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Spectroscopy
Some Dienes
Vitamin A O
Benzene
Cyclohex-2-enone
CH3
Orbital Depiction
DHhydrogenation
+ CH2
CH2-CH=CH-CH 3 1o allylic
Carbocation Stability
CH2=CH-CHCH 2 BrCH 2-CH=CH-CH 2 2 1 4 1 k inetic thermodynamic forms more rapidly is more stable
H-Cl 80 oC
Thermodynamic Products
Cl CH2 H H-Cl 80oC H CH2 Cl
Addition to 1,3,5-Hexatriene
Br H
6 5 4 3 2 1
HBr
O N-Bromosuccinimide
O N Br O
. + N
O
Br
CH2=CHCH 2 + HBr
.
O
CH2CH=CH 2
Br 2 +
N H O
ii)
CH2=CHCH 2
CH2CH=CH 2
+ Br 2
CH2=CHCH 2Br + Br
. .
. .
Br Br + Br major + + Br
Diels-Alder Reaction
a Pericyclic Reaction
CH2 C H C CH2 H EWG C C H dienophile [4+2] cycloaddition H H H C C C C H H C C H EWG H
cisoid diene
H H adduct
EWG
O O
HC
CCO2CH3
CO2CH3
Stereochemistry
H H CN H endo
exo
Endo Addition
CN H2C=CHCN heat
H H CN H
Endo Rule
O CH3O CH3O O
H
2
H H
H retro-D.A.
O
1
2 3 4
+
5
diene
diene
dienophile
A Radiosensitizer
OH O H Okadaic acid O H O OH
HOOC OH
O O OH H O
Synthesis of LS-5
O + furan maleic anhydride O O O O O O O
Cytotoxicity
of asynchronous DU-145 prostate cancer cells exposed to drug for o 2-h at 37 C Cantharidin Cantharidic acid LS-5
Survival Curves
HT-29 colon cancer cells Irradiated after 2-h exposure to 2 M drug
LS numbers
OCH3 D
OCH3 or CN CN
OCH3 CN
OCH3
O COCH3
o 2
Intermediate is Preferred
AlCl3 O AlCl3 OCH3 2
o
O COCH3
O COCH3
major
S HO S
2
enzyme O H3COCN O H OR
9 7
O H3COCN O H
OR
Calicheamycin(R = sugar)
O H3COCN O H OR
O H3COCN O H
.
OR
.
200 C
o
Suprafacial Allowed
Antarafacial - Forbidden
Cycloaddition Reactions can be Planned Based on the Number of Pairs of e-s that Move
Formation of Cyclobutanes
h [2+2] H2C CH2
dicyclopentadiene O heat
h [2+2]
Ultraviolet Spectroscopy
The absorption of a 171-nm photon excites an electron from the p bonding MO of ethylene to the p* antibonding MO.
lmax (nm)
Conjugation lowers the energy differences between the HOMO and LUMO energy levels, and so conjugated dienes absorb at longer wavelengths than isolated dienes, and trienes absorb at longer wavelengths than dienes, etc. Alkyl group substitution on double bonds also causes absorption to occur at longer wavelengths.
226
227
232
lmax = 217nm
lmax = 232nm
240
HOMO-LUMO Gap
lessens with increased conjugation
Woodward-Fieser Rules
for Predicting lmax
Base value:
30 nm 5 nm
Alkyl group
Cl, Br OH, OR
5 nm
5 nm 6 nm
cisoid diene
253 nm
SH, SR
NH2, NHR, NR2
30 nm
60 nm
OCH3
Determination of lmax
Base: 214 nm R groups: 4 x 5 = 20 nm exocyclic db = 5 nm predicted lmax= 239 nm
Determination of lmax
OCH3 Base: 214 nm double bond ext. conj. = 30 nm OR group = 6 nm R group = 5 nm predicted lmax = 255 nm
Determination of lmax
Base: 253 nm db ext. conj. = 30 R groups: 3 x 5 = 15 exocyclic db = 5 predicted lmax =303 nm