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TatianaPachovaBSc2,chemistry

Assistant:ChandanDey
SciencesIIlab.A

Benzoincondensationcatalyzedby
thiamine(n38)
1. INTRODUCTION

1.1)

1.2)

Purpose

Theobjectiveofthisexperimentistosynthesizebenzoinfromthebenzaldehyde,
usingthiaminehydrochloride.

Scheme

Thiamine
OH

benzaldehyde

1.3)

2-hydroxy-1,2-diphenylethanone
(Benzoin)

Mechanism

Step1:Deprotonationofthethiamine:

NaOHattacksthiamineanddeprotonatesit.Itisacondensation,sinceamolecule
ofH2Oisreleased.Thereisaformationofacarbine,whichisveryreactive.

R1

N
N

S
H

NH2

OH

R2
S

Step2:nucleophileattackofthebenzaldehydebythedeprotonatedthiamine:

R1

R1

R2

R2

S
H

Intramolecular H transfer

R1
N

R1
N

R1

H2O

R2

HO

R2

R2

HO
S
Ph

Ph
S

Ph

Ph
Ph

HO

R1
N
R2

H2O

S
OH

2. PROCEDURE
2.1)

2.2)

Reaction

Reagents

molarmass[g/mol] wt/voltaken

n[mmol]

equivalence

Thiaminechloride
300.81
3.55g
0.012
1
Benzaldehyde
106.12
20.0mL
0.196
16.33

Ina100mLtwinneckroundbottomflask,3.5gofthiaminehydrochloridewere
dissolved in 8mL of water. Then, 35mL of EtOH at 95% were added and the
solution was cooled down to 0C. Into the agitated solution, first were added
slowly7mLofcoldNaOH3Mandthen20mLofbenzaldehyde.Themixturewas
heatedat60Cfor90min.Thesolutionwascooleddownnaturallythenwithan
icebathuntilcrystallization.

Isolation

Theobtainedcrystalswerewashedwithwaterandthenrecrystallizedinethanol.

3. DISCUSSIONANDRESULTS

3.1)

Observations

When the mixture of thiamin, water and EtOH was cooled down, a white
precipitatewasformed.
Thefinalproductisalmostpearlywhiteandspikycrystals.
Its fusion temperature is 134.7136.2 C which is in agreement with the values
givenbytheprotocol:134136C.

Yield

nexp
molarmass[g/mol] nth[mmol]
yield[%]
[mmol]

3.2)

212.24

196

44.1

23%

9.3679gofproductwereobtainedafterrecrystallization.Thisrepresentsa23%
yield. The protocol said that the mass should be 10g (48%) but actually 10g
represent 24% of yield (taking benzaldehyde as the limiting reagent). So the
resultissatisfying.

4. SPECTROMETRYDATA

4.1)

NMR1H(CDCl3,400MHz)

H6
H7

H5

H1

H6

H4

H2

H5

H3

H1

H2

H8

bond

shift[ppm]

multiplicity

hydrogen

CH
CH
CH
OH

7.92
7.557.27
5.97
4.57

multiplet
multiplet
doublet
doublet

benzeneH1
benzeneH2,H3,H5,H6,H7
H4
H8

4.2)

7.92(m,2H);7.557.27(m,8H);5.97(d,J=6.0Hz,1H);4.57(d,6.0Hz,1H)

Thereisaproblemwiththemultipletcorrespondingto7.557.27ppmbecause
the integral should show only 8 hydrogens, but atually shows 9. The problem
couldbethesolvent(CDCl3)thatwouldhavebeenleftintheproduct.

IR(neat,cm1)

3404;1679;1263;1204;1092;1068;977;753;696;673

We can clearly see major peaks: one at 3404 cm1, corresponding to the OH
stretch and another at 1679 cm1, corresponding to the C=O stretch of an
aldehyde.

ThereforetheIRconfirmsthatitistheexpectedproduct.

5. QUESTIONS

1) Whatisthethiamineformulaandwhatisitsactionmechanisminthereaction
ofbenzoincondensation?

Seemechanism.Thiamineisacatalyst;itisregeneratedeachtimeabenzoin
moleculeissynthesized.

ClN+

NH2

OH

3-((4-amino-2-methylpyrimidin-5-yl)methyl)-5-(2-hydroxyethyl)-4methylthiazol-3-ium chloride

2) Showhowcyanidecanreplacethiamineinthisreaction.

OH
O

O
CN
H

CN
H

easy deprotonation because


of the dipole in C-N

OH

CN

CN

OH

OH

It is the same mechanism as the one with thiamine. So cyanide can also be
usedasacatalyzer.[3]

3) The pyruvate decarboxylase is an enzyme depending on the thiamine which


catalyses the decarboxylation of pyruvic acid to acetaldehyde. Write a
mechanismforthistransformationandnotedownthebibliographicreference.

Themechanismisanoxidativedecarboxylation,withareleaseofCO2.[4]

O
R1

O
N+

OH

R2

OH

R2

OH

S
OH

R2

N+

N+

R1

R1

2-oxopropanoic acid

CO2

OH

OH

R2

R2

R1

R1

H+
H
O
R1

HA

R2
S

6. REFERENCES

N+

H3C

acetaldehyde

R2

OH
N
R1

A-

R2

OH
N
R1

[1] Travaux Pratiques de Chimie Organique 3me Semestre, 21 Novembre 2011 16


Mars2012,38
[2]Silverstein,Bassler,Morrill,Spectrometricidentificationoforganiccompounds
[3]Organicchemistrylessons,Dr.A.Zumbuehl,p.52
[4]VollhartSchore,Traitdechimieorganique,5meedition,2009,p.1080

7. ANNEXES

IRspectrum,NMRspectrum