Physical Organic Chemistry: CHM 2L4

Problem Set no. 1

Catheri ne Firmase-Monarquia

From: Advanced Organic Chemistry FIFTH EDITION

Part A: Structure and Mechanisms
FRANCIS A. CAREY and RICHARD J. SUNDBERG

[1] 1.1.
Suggest an explanation for the following observations:
a. Although the hydrocarbon calicene has so far defied synthesis, but it has been estimated that it would
have a dipole moment as large as 5.6 D.

Calicene has two rings - five membered ring (left) and 3 memebered ring (right) and both are attahced by
by a double bond now if we move one of the bonds in the double bonds torards the five membered ring
the carbon (attached to the double bond) will get a G) charge and carbon of the three membered ring will
get a (+) charge now this is an exceptionally stable structure as both the rings are aromatic, because it
satisfies huckels rule (4n+2) pielectrons

for five membered ring: 2 + 2+ 2 (+ charge) = 6 pi electrons

for three membered ring: 2 pi electrons

so it satisfies huckel rule so both the ring are aromatb and hence they will tend to be like that and since
there is a separation of charges ....thats why it has a large dipole moment

b. The measured dipole moment of 4-nitroaniline (6.2 D) is larger than the value calculated using
standard group dipoles (5.2 D). ql,a./"ard

HzN Noe t^-

('
fttrz
?.*^P fiyrrbr: T'U
(/\
tl
nJ 0z

4-nitroanifine -V \t l\l <)

.Lt AAa f ,g3 D
41 : 3'qs D
hl 0I
,1A-- {,' I D

v t{,s d, pule h^^ n-r rJ V $r I o Lt,nl&hL ^^d at^^ L'nL ,lrtaw .n+AA
rrful,f J run

,n/,a14 &frul" fir.r],r."{rfu f h op 5 nl

N\'l a on'.d l..l of troTI
Pnn"l-t dar{ uf
Irt > ,(-,J f" fh, [e r..,Lth+ , in6, l]ut i ,.... 4 -n i l.u ay\,^|,\ g tfu d^
yrolC /h/il rnr^{ S

rhq;v q.o Y. r"{,\ r. h r Ct L6L[" o{l-, ( r .l-o CfvA W rh+ nL+ val&{. r ,^
c. The dipole moments of furan and pyrrole are in opposite directions,

CJ q)
furan l
pyrrole
H

Both pyrrole and furan have a lone pair of electrons in a p-orbital, this lone pair is
extensively delocalized into the conjugated pi framework to create an aromatic 6 pi electron
system.

Where pyrrole andfuran significantlydiffer is that,

. in pyrrole there is an N-HN-H bond lying in the plane of the ring and directed away
from the ring
r whereas in furan, there is a full lone pair of electrons in roughly the same position.
The localized lone pair of electrons pointing away from the ring has a very significant effect
on the dipole vector and is enough to cause the observed reversal in dipole moment
direction between furan and pyrrole.

I
H

trt
-1 5-2 1 D
,/\
\_/
--07D

t2l t.7.
(Old 1.16)The propellanes are hiehly reactive in comparison with unstrained hydrocarbons and readily
undergo reactions that result in the rupture of the central bond. For example, it has been suggested that
the polymerization of propellanes occurs by initial dissociation of the center bond. Perhaps surprisingly,
it has been found that [1.1.lJpropellane is considerably less reactive than either [2.2.1]propellane or
[2.l.1lpropellane. Use the computational enthalpy data below to estimate the energy required to break
the center bond in each of the three propellanes. Assume that the bridgehead C-H bonds in each of the
bicycloalkanes has a bond enthalpy of -104 kcal/mol. How might the results explain the relative
reactivity of the propellanes.

-4i
N #H2 r)__/
\2t
-N-=

JH = -99 kcaUmol
4 tH = -73 kcal/mol JH = -39 kcaUmol
Required:

Energy required to break the center bond in each of the three propellanes.

Given:

Bridgehead C-H bond energy = -1,04 kcal/mol

A H of each propellane

Solution: LH ,= +J gr'/c/ [l .* c,tar*

H p^^ h^d 3 H '\'& f"u Pu1'k b"r""l

$
**?
\
:e0 *,0'l
\t
Af+r-fr rv+= Fc,,t/* ft*t /*l
.3 I

= - J/\gl-'^Jl^l

L-al/rrf Lo'{ |*J|Y.AI

Uf,J 13

* ?g K Nl rvnl = -' t1 I \\/*) l,.,;\

,.1.1

rrq
a^,1?q
=q [rr.^ t/ rrr*l
' fiz l-^;' l*l
l,l - I

il .,ttl {- {'}< 6JL

l. l. , p- yll aw hor t\* r\n"'F{-z *t"t4'rut' I

,^, F t\ rvnnFt *llfvtb!/i {r $"ltrfio

n bond- lnrGr^",t i-l ".rt\
? )'l t- t.f-l .

il a"li Y*tr h q^^dl^*

R^d &*,
 [3] 1.1s.

a. Sketch the nodal properties of the Htickel HOMO orbital of the pentadienyl cation.

b. The orbital coefficients of two of the MOs of pentadienyl are given below. Specify which is of lower
energy; classify each orbital as bonding nonbonding, or antibonding; and specify whether each orbital is
S or A with respect to a plane bisecting the molecule perpendicular to the plane of the structure.

rf, - O.5Og1 *O.-5Og, - O.5()9. - 0.5O05

r|, - 0.51{9, - 0.5t{g.r *O.5fig.

,iu
,1 i':t*C +,>

rb lrrnd;r,
4t
x..\"r rtl 0
'1*cdqr,
1V hr,rltt
Inod*
'd# FS :
on,yrrr$_$&-{-f; -lL-

?rr.ta,[ \n/ 5 e'

ditn1
v)
Yr' o9oV, f soyz 0S0"fq 0,So&s d2
s-. q2
r)";1 rn 4tY '' U
"J

v),
8 ;+
0.q,By, e 0-92y* 1
I

11 "!fW, "+ T,*

8 {
vg^

{r tily I' I L'

d-^ ,r,6 , A'61 rn,-t
/Nonbp^
 14lL.L7
a. Calculate the HMO energy levels and atomic orbital coefficients for 1,3- butadiene.
b. Estimate the delocalization energy, in units of $ of the cyclobutadienyl dication C4H42+from HMO
theory.
c. Estimate, in units otS ttre energy assoclated with the longest-wavelengh UWIS absorption of
1,3,5,7-octatetraene. Does it appear at a longer or shorter wavelength than the corresponding
absorption in 1,3,5-hexatriene?
CtC2qCq
ar f f'l Li{'r t"' * r"' 3
,N (,t Wl
? t.tr :
e1 >,7
+-o: o tv', 0"31 l-r * 0-6 bts 0-(rds - 0 3-)t-t
YCr { Cl t O
a,
J
,
i,! -lrulnrl,tlru'
-'
Cr + XCI {C3*u O Uz F. bo t( - o31fl '- $ "3111 0' 6 o tf
O I t2 +r;X+e{ :e t# o'L,otf o'nn -0'31t1 - 0 &otf
0't D t Cg +C/l/(:D {$q o31 t} o-b0tS o.but5 oZtrl
i

E-T\ H?6 Y l"l lh o

I r^ Q_t ; d,+ lt,t90 Q, : o.Ttr-t Q, 1#. trots +" r *.&orS$j \6itn0v
'
hsht{tl,J:,it,?,4 n :+ f=
Y7 c,( t b,Ulg p !r = f {oof u[, t0,z-ll?']a -g3t 11 d3
o-btl5 S u
(h'
' l, (!l gD
ttl? z 0.ft1S0
?t, { o. bt8 & \'== CI.(0015$,*03lllhr*s.91 zQS+ 0 b0rS,bq
h3' o'b tg o E ,+, d\ lbtfcP Q,q =- 0.3lll4r * 0,bor5 dr- 0 bur S(be r0 }l l?4q
h.l : 4l'6 l9D
J Ui cl +ry ctl , pls ect Wln $.)q Pnbl"nrc,t-l | "ltlb1 o hlqf'on.xlSx
{ Ct( c al s^lal'on
r*rh eur;lc,a.l.'1r-,( f *.ots ' e)/,.ht'r;-
r) F" TE= )o{129
sTt e- q? o'hit"Is ,"rt, .
l,-fl n't)
m a(.)
Lo[tuo(. t,o Evu ,T\ efg: g("t f 2p ) r
Vt !ot, t q(
,tr1 tp

I
P'.:
vdt
yrr:
O\
9 Tt e '6 €lt t t\-\'-' :: !vtrAtt U
c{ ,'
a q./i+g
t dt 4- 2p
L**k, = Lt' F t [n c,
t@ r Il E
=1r
WtnLttth'h$ /h
: 4e 4n"try
4d. I
o hbrorYhrh 4 a L'L d'o*Ll(, bord ,{ y ;k: & TT a)<c+,.o,. d" fu 61A

Ti the cini :lr" 'i,i t,i*(*r a*l{v|fl rJ Aa',e l" op

o r'h [o^d^tt cnhihJ- 'o I

u l^'
7* 4rAr h k.oh . r hE rY\& ' Y6,a-1 I \"' 1 [ ur-' AV-jror yb-
'W'tvA
'l -->'\ f'rna{..0n'b *kc Wtna-Lt^fwr frmf (ft)
nidt \ A r 0,r. Ch -l I
P^ )

t0M'.
i4 fto.,/
r8
far: \,7,5 hc744ri'tnL
zl trg
3 "2tut n/n

l'] , !l oqfi4k{'h €h{

, Sotl nn^
4o?
q

-vttryv
I,l oul'kku<*t- "l I ;3, I hrar ^,\^'{ h(-
Honn0
C""ryo( i^b 1,7, V^f
o.{-k-tv sar.</ hal a ftv^allq' &r\tr[% YY
te Z)
 [s] 1.1e.
predict whether the following gas phase reactions will be thermodynamically favorable or unfavorable.
Explain your answer.

a. CHa + :- CHt+
/l?
4t"

b. CHs + N-CCH2- N-ccH3

q9 4{
tt ';t
B

c. Ch{Fg +
{,
CHg- CHc
q?
9x'zt
{rllv^$ $ o'* vv i fq,, pt l'" a
Fw. '. GE- | A. lo'f o*ltr
J
P
l<o.

A (l( { cl-'u 5
'6os Vb'^ ><- 1n"r,r.rS
PK
ClJ.\ +B

a) r ^ {av or o.t le : bo{t^, rn+fh?'t o,tvri o,h a^d o3 cIrt P,* l'o }tL

tlnrhtk, C, n,Ygt*rd to t-{w FLA L{ahfj

^tv
q^n{*
r) [^n bn o y ublc " +{q- ^*tt+ c'^A'* t I NryZ w\r-$'{k
hos o. IarS" pl(q
*^lfrr\pL .l"l\ +1* Fta c{ a"t 1;d^
1[^er A0l'{-'o p}^ F '1.
yh lJ-- t"* d^" Llr \|C14, ^f, ' s #'r-
hqk(
flvu I\t- *nu;,
y^vo(ablu |fr- tt r#.r"f-. a r-'' o* ' r { a(v r^^ s {^ Lo C/\W qRaL
o
1,
I
a
(
\r

w d/*v\ hq,ul-ha'-( , +{*- lr-Aproft* Qtw dl^lJ

.1lro 10

t ,r.crv a\.\ q'tt

-{,fu L.,{' o n-t
}'arhu*r, , " l('
^1w ^r,U
Book: Modern Physical Organic Chemistry

Eric V. Anslyn & Dennis A. Dougherty

(1) 1. State the hybridization of the non-hydrogen atoms in the following structures.

il tl
ii t.l i:i
C{}
- C. iN D. ' .'
;

A. B. E-

(2) 7. Discuss the hybridiza tion in the C-C and C-H bonds of cyclopropane, given that the H-
C-H bond angle is 1180

(3) S. Carbontetrachloride has ne ither a dipole moment nor a quadrupole moment, but it
does have an octo pole moment. Provide a simple description of this moment.

(4) 24. Sketch the 'lT* MO of propene. Consider the methyl C-H bonding in your answer,

(5) 32. Sketch the 'lT orbitals for allyl anion and for an enolate anion, and di scuss the
differences.
n C\l ,'0 Cg: tr= tf
uD ,.
f1 t
t-'1
'
fr=
II
l-
Ll
I

r.l ,,Q "l t4aQ z

rt '*rt '"1| ,.-E--
'*4 qN e'l "-W*
/\r
/3 Q-2 i 0-' 3 oLt tr, t

Ly. 0 LY' 2
/) C
6rl "- 5=
J'-4
^nL
6Ir fpl: o : fl*r
"o
:'4 *'-'ee*8

l"
,4 Cr " f =
lP=
w' e i
O
3

^e+e+n-*
by-:-*
)
-
C.n:0i=
"5 1
W;o
e::*:_:_Yf
s
r{
'F-

La.: tr*9 nr f=2 ln L-D

,- Vr-b-C-
)
--t;

u(:0 .)
4-
2
wrg.?T-
.'\-*
?
z

_..

u) Cl 2 f :2o Cj'- tr=L

w:b
K;? 1,p* sf{ ik:
N t tr-
I
q, o*; g
w= 0 LP'#:l

d,) ,h"\
H :% ,2_
qdil '+\ 'e-= ry

'\Ys/f" q (\.
t"-l
'. f'
uP: o
3
L C"t I f= 3
J/ 1Jp;.o c_.,L
dv
)tt ' 3= **-4 /
Lz' u-= 3 ';'. -!i!6***r!#-*-'*--*J-

w,0 N: $-7 3
5 '-r*f LV= S 3- o r

S '-r' Q
3
L3' r;'i
f"r

lrp;0 r,.rr{*F -1s*1i1o1r&ri|lee{a-,k.r*.E,

M

??r; \ r "n1'

N
 i 0: il- *
^. ' [- ':
I
H t"-l I
-o
b) tt
l, 1l
w: o Wi l-r'2 ,ttl r&
e
r)

t/Nv0,r 'ut't '

q
NIL 2 z
ll l- n $1.t *-\-'--1t
ll
,\/q
\ -------
'.
8iN ' ItZJ TTsr
/t^
\JI
V

t\" f ;
b
t'lt:D a 3
t: $ ' tl(' q \rP 5 3 0
- =

-
I
:

t3: o-;3 z 2
,J

LT" D rr r 3 t f ; tt s Y
i l'l : 'i'

/\ ,
t-,tl ,
Fi 3

Lf D
t)'

?nt :
')
nTVb
|
"-"---,-^* *---*-C!

hr,) l^Yl I
6nr
ffi L?l C\ot F P*?
1kt
<\+Ct] = \tgo o

<LW = 11o t x ?\ = fs" \

2'
br.c a^ !! % fft-- l?^)
L
\*-c-b'tr orbi
\*-o-Ft"9rDtt7\lt hl * -\\Y"r'vr
tqYI6(A i nb"
carlo ort G ot f\'t{<-
n.uf ^,f:T,.1*1*.
Il Tin tl,e {l r*q { ad o^ n'

Q, L-c: o,bt4^l s h*
o^r c\ *he
t +e c"cSd : O

u L,e.E '. o( - bnd q

- fsrrYlad \trT ^o L
/ |
{A thct(l2 '

o'dr,hl: *lc
>t'o^
rncffd +' \lu
thi s
l+ q
:-o
cnb l&o-

\ +,4 ( - o',.o) =a
q5 "**, t=

orb; t^ {s
* nft hb'idn-wd
tTonJ :
+t*l '. s ?t \o t c4'
2- t. q-H !rot'/:
sg tr4(
 H
Q: r*n: i 0: u- ' I

b) l,
2 -o
t/
rn
N
\-- 0
It
Q:0
;') ,Lo w; U-
a-,-ffi

lllr - 2
Y t
||
6n.t
*"--41 v
2 z
,\7Lr I
?,7tr
b -/ I o-3
L" 1:_,r25
VY:D
'-fl '* '3
-1
{9i-
N',0-,
,

-ll
,,, kn
it 'w= s 3 0

c_3 : 0-, g
L
tP- r)
!ru: -i- '-tj'2 I
qdt'd:'Z+t
:*W__ = 9 = \ry

qn, D-i 3

Lf,fD
n:j ?:yl*,
w r'l 6t*r-
lvr r {4^ AJ
%ct'" Pt*f
o

("u CIo 4+ CH -n llgo

rJ
"l ,{
cs H; \
P
1cU'(to+l21l =rc"
l+-C- Ftl rg rbi hle hw a,rd +f.r" pM hn aEL b-t tautW n* l?^) L
C - C-C 1 0, htFd,( S hN orcl thq, C[^(t on s ot ,Air^<{lu
ry" *f,e ;".a%I a,-fi'on
l,a fi ,.

\\u\N\\: s

1L'r{'
1- y:_ '\n *(
q
o, 1-
tF on +helo2
**u orbifa(s * lc
:

rhi s na.d;{ns $r
I + q. 69 t a-'o " --'6
-;.Gr \- S ->'s\ -n

4
sF-:{a-
\q=- +: _
-

Lts tn.s
t 0 ,1 o1 - O-lol
 T c.l
e rel ,-L i *# I'-,
{*-"T;:*-r-=; .{ ilto nuo\q w\ar 'ti P
le, or
n"-d, ,,rrolc &uA h Uu u Ilad",-
a,lrCI
L[ --^ U -' t
t

fll;. ./{
An 0'\,,^folu I"l st l snr*r-s, ;{ l"ns + A^pok,s
ltL
a\\cuma\ t,;;{ urL. t, W l<Jxa ['tdro I u+^'y ond

\arP r furt'ox-r&^ {-"''' t-d lrr,{hr,4rr *S-" $ ano{ &.q,ktwS.

0 taql
"--\
\'[rdnfr-\
L)o n(r'
't

\ ' Ar'l T)
'\ i\\\l pfu Yttl<- b
,((r, i\ tl
'\ ,,,/'
1
!
ri
,I
.*^y
)t-
JI

l^k ahirt
T ah:Fr,t+ {r{^
til 'nl r-/
Ti s,b;b*[s il!* av(n:
\-/

--'#.0: \J o'
,'t/ ''"i"'
'. ..- j"

4n t in 3Fott'tl'-{5

+rte rA [^Ir ,yi'r 0

tn[ r
3 t un'n
{r 0.3 oQ

Unn
t

ol *-0 Ig{,
') q
[4a r\D 10
0101
t 0 ,1 0-l