18-1(a) 5-hydroxyhexan-3-one; ethylj3-hydroxypropyl ketone

((bc)) t3-rapns-2-met
henyl buthaoxycyclnal;j3-pohenyl butyraldehyde
CHAPTERl�KETONESANDALDEHYDES

(d) 6,6-dimethylcyclohexa-2,4-dienone;dehyde hexanecarbal no common (or nameif you named this enantiomer); no common name
18-2 O 5 el e ment s of unsat u rat i o n
(R,R)

(a) C9Hl IH5H doublO e t (very smal l coupl i n g const a nt ) at 9. 7 al d ehyde hydrogen, next t o CH
mUl t i p l e peaks at 7. 2
IH multiplet at 3.6 and 3H doublet at 1.4 CHCH3 -7. 4 monosubst i t u t e d benzene
=:}

0 =:}

0 =:}

-CH- -CH
0 0 =:}

<� CH3 �
o
II
+ +

Thelookssplliikteinagquart of theet duehydrogen onsplcarbon-2, nextthe tadjacent

o the aldCH3. ehyde,Aisclwortoserhexami
examininatniog.n ofIn tihtse overal lsho\NS that
I

each t o t h e i t i n g from peaks

alconstdehydepeak of the quartandet tishesplmetit hinyltohydrogens
hydrogen two peaks:arethnotis isequiduevtaloetnt,he splso iitt iins gtofrombe expect
the aleddehyde
t h at t hydrogen.
h e coupl i n gThe
sh:lpe, it

coupl ainntgsconst
wil notantsbe, thequaley . Ifbea hydrogen
must consi d ered is separat
coupledeltyo, justdifferentas you neiwoul
ghboring
d by hydrogens
drawi n g a byitdiinfferent
spl g tree for
each type of adjacent hydrogen.
(b) clCgHgO 5 el e ment
upeaksteatr of 1974 peaks atcarbonyl s of un sat u rat
128-145carbon (tmono-ori o n para- s ubst i t u t e d benzene ring
peak at 26 methyl next to carbonyl or benzene h e smal l peak hei g ht suggests a ket o ne rat h er t h an an al d ehyde)
=:}

0 =:}

0 =:}

< }- C -CH3 or CH3 -o- C- H

0 =:}

more likely also possible

o

M18-cLaffert
3 A compound y rearrangement has to haveto occur. a hydrogen Butan-2-onoaney carbon hasy posino (y-hydrogen.
or other atom) in order for the
tion-no carbon
a
CH3-C -CH2 -CH3 t
o
II

a J3

401
18-4
�H2CH2CH2CH2CH2CH3
CH3 It 1j :+R:C-CH3 :I�C-CH3
; Lr ]
[
t

85 rnIz 43
rnIz
--- ---

�+CH2CH2CH2CH2CH2CH3
43

rnIz 85
128

McLafferty rearrangement

The first value is the to the second value is the n to The values are approximate.
(a) 200 nm; 280 nm; this simple ketone should have values similar to acetone
18-5
n*; n*.

si(b)mi230lar tonm;Fig310ure nm;18-7:conjugat

ketonee(280d systnmembase(210)valpluue)s 2plalusk30yl groups
nm for (20)the conj230;ugattehdedoubl
valueeofbond310 nm310 nm
n

<

(280;c) 280simnm;ilar reasoni

360 nm;ngconjugat
for the otedhersysttreansim (210)
tion, stplaurtsin1gextwirtah doubl e bondbase(30)valpluuse 4ofal290kyl groups (40)
is

an average
=

(d) 270 nm; 350 nm; same as in (c) except only 3 alkyl groups instead of 4
=

REMINDERS ABOUT SYNTHESIS PROBLEMS:

getsBegilonger.n your analysis by comparing thateetaapproach
There may be more t h an one l e gi t i m to a synthesis, especial y as the list of reactions
rgetoneto tofhe tstheartsmaling lmatnumber
erial. ofIf react
the product hasformmorecarbon­
carbons t h an t h e react a nt , you wi l l need to use
carbonWherebonds.possible, work backwards from the target back to the starting material. i o ns t h at
1.

4. KNOW THE REACTIONS. problems. There is no better test of whether you know the reactions than
2.

3.
attempting synthesis

402
18-6 Alclarbon-bond-
carbon- three target fmolormieculng ereact
s in ithions.s problSo far,em thave
h ere more
are t h thantysipesx carbons,
ree of react isoonsaltlhanswers
at form wil include
carbon-carbon
(albonds:kylatitohne andGrigacylnardatreact SN2 substitution by an acetylide ion, and the Friedel-Crafts reactions
ion) ionon,benzene.
f 0 OH 0
0 Bf � 0 MgB l) H �
ether 2) H30+ � H2C�; �
(a)

(b) Bf 0
..

identical sequence as in part (a)

UI �
OR 0
..

~
Cl �... � ithis more s metheffiodcusiientngasFriit eidels onl-Craft
y one s acylstepation
o AlCl3 U
o

(c) a synthesi s as in part (a) could also be used here

OR
� Br Mg � MgBr
0
� �
2) H30+ L-.l 6H �C
�4
1)

OR
L-.l � L-.l
..

(:j' Br Na+ -C=CH (:j' C=CH Hg2+, H20

H2SO4 og
18-7
.. ..

(a) (J BuLi (J BrCH2CH2Ph (J H30+... PhCH2CH2 -CH0

SXS S C'" S S X S HgCI2
H H H PhCH2CH2 H
II

::- I
... ..

• •

(b) (J CH3I (J BuLi (J Ph H30+ 0 Ph

S ::-C" S SXS Ph � HgCI2 �
H CH3 H Br �
from
• •
.. ... ... �

(a)

403
18-7 continued
(c) rl PhCH2Br SrlS BuLi PhCH2Br SrlS HgCl H30+ Ph � Ph o

S' " S
CH 2
PhCH2 H PhCH2 CH2Ph
• • • •

• .

X X

rl Q- CH2B' rl BuLi PhCH2CH2Br

I

from (a)

(d)
o-:x ('j()
H (a) H
S:-C"S S S
-

� Ph
� •

Ph H30+ , HgCl2
I

('j
� � �
18-8 0
from

( a) (b) �0 (c) CH3(CH2h -C0 -CH2CH3

if
II

Ih

18-9 0
(a) CH3(CH2h -C-CH2CH3 (b) (siPhCH2CN
II

mple SN2) (c) PhCH2C\l-(J

(a) I � Br � MgB' CH3CH2C= � H30+ CCH2CH3
o

O ether O
18-10
II

O
(b) CH3CH2C::N BrMgCH2CH2CH2CH3 --- H30+ �
--

H30+
+ --

(c) CH3(CH2hCOOH 2 CH3CH2Li -----

+
�
o

CH2Br CN MgBr 6 CH2C -o

6 H,o '
o

NBS. 6 NaCN.
(

6 I�
d

6 ::::'--1�---

404
IS-II OH (d)
(a) CH, H (b)
o CH
o
II

(C) � �
o

V V
IS-12dirRevi
more ect routew tehwie remithPhBrfewer
ndersstonepsp.i s402.usualThere
ly betareter. often more than one correct way to do syntheses, but
( a ) � . Mg OH 0
a

-..;: :: PhMgBr H30 + � Cr03,H20 �

o

H •
Ih
V V H2S04 V V
PhBrMg
• •

� PhMgBr . H30+
VV
• •

(c) 0
� Li A I H 4 H,o'. �
OH
OR NaBH4
CH30H
VV
HC::CCH2CH3
VV ( s ol v ent )
.. •

(d) 0 t NaNH2 OH
�Ih
H Na_
+ C::CCH2CH3 H30+ � C�CCH2CHJ
replIS-13acedThethreetriahydri
cetoxyborohydride
des. ion is similar to borohydride, BH4-, where three0acetoxy groups have
V
• •

(a ) C (b) .... C... .... C...0 :0:

" '- 0 0 ' 0
o o

0 0 0 '
� O - B + R--1' H
Na+ H- 0� -O -1/\ \. - Na-+ +. )!.::
)
R H
II II II

O O H
1
• •

�O-B-=-H
�
-I

0
/ /
--

y �
• .
I I

y y
H3CCOO-H
o o

1O-H
405
R+ H H
ylides. TrimCH3ethylphosphine has a-hydrogensCH3that could be removedCH3by butyl ithium, generating undesired
BuLi CH3-P-CHR CH2-P-CH
18-14

CH3-P-CH 2 R 1+ -
2R
CH3 CH3
1+

CH3
1+

desired ylide wrong ylide

1 1 1
� +

: �h PPh3
rotation '" I" I I
�+

HMe MeH
• •

.. \\
\

H I I I C - C """ H Ph3PO :O---! PPh) /

"""" ' 1.:1:1 I I I
Me cis-2-butene Me +

H',
Me �Me/ H
r
_

Thefashistoen,reochemi
yet the tsrtirpyhenyl
is inpverthosphied. nThee oxinuclde emustophielleimitripnathenyle wipthosphi ne mustry.attack the epoxide anti
.
....
..
f- . -
- " ,

h syn geomet
(b) :0: rotate and
'H
in an

el i m i n at e ..
O PPh3
. .

o . fl 1 7
trans
"

o ..

�
:
,

(a) CH2=CHCH2Br 1)2) Ph3P PhCHO

CIS

BuLi .. CH2=CHCH-PPh3 +
PhCH=CH-CH=CH2
18-16

1) Ph3P... PhCH-PPh3 O=CH-CH=CH2.. PhCH=CH-CH CH2

�

OR 2) BuLi
+

PhCH=CH -CH2Br 1)2) Ph3P

-

BuLi... PhCH=CH-CH-PPh3
=

(b)

CH2-PPh3 PhCH=CH-CH=O PhCH CH-CH CH2

+

+
� = =

406
The18-17onesManyshownalkhere
enes form
can bethesyntphosphoni
hesized ubym tsalwot difromfferentthe Wilesst ihignreact
deredionsalk(asyl halin itdhe.e previous problem).
(a) PhCHzBr 1) Ph3P BuLi.. PhCH-PPh3 )l
+

+
o
PhCH=C(CH3)z
(b) BuLi CHz-PPh3
-
2) H3C CH3

(c) PhCHzBr Ph3P.. PhCH-PPh3 PhCH CH-CH 0.. PhCH CH-CH CHPh
2)

2) BuLi
O �CHz
1) + = =

CHz-PPh3 �
= =

+ _

U U
+

18-18
(a)
OH
Cl3C-C-H I

OH I

"
:O: � H-OH OH
CH3 -C-CH3 CH3 -C-CH3 HO- I
. .

OH OH
I

I I
+

18-19

lofeasthydratamounte great est amount

of hydrat e
407
 :0 : H-CN 3 OH
CH3CH2-C-H CH CH2 -C-H
�
18-20

'"""
. .

I I

I
CN CN
..

(c) t-Bu-C-t
err -Bu t - B
:o:� '"""
u-C-t I
- B u H-CN OH
� :C N CN - t - B u-C-t I
- B u
CN
::::..;:::
:: � ::=

0
I I

OH
(a)�
18-21

V HCN vi'
(b) OHI pcc 0 OH
� . .
H H - �
· II
H HCN �H CN
(c) OH
CHCOOH
I

u
Nposioteti:veMechaniand smsivofe charnuclgees.ophiThese
negat ack atescararebonylverycashorrbont-lifvredequentas eachly incharcludegespeciis quiecsklwiythneutbotrhalized
lic attspeci
tbbyheenisaSolrapiadmoni
udtioprnsoshedtManual
on tr ansfwierl; ishow
n factt,htesehese stepsstearpseasthoccur
e fasterstingofatththeewholsamee mechanit i m e, evensm.thoughIn mostyoucahases,ve
transfers in one stetop show is legitimstateepsasofloangmechani sm separstoodatetlhy.atThethesepraracteice offashowi st steps.ng these proton
two
all
as it is under two

408
(a)
18-22

(J<-:NH;
0:

H H
)' H
H

(J h : JW �20: O �

d,+NHPh HO+3 . C} NHPh HO+

:0:\ :o-�
(
HI
3

H20:
_

two fast prot'---./

on transfers
• •
• •

Ph-C-H
:o:�
1 ��
Ph-C-H
:O�
��
H- O-H
- Ph-C-H( 1+

NHCH3
1

NHCH,
(twro fast�
1 1 1
----
• •

proton transfers
+ - H20
Ph-C-H .. H20: i Ph-C-H Ph-�-H }
II
�U�CH3 II
�

H- NCH3
I

plposiusttihvreee charge
resonance
on theforms
benzenewith
: NCH
3

ring

409
 Z E isomers.a double bond is formed, stereochemistry must be considered. The two compounds are
t18-he 23andWhenever
Z

18-25 This mechanism is the reverse of the one shown in 18-22(c) on the previous page.
H20: H-O-H
Ph - C - H H30+ Ph-C-H Ph-C-H
+ � .. Ph-C-H
.�

1+
.NCH3
.1 1
j
1 plus th+ree resonance forms with ') t
NCH3
II H-NCH3
I NHCH3
I
• �

H -
( Positive charge on the benzene ring
�
• •

: II0 : H-O: -CH3NH2 H-O:

..
H-O:
Ph-C-H .. Ph-C-H .. Ph-C-H .. H 3 0+ Ph-C-H
. . ..

1 I 1
H-NHCH3 I CH3
+
t (I �
....f----

NH

Ph-C-H
H-O+ +

VII
18-26 02N
NH2-NH -O- N02 A
o

abbreviY. ate "Z"

..

:o � + H-O-H
\ )

CH3-C-CH3
Q: CH3-C-CH3
:o:�
H30+
--- CH 3 -C-CH 3 H 30 CH3 -C-CH
'-- :NH2Z H2 :
I I ( 1 +
+ � 0 I
NHZ
I
NHZ
(k�
-­ •
3

two fast proton transfers

CH3 -�-CH t
H-NZ
•
3
I
..
 N-
(b) oJ 2NH N ",NHPh
Ph )l Ph
(d)

o
I�
.b

(a) PhCHO + H2NNH -C -NH2 ho + H2NOH

18-28

(b)
II

(c) 0 0 02N
H2 N-NHPh
(d)
0 + NH2-NH � }-N02
oJ
(e) C(f NH2 CH3
+

I o
0

·0· + � :O-H
+
:O-H O-H
Ph-CH H Ph-CH
plus resonance forms

. . �

Ph-CH•• }-H�CH3 .-----l Ph- 1 +

18-29

. �
with (+) on benzene ring

II
II +1
"---.:.
. I

: OCH 3
--- ---- CH
'" J

H.qCH3 �
�k
)

: � � : } H 2 0 H-O-H
Ph-CH ---H+ Ph-CH
,----- :O-H
j Ph CH ,...-W ---j
�� ili � I
plus resonance forms

� +1)

1 + �CH3 (�H3 OCH3 OCH3al

(+ ne ring

hemiacet
I
...
....
_

H..2:0CH3 OCH3
Ph-CH Ph-CH acetal
I

OCH3 OCH3
VI

I I

41 1
18-30CH3 CH3 CH31 CH31
:000: ""\H 0+
1 1
:0, :�
.�H20: ! V
t +

�
• • • .

. .

CH3 H CH3 H
0+ 0
H�
:0
f
0
1
: o
:O
1
O-H 1 + 1"

H20:
. . • . . . . .

t -CH30H
.. ..f---
....

oo:0 / H : O�H :0:

H2O:
+

6 .. •

6 •

6
18-31
(b) 0
CH3 -CH + 2 (CH3hCHOH
(c) 0 0 (d)
II

+ 2 HO OH r\
O HO) O + HO
�
(e)0 HOD
H+
(f)

HO )(l OH II
o

412
�';led lX�U uo p�nu!luo:>
WSlUnlj:>�W S!SAI0.1pAlj

t
:9
zH

o o- -Q�Q+0
:0 '0 '0: 0: 0 0 �:o
H
H-O�
H J� J, J,

'---(q)
. ..... +
H-O H-O:
• • • •

'----1 '----1 '---1 -1

+
+
��
HO

0- Q
H - 0 '0: H 0: 0:
J,

'----1
+
-
• •
J,

'----1
+
• •

FHQ
Q-Q � :0: (n)

H
+6 :0·o/�
H

:0 -------
+
(b)18-33hydrol
contiynsiueds mechanism continued
r
OH
+ r
OH
I\
6-6 �6
.. H + H

((·O �
:0, .... OH
C,
____
H-O� .... OH
C
� rOH ·0· +

� H30+
(c) The mechanisms of fonnation of an acetal and hydrolysis of an acetal are identical, just the reverse
order. Thipaths,hasthentothbee reverse
true because thave
his process iws antheequiidentlibiricalum:minifimthume forward stpatepsh. folThiloswis tmihenimum
HO

energy st e ps t
Principle Microscopic Reversibility, text section 8-4A.o fol l o energy a
famous

(d)
of

CO-;
o ;;o:CO
9 RJ 0 � + o �
00-00
··� • • • O +0 • •
:0
I

�
H H

H20:

CJ:::'t �+ CCl �CCl �

/h·· + O� OH OH '--- R
'--- RH OH \ � +O
H
1
OH

;-0- W � CO
��
0 OH .: OH

18-34 tAlAlhidtseehydes arecolreduced fastcreaseer thselaneketctivonesity). (keeping

.. .
1 equivalent reaction d wil l i n
be usedrnatiforvely,thissodireductum itorin;acetseeoxyborohydri
problem 18-13.de could
a
0

( ) A NaBH4

equivalent
V CHO CH30H

1\
1

HO OH ..

414
18-34 continued equivalent
0
(c) CH2B' HO OH o 0
1
(\
Mg o 0 (\ 0 (\

6 H+ a ether a + H� CH2 R' CH

..
2 MgB' ..

\.. )
V

Theoxygen,last stdehydrat
ep protoesnattheesalthceohol, 0 t

and hydrolyzes the acetal. ..

[MgBr]+

t
HC::C -CH2 -CH2 C
+
H30

18-35
- - CH3
a

(a) oCOO O
II

(b) DCOOH (c) COO:

HOafter adding H+ : Ag o y
0
after adding H+
A gO

(d) HO COOH
HO V
415
 j
18-36 :
hydrazone formation -000
0, ..
+ H0 �

cJ'-
:OH
• •

..
• •

"
2
NHNH2_
(I " NJfNH 2

two ofastn transfers

",-- :NH2NH2 :OH
H--./ ..
prot

reduction of the hydrazone

C ....... N
H-N

..
O
II
•
•

-·..N
� ('i2:�IIN
�H
H
C� H --
O
"H"OH H
V V

416
18-37
(a) (b) (c) 1\
(d)
� �
H H H
H

CO V H ' 'H
18-38 Please refer to solution 1-20, page 12 of this Solutions Manual.
18-39 nIgUPplacement
regardi namesoffiposirst; ttihoenn numbers.
common names. Please see the note on p. 136 of this Solutions Manual
(a)(b) hept hept aan-n-24--oone;ne; metdi-nh-propyl
yl n-pentketyloneketone (gh)) 4-3-phenyl
( bromo-p2rop--met2h-eylnalhexanal; ci n ; no common
namal d ehyde name
AC

(d)((ec)) buthept anal; no simdiplpehenyl

benzophenone; commonketoname
ne (i) hexa-2,
(j) 3- o xopent 4-dainalenal; ;nonocommon
commonname name
a
(18-f) 4propanone; nal ; but y
acetralodneehyde accept s "acet o ne") (
(Ik)) 3-
ci o
s -xocycl
2 , 4 -di o
m pent
et h a
yl necarbal
c ycl o pent daehyde;
none; no
no common
common name
name
0 I0n order of increasing equil0 ibrium constant for hydrat0ion:
(lUPAC

lofeasthydratamountion l o
2
o

ofgreathydrat
est amount
ion
II II I I

CH3-C-CH3 < C CH C-H < H-C-H

18-4 1
-

II
o
-
CH3
I
b2
H-C-CH -C-CH3 -
I
}c �
9H

f!
CH 3

18-42
A By1t--t1t
comparison with similarly substituted molecules shown in the text:
o

* value (210) plus 3 alkyl groups (30) 240 nm

U CH3 n--t1t* base
300-320 nm =

417
18-43
C6HJ002 indicates two elements of unsaturation.
Thetwo elIRement
absorpts ofiounn atsat1708
u rat i em·
o n. 1 suggests asiketngloene,ts inorthpossi
The e rat biolyoftw2o: ket3 inodinescatsienacehitghhlerey symmet
are two rioxygens
c mol e ande.
cul
liThekelysintoglbeet atCH22.15on thise probabl other siydemetof hthyle next to carbonyl
carbonyl . , and the singlet at 2.67 integrating to two
NMR
(5 (5 is

> H3C -C -CH2 -CH2 -C -CH3

Since the molecular formula is double this fragment, the molecule must be twice the fragment.
o o
II II

Two questofionshydrogens.
numbers, arise. WhyWhyis tdon' he inttethgrate twioonmet: hylandenesnotshow4 : 6?splIint tiengratg? iAdjacent
on provi,des a hydrogens, not absoluwite th
identical chemical shifts, do not split each other; the signals for ethane or cyclohexane appear as singlets.
2 3 ratio,

ant18-heal4unknown
4dehyde ormusta ketabeCone,JOa HIketbut2Oone.ainegat
The formul ndicatievse 5Tolelelement
ns tesstofpreclunsatudesurattihoen.possiA solbiliidty2,of4-DanNPaldderiehyde;vativtheerefore,
suggests
identical

ThemonosubstNMR ishows
t u t e d the typicatal et7.hyl3 pat5H,temulrn attip8le1.t)0. The tsirinpglleet)t andat 3.7.5i s a CHquartet
benzene (3H,
2 , but ), andte fara downfield,
qui
apparently deshielded by two groups. Assemble the pieces:
(5 2 (2H,
8 ( (5

0- CH2 C [
o
II
+ +

18-45
(a) 0 H " CH,CH3 . H
CHCH3
H /C ,�CH
CH2 2
) (

r
+

H J:CH2 CH2
..

rn/z44 mass 42
II I

rn/z 86
+ II

)H>-. �CH3 .
(b) � CH 0....... H . CH/CH3
CH3/C,�,CH2 CH/3 C',CH
+

CH
+

CH2
..
o

rn/z 114CH3 CH3 mass 42

II I I
II
I

z72
+

rn/

418
18-45 continued .
(c) O} (
[ r
+
H . CH3 ....... H
•

CH 0

mJz 58 mass 56
II I I CHCH3

mJz 114
..
C .Jr-.... CH ....... C" + II
H3C"""" 'c"""" 'CH3 H3C -""':CH2 CHCH3

18-46
H2

�O HO XO
0

OH
+ X
ATol18-mol4le7nsecultestariniodincofatemJa zket70one.meansThe°a carbonyl
0
0

fairly smal(CO)l molhaseculmasse. A28,solsoid semi 70 - derivativmass

c28arbazone42, enough e andfora negat
only ive
canmoreincarbons.
fer the presence The molofecula doubl
ar formul
e bonda isorprobabl
a ring yin addition(mtoassthe70);carbonyl with t.wo elements of unsaturation, we 3

Thecm-IIRregishows a st r ong peak at 1790 cm- I, indicative of a ketone in a small ring. No peak in the 1600-1650
=

C4H60

carbons are these: o n shows the absence of an alkene. The onl y possi b i l i t i e s for a smal l ri n g ket o ne contain ing f our

4<)' �
0 0

A B

The HNdoes show can dias4Htinguitripslhetthatese.3.1;Nothmetis sihylgnaldoublcomeset appears ienttwheo NMR spect r(C-um,2rulandingC-out4) adjaThecent to
3

from t h met h yl e nes

CH3

the carbonyl
roughl y a qui, nspltetitbecause
by the twoof splhydrogens
it ing by onfourC-3.neigThehborisinggnalprotforons.the methylene at C-3 appears at 2.0,
MR B.
NMR &

unknownion ofis cycl

TheIR absorpt obutanone,at 1790Thecm-symmet I ry inediricsatticedofbysmalthelcarbon NMR rulrinegsstoutraistn rstuctrengturehensThe
8

t h e carbonyl i s charact
carbon-oxygen double bond, increasing its frequency of vibration. (See Section 12-9 in the text.)
A.
ri n g ket o nes; B.

18-48The conjugated diene has a maximum at 235 nm (see ved Problem 15-3) and the ketone has a
the

(a) mum at about 237 nm, so the to transition cannotSolbe used to differentiate the compounds.
maxi
(b) The ketone has an n to transition around 315 nm that the diene cannot have.
n*
n n*

41 9
18-49 (X
(a) (�l���etal) (e) acetal
H
0H H
=(
o
II
+

6
O

(hemi
old: ahemi
cetalketal) (f) diether, inert to hydrolysis
CH3CHCH2
2 -C -CH3 + 2 CH0
3 H
OH
o

(b) + CHC
3 Ho
, H

(c) acetal imine(s) (

0"
H2 0
........CH
(g) + I

",CH

(d) (olacetd:alketal) (h) imine 0=0

NH2

1\ -Q
18-50
+ HN
2

(a)
HO OH

..
G.o: II
: NH2NHPh
:0: �
I
:o�
I 1+
+NHNHPh 2 • NHNHPh
H-O-H
(
,--
H30+ H30+

I O. I
3
HC-C-H .. H 3C-C-H .. H3C-?-H .. HC-C-H
3
H

(� J
two fast proton transfers
NHNHPh

: NNHPh 2 i � NNHPh NNHPh

� -H }
+
II I
H3C-C-H .. HC-C-H
0:
3 H3C-

l l -
---

"----/' U
II H
H- • •

1+ ·
I I
O-H :O-H

hemiacetal
I

:kV
CH3-CH CH3-CH
O
•

H CH3
OCH3

OCH3

I
I

acetal
CH3-CH

OCH3

420
18-(c) 50 continued. � ,P h ) crP h 3 P O C H2 ..

U"---- CH2 tPh, �V C�2 V rCH2

� ' ; Ph'
+

: C0

o
� �

(d) o
-

/\ /\
: O � O-H
/\
0 o
° � °0�-H 'O-H
:�H30+
�
:
+ +

9
�
. ---- ..

OH Hi)
OH <---JOHH : �
H-+/0 �O r'0"� H
"c/ OH
· ' H
O
/ �/+

H 30+ H2 0.
o

o ,. 0 :
.

...

l 0' H H
OH :
-6 r�:. 6
• • �
+

HO� o
I
+

(e) � H1 +
H H,O+ � m o : 02 ' O -H
��
N
+H
H �
..
c 1 1
N/
+
•
..
�
H

H
O.. C,H 4) <;:,H
' + H 0 ' O - H r:J2-�';- H H ..H3. EJD2 :�.;-H
HH H
� �b +
/ .'

N
H

H
--

H H
.. +

H
/N, /N, /N �

.
, I

� O· C,; 0.
� 'H H30+ 0 N H 3
'
C ,H0 '/ •

•
� .'

H 'H �
• •

/N
421
18-51 o OH OH
(a) CH3-CH KCN .. H30+ ..
HCN CH3-CH-C::N 0=CH3-CH-COOH ,Ph
HC
PhCH2Br Ph3P BuLi .. PhCH -PPh3 ..
II I I

o
0 0 1 equivalent 0 0 6
+

(c) NaBH4
(b)

Al ternat iv ely, usin g sodi u m triacetoxyborohydri de

..

CH30H .. sele cti vel y reduces t h e al d ehyde; see Problem

CHO CH20H
o 1I10equi/\val0ent1! �o NaBH4 H OH 30+.
18-13.

(d) 0 � ,H CHPH" 11
C C
0'" '0 Q 0'"C'0 Q�1I0
'

LJ '--1

CH3CH2CH2Br PPh3
tBuLi CHCH2CH3 5112:113
+

1 equi v al e nt
t

(e) 0 HO/\OH.. o CII3CH2CH -PPh�

o o
1130+.
C C H o o,..C,0 Co
+

0'" '0
,II

o 1 equiH2valent.. roo
LJ LJ
II

(
ro Pt OH
(g)
f) ro RaneyH2 .. co- H
o
OH
Ni

(h) roo NaBH4

CII,oIl· roll
422
18-52 All of these reactions would be acid-catalyzed.
(a) q + H2NOH (b ) 0
+
H2N 'O
�CHO
(c) (d) ro +
o

� O � 1\
� NH 2+ LJ I
0 HO OH
�

,
C H3 (f)
o

ONH2 O=CCH3 +
\
6 + CH30H 2

18-53
(c )

a( ) °2N (b) 0
C NH2
N/ N H � } N O ,
cf N - r - II

V
(c) NOH (d) 1\ (e) CH3-CHOCH3
L � OCH}
I

(g) ( h )
I

( f) OH CH2C H3
H -OCH3
CH < }- CCH2CH3 rl
...

I N
SX S
I

CH3CH2 H

423
18-54
(a) (] BuLi CH31
SX S S, .. ..... S
(]
_C S(]S
H H H CH3XH
..
..

C '/ HeH, /' CH, H2O:

C:··S ' H t "c
:··S ' HH
• •

+
.. .. ..

HS �S-H

H ..... C ..'CH3
..
0:
II

(stcr)engtMercuri c i o n, Hg 2+, assists the hydrolysis in two ways. First, mercuric ion is a Lewis acid of moderate
h, performing the same function as a proton from a protic acid.
Theits charge:
effectiveven of Hge2xed+ aswia Lewi
enesscompl th a s acifur,d tihs epartmercury
sul ly dueatom
stil has a positive charge, attracting the sulfur's electrons.
to

Athisecond expl a nat i on for mercuri c i o n' s effect i v eness i n hydrol y si s of S ...... Hg2+
sulfromofuracetthateaoequi
lms.s liesThiin sthestacompl
l i b ri u m, bl
shiefcompl
t i n
ex formed
g t heexequi
betivweleeny removes
effect
l i b ri u m t o
the ion andHSCHthe2CHtwo2SH
product . ( A n exampl e
of whose principle? His initials are "Le Chatelier".) S
t

Thiols are often referred to as "mercaptans" because of their ability to CAPTure MERcury.
424
18-55 icTheallykeyaffectto thitheis rproblchemistem irsy.understanding that the relative proximity of the two oxygens can
dramat
0
()
Thedescribed: 1 , 2 -
"second"twoisomer d i oxane 1,
Thetwo oxygens 3 - d i
"third" isbondedo xane
omer descrito thbeed: l, 4 -di o xane
Thean excel"firstle"nti ssolomerventdescri bed:gh
oxygens (al t hou
o

connect e d by a si gma bondbondarei s same sp 3 carbon constitute an toxic), thapart ese oxygens are far
aeasiperoxi
l y cl d
e e.
avedThe to 0-0
gi v e radi c al s . acetal whiacichd.isSeehydroltheyzed in
aqueous enough t o
dently. It is a simple ether. act i n depen­
In the presenceradiofcalorgani
compounds, react cions mechanism below.
can be explosive.
Mechanism of acetal hydrolysis
0 2 "C ' H H2O:
C:0 (:'0
. .
H
CH
+
/
.. .. ..-
•

" ' " '

H H

HO �O - H ---

:0 / H
H/C, H
I

}
• •

....
..
f--. ..
-i�
+

425
(a)18-56 (b) 6 (c) NOH (d) 1\

6 6 0
] CH ] CH]

(e) N-N-Ph PoH (g) no reaction (h)

H

er
(t)
/

.;; C

6H
H

(i) 0) c5 (k) Na+ -(j ON (I)

0 0
HO COOH

18-57 Thecomesnewfrombondthteoprotcarbonic solcomes

oxygen vent. from the or shown in bold below. The new bond
(a) NaBD4
NaBH4 NaBD4, to

0 OH
H2O

(b) OD
II I

NaBD4
CH3 - C - CH2CH3 .. .. CH3 - C - CH2CH3
I

D
0

(c) OD
" D 20 I

NaB
CH3 - C - CH2CH3 .. .. CH3 - C - CH2CH3
I

D
0
" H4 D 20 I

iThi18-t prefers
58 Whito lapproach
e hydridefromis a smal legroup, the actsiduealofchemi cal especi e, sthsuppl ythinegsiitd,eAlopposi
H4-, itsefaitherlymetlarge,hyl . so
CH3 - C - CH2CH3 .. .. CH3 - C - CH2CH3

t h e l ss hi n dered t h e mol cul e at i s ,

I

s forces the oxygen to go to the same side as the methyl, producing the isomer as the major product. cis

� O
�fd
H

Q
H
H

lessndered AI·
" /
C H3C 0

hiface
/ H+

majproductor
_-,

� H
H � ---.

"- I -
..

H H H
H·
CIS CH3
H
H

426
18-(a) 59
BuLi CHz -PPh3O•O O CH2 lAndoubl essexocycl
steablbond.e tihcandoublan endocycl
e bond i sic
methylenecyclohexane
- +

(b)reactTheion direstffisciulnttyheinstsyntabilhitesiy ofzinthgemetdoublhyleenecycl

bond ionhexane
si d e th e from
rin g cycl
( e ohexanone
ndocycl i c ) withoutoutsusiidentghethrienWig t ig
versus
(exocyclic). HOoCH] :
H20. +.
6
Amechani
dehydratsmiopassi
+ CH] MgBr

n folnlgowithrough
ng the a
�

t cold maj o r
+

mi n or
carbocat i o n i n t e rmedi a t e will gi v e t he
El

more assubsttheitmajuted,orendocycl
bond product . icThedoublonley Br CH3
he exocyclis toicdodoublan e o K+ -O-I-Bu
HB r

chance
bondeliasmofitnhatmaking
eimajon usior ntproduct
give Hofmann orientgaatibulon k(Cyhaptbaseerto7).
E2 E2
•

c5 6 minor major
+

18-60 CI -CCHzCH2CH3 zn(Hg� �

(a) • � HCI V
°
°

0
II

(b) V C'N CH3CHzMg ether

Br H3O+ 1 .0 C-CH2CHl
°

¢l
II

Cl OH V OCH3
CI2 • 6 ,!;l 6 HCl •
• �

NaOH I) Na0
0 AICI3 3500 C 6 CH31 .0 AlCuCICI3
co

2)
1

CHO
(e)

0::5
.0

(d) H Cr 0 0
Z 2 7 I: conc. H2SO:
c6
°

0:>
I � •

AlwittehrnatSOCIivelz,yt,htenhe cyclacidizchledobyridFericouledeld-Cberaftmades
acylation with AICI3.
�

427
 ()N-N-C-NH
18-61 H 0 I II
(a) OHCP , 0C(b) (c) 2
I II II

(y h H
()
.0- C-H
V + AgO
('I ()CH1
(e)
(d) OCH2CH3
I
c: � (f)

()OCH2CH3 d
CI, H
+ c
� H ether
18-62
CH3Mg1 H30 ..
r03, H20
�
OH H2S04 �
(a) ..
�
I
o o

(b)�C=CH HgS040
H2H2S04 � ..

(c) ('I ('I

1) BuLi
.. ..
+ /"'.-..
I I
SXHS CH31 Sx S CH3 CH2hBr S� HgCI..2 �
--��

2)
( 1) BuLi
2)
H 3 0 0
H CH3 Hc CH3
(d) � H2S04 r03, H20
�
..

(e) � OH excess +CH�Li 1)

o
H30 � 2)
o

M +
(f) �
CH3 g1 H30
�
.. �
_

C=N ether
o

,CH3
(g) 03 1)
Me2S � + CH3
2)
..
O=C o
\

428
18-63 o

(a) � H O PCC
---.-
�H
o

(b) �CH2 �H
(c) �C=CH

1) BuLi o

�H
..

HgCl2

Cl o

(e) � Cl KOH
---.-

H20 �H
(This reaction needs a solvent like THF to keep all reactants in solution.)
o o
(f) � II 1) LiAIH4 PCC II
� �H
..

2)
OH H30+ OH � --

ft
(
OR �
ft SOCl,
" � Cl
Ot-BuhH
OH
18-64

(a) � (b) � + � (c) �

o o 0 o

(e)
+

18-65
(a) ketone: no reaction
(b) aldehyde: positive
(c) enol of an aldehyde-tautomerizes to aldehyde in base: pOSitive
(d) hemiacetal of an aldehyde in equilibrium with the aldehyde in base: positive
(e) acetal-stable in base: no reaction
(f) hemiacetal of an aldehyde in equilibrium with the aldehyde in base: positive

429
18-66 A
stirouctns uisrethofe heptcanan-2-01
be deduced from itsioreact J K.
ion wibethGrigandnard reactWhationsiswicommon tn-2-one,
o both product s
ofmustthesebeThereact
heptan-2-one. part; t h e react ns must t h hept a A
so
S(lX
S �C=CH
~
H H3 BuLi '
C

�H�
1)
) 4B
D
H2S04
HgS04F
G

S S H 20
�CH3 E

1 MgBr Hg 2 ++
� H30
1) CH3CHO +B

2)
� a2Cr207 �
H30 OH N 0
c
H2S04 • A

N�
MgBr
� 1)
J
PhMgBr+ 1)
6 0�
! H3:'
K
2) H30
�OOH
�Ph
OH
I

430
18-67 The very st r11:
ong t o 11:*
a bsorption at nm in tbhe spectrum suggest
225 IUV s a conj u gat e d ketone or
alThedehyde. IR
ba senceTheof peaksconfiatrms this: strong,m I conj u gate d car onyl at em- and smal l 1690
al k ene at 16 10 em-I.
2700-2800 e -
shows that the unknown is not an aldehyde.
96
The molecular ion at leads to the molecular formula:
o
II
96
-64 b
,
C=C-C-C
'(
I
32 =>
mass units add car ons and hydrogens 2 8
64
mass
molecular formula C6H80 elements of unsaturation
= = 3

Two elements of unsaturation are accounted for ibn the enone. The other one is likely a ring.
NMR
neiTheghboringshows carbonstwo(twovinyldoupeaks
hydrogens.
one =
neigh
1
b orin g t
H )
at 86.0
blet: neighboring H . says that the two hydrogens are on
The dou l e
..-I--.

I
H H 0
I II + 1 + 6 + 1
C-C=C-C-C C H ring
NComo metbinhiylngstarehe piapparent NMR, 6H
eces: in the so the group of peaks at is most likely CH2 groups. 82.0-2.4 3

b b
The mass spectral fragmentation can e explained y a "retro" or reverse Diels-Alder fragmentation:
+ +

� H xC
. .
0 0 II
H TH 2 CHz
�CHz -- + II
H CHz H CHz C Hz
loss of 28

rnIz 96 rnIz 68

HNMR ,
Ibnecause
the of the resonance
one of the form
vinylthydrogens appears at I3
Thi s is t y pi c al of an a,j3-unsaturated carbonyl
87.0.
hat shows deshielding of the -hydrogen.
87.0 --.....
H H 0 I I II
H H :0: +1 I I
C-C=C-C-C ....
..
f--. -t
..
�

13 a
C-C-C=C-C 13 a

431
(a) Building a model wil help visualize this problem.
18-68

• •

y
:O-"":CH O CH20HI
H
w
--
I
y H H I
:O+-"":CH O CH20H :O +CCH:O CH20H
- -
I
• •
y H " ··H
I

HO OH
open-chaiOHn fonn
OH HO y .y CH20H �
HO OH same as HO � OH
OH
cyclic fonn-hemiacetal
(b) Yes, the cyclic fonn of glucose wil give a positive Tollens test. In the basic solution of the Tollens test,
tconcent
he hemiratacetion.al iHowever, s in equilibitriiusmthewiopen-chai
th the open-chai
n al d n aldtehyde
ehyde h at wisthwiththe cycl
react si l v icifonn
er o n, inevenmuchthough
so largerthere is
as
oxionlof tydhieazedcyclsmalbyiclsiamount
lfonnver iwion,lofmore
open-chai
cycl inc fonn
fonn present
wi l open at tanyo replgiavceentthime consumed
e, more open-chaiof the open-chai
n fonn. n fonn
Event isually all
the
carboxylate. Chatelbeier'dragged
Le s Principkilecstkirinkgesandagaiscreami
n! ng through the+open-chain fonn to be oxidized to
cyclic fonn """"" open-chain fonn NOTAg carboxyl •
oxidized attoe
libriumration smal
latargerequiconcent at equilerliconcent
brium ration reversible

432
18-69

Any
belongscarbonto thwie acetth twalofamioxygens
ly. Ifbonded
one of tthoeitoxygen
with singroups
gle bondsan
is OR,
then the functional group is a hemiacetal. Thus, the functional
C-2
groupketatal as iits came is
a hemifromacetaal.ket(Tohene.ol) d name for this g;rollp
hemi
OH H
(b) Models wil help. Ignore stereochemistry for the mechanism.
OH
1 oo f' H+
0
H
HO o *' HO O�
o

HO OH HO OH

\ H
OH I OH
00 \. (00 H
,... 00,...
H
o HO ---" C-O
+

OH HO OH

H2�
1 OH
HOH2C OH
HO OH
same as
HO OH OH H

433
18-70
Recall that "dilute acid" means an aqueous solution, and aqueous acid wil remove acetals.
&H
XMgJ
1__)) _ _ _+�
2 H30 -=�. _ �
V U
+ I

Ht II

H3C()' OH �aBH4 � H
OH H 3 C OH 0
H G � )) CH3MgI
(2removes
H30)
+
acetal
cY OH excess �
(P�
OH 0 0 equi1v .
(\
+
PCC
--
H HO + OH .. --
Ag no reaction
H D A

j H2Cr04
B A
is identical to
H20
�H
PhNHN NNHPh o 0
cr OH
c

j HCIZn
E

(Hg)

(i'oH
o

434
18-7 1

C, H HSfI fI
0

fi
II

()
0+ 0
II
H3 .. '
I fu Ph/"C, CH2 Ph HgCI2 Ph/"C CH2Ph
SH S/" /S
' BuLi S 1)
/S
-
..
-----. , ,
H
W 2)
� Ph C H PhCH 2
18-72
)(a H H
Cl:
�
d --- (1-:
H w
OH �
H
l...... _� H
•

C+'
o 0"""" � H
� R

�H /..
__

RH

0=:OR
(b) This is not an ether, but rather an acetal, stable to base but reactive with aqueous acid.
(C)Q- .. 9-: - ROH. { QtC:o H}
H O:R W

U
H2� !
O-O-HH -Ct- .. H H2.. Q
O
O
w
('O +
· -H
H

/
o

t
.. 0
'--- .. / · \

/ '-... . H
• •

H : -

�� +-H .. . 0
l...... _ : H �- � \L)
" U -H
J
O
H O-
o I
- H H2 o IIY"\ o II
I I :0- I :0:
• •

• •
H + H
435
18-73
(a) First, deduce what functional groups are present in A and B. The IR of A shows no alkene and no
carbonyl: the strongest peak is at 1060 cm-1, possible a C-O bond. After acid hydrolysis of A, the IR of B
shows a carbonyl at 17 15 cm-1: a ketone. (If it were an aldehyde, it would have aldehyde C-H around
2700-2800 cm-1, absent in the spectrum of B.) What functional group has C-O bonds and is hydrolyzed to
a ketone? An acetal (ketal)!
°
R'O OR '
'\.. / II
C R-C-R
/ ,
R R B
A
mol. wt. 1 16 =>

C6H 1 ZOZ
There is only one ketone of formula C4HgO: butan-2-one.
°
II
H3C - C - CHzCH3 t---
...
..

A must have the same alkyl groups as B. A has one element of unsaturation and is missing only CZH4 from
the partial structure above. The most likely structure is the ethylene ketal. Is this consistent with the NMR?
03.9 (singlet, 4H)
�
HzC-CH2
I \
0 O A

o 1.3 (singlet, 3 H) i H3C

X� - CH3 } 00.9 (triplet, 3H)

0 1.6
(quartet, 2H)
What about the peaks in the MS at rnJz 87 and WI? The 87 peak is the loss of 29 from the molecular
ion at 1 16.
+
.

'W
plus two resonance
forms with positive
charge on the oxygen
H3C CHz-CH3 atoms

rnJz116

plus two resonance

_---I..�
..... forms with positive
charge on the oxygen
The peak at rnJz 10 1 atoms
comes from loss of CH3
from the molecular ion at rnJz 101
1 16.
436
 }
18-73 continued

. : or:"
"c O H

/ "-
Me Et

3VH p
1 1
: -H : . :0:
II H20 II
C+
• •
....
..1--__
• _ C � C
/ "- / "- / "-
Me Et Me Et Me Et
B

18-74 The strong UV absorption at 220 nm indicates a conjugated aldehyde or ketone. The IR shows a
strong carbonyl at 1690 em-I, alkene at 1625 em-I, and two peaks at 2720 em-I and 28 10 em-I -aldehyde!
o
II
C==C- C-H
The NMR shows the aldehyde proton at 89.5 split into
a doublet, so it has one neighboring H. There are
only two vinyl protons, so there must be an alkyl group coming off the B carbon:
H H 0 ,..-----,.
I I II
I
H H 0
R-C==C-C- H I II
CH3-C==C-C- H
The only other NMR signal is a 3H doublet: R must be methyl.
"crotonaldehyde"
18-75 .r-" ·0·
� EtO· I ...
" �: ;
EtO l.O
"
D
(a) 0 0 •

II H II � :O.
I) R
EtO -P � O.
.

. -
•
EtO-P 0
R + " II I� I
. .

P,- ·B P,- ..... 1'\'-- 1

EtO""'" I EtO""'" I C -
• �

+ -- --
C ...... -- ...... C R- C-C - R ' R-C ..!.. C -R'
OEt 1 OEt I R './ "' R '
I I I I
R'
I R'
R R R
R

R R'
, /
(EtOhP02- C==C

�
+
437 '
R'
18-75
(b) conti(X
R
nued OEt�
: -OEt +
� /1
� OEt
(c)
(i)(EtOhP + Br � .... COOMe .. (Et0}z0P, � .... COOMe

� COOMe (CH3}zCHCHO MeO­

_

� � -EtBr � �

I
t
(-------
...
..
°

-- �)
(ii)
(EtOhP BrCH2COOMe .. (EtOhOP COOMe
+ +
-EtBr "- � -' ------
�
COO M y -----

eO-
18-76
(a)�
U e2 ..
NM H+0

H
('::�( )�.- H
1
\!!.)C+

(b) Aminoacetallinkage�� in the dashed bOXCS' 2 � ((c) The first step in the mechanism in part

-olD
painucla) ri.seosiprTheodtes,oninatthowever,
roiogensn of ofthearethamie partDnNe'Asofelaromat
ectron
.----1 N�lo
: /.: : rithnegs,aromat and tihcietyelofecttrhone ripaing.rs (areSeerequi r ed ifcor
:
HO N : N HO the ion
W W
16-42
solof tuhteioarn otomatproblicityemof these fornuclaedescript
'0 : '0 : osidwie l not
)
I 1 I
I

�-----
-' .�---- --
bases. ) Prot o nat i o n of t h e ni t r o gen
OH
deoxyadenosine deoxycytidinOHe 438
dioccur
ute unlacidethsssewitnucl
ltherefore hlel notacidprotis extonatremele they Nstrandong;
eoside wil be stable.