Академический Документы
Профессиональный Документы
Культура Документы
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
OH
CN
CN
OH
OH
It is the same mechanism as the one with thiamine. So cyanide can also be
usedasacatalyzer.[3]
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
7. ANNEXES
IRspectrum,NMRspectrum