexesare
good catalysts for this reaction. The next figure shows the different substrates tested, along with the time,
conversion, and substrate/catalyst ratio. Using these data, calculate for each reaction the catalyst TON and the
averageTOFalongthewholereaction.

5.

Naproxenisanonsteroidalanalgesicandantiinflammatorydrugwidelyused.Thedrugissuppliedasthepure(S)
enantiomer, since the (R) enantiomer is a liver toxin. Although enantiomerically pure Naproxen is industrially
produced by resolution of the racemate, it can be prepared by asymmetric hydroformylation, followed by the
oxidation of the enantomerically enriched aldehyde to the corresponding carboxylic acid, by using in the
hydroformylationstepthehomochiralcatalystRhH(L)(CO)2(L=(R,S)BINAPHOS)developedbyNozakietal.

Assumethatyouarerunningapilotplantinvestigatingthisreaction.Startingwith153.0molsof2methoxy6
vinylnaphthaleneyougetthefollowingreactionmixture:

Calculate:
a) Thereactionconversion
b) The chemoselectivity, the regioselectivity in the branched aldehyde, and the enantioselectovity in the (S)
enantiomer.
c) Theyieldin(S)2(6methoxynaphthalen2yl)propanal

6.

The following graphics represent the % of conversion versus time (in minutes) in experiments corresponding the
hydrogenationof(S)limonenewithRhCl(PPh3)3catalystsindifferentreactionconditions:

Exp1:0.100mmolofcatalyst,12.0mmolof(S)limonene,P(H2)=20bar;T=80oCwith10mloftolueneassolvent.
Exp2:0.400mmolofcatalyst,200mmolof(S)limonene,P(H2)=30bar;T=50oCwith60mloftolueneassolvent.

Fromthedataabove,calculate:
a) TheinitialTOFofeachreaction
b) TheaverageTOFforeachreactionduringthefirst20minutes
c) ThemaximumTONforthehydrogenationof(S)limonenecatalyzedbyRhCl(PPh3)3