Ochem exam 2


OH


Strong activatorO,P director


NH2


Strong activatorO,P director


OR


Strong activatorO,P director


NR2


Strong activatorO,P director


alkyl groups


weak activatorO,P director


CH3


weak activatorO,P director


CH2CH3


weak activatorO,P director


halogens


weak deactivatorO,P director


Br


weak deactivatorO,P director


Cl


weak deactivatorO,P director


F


weak deactivatorO,P director


CF3


Strong deactivatorM director


SO3H


Strong deactivatorM director


NO2


Strong deactivatorM director


C=O


Strong deactivatorM director


CHO


Strong deactivatorM director
C=OlH


CN


Strong deactivatorM director


Reactivity of benzene-OH


very fast


Reactivity of benzene-CH3


fast


Reactivity of benzene


average


Reactivity of benzene-Cl


slow


Reactivity of benzene-NO2


very slow


NR3+


Strong deactivatorM director


Substitution is controlled by_______


Substitution is controlled by THE STRONGEST ACTIVATOR


a DIENE is electron_____ and has electron______groups


a DIENE is electron RICH and has electron DONATING groups

i.e. alkyl groups


C6H6 is __________


benzene


C6H5CH2--- is


benzyl


benzene +

H2NO3
--------->
Fe, HCl


benzene-NH2


benzene +

H2NO3
------>
H2SO4


benzene-NO2


benzene-NH2 +

CF3C(O)OOH
---------->


benzene-NO2


benzene +

SO3
------>
H2SO4


benzene-SO3H


benzene +

CrO3
---->
H20;H+


benzene-OH


benzene-OH +

H2
----->
Pt


benzene


benzene +

ClC(CH3)3
-------->
AlCl3


benzene-C(CH3)3


benzene +

X2
------>
FeX3


benzene-X


benzene +

H2
------>
Pt


cyclohexane


benzene +

ClC(O)CH3
------------>
AlCl3


OllC-benzenelCH3
*no rearrangement, but can't be done in presence of meta directors*


benzene +

ClCH2CH3
------------>
AlCl3


benzene-CH2CH3

*will rearrange if adding anything longer than ethyl,can't be done in presence of meta directors*


benzene=O +

Zn(Hg)
---------->
HCl


benzene


benzene +

CrO3
-------->
H2SO4;H+


benzene=O


Acylium ion


CH3C+=:O: ....or.... CH3C=O:+


benzene-SO3H +

H2O
------->
heat


benzene


allyl carbocation is ______ stable than primary carbocation


allyl carbocation is MORE stable than primary carbocation


Carbocation stability

_____>__________>_______


3o > allyl ~ 2o > 1o ; CH2=C+H


NBS creates ___________


NBS creates bromine radicals


SN1 carbocation stability
______>_______>________


3o > allyl ~ 2o > 1o ; vinyl


SN2 carbocation stability
________>__________>_________


allyl > 1o > 2o > 3o ; vinyl


a DIENOPHILE is electron _____ and has electron _______ groups


a DIENOPHILE is electron POOR and has electron WITHDRAWING groups

i.e. CF3 , O=C-R , C=N


the DIENE in a Diels-Alder rxn works better when in the _________ formation


the s-cis formation

("c" shaped molecule)


in a Diels-Alder rxn the alkene is also known as what?


the dienophile


Factors affecting value of lambda max
1)
2)
3)


1)extent of conjugation (incr. w/ # db's)

2)conformational effects (s-cis>s-trans)

3)alkyl groups (incr. w/ # alkyl group)


What is the primary type of transition observed in UV-Vis spectroscopy?


pi--->pi*


aldehydes and ketones show additional transformation in UV-Vis spec which is symbolized by _________


n--->pi*