KIC Document 21 PDF

24
Carbohydrates: Polyfunctional Compounds in Nature
In this chapter you'll begin to apply the material you've just seen to a major class of real world molecules,
carbohydrates (sugars). For a change, nomenclature will play a more central role: The names of sugars and
sugar derivatives follow their own independent system, which includes some special stereochemical terms. On
the other hand, most of the reactions are old ones and are needed for only a limited number of purposes such
as structure determination, interconversion of derivatives, and synthesis of one sugar from another. You need
to be good at deductive reasoning so that you can solve the puzzles posed by some of the problems. If you
can, then this chapter should not be too hard for you.
Outline of the Chapter

24-1, 24-2, 24-3 Names and Structures of Carbohydrates
Be prepared for a lot of new terminology.
24-4 through 24-8 Polyfunctional Chemistry of Sugars

The basics: mostly (but not entirely) review material.
24-9, 24-10 Step-by-Step Buildup and Degradation of Sugars

Application in synthesis and structure determination.
24-1 1, 24-12 Complex Sugars in Nature
Keys to the Chapter
24-1. Names and Structures of Carbohydrates

The naming system presented in this section comes from an assortment of historically derived common names
organized into a semiofficial framework that is universally used. So, sugars are all ketones or aldehydes con
taining alcohol groups, and their names all end in -ose. Almost all of them have stereocenters; and they are
usually drawn in Fischer projections, with the carbon chain vertical and the carbonyl group nearest the top. If
the stereocenter nearest the bottom of the Fischer projection has the OH on the right, it has an R configuration,
and the sugar is said to belong to the D family. If this OH is on the left, you have an S configuration and an
L-sugar. Look at Figures 24-1 and 24-2. Each horizontal row contains structures that are all diastereomers of
one another. None of the mirror-image structures (enantiomers) of any of these is illustrated; the mirror image
of any D-sugar is just an L-sugar with the same name and all the stereocenters reversed.
466
Keys to the Chapter • 467
24-2 and 24-3. Conformations and Cyclic Forms of Sugars; Mutarotation

Because sugars contain alcohols and carbonyl groups, they can (and usually do) form cyclic hemiacetals,
typically with either five- or six-membered rings. Translating an open-chain structure into a picture of the
cyclic hemiacetal is tricky: Here's a step-by-step way to do it.
1, Write in wedges and hashed lines and (for a D-series sugar) lay the structure on its side, with the top
moved down to the right (a 90° clockwise rotation). Then, locate the OH group that you will use to form
the cyclic hemiacetal with the carbonyl group.
CHO CHO
H H OHH
H- OH H«— ——•OH
HOCH2» •CHO
HO- •H
•OH OH OHH OH
H-
t
H- OH {•- •OH Will form a five-membered
ring (a furanose)
CH2OH CH2OH Will form a six-membered ring

(a pyranose)
D-Glucose
2. Rotate around the C-C bond to the right of the OH group you picked out until the OH is
pointing away from you. (Make a model!) Then wrap this left-hand end of the chain behind die plane of
L paper to put the OH near to the carbonyl carbon. Finally, make the hemiacetal bond. (This sequence
is shown step-by-step on the next page.)
By convention, the procedure for L-serieis sugar^ modified
being down and /3 being up.
CH2OH Mirror
HO
OH p-L-Glucopyranose
p-D-Glucopyranose
468 • Chapter 24 CARBOHYDRATES: POLYFUNCTIONAL COMPOUNDS IN NATURE
For a pyranose (six-membered ring)

For a furanose (five-membered ring)
1 11 C)HH 11 1 mii
HOCH2 CHO HOCH2 CHO

1
C)H OH I1 )H ()H OH I1
X
Rotate
Rotate
CH2OH
HF (: OH
1 OHH HOCH2H OHH
HO CHO HO CHO
1I H OH
Wrap OH
around back
CH2OH
HO—C—H ..
HXH-
\ OHH
CHO
HO
CHO
H OH H OH
Close Close
ring ring
/\
HOCH, HOCH2
HO- -H HO- -H CH2OH CH2OH
-0. H Os OH OH H OOH
+ +
OH \0H H/ OH \OH H;
H OH H H HO OH HOvJ ViH
H OH H OH H OH H OH
a-D-Glucofuranose P-D-Glucofuranose a-D-Glucopyranose P-D-Glucopyranose
Anomers Anomers
If you like, you can derive the cyclic structure of an L-sugar by doing the D-sugar first and then writing its
mirror image.
Remember, sugars in solution typically exist as equilibrium mixtures of open chain plus cyclic hemiace-
tal structures. For glucose, this equilibrium mixture contains 63.6% 0-pyranose, 36.4% a-pyranose, together
with just traces of open chain and furanose structures. The interconversion of (3 and a anomers is called
mutarotation.
24-4 though 24-8. Polyfunctional Chemistry of Sugars

Although most of the reactions in these sections are old ones, typical of either alcohol or aldehyde/keton
chemistry, a couple of new reagents are introduced. These mainly allow selective reactions to be carried 01
on the multifunctional sugar molecule. Examples are Br2 in H20, which oxidizes only the aldehyde group (
an aldose to C02H, and HN03, which oxidizes both the end carbons of an aldose, forming a dicarboxylic aci<
Solutions to Problems • 469
The reactions in these sections have been chosen for their importance in practical aspects of sugar chemistry,
the material in the latter half of this chapter.
24-9 and 24-10. Step-by-Step Buildup and Degradation of Sugars

Determining sugar structures was a major effort involving the development of reaction sequences to lengthen or
shorten sugar chains and the use of some very clever logic dealing with the consequences of the stereochemistry
of sugars and sugar derivatives. The "Fischer proof' illustrates the main techniques used. Note that the process
repeatedly makes use of the synthesis of dicarboxylic acids, which are tested for the presence or absence of
optical activity. A sugar-derived optically inactive diacid is assumed to be a meso compound, containing a
plane of symmetry, and this kind of information is used to narrow down possible structures for unknown sugars.
24-11 and 24-12. Complex Sugars in Nature

These sections present simple extensions of the material just completed. Mother Nature has developed a conve
nient method for linking sugar molecules together: An alcohol group of one sugar forms an acetal by reactions
with the hemiacetal group of another. This connection, called a glycoside linkage, is just a fancier ^version
of a simple acetal formed by reaction of a sugar with an ordinary alcohol, like methanol (to form a "methyl
glycoside," as in Section 24-8). Again, the determination of unknown structures represents a common type of
problem. There are two important features that distinguish sugars containing free hemiacetal groups from those
lacking them. In solution, hemiacetals are always in equilibrium with aldehydes. So, hemiacetal-contaimng
sugars (1) undergo mutarotation and (2) are readily oxidized by mild oxidants like Ag . The latter feature is
the basis for the Tollens's test for "reducing" (that is, oxidizable) sugars. Some of the sugars in this section
contain acetal but not hemiacetal groups. Find them! These are examples of "nonreducing sugars.
Solutions to Problems
This compound is the mirror image (enantiomer) of D-lyxose (Figure 24-1).
34. You get CHO
Therefore, this sugar is L-lyxose, a diastereomer of o-nbose.
H- -OH
H- -OH
HO- -H
CH2OH
15. (a) o-Aldotetrose (Note: Only one s.ereocenter!); (b) L-aldohexose; (e) o-ketoheptose
CHO
36. CHO
HO- -H
HO- -H
H- -OH
HO- -H
HO- -H
HO -H
HO- -H
CH2OH
CH2OH
L-Ribose L-Glucose
Systematic name: Systematic name:
^,iS,46)-Z, w
(2S,3S,4S)-2,3,4,5- (2S,3/?,4S,5S)-2,3,4,5.6-
Tetrahydroxypentanal Pentahydroxy exan tQ review Sections 5-5
.7.,
tnd 5-6 for this one. The Study Gut e tex ^
(a) L-Glyceraldehyde; (b) D-erythrulose,

(d) L-xylose; (e) D-threose
38. Make models if you need to.
(a) CHO (b) CH2OH

=0
HO- -H
H- -OH H- -OH
H- -OH H- -OH
H- -OH H- -OH
CH2OH CH2OH
D-Altrose D-Psicose
(C) CHO (d) CH2OH

=0
HO- -H
H- -OH HO- -H
HO- -H HO -H
H- -OH HO- -H
CH2OH CH2OH
D-Idose L-Psicose
39. Hint: Use the structures and optical rotation information in Figures 24-1 and 24-2 to get you started
(especially to decide to which enantiomeric series each one belongs). See procedure for chain to ring con
version in the Study Guide text for this chapter. Careful—(b) and (c) are L-sugars. Their Haworth formulas
are drawn with the anomeric carbon on the left rather than the right.
OH
OH H
a-Furanose
CH2OH
CH2OH
H- OH HO
>4 HO- 4H HO
H
(B) H<F H HO OH
OH OH H H
OH OH
a-Furanose a-Pyranose
HOCH2
HO
O
(c) }
HO HOCH2
OH OH
a-Furanose
H°CH2 CHoOH
OH CH2OH OH
A
(d)
H
OH
OH
{ \/
CH2OH
H OH H OH CH2OH
a-Furanose P a-Pyranose P
HOCH2
CH2OH
HO- "H CH2OH OH 0CH2OH OH
O. H
A \
\OH HO/ (OH HO) { \/
(e) H HOy\I V
OH CH2OH OH CH2OH
H H H H
a-Furanose P a-Pyranose P
40. No. They are all hemiacetals and therefore are capable of readily interconverting their a and 3 anomers.
h9CH20H
o-/ÔH
41. (a) (b) hoVAVoh
OH OH
HO
OH CH2OH
HOCH2
.0
HO HO AO^--OH
(c) HO .OH (D) OH
HO
(d) is an unusual case where the CH2OH is forced to be axial to allow all four OH's to be equatorial.
42. Base-catalyzed enolization allows the interconversion to take place. But ootic=e' ^ ^^not
an
when it tautomerizes it has the option
the original ketone or the isomeric aldehyde.
HC-OH HC-OH
CH2OH CHOH
H20n
"OH 11-8=
y*
C=0 c=o "OH
h2o
Enediol
Enolate
Ketose
"OH,
HC=0 HC-O: H20
HC=0
"OH C-OH
Tc-OH +
HC-OH
H20
Other enolate
Aldose
43. Each carbon atom in the starting sugar is alongside its product after HI04 cleavage. The number of
hydrogens on each carbon remains the same before and after cleavage.
(a) CH2OH H2C=0

C=0 » C02 that is, 2 formaldehyde + 1 C02
I
CH2OH H2C=O
(b) HC=0 HC02H
HC—OH HC02H
HC—OH HC02H
> that is, 4 formic acid + 1 acetaldehyde
HC—OH HC02H
HC—OH HC=0
CH3 CH3
(c) CH2OH H2C=O

(HC—OH)4 * 4 HC02H that is, 4 formic acid + 2 formaldehyde
CH2OH H2C=O
44. (a) (i) COOH (ii) COOH (Hi) CH2OH

HO- -H HO- -H HO- -H
H- -OH H- -OH H- -OH
CH2OH COOH CH2OH

D-Threonic acid D-Tartaric acid D-Threitol
COOH COOH
(iv) CH=NNHC6H5 (b) (i) (ii)
H- -OH H- -OH
C=NNHC6H5
HO- -H HO- -H
H- OH
H- -OH H- -OH
CH2OH
D-Threose
CH2OH COOH
phenylosazone* D-Xylonic acid D-Xylaric acid
Solutions to Problems * 4 7 3
CH2OH (iv) CH=NNHC6H5 (c) (i) COOH

(iii)
-OH C=NNHC6H5 H- -OH
H-
-H HO- -H HO- -H
HO-
-OH HO- -H
H- -OH H-
H- -OH
CH2OH CH2OH
CH2OH
D-Xylose
D-Galactonic acid
phenylosazone**
(iii)
(ii)
CH2OH
D-Galactose
phenylosazone***
*Same as D-erythrose phenylosazone.

**Same as D-lyxose phenylosazone.
***Same as D-talose phenylosazone.
45. (a) D-gulose (Figure 24-1); (b) L-allose (all OH's
46. Steps ,-4 are by— fo—
insteps*3 Mid fi^t 0 andVen N into better leaving groups.
H2NNHC6HS
:OH u
.OHNHC6H5
^JÔH NHC6H5
RH+
NHNHC6H5
/^H+
^^NNHC6H5
xA0H
H
Hydroxy hydrazone
O ^-NH-r-NH^Hs •
-C6H5NH2
r-y™
Imino ketone
From the imino ketone, repeat steps 1-4 twice with two more molecules of C6H5NHNH2, in order to turn
both the imine and the ketone groups into hydrazones. Done!
47. (a) Arabinose and lyxose. Ribitol and xylitol are meso compounds.
(b) CH2OH CH2OH CH2OH
=0 H- -OH HO- -H
HO- -H NaBft, HO- -H HO- -H

+
H- -OH ch30"
H- -OH H- -OH
CH2OH CH2OH CH2OH

D-Fructose D-Glucitol D-Mannitol
A new stereocenter is generated at C2, so two diastereomeric alditols are produced. In contrast,
reduction of any aldose will be simpler because no new stereocenter will be generated; therefore,
only a single product can form.
48. (a) and (d), because they still possess hemiacetal functionality. In (b) and (c), the OH at CI in glucose
has become OCH3, and the molecule is now an acetal, incapable of mutarotation.
(e) is HOCH2 Also with an acetal, not a hemiacetal, at CI.
H0\—
o
h3C-A
CH3
49. (a) The oxygen at CI of an aldopyranose is a hemiacetal oxygen, not a simple alcohol oxygen. It can
therefore be methylated the same way a hemiacetal can be converted to an acetal—with methanol
and acid via a stabilized carbocation.
M . P v
1*.. -H2O
CH3OH
0 "c?CH' *
H
<Q^-och3
(b) The oxygen at CI in this case is an acetal oxygen, not a simple methyl ether. As in (a), mild
aqueous acid is sufficient for hydrolysis as a result of the same stabilized carbocation intermediate
shown above (the mechanism is just the reverse of the one shown).
(c) Four methyl glycosides are possible (refer to the structures for fructofuranose and fructopyranose in
Section 24-2).
HOCH2 CH2OH HOCH2 OCH3

.0. .0.
\H HO/
H H
OCH3 CH2OH
HO H HO H
Methyl
a -D-fructofuranoside P
CH2OH h OCH3
H
0
(H
/
HO/
/
\H HO/
HOv\| J/fOCH3 HOv\] l/rCH2OH
HO H HO H
Methyl
a -D-fructopyranoside
50. Aiabinose (as a fi-pyranose) forms a double acetal (Section 24-8). So does ribose, because in its
a-pyranose form all four hydroxy groups are cis.
ch3coch3,h+ 0^^"°\
HO °HOH
h3c h3c\
a-D -Ribopyranose ch3
of adjacent cis hydroxy groups, so these readily

The best xylose and lyxose can do is have only one pair
form only monoacetals.
ch3coch3.h+ v ho^^°\
HO^^r^,
o '
HO <„ H3C/0
OH
a-D-Xylopyranose ch3
h3c
ch3
0
0
OH
0, CHjCOCH^H^. HOr ^ - A /
HO OH — * HO^^^
HO-
p-D-Lyxopyranose
HTO treatment produces a mole of C02

a 0) The sugar has seven carbons and is aM^because HK^ ^ groups (leading to two
(see a similar reaction of D -fructose, Section ^ moi 0f formic acid),
formaldehydes) and four CHOH groups (leadi g
476 • Chapter 24 CARBOHYDRATES: POLYFUNCTtONAL COMPOUNDS IN NATURE
(ii) Because the sugar forms the same osazone as an aldose, its ketone must be at C2. So far, therefore,
have the following partial structure:
CH2OH
c=o
CHOH
Stereochemistry
CHOH unknown
CHOH J
H—C— OH « D-sugar
CH2OH
(iii) and (v) tell you that
CHO
CHOH CHO
I
CHOH CHOH
Ruff Ruff
CHOH CHOH
CHOH CHOH
H—C—OH H—C—OH
I
CH2OH CH2OH
Aldoheptose A Aldohexose B
CHO
H- OH T You now know these
H- -OH J carbons are R in
sugars B, A, and
H- -OH D-sedoheptulose as
CH2OH well.
D-Ribose
Next, (iv) tells you that
CHO COOH COOH

CHOH CHOH <— This carbon
HO- -H
I must be S \
H—C—OH HNO3, H2O. A H—C—OH H- -OH
H—C—OH H—C—OH H- -OH
I
H—C—OH H—C—OH H- -OH
CH2OH COOH COOH
Aldohexose B This is said to be Otherwise the product
optically active would be meso
From this information, you now can work backward toward the unknown: The stereocenters in
D.sedoheptulose must be 3S, 4R, 5R, and 6R.
CH2OH
=0
HO- -H
H- -OH
H- -OH
H- -OH
CH2OH
D-Sedoheptulose
W No Kiliani-Fischer elongation does not alter the stereocenters in the starting material. The two pairs
of products of Kiliani-Fischer elongations of any ,wo aldoses will differ a, the same stereocenters as d,d the
slarti„g materials. Thus *ey will be diastereomers of one anothen ^
B y7 J » r ; l a l l t o i row into the two aldoses immediately below it.
:\rôsIf,n o« row ty, -he pentoses, give the same aldose (hexose, in the next.
53. Refer to Figure 24-1. Ruff degradation converts an^seta one row to tlm aldose
^^(îrS^êgWesarabi^.
54. Two aldoheptoses are formed. After HNO3 treatment, one gives an optically active diacid, the other an
inactive meso compound.
COOH
CH2OH
Active
COOH
CHO
TT OH H— — OH
H TT
HO —H
*T
HO-— H
HNO3 HO— —H
HO— —H H
HO—
T T/"\ —
T T/~\ ____
HO— H
TT
H-— OH
rT
H— OH
COOH
:H2OH Meso
HOCH2 HO—CH2
0
55. (a)
" CH2OH
OH H OH H
H/ °X CH2OH
(H HO
HO•A OH
CH2OH
OH H OH H
Product after protonation
(both anomers)
P„ OH (Three equatorial and

2 two axial substituents)
(c) 0.65 kcal mol 1 (Table 2-1)

(d) An example of a "weighted average": [a]mixlure = XA[a]A + XB[a]B where X = mole fraction for
each component. Let A = pyranose and B = furanose. So, —92° = (0.68)(—132°) + (0.32)[a]B,
and [a]B = —6°.
56. For all but (a) draw the cyclic structure and identify the anomeric carbon. It is the carbon attached
to two oxygen atoms. If one of the oxygens is part of an OH group, then a hemiacetal function is pres
ent, and the substance will be a reducing sugar. Reducing: (a), (b), (c), (e), (f), (h), (i), and (j). (All have
hemiacetal groups.)
57. Yes. At the lower right of the formula (Section 24-11) is a hemiacetal group.
58. Trehalose must be (d), the only nonreducing sugar illustrated. Turanose is (c), the only one containing
a ketose (the bottom half). Sophorose is (a) (top half is an a anomer and bottom half is a (3 anomer). Sugar
(b) is composed of two aldoses that are epimers of each other at C4.
Unravel each structure
part is trickier; use models if necessary
CH2OH
This one is a surprise: it is the
enantiomer of one structure in Our old friend, D-glucose
Figure 24-1; it is L-arabinose
, , 1 j Redraw each one separately,
cture is shown below, with *e ^^

e it such that it is presented in a mor
know.
C OH
OH CH2OH
HO^^°\
HOT^^ÔH
A HO-^7^0 HO-^Â^-OH
CH2OH rotate 180° OH
around horizontal axis
is just p-D-glucopyranose.
HO ch2OH
B HO-^^ÔH 4" HO^'VÔ
HO^Ô^CH2OH rotate 120° (1/3 turn) HOO^-^-\_ÔH
around vertical axis OH
is just P-D-glucopyranose again,
CH2OH
C HO-^^^°x
hoA-^Â-OH
OH is also (3-D-glucopyranose. Stevioside contains three molecules of glucose
in its structure.
61. You can find a good conformational picture of p-D-galactose on page 1202 of the textbook, as the left-
hand part of the structure of lactose. Switch stereochemistry at CI for the a isomer. Notice in the answer
below how the name, 3-(a-D-galactopyranos-l-yl)-P-D-galactopyranose, translates into the structure:
I OH
62. The hydroxyl group at CI leaves most readily when protonated, because a resonance-stabilized
carbocation is produced.
CH2OH CH2OH CH2OH

HO \ + V HO'"\AÔ :NHJ
HOV^ÔH2 -H20 Ho\^\< Then -H+ hoo^Â^NH2
0H OH OH
63. (a) Aldol condensations! Abbreviated mechanisms are shown below. Refer to Section 18-6 for more
details, if necessary.
H
A,
CH2OHR^ CH2OH R^C=0
HO: |
c=o - " ' c=o + D-sorbose and D-fructose
mainly
CH2OH CH2OH
dendroketose
(b) The hint is supposed to make you think about enolate ions. Glyceraldehyde and
1,3-dihydroxypropanone are readily interconverted in aqueous basic solution via enolates and enols.
A
HC-0 H4" \
Enolate
.„ , „ —ivtnrp nf the two, and the reactions in (a) can

So a basic solution of either one rapid y j Glucose and fructose are interconverted
then occur. This aldose ^ ketose interconversmn « gene ^ ^
by aqueous base, for example. We saw this same mechanism
AM. ir1 TH OH H+- (d) ester of acid in (b): —COOCH, at

64. (a) Br2, H20; (b) see answer to Problem 44b. O ^ •
the top; (e) forms the amide. CONH2
CHO
CONH2
H- -OH
Brz.NaOH ^ QQ^ + H0
HO- Hofmann
degradation
H-
CH2OH D-Threose
(g)
CH2OH (f)
(e) VP the aldehyde. This sequence achieves
The hydroxyatnine (f) readily loses NHi on ^ 0„e less carb„„, jus, like the Woh. and
the removal of CI from an aldose to form a new
Ruff degradations.
65. (a) CH3OH, H"
CH2OH COOH
(d) CHO (e) CH2OH (f) CH2OH

HO- -H HO- -H -H
H- -OH H- -OH O H- -OH
COOH COOH
O
(g) CH2OH CHO
H- -OH HO- -H
HO- -H HO- -H
Rotate 180°
H- -OH -> H- -OH
H- -OH HO- -H
CHO CH2OH
As you can see, the gulose Fischer synthesized was the L-enantiomer (hydroxy group on C5 is on
the left).
O
V
66. First, D-glucuronic acid y-lactone is HO- -H 0

HO- -H
H-
HO- -H
CHO
L-gulonic acid y-lactone has already been illustrated [answer to (f) of Problem 65],
•
(a) NaBH4 (b) CH2OH (C) H Q OH
H- -OH
HOH2C CH2OH
HO- -H
OH H
H- -OH
=0
CH2OH
(d) 1 2 CH?COCH„ H+, 2. KMn04 to oxidize unprotected primary alcohol to carboxylic acid;
(e) H20, H+ (hydrolyze acetals); (f) A (-H20)
67 Follow along with the actual structure of D-lactose in Section 24-11.
-Ebrsrsr:tsssasLzzsss—
meric carbons are connected by an foUowed „y ^ acid hydrolysis is
3. Complete methylation [with (CH3)2S04J ot all tr g Therefore it
revealing. The galactose portion adds four
is the galactose whose anomenc carbon p methylation-hydrolysis sequence with
4. and 5. Comparison of the m-O-methylglucoêpmduc.of *c4 ^ c5 were not meth-
known compounds would be one way to a cert disaccharide (acetal) Unkage> the other is part
ylated and, therefore, one must be responsi use other chemistry to open the
of the cyclic hemiacetal, but we don't know wh ch ,s^ Wen ^ ^ & ^ ^ ^ 24.4
hemiacetal ring and identify which hydroxy g P idized at C1 by bromine in water to
we learned that aldoses (which exist as cywould have
give (acyclic) aldonic acids. Starting with lactose, we
CH2OH
OH
-SV
Ht\2°o CH2OH Br2.H20 ^ HQ
COOH
OH OH
Lactose
• leaves the disacchariue
This oxidation frees .he hydroxyl

acetal linkage unaffected. Now m y hydrolysis, the presence o hydroxy group of the
the actual structure (see above). After mddahy ^ uffllzed he C41P &
free -OH at C4 reveals conclusively that the u> ^ contaimng the oxygen
glucose unit, and that the latter was present py
68. (a)
69. (a)
70. (d)
71. (d)
72. (a)
25
Heterocydes: Heteroatoms in Cydic Organic Compounds
The material in this chapter falls into two broad categories: nonaromatic and aromatic heterocycles. You have
already seen many examples of nonaromatic heterocycles (see the section references at the start of the text
chapter). There will be new ones, especially compounds containing nitrogen atoms in three-, four-, or five-
membered rings.
Heteroatoms may also be present in aromatic rings, and compounds with this feature are the subject of the
last six sections of the chapter. In general, the properties of heterocyclic compounds will be predictable from
principles you've already seen: They will be similar to acyclic compounds with similar heteroatoms unless
(1) the ring is strained or (2) the ring is aromatic. When the ring is aromatic, the effect of the heteroatom on
its chemistry will be important, and this will be a new topic to which you will need to apply your knowledge
of inductive and resonance effects.
Outline of the Chapter

25-1 Naming the Heterocycles
25-2 Nonaromatic Heterocycles
25-3, 25-4 Aromatic Heterocyclopentadienes: Pyrrole, Furan, and Thiophene
25-5, 25-6 Pyridine, an Azabenzene
The most common monocyclic heteroaromatic compounds.
25-7 Quinoline and Isoquinoline: The Benzpyridines

25-8 Alkaloids
Even more rings!
Keys to the Chapter

25-1. Naming the Heterocycles
Note simply that the text sticks to strict systematic nomenclature for nonaromatic heterocycles but uses the
universally accepted common names for the aromatic systems.
25-2. Nonaromatic Heterocycles

This section generalizes what you have previously learned concerning the preparation and reactions of cyclic
ethers. Rings contamrng nitrogen and sulfur illustrate the principal similarity with their oxygen relatives: Ring
opening to relieve strain governs the reactivity of the smaller rings (three or four atoms)
484
25-3 through 25-7. Aromatic Heterocydes

cjve- and six-membered heterocyclic compounds make up the vast majority of aromatic heteroatom-containing
terns Counting electrons in the tt systems of these rings is occasionally confusing. Here is a simple way
determine whether a lone pair of a heteroatom is part of the cyclic it system: If only single bonds link
the heteroatom to its neighbors in the ring, then one lone pair from the heteroatom may be in a p orbital and
become part of the cyclic ir system. Examples are pyrrole, furan, and thiophene. Notice that in the latter two,
1 one of the two lone pairs on the heteroatom is part of the it system: The other is in an sp2 orbital and
^thing to do with the molecule's aromaticity at all. If the heteroatom is doubly bonded to another ring
SS n as is the case with pyridine, a lone pair on it will be in an sp2 orbital and will never count toward the
^clic it system in the molecule. Try to apply these rules to as many structures illustrated in these sections as
n. -phey are all aromatic, so you know what the answers should be.
Cy
y°Tvnicallv syntheses of the aromatic heterocycles utilize combinations of carbonyl condensation reactions
H 1 ?- or 1 4-additions of enolate and heteroatom nucleophiles to a, ^-unsaturated carbonyl compounds—no
fundamentally new chemistry here. Reactions of these systems show a blending of benzene-aromatic chemistry
and the chemistry of nonaromatic analogs with the same heteroatom. Furan is a good example: It undergoe:
tii^Stitution (aromatic chemistry), ring cleavage in acid (ether chemist^), and Diels-Alder cy -
Putting the iarge number of reactions here into their appropnate compartments
Should help you organize them for study and problem-solving.
30. (a) (b)

rf°
vi—'
HN
c6h5 c6h5
(c) O S (d)
s
^N
CH2CH2CH2CH3
, , j / „r__rphiv f f t N-methylpyrrole or 1-methylpyrrole,
(e) 2-Formylfuran or furan-2-carbaldehyde (pr
(g) quinoline-4-carboxylic acid; (h) 2,3-dimethylthiophene dihvdroxY.!,3-
11. 1. Azacyclopentane (pyrrolidine), ™dazo1^

iiazabenzene (pyrimidine) in its diketo tautomer. tan_2-one, l-aza-4-oxacyclohexan- -one,
is a diketo derivative; 4. thiophene, l-aza-3-oxJ' P 8. 1,3-diazabenzene (pynmidine),
7.1,4-diazacyclohexane and 1,2,4-triazacyc op
10. pyridine and imidazole.
X\ZA'0H / \CH2OCH2CH3
2. (a) (W VAnHCH,
H
^
(c) A bit tricky, so follow this mechanism.
M ;5h
toil ;OH
:OCH2CH3^ _ ch]A"H3 -f - ACH2A + CH3CH2OH
.y^n2^n3 ST'--;U , CH3CCH2CCL, _H ,
H3C-j--0: ^ * H3c-GO±-H , ch3
LT ch^ 4-a
H"P3 ch3
ch3
486 • Chapter 25 HETEROCYCLES: HETEROATOMS IN CYCUC ORGANIC COMPOUNDS
33. (a) C6H5CH2C
nucleophiles O
COOH
O
C6H5CH2CNH Ring-opening
•"3 relieves strain
HÔ
C6H5CH2CNH
\
CH- CH3
C N CH3
/ % H
Protein—NH O COOH
Penicilloyl protein
o
(b) C6H5CH2CNH Formed via a parallel mechanism, with H20 as the

\ nucleophile. This product, penicilloic acid, no longer
cH-ry",
possesses the necessary strained azacyclobutanone ring
HOOC NÂCH3
for reaction with bacterial protein. It therefore lacks any
H
antibiotic properties.
34. Use the Lewis acids to activate the ring oxygen in (a) and (b).
Hydrolysis
O—SnCU
CH2OSnCl4" CH.OH
(A type of Friedel-
Crafts reaction)
H5C6^+ BF3"
0
(b) CH3CH2CH2CH2—Li Hydrolysis
product
C6H5
(c) Use the Lewis acid to activate the anhydride and form an acylium cation, similar to the first step
in Friedel-Crafts acylation.
O O O
CH3C — O—CCH3 CH3CO+ + CH3C—O—MgBr2~
MgBr2~
and
O O
CH3C—O—MgBr2" CH3C—O—MgBr + Br"
Then, the acylium ion converts the ether oxygen into a good leaving group and allows SN2
displacement by bromide to occur.
H?C^ / 4"\ - Configuration is

H3C H inverted here (SN2)
H-.C' 0
35. The order of basicity is the reverse of the order of the acidity of the conjugate acids (pKa values shown
below the structures).
Conjugate acids
H > H30 > NH4+ > H2O

s+
N H
H
9.2 15.7
-1.7
PKa = -4-4 Weakest acid
Strongest acid
m, ..1.. f„. h,d™™ ™ "*
36. (a)
H H u- 1 - * TT electrons, so all are aromatic. All have

All have two double bonds plus one lone>r in ap »bUa ' ^ ^ are
^-hybridized lone pairs on nitrogen not£ lone pair; therefore all the compounds
in a Lewis-base manner. Pyrrole lac s

stronger bases than pyrrole. electrons and trigonal planar geome ry.
w < „ « c — . W
orbital (Section 12-9), occupied the p orbi . d d nitrogen atoms
488 • Chapter 25 HETEROCYCLES: HETEROATOMS IN CYCUC ORGANIC COMPOUNDS
(ii) Thiazolium salts, which include the natural vitamin thiamine (Section 23-4 and Real Life 23-2),
are related in that one of their resonance forms displays carbenoid character at the nucleophilic
carbon located between the heteroatoms. Like NHCs, the carbenoid lone pair in these salts is
not necessary for aromaticity and occupies an sp2 orbital.
(iii) HO
:6:>
H (now acidic)
NR
As in the case of thiamine and other thiazolium salt adducts, the former carbonyl carbon is
now nucleophilic. It is at the end of an enamine double bond (Section 18-4). So:
H ~ _
OJ :0:
Furan- ruran \ / Product
Furan +
NHC
38. Abbreviated mechanism
fO
Ml
O
II
C6H5C-CC6H5
OH
V
cf +
C6H5C—_CC6H5
CH3OOCCH CHCOOCH3
CH3OOCCHNCH2COOCH3 N
CH3CO CH3CO
Under these reaction conditions

OH OH
(NaOCH3, CH3OH, heat) the C6H5^ t C6H5 -CH3COOCH3
amide is cleaved by methanolysis,
2H20 product
a process similar to transesterifi- CH3OOC COOCH3
cation. See p. 939 and
Chapter 20, problem 60. CH3CO
-
Synthesis
0 0 II \\
NaOCH3 /\„/\ NaOH H?0
HC-CH + CH3OOCCH2SCH2COOCH3 > CH3OOC s COOCH3 product
39 There are three factors to keep in mind: (1) the inherent preference of these compounds for
btitution at C2 over C3, (2) the much greater reactivity of all of them compared with benzene, and
(3) directing effects of substituent groups (which work the same way as in benzene). These are toughies!
(a) Two conflicting preferences
m-directing group
Preference of ring > Q COOCH3
In this case, a mixture might be expected:
CI
\4
jC\
Clô C00CH3
+ (X
^0 C00CH3
The firs, is actually the major product; the directing effect of the activating ring oxygen to C5 wins
L, over ft* of the moderately deactivating COOCH, group to C4.
(b) Easier
ô,p-group
fj ^ C5 is strongly / \
o, p-group —>J\ activated N02 S CH3
/ l_n3
Ring /
preference
(c) Tricky. If this were benzene, the is much more

presence of the COCH, group. It ^ duri„g the reaction, making it even more
reactive. The carbonyl substituent is complex^bJ ^ ^ ^ fonnatlon of
strongly deactivating and meta-directing, however.
(CH3)2CH
\ CH,
0
II
0
(d) Easy
,P'gT\ Br
° B
'S
Ring ^ Ring preference
C2 is doubly
preferenCe
preferred.
490 • Chapter 25 HETEROCYCLES: HETEROATOMS IN CYCLIC ORGANIC COMPOUNDS
(e) Now you have to work from scratch! Compare attacks at various carbons.
C2
+• •
/=N /=N
.E
+(*0. ^+
SN' NH VN" SH N' NH
H H H
Poor! (N at top lacks octet)
C4
E
H- ~N
N
H
Only two resonance forms
C5
/= N* =N
Es
H' XN' h/xnx
H H
Three good resonance forms
Rule out C4 (only two resonance forms for cation). Rule out C2 next, because attack results in an
electron sextet and a positive charge on one of the electronegative N atoms. Thus, C5 is the site
of attack by typical electrophiles. In this particular example, however, the major product is due to
diazo coupling at C2, because under the basic conditions the imidazole anion is attacked, and
reaction at C2 gives a symmetrical intermediate with two equivalent resonance forms.
XN E N N
N
£.X < Q <h "X
N
Tautomerizes
\
N
N=N /"A
H
Product
-6n5^2
(CH3)2N
SO3H
40. (a)
(b) Diels-Alder: ft
Solutions to Problems *491
0
(e) | | (d) CH3CH2CH2CH2CC6H5 I via
^n^Sh \ \s/^C-C6H5.
(e)
N C(CH3)3
H3CX CH3 H3C

W
CH3
\zCH3
P2O5, A
41. (a) I II > H3C-^\/~-CH3
00 0
o 0
H2C=O,NH3
(b) Hantzsch C6H5CCH2COCH2CH3
1.HNO3, H2SO4
CH3CH2OOC COOCH2CH3 2. KOH, H2O
5 3. CaO, A
* product
:6HS N C6H5
H
(c) Paal-Knorr
O O
II II NH3 , ,
HCCH—CHCH > product
CH3 CH3
CH3
CH3 , /
(d) "•cr o
~V
o
H.C-V
of n mpthvl 2roup on a caffeine nitrogen, which in
42. The only structural difference is the presence should be usefully acidic because the nitrogen
theobromine contains a hydrogen. Fortunate y, t is . 21.5) that the similarly placed hy rogen in
containing it lies between two carbonyl groups. deprotonate with base (NaOH should
1,2-benzenedicarboximide (phthalimide) has a pKa of about 8.

be more than adequate) and 2. alkylate with 3 •
43. (a) I hope you haven't for8ot^

36 (three C) + 6 (six H) + 84 (six N) >
* N = (84,126) • K« - ^ ^ wm . ^ ,he % N
Clearly even a fairly small amount of melamine as' an ^ actually is the case,
analysis, giving the impression that more protein is present
(b) The reaction is a nucleophilic aromatic substitution via the addition-elimination mechanism
(Recall Section 22-4):
NH3
H3N:^C1 H3N^CI
:NT) N: ":N
... N:
„
:N N:
CL^N^CL CL^N^CL ° CL^N^CL
NH2 NH2
Repeat sequence
twice more . N•
:N N:
CI AN X CI H2N N NH2
Melamine
This process is favored by the presence of three electronegative nitrogen atoms in the ring as well as the
chlorine substituents, all of which help stabilize the negative charge of the intermediates.
44. O
II
CH3CCH3
CH3CH2O^ 0 ÔCH2CH3
c + c NaOCH2CH3, CH3CH2OH
Double Claisen
condensation
\
CH3CH2O'/ O OCH2CH3
o
II
CH2 CH2
HCI.A
CH3CH2OC </ COCH2CH3 hydrolysis) HOOC COOH

o o
Compare synthesis of furans, etc., from 1,4-diketones.
45. Protonation of ketones and aldehydes can give rise to electrophiles capable of aromatic substitution:
H+
: O:—J
Then,
Next, protonation of the hydroxy group enables it to leave. The carbocation that results can undergo
substitution with a second pyrrole ring:
46, A six-electron cycloaddition takes you directly to the product:
R'C-N-or N
RC=CR R R
first, followed by intramolecular amide

47. (a) H2, Pt (b) Stepwise, ring opening of azacyclopropane
(lactam) formation.
^COCH^3 _CH3CH2OH_
+ YA —" l^N NH2
SN' ^02CH2CH3^/
H
NH->
o
II
CH3CCI, py
48.
HO-, H20, A
NHCCH3 > Product
49. Reaction with an activated derivative of acetic acid such as the anhydride would provide the product.
O
V H
/CH3
Further A
r^YNH2 + /-CH3 _a_ product
1- II \ Make \\
-H20
NH2°
NH? c—CH3 amide
// + CH3COOH
o
O CI -:0:
<r
-cr
50. (a) C6H5CH + C6H5CCOOCH2CH3 > C6H5CH—CCOOCH2CH3 product
C6H5
^NC6H5 C6H5N:-\C\J
-Ci"
(b) C6H5CH /+ C1CHC00CH2CH3 C6H5CH—CHCOOCH2CH3 product
51. (a) 1,3-Dibromo-5,5-dimethyl-1,3-diaza-2,4-cyclopentanedione.

(b) Thinking mechanistically, you have the following:
«3C H3Cx Br^Cft
/C=C\ * /—C
H3C CH3 H3C
(CH3)2C-C(CH3)2 (CH3)2C-C(CH3)2
AgBr f
OOH HO—O
(CH3)2C-C(CH3)2 (CH3)2C—C(CH3)2
^yO-O 0-0
H
3,3,4,4-Tetramethyl-
1,2-dioxacy clobutane
52. Abbreviated mechanism (note the "double" Michael addition).
o
<L' Again
(CH3)2C=CHCCH=aCH3)2 + NH3 > (CH3)2C=CHCCH2C(CH3)2 ^ product
-:NH2
« The hydrogen atoms on the nitrogen are relatively acidic because of resonance stabilization of the an-
ion'that results from deprotonation. Conjugate addition followed by intramolecular aldol condensanon gives
the product:
Aldol
condensation
14. To answer the second question first, the^rocess {& a strong deactivating group toward electrophilic
titration is an electrophilic substitution, and the a y gr ^ which is more reactive toward elec-
iromatic substitution. Substitution will take Place °n substitution would be expected to occur at
rophiles than is the pyridine ring. Without the exda^ these positions do not disrupt die
lositions 5 and 8, because the cationic inteêdiatfaSs^stituent deactivates position 5 (see resonance forms),
iromaticity of the pyridine ring. However, t e ex
leaving substitution at position 8 as the mos i
Substitution at C5:
Substitution at C8:
55. Hsa, = 16 + 2 = 18; degree of unsaturation = = 5 it bonds or rings. NMR: C6H5 group is
present, accounting for 4 degrees of unsaturation. No alkene C-H signals, so the last degree of unsaturation
is probably a ring. So far: C6H5—, 2 C, 3 H, O present, adding up to C8H80. The three H's all couple to
each Other (all three signals are split), so an —OH is unlikely. Therefore, the 0 is an ether oxygen, giving
as the only possible answer
Nonequivalent (one is cis to the phenyl group

s and the other is trans!)
C6H5-C
H (H/
2-Phenyloxacyclopropane
Cone. aq. HC1 causes ring opening to
4.2
OH OH
I I
C6H5-CH-CH2
4.8 3.6 and 3.7
The hydrogens of the CH2 group are not equivalent because of the adjacent stereocenter.
56 = 10 + 2 = 12; degree of unsaturation = ^ = 3 ir bonds or rings in C. D has 1 ir bond
perhaps thre^CH^sJeîôi^ ^
alcohol, so assume the O is an ether. Some possibilities.
H3C Vf Unreasonable. Methyl signal should be further downfteld. and the ring would be very
HC=CH unstable (Section 15-6).
H3Cn ^ Roth reasonable possibilities at this stage.
V> X3
;
Hsc^cr
NMR spectrum of D: Complicated, but two pieces of information are extractable. First,
(5 = 1.1) and a doublet, consistent with either
H3C^CH_CH2 CH2-CH2
/ 01 u c -m c©
<$® c© 3 T.o/®
0 3 H near 0
4 H near 0
0 integrate to 3 H, consistent only
Second, the signals between 8 = D is 2-methyloxacyclopentane.

with the. ser.nnd structure. So C is z-m y
57. H„, = 10 + 2 = 12; degree of unsaturate = ^f ^ = 4 "it bonds or rings. NMR: 8 = 9.6
suggests aldehyde (supported by IR data), together with 3 CH's. Similar to Problem 49, try furans as
possibilities:
CHO
or
No' O CHO
How to choose? Which is more likely to come from an aldopentose? A possible (abbreviated) mechanism:
CH2—CH— CH— CH— CHO / CHO

-H2O
^ CHO
OH OH
OH OH OH OH E
NH3, NaBH3CN Excess CH3I

E 2—
(Reductive ôXx"CH2N(CH3)3 r
0^CH2NH2
amination)
Furethonium
r 5
CHR
13
-A.
(Compare LiA!H4 1,4-Reduction
N + amides,
Section 18-5)
/CH2R Then
H+, H20
product
N'
Imine
60. Begin with the hydrazone shown in the middle of the reaction scheme. Examine the structure of the
roduct: A bond is needed between the methyl group and the benzene carbon ortho to the nitrogen. For
brevity catalytic protons are shown attaching in the same step as the reactions they catalyze. In fact, the
protonations generally occur first, with tautomerism or addition taking place afterwards.
Cope-type
electrocyclic
rearrangement
Necessary new
C—C bond
H
NH2 H"1
That's the Fischer indole synthesis. The ^^^Tuta (nitro-group stabilized) benzylic anion takes
first step is a distant relative of a Claisen c0 ' of the ester as shown:
the place of an enolate anion to add to the carbonyl group
Claisen-type
addition-elimination
OR
RO'
N02 o
N02
(R_ = CH3CH2-)
After hydrogenation of the nitro group, the sequence finishes similarly to the Fischer above.
61. (c)
62. (e)
63. (d)
64. (c)
26
Amino Acids, Peptides, Proteins, and Nucleic Acids:
Nitrogen-Containing Polymers in Nature
Here it is' the last chapter! It is, however, as much a beginning as an end. Chemistry in general, and organic
« ,n particular" are no, isolated fields. Organic chemistry is the basic stuff o btology, an to chap-
er bridges the two. The basic principles that govern the behavior of organic molecules in general are shown
Im-ete be directly appl.cable to molecules of greater and greater complexity. You see here someof to most
futomental molecutes of life viewed from the organic chemist's point of view. The next step tn to dtrectron
is biochemistry.
Outline ot the Chapter

26-1 Structure and Properties of Amino Acids
Nature's most versatile building blocks.
!M '2"
264 Peptides and Proteins: Amino Acid Oligomers and Polymers
The whole is greater than the sum of its parts.
26-5 Determination of Polypeptide Primary Structure: Sequenang

Exercises in logic, plus a lot of hard work.
26-6, 26-7 Synthesis of Polypeptides: A Pr°te^n9 r°^
??n °
Even fancier footwork; how does Nature do it so y
26-8 Polypeptides in Nature: The Proteins Myoglobin and Hemoglob,
26-9, 26-10 Biosynthesis of Proteins: Nucleic Aci s

How Nature appears to do it so y-
26-11 DNA Sequencing and Synthesis: Gene Tec noogy

The future is now!
Keys to the Chapter
26-1. Structure and ProPert,eS ®^te ?stcttn'and then come back

X and
Read the introduction to the text chapter a , Structures have to be bui majntain life, such as
the big picture. The chemistry of life » comP''êXm the various funcuons tha, mam,a.
a lo, of chemical reactions have to be gotng on to perto 50)
502 • Chapter 26 AMINO ACIDS, PEPTIDES, PROTEINS, AND NUCLEIC ACIDS: NITROGEN-CONTAINING POLYMERS IN NATURE
energy storage and utilization. These all have to occur under a very constrained set of conditions: Water is the
only available solvent, and in general only very narrow ranges of temperature and pH are acceptable. Otherwise
everything falls apart. So how is it done? The answer begins with the amino acids.
Look first at the structures of the 20 most common examples (Table 26-1). They differ only in the group
attached to the a-carbon. The variety in these groups establishes the versatility of amino acids. There are non-
polar groups, both small and large, capable of various degrees of steric interaction. There are uncharged but
polar groups, capable of hydrogen bonding. There are nitrogen-containing groups of various base strengths,
some of which will be protonated and positively charged at pH 7. There are oxygen and sulfur groups of various
acid strengths, some of which will be deprotonated and negatively charged at pH 7. Because of this variety,
Nature can choose from among these 20 compounds just the right one to fill any of a number of chemical
needs. One feature that is emphasized in this section is the acid-base behavior of the amino acids. Table 26-1
lists pKa values for all relevant groups. Notice, for one thing, that the way the amino acids have been drawn up
to now, H2N—CHR—COOH, is wrong. In solution, amino acids in fact never exist to any significant extent
in this form, with neutral amino and carboxylic acid groups present at the same time. Depending on the pH,
one or both of these groups is always charged, with the pH 7 structure being +H3N—CHR—COO". Because
of this feature, amino acids are very good buffers at a variety of different pH's, depending on R. Obviously the
effects of pH on amino acid structure are important, and Problem 34 will give you several examples to work
on so you can get the feel for it.
26-2 and 26-3. Preparation of Amino Acids

Although none of the individual reactions in these sections are new, the sequences present them in powerful
combinations aimed at solving the problem of introducing basic and acidic groups into the same molecule.
26-4 and 26-5. Peptides and Proteins: Amino Acid Oligomers and Polymers
Techniques for determining peptide and protein structure are extremely well worked out (and Problems 52-57
will give you plenty of chances to try them for yourself). The results, especially in the subtleties of folding of
these polymeric chains, reveal the extent to which the characteristics of the different amino acids are combined
and used in nature to generate large molecular assemblies perfectly suited for very specific biological roles.
Problems 48-51 are intended to give you something to think about in this regard.
26-6 and 26-7. Synthesis of Polypeptides: A Protecting Group Challenge

Don't ever lose sight of the fact that the linkage between amino acids is nothing more than a simple amide
bond: —HN—CO—. Nonetheless, the construction of peptide chains from simple amino acids in the laboratory
was once a major challenge for the same reasons that, say, mixed aldol or Claisen condensations (Sections 18-6
and 23-1) are tricky things to do: Each amino acid involved has both a potentially nucleophilic atom (the N)
and a potentially electrophilic one (the carboxy C). Thus, an attempt at linking, say, the amine of amino acid
1 with the carboxy group of amino acid 2 is going to be complicated by the need to prevent the simultaneous
linkage of either two molecules of a.a.l to each other, two molecules of a.a.2 to each other, or a.a. 1 to a.a.2 in
the wrong sense: carboxy of 1 to amine of 2. The solution to the problem lies in, again, a very well worked
out array of functional group protection-deprotection procedures, which are now so well refined that they have
been automated. The simplest of these are presented here. Problems 58 and 59 will let you try them for yourself.
26-8 through 26-11. Proteins in Operation; Biosynthesis;

DNA and Gene Technology
Obviously only a tiny taste of what s involved with these topics can be presented in the space of four chapter
sections. Nonetheless, you should be able to sense the remarkable way in which the linkage of relatively small
units gives rise to structures of such highly elaborate function. This stuff is really neat. You might like to read
more about it some time.
32, COOH COOH

^ -f
H2N- -H H2N- -H •R
H3C- -H H- -OH
CH2CH3 CH3
L-Isoleucine L-Threonine
Systematic name for L-threonine: (25, 3/?)-2-amino-3-hydroxybutanoic acid.
33. COOH
—s
H2N- -£-r
H- -CH3
CH2CH3
Allo-L-isoleucine
Systematic name for allo-L-isoleucine: (25, 3S)-2-amino-3-methylpentanoic acid.
34. Structures are presented in order of increasing pH (in parentheses).
COO" COO"
COOH
H3N —H (7) H2N- H (12)
(a) H3N 4-H (D
CH3 CH3
CH3
COO" COO"
COOH
H3N H (7) H2N- —H (12)
(b) H3N 4-H (D
CH2OH CH2OH
CH2OH COO"
coo COO
COOH
H2N- H (9.5) H2N- —H (12)
H (1) H3N- H (7)

(C) H3N- (CH2)4-NH2
(CH ) -NH3
(CH2)4-NH3
2 4
(CH2)4-NH3 COO"
COO"
COOH COO" H (12)
H2N- H
S (5) h 3 5+ H H p )
S (1) H3N- H CH2
(d) H3N—H V-N
CH2 CH2 -NH
NH
+
+
COO"
COO"
COOH COO"
H2N- H (12)
H3N- H (9)
(e) H3N- —H (1) H3N- —H (7) CH2S"
CH2S"
CH2SH CH2SH
COO
COO"
COOH COO" H (12)
H (7) H2N-
H3N
(f) H3N- -H (1) H3N —H (3) CH2COO"
CH2COO"
CH2COOH
CH2COOH
COOH COO"
(g) H3N H NH2 (1) H3N H NH2 (7)
(CH2)3NHCNH2 (CH2)3NHCNH2
COO- COO"
H2N H NH2 (12) H2N- -H NH (14)
(CH2)3NHCNH2 (CH2)3NHCNH2
35. (a) Arg, Lys; (b) Ala, Ser, Tyr, His, Cys; (c) Asp
36. First identify the net charge-neutral structure, which is always the one with a single + and a single -
charge. Choose the two pKz values that bracket that structure. They are, respectively, the pKa for deproton-
ation of the most acidic group in that structure and the p£a for protonation of the most basic group. Their
average is the p/.
(c) (9.0 + 10.5)/2 = 9.7
(d) (9.2 + 6.1)/2 = 7.6
(e) (8.2 + 2.0)/2 = 5.1
(f) (3.7 + 1.9)/2 = 2.8
(g) (12.5 + 9.0)/2 = 10.8
(h) (9.1 + 2.2)12 = 5.7
37. The solutions for all three follow the same pattern. First, find the structure of the amino acid target.
Then, based upon the reactions you have been told to use (which result in attaching an amino group to the
a-carbon), begin each with a carboxylic acid lacking the amino group:
(a) ForGly, CH,C02H B"'"LPB". BrCH2C02H NH3'"2°> +H3NCH2C02"
(b) ForPhe, C6H5CH2C02H PB" > C6H5CHBrC02H NHjlH'°> C6H5CH(NH3+)COr
(c) For Ala. CH3CH2C02H C"'PB" > CH3CHBrC02H NH''"20> CH3CH(NH3+)C02"

38. This problem is related to the last, except that the starting material for a Strecker synthesis is an alde
hyde, and the Strecker sequence adds a carbon atom (as a nitrile, CN, which becomes the carboxy group)
So each starting material must be one carbon shorter than the intended target:
1.NH3
2. HCN
(a) For Gly, H2C=0 — > H2NCH2CN H+,"2° > +H
3NCH2C02-
1.NH3
(b) For lie, CH3CH2CH(CH3)CHO CH3CH2CH(CH3)CH(NH2)CN
CH3CH2CH(CH3)CH(NH3+)CCV
1.NH3
(c) For Ala, CH3CHO 2'HCN > CH3CH(NH2)CN H*'H2° » CH3CH(NH3+)C02"
,N-C(C02CH2CH3)2
39. After steps 1 and 2 you have
CH2CH2CH2CH2NHCOCH3
Acidic hydrolysis cleaves not only the phthalimido group from the ring nitrogen but also the acetyl group
from the second nitrogen, giving ~02CCH(NH3+)CH2CH2CH2CH2NH3+, Lys.
40. (a) Because the R group is secondary, alkylation routes should be avoided. Use the Strecker synthesis.
1 NH NH2 +IFH3
(CH3)2CHCHO (CH3)2CHCHCN (CH3)2CHCHCOO-
(b) The R group is primary; now you have a choice. Either the Strecker synthesis starting with
(CFl3)2CHCH2CHO or a Gabriel-based method will do.
O l.Na0CH2CH3,CH3CH20H +Nh3
2. BICH2CH(CH3)2 |
N-CH(C02CH2CH3)2 > (CH3)2CHCH2CHCOO-
Even the Hell-Volhardt-Zelinsky-amination sequence works just fine here.
Br
(CH3)2CHCH2CH2COOH (CH3)2CHCH2CHCOOH
+NH
3
NH3,H20 V (CH3)2CHCH2CHC00-
(c) Several ways to go, but you have to first recognize the need for a three-carbon building block with
leaving groups at each end to allow linkage to both the a-carbon and (later on) the amine nitrogen
to form the ring. Start with a Gabriel-type sequence.
1.NaOCH2CH3, CH3CH2OH
O
II NH3
2. BrCH2CH2CH2OCCH3
3. H+, H20, A
N— CH(C02CH2CH )2 3
HOCH2CH2CH2CHCOO
+NH
3
Cone. HBr
(Converts -OH BrCH2CH2CH2CHCOO"

to —Br, a good
leaving group)
COO"
:NH,
— Br"
H+ + BrCH2CH2CH2CHCOO"
(d) Use a Gabriel-based method. Instead of forming the necessary carbon-carbon bond by SN2
reaction with a haloalkane, use an aldol-type condensation with CH3CHO.
1. NaOCH2CH3
2. CH3CHO
NCH(C02CH2CH3)2
HO NH3
N—C(CO2CH2CH3)2 H+,H2°,A > CH3CHCHCOO"
HOCHCH3
(e) The extra amine group must be present in protected form, irrespective of the method used. Here's a
Gabriel-type sequence.
N _ K + Br(CH2)4Cl
Introduces the
extra amine in
protected form.
rY> NCH(C02CH2CH3)2>
0
NaOCH2CH3
N(CH2)4C1
+NH
3
N(CH2)4CH(C02CH2CH3)2 H ,H2°,A > H3N(CH2)4CHCOO"
1.NH3
HNH
2. HCN r * 3 Chiral, but
racemic
41. (a) CH2CHO /VCH2CHCOO- (i.e., not
optically active)
Stereocenter
(b) The use of an optically active amine (an S enantiomer is shown) means that the addition product
is actually a mixture, because a second stereocenter is generated, which can be either R or 5. This is,
therefore a mixture of R,S and S,S products. Because these are diastereomers of each other, they
don't necessarily form in identical yields. In fact, the S,S product (illustrated) greatly predominates
and, after hydrolysis and removal of the phenylmethyl group with H2, mainly S amino acid is obtained.
42. Begin by looking for an amino acid in Table 26-1 that has the same carbon skeleton as ornithine and
also has a nitrogen in the right place. Can you find one? Yes:
COO"
COCT
H
kH
3N- •H
NH2+
II
CH2CH2CH2NHCNH2
CH2CH2CH2NH3"
Arginine
Ornithine
We're showing these structures in the forms they wouldmostliky tQ the sjmpie amine function of
Nature has an enzymatic method to degrade the Suanld™ «
r° p J. of carbon dioxide. In the laboratory,
ornithine. The process involves loss of two molecules of ammoma a* ^ aqueous
a hydrolysis would do the trick. The actual procedure tn the literature

barium hydroxide at 100°C for two hours. ^^ w omithine precursor? Agatn, look
for^si^larcarbon' skeletorMsdth anâppropriately pos,honed nihogen atom.

an
approach to serine.
NaOH, H2C—0
NCH(C02CH2CH3)2 Aldol cond. [compare
Problem 40(d)]
l.PBr3_
N-C(C02CH2CH3)2 I || N-C(C02CH2CH3)2
o H0CH2 HSCH2
Hydrolysis at this
stage would make serine
Treatment of this product with hot aqueous acid gives cysteine directly. Otherwise,
t. Na°H 1.H2O2 9
2. H2c=CHCH2Br ^ r || N —————— > H2C=CHCH2SCH2CHCOO~
Alkylate on sulfur L JL / \
C(C02CH2CH3)2
0
H2C=CHCH2SCH2
44. The alloisoleucines are diastereomers of the isoleucines, so simple recrystallization will separate them.
Crystals .
1. Dissolve in ,— > (+)- and (—)-isoleucine
hot 80% ethanol
2. Cool to 0°
Mixture
> (+)-and (—)-alloisoleucine
Continue with each mixture of enantiomers separately, making use of brucine as a resolving agent.
+NH-J 0 0
I 3 II II
I RCOCR, A
CH3CH2CH(CH3)CHCOO~
nr . (e.g., R = C6H5)
(+)/(~) Mixture
0 1. Brucine
CH3OH,O°C ! • salt of (+)-acid
RCNH 2. Separate
(crystallization)
CH3CH2CH(CH3)CHCOOH
(+)/(-)
salt of (—)-acid
Finally, FT, H20 treatment releases each pure amino acid enantiomer in turn.
45. (a) Tripeptide; (b) dipeptide; (c) tetrapeptide; (d) pentapeptide. The peptide bonds are simply the
amide linkages,
—C—NH—
t
For example, in tripeptide (a):
(CH3)2CH 0 CH3 0 HSCH2

+ I 1 I II I
H3N CH C—NH CH C—NH—CH—COO"
46. By convention the short notation format always begins with the end of the peptide chain with the
amino group (the 'TV-terminal or "ammo-terminal" end).
(a) Val-Ala-Cys; (b) Ser-Asp; (c) His-Thr-Pro-Lys; (d) Tyr-Gly-Gly-Phe-Leu
47. Determine the net charge on the amino acid or peptide at pH 7 and then recall that negative species
migrate to the anode (A), positive to the cathode (C), and neutrals do not migrate at all (N).
Amino acids (Problem 34): (a), (b), (d), (e) N, (f) A, (c), (g) C
Peptides (Problem 45): (a) N, (b) A, (c) C, (d) N
48* The side chains are all small ( H, CH3, or CH2OH), and mostly nonpolar. In the illustrations,
especially Figure 26-3, note that the sheet structure packs the R groups into small channels between layers of
sheets, where only small groups will fit easily. The nonpolar nature of five of the six groups is also
compatible with their location, a relatively nonpolar region with few hydrogen-bonding groups in the vicinity.
49. The a-helical stretches are fairly noticeable by their spiral shape (compare Figure 26-4). Myoglobin in
fact contains eight significant a-helical stretches, which are labeled by the letters A-H:
a-Helix Amino acid numbers a-Helix Amino acid numbers
A 3-18 58-77
B 20-35 86-94
C 36-42 100-118
D 51-57 125-148
In the figure, all but a-helix D (which is viewed on-end from this perspective) are fairly easy to pick out.
The four prolines are located at or near the ends of a-helices and coincide with "kinks" in the overall
tertiary structure of the molecule, a result of the conformational characteristics of the five-membered ring.
Pro 100
Pro 120
50. Except for the two histidines associated with the heme^ [he nonpolar side
well positioned for hydrogen bonding with solvent molecu •
chains adopt interior positions, avoiding contact with polar so ven mo
5 1 . (a) The sheet structure is favored by amino acids with1 small, °°^°1?)êJo5ular proteins the polar
ability to hydrogen bond to a polar solvent like water molecuie (Problem 50). Similar effects
side chains are exposed to the solvent, solubilizing on the surface,
are seen in micelles formed by soap molecules, in w ^ ^ inside (Real Life 19-1). (c) If
facilitating water solubility, whereas nonpolarf1. amino acid side chains become
the tertiary structure of a globular protein is srup , ... ^ ^ protein molecule,
exposed to the polar solvent, greatly reducing the overall ty
n im m On a portion of the sample, aegrauc
52. (1) Purify and cleave the 6* to determine amino acid composition by using an
entire c h a i n b y a m i d e h y d r o l y s i s ( 6 N H C 1 , H O C ,
amino acid analyzer. (3) On another portion of this material, apply repetitive Edman degradation to determine
the sequence of amino acids. Because only nine are present, the entire chain can be sequenced in this way.
S
/"X ^-NH
53. (a) { ,)-N I + Ala-Cys
\_/ y.CHCH(CH3)2
o
s
/=\ )^NH
(b) { )—N I + Asp
\ / y^CHCH2OH
o
a v
N
o
/^NH
I
v
/M |1
y.CHCH2^ J
N
+ Thr-Pro-Lys
(d) (
V_/
V-NyCHCH
^ / \
^^-0H
+ Gly-Gly-Phe-Leu
2
=
54. Because the peptide is cyclic, the Edman process will not give a normal result. It will simply form
thiourea derivatives at the two "extra" Orn amino groups:
NHCNH(CH2)3-j-
Because there is no a-amino group available to react, mild acid treatment will cleave no bonds in the
product, and the cyclic polypeptide structure will remain intact.
55. Complete hydrolysis indicates that a total of nine amino acid units are present. Examine the four
fragments of incomplete hydrolysis. You know that the peptide begins with Arg (given), so the fragment
Arg-Pro-Pro-Gly must be first. There is only one Gly present, so the last Gly of this tetrapeptide must be the
same one that is at the start of the tripeptide fragment Gly-Phe-Ser. You can use the same logic to start
overlapping all the pieces to generate the whole solution. Thus, because only one Ser is present, the last Ser
in the above tripeptide must be the same as the first one in Ser-Pro-Phe. So far, you have
1 2 3 4 5 6 7 8
Arg-Pro-Pro-Gly
Gly-Phe-Ser
Ser-Pro-Phe
The final fragment, Phe-Arg, clearly is at the end, overlapping the Phe in position 8. So the answer is
Arg-Pro-Pro-Gly-Phe-Ser-Pro-Phe-Arg.
56. Products of degradation, in order of appearance
S. S
~NH „ f~\ )^NH
O-yj
= y^CBrT) ch2ch2sch3
The last product to appear from leu-enkephalin is
fVT
W "CH2CH(CH3)2 y\
o
57. Look first for a piece that ends with an amino acid that should not be a site of cleavage by one of the
Zn mes All the chymotrypsin fragments end in Phe, Trp, or Tyr so that's nc^--
useful. It cleaves only after Arg or Lys, so the 18-amino acid fragmen endIm n P e j be the
end of the intact hormone. Now it's a matter of matching up all the pieces. Start with this end piece from
trypsin hydrolysis and overlap it with chymotrypsin fragments.
(Trypsin piece) Vai-Tyr-Pro-Asp-Ala-Gly-Giu-Asp-Gln-Ser-Ala-Glu-Ala-Phe-Pro-Uu-Glu-Phe
(Chymotrypsin pieces) Pro-Asp-Aia-Gly-Glu-Asp-Gln-Ser-Ala-Glu-Ala-Phe-Pro Leu-G.n-Phe
Now identify a chymotrypsin p.ece to overlap with the

continue the process, all the way to the A-terminal (
Ser-Tyr-Ser-Met-Glu-His-Phe-Arg Trp-Gly-Lys Pro-Val-Gly-Lys P™Val ? *

Ser-Tyr Ser-Met-Glu-His-Phe Arg-Trp Gly-Lys-Pro-Val-Gly-Lys-Lys-Arg-Arg-Pro-Val-Lys-Val-Tyr
• , ster-Tvr- (iust above), overlapping Val-Tyr with the large

The complete answer is read directly, starting ^S^^.^.S^phe.A^-Trp-Gly-Lys-Pro-Val-Gly-Lys-Lys-
trypsin piece, and then on to the end. Ser-Tyr Ala-Glu-Ala-Phe-Pro-Leu-Glu-Phe
Arg-Arg-Pro-Val-Lys-Val-Tyr-Pro-Asp-Ala-Gly-Glu-Asp-Gln-Ser Ala
58. Start at the carboxy-terminal end.
O O
Boc-Phe
1. Phe + (CH3)3COCOCOC(CH3)3
/w-nrnfftrted Phe)
CH3OH, H /"hPl-l
2. Leu * Leu-OCn3
(Methyl ester:
carboxy-protected Leu)
5 1 2 • C h a p t e r 2 6 AMINO ACIDS, PEPTIDES, PROTEINS, AND NUCLEIC ACIDS: NITROGEN-CONTAINING POLYMERS IN NATURE
DCC Dil H+
3. Boc-Phe + Leu-OCH3 > Boc-Phe-Leu-OCH3 : * Phe-Leu-OCH3
O O
4. Gly + (CH3)3COCOCOC(CH3)3 * Boc-Gly

(/"/-protected Gly)
DCC Dil H+
5. Boc-Gly + Phe-Leu-OCH3 > Boc-Gly-Phe-Leu-OCH3 : > Gly-Phe-Leu-OCH3
DCC
6. Boc-Gly again + Gly-Phe-Leu-OCH3 •
Dil H+
Boc-Gly-Gly-Phe-Leu-OCH3 : > Gly-Gly-Phe-Leu-OCH3
O O
7. Tyr + excess (CH3)3COCOCOC(CH3)3 * Boc-Tyr

(N- and phenolic
O-protected Tyr)
DCC
8. Boc-Tyr + Gly-Gly-Phe-Leu-OCH3
l.H+,H20
Boc-Tyr-Gly-Gly-Phe-Leu-OCH3 1"° 'H2° > Tyr-Gly-Gly-Phe-Leu

Leu-enkephalin
O O
Cbz-Cl
59. 1. His ^ rin0N.nmte^^n:. (CH3hCOCOCOC(CH,)3
ring in protected (Cbz) His > amine W-protected Boc-(Cbz)His
The purpose here is to block both reactive nitrogens of His differently. The Boc group will be later
removed by acid to allow a peptide bond to be formed, while the ring^N
„ „ CH3OH, H+
2. Pro Pro-OCH3
(C-protected Pro)
I
3. Boc-(Cbz)His + Pro-OCH, Rnr.rrhûi, Dil.H
3 - Boc-(Cbz)His-Pro-OCH3 (Cbz)His-Pro-OCH3
„ 135-140°C A .
4. Olu > pyroglutamic acid Ine grouP1S now an amide, so
no further protection is necessary.
5. Pyroglutamic acid + (Cbz)His-Pro-OCH, -DCC >
1.HO-,H2O
2. DCC
pyroglutamoyl-(Cbz)His-Pro-OCH, -3,N"3
pyroglutamoyl-(Cbz)His-Pro-NH2 "2'Pd > TRH

NH
N
NH
A : (
N- ~N'
H
OH
G: (
\
N
_
rf^N
(b)
C:
This mispairing makes the A

look like a G (it pairs with
C instead of a U)
Imine-A
(c) Amino acids: Tyr-Gly-Gly-Phe-Met. Possible codons: AUG-

If an A in the DNA shand were tortpowhich codes for His instead of Tyr.
the circled position, the result would be CAC in.
So, the peptide ultimately synthesized would be His-G y- y-
61. 2332 X 3 + 3 (initiation codon) + 3 (termination codon) = 7002.
62. (a) The more acidic SeH group will be deprotonated at pH 7:
coo
COO-
compare H3N- H
H3N- —H
CHISH
CH2Se"
A, «*< « -»-» ' » ' ' " * • ' " " " " " "
(b) The pH 7 structure for Sec above is negative. You need to reduce the pH to below 5.2 (the pATa for
the SeH group) to begin to see appreciable concentrations of the charge-neutral structure, which
would resemble the Cys structure above, right. So the pi = (5.2 + 2.0)/2 = 3.6.
(c) More acidic, but also more powerfully nucleophilic.
25
(b) (i) N" K+ (ii) 1. H+, H20, A; 2. HO",H20, A
Mechanisms:
(i)
O .. 02 /OCH2CH3
NCH2CHCH2CHCOOCH2CH3
0
O- >CH2CH3
NCH2CHCH2CHCOOCH2CH3
(ii) The substituent on CH2 in the final product of part T is abbreviated as "R" for the structures
in the first three lines on the top of the next page.
H
$
NCH2R
:0:
H^Coh
COOH
r^=#sS"NV
CC^CH,
7%
"H+ ULNHCH2R
:o:
H20: "
COOH
H2NCH2R
rNH2CH2R _H» -^YCOOH (Acidic
HOÔH ^XOOH conditions)
H3NCH2 H3NCH2 H3NCH2
0 LEI * A:°OCC1
COOCH2CH3 Xcll^COOCH2CH3 /+ +:OHbH
COOCH2CH3
:0:V^
1 +QH f\
.H+
H20: H
OCH2CH3
H3NCH2
_> H3NCH2CHCH2- O
-C02; tautomerize
-H
H
COOCH2CH3 0H 0^0'
H0:J OH
CI H+, H20,
hydrolyze ester
H3NCH2CHCH2CHCOOCH2CH3 * (Same mechanism

as for lactone)
HO
CI
HO" H2fcH2CHCH2CHCOO^
P Hyp
H3NCH2CHCH2CHCOOH
HO
HO
(c) There is no codon for Hyp in the table. Free Hyp'is of ^ ^ jnto peptide chains. Gelatin
collagen, because the body has no way 0 in rp ^^ does not repiace the indispensa e
does supply a lot of Pro, so it is useful 1
need for vitamin C in collagen biosynthesis.
64. The process is a form of nucleophilic displacement. The reaction takes place at CI of the galactose
portion of the starting uridinediphosphate-galactose molecule. CI is the anomeric carbon, the position where
substitutions occur most easily, typically SN1 under dilute acid conditions (recall glycoside formation and
hydrolysis, Section 24-8). In this case the entire uridine diphosphate (UDP) molecule is the leaving group,
and the C3 hydroxy group of the protein-bound ^-acetylgalactosamine is the nucleophile.
65. (a) AUG-GUG-CAC-CUG-ACU-CCU-GAG-GAG-AAG-etc.

f Val- His- Leu- Thr- Pro- Glu- Glu- Lys- etc.
Initiation
(b) GAG —> GUG. now codes for Val
(c) Replacement of Glu, a polar (anionic at pH 7) amino acid, by Val, a nonpolar (neutral at pH 7)
one, reduces the overall polarity of the molecule, making it less water soluble. Because the
nonpolar Val will prefer to reside in the interior of the molecule (and it replaces an amino acid that
preferred to stick out into the water), the overall shape of the molecule (i.e., the tertiary structure)
is changed. This change is especially disastrous because this substitution occurs very near the
beginning of the first long stretch of a-helix in the molecule. The result is a defective hemoglobin
that tends to aggregate into insoluble clumps that can block blood vessels and generally reduce the
blood's capability to transport oxygen.
66. A: B: ^ ^°2CH3
cr "co2h
Major diastereomer:
Substituents are cis and both are equatorial
HN' "NH
or
cr "'co2k co2k
Major diastereomer:
Substituents are trans and only tert-butyl is equatorial
C:o^ ^
0
An imine
67. (b)
68. (c)
69. (c)
70. (d)
71. (c)
Glossary
Absolute configuration The arrangement of substituents about a stereoisomer, labeled R or S according
to sequence rules.
Abstraction The removal of an atom.
Acene A linear arrangement of fused benzenes, such as the three-ring system anthracene.
Acetal R,C(OR')2, the stable product of acid-catalyzed addition of excess alcohol to an aldehyde or ketone.
Acetaldehyde CH3CHO, the aldehyde corresponding to acetic acid.
Acetal hydrolysis Conversion of an acetal into a carbonyl compound and an alcohol in the presence of
catalytic acid and excess water. ...
« »• * JJ CHuCOOH the carboxylic acid familiar as a dilute aqueous solution—vinegar.
Acetoacetic acid synthesis Synthesis of a 3-substituted or 3,3-disubstituted methyl ketone by alkylate
of a 3-ketoester. wrHir_n
Acetone The common name of 2-propanone (dimethyl ketone), (CH3)2C-U.
Acetyl group The group CH3CO—. _
Activating^gro speeding up a reaction, like electron-donating groups on benzene under
A^S^cien, A reagent bearing a negativeiy charged carbon atom tha, can be converted into
A^rTp ^RCO-^s in the acyl halides, (

M ado„).
tetrahedral intermediate. polyfunction^ bicyclic nitrogen heterocycle.

Adenine (A) One of the four bases in both DNA and kwa, M _qh
Alcohol An organic molecule whose functiona §r°uP d b v gorous oxidation of sugars wi
i
Aldaric acid A dicarboxylic acid, also called sacchanc acid, torme
nitric acid. , I „r0UD c=0, is bound to either two hy roeens
Aldehyde An organic molecule in which the carbo y c
(formaldehyde) or one hydrogen and one car on a 0
Alditol A polyhydroxy compound produced y sug ld h des thr0Ugh an enolate by cata ytic
Aldol addition Conversion of aldehydes to 3-hydroxyal y
low temperature. R unsaturated aldehydes through an enolate y
Aldol condensation Conversion of aldehydes to a, (^-unsaturate
base and heating. hlinp's and Tollen's tests or bromine 0x1 a 10
Aldonic acids Carboxylic acid products of êh ing bon chain would be an aldotnose,
Aldose A sugar based on aldehydes so a hpterocvcle—such

Aliphatic compound A nonaromatic compo . containing nitrogen, often in a
Alkaloid A physiologically active polycychc compound
as cocaine. , rb as methanal for formaldehy.f
OT1„m;ne (methylamine,
Alkanal The systematic name for ana e y ' aijphatic amine, such as me
Alkanamine The Chemical Abstracts name for an alipha
aminomethane).
518 • Glossary
Alkane A hydrocarbon containing only single bonds, and so an organic molecule lacking a functional group.
Alkanoate An organic ester.
Alkanoic acid The carboxylic acid derived from an alkane, such as butanoic acid (butyric acid).
Alkanol The alcohol derived from an alkane.
Alkanone The systematic name for a ketone, such as butanone.
Alkene An organic molecule whose functional group is a carbon-carbon double bond.
Alkenol An enol, or alcohol containing a carbon-carbon double bond.
Alkenyl An alkene as a substituent—as in the alkenyl halides (haloalkenes), useful intermediates in synthesis.
Alkenyne A hydrocarbon containing both double and triple bonds.
Alkoxide ion RO , the ion derived from deprotonation of an alcohol.
Alkoxy group —OR, the functional group of the ethers.
Alkoxycarbonyl An ester as a substituent, —COOR.
Alkyl An alkane fragment as a substituent.
Alkyl azide R—N3, the product of attack by an azide ion on a haloalkane.
Alkylene The common name for an alkene, such as ethylene (ethene).
Alkylthio group The RS group, called alkanethiolate as an anion.
Alkyne An organic molecule whose functional group is a carbon-carbon triple bond.
Alkynol An alkyne incorporating a hydroxy group.
Alkynyl An alkyne as a substituent.
Allene A diene in which the tr bonds share a single carbon atom.
Allyl The common name of 2-propenyl, a resonance-stabilized three-carbon intermediate.
Ambident species A species subject to attack at two different sites to give two different products.
Amidate ion RCH2CONH~, the anion formed by removal of an NH hydrogen from an amide.
O
Amide An organic molecule whose functional group is —C—N—, singly bonded nitrogen bonded to a
carbonyl group.
Amine An organic molecule whose functional group is a singly bonded nitrogen atom.
Amino acid A carboxylic acid with an amine group-at C2 in the 2S-(o-) form used as building blocks
in nature.
Amphoteric Both acidic and basic.
Amylopectin A branched polysaccharide component of starch.
Amylose A helical polysaccharide component of starch.
Anhydride An organic molecule in which two carbonyl groups are singly bonded to an oxygen atom.
Aniline The common name of benzenamine, C6H5—NH2.
IN]Annulene A conjugated monocyclic hydrocarbon of N atoms, with aromatic character governed by
Huckel s rule. b J
Anomeric carbon The carbon attached to two oxygen atoms in the cyclic form of a sugar
Anomers Sugar hemiacetals, diastereomers with a new stereocenter called the anomeric carbon
Anthracene A linear arrangement of three fused benzene rings
Ananart0n!nZ°,,rI«n, ^ arrangement such that groups on adjacent carbon atoms are far
apart—in contrast to gauche.
A auacdhmentTrwn,i0nH A" 0xida"on"h>'drolysis se(luence in which a diol forms from an alkene by

attachment of two —OH groups to the opposite faces of the ir bond.
Aprotic solvent A solvent not containing positively polarized hydrogens
Arene A substituted benzene.
Aronfaticômc>ourid' m Re^ °f f .resonance"^bilized benzenediazonium cation, C6H5N2\
six-membered carbon ring; or (2) Any compound witl"i a cyclic arrav f l * *

An + 2 TT electrons cyclic array of ir-overlapping p orbitals containing
Aromoticity Resonance energy, the stabilizing energy difference between benzene and a nonaromatic cyclic
or between a°y ar°™tic compound and a nonaromatic counterpart Y
Glossary • 519
Ary| (Ar) An arene as a substituent, beginning with the phenyl group.

Asymmetric carbon A carbon stereocenter, one connected to four different substituents.
Asymmetric hydrogenation A highly selective addition of hydrogen to alkenes used in the enantioselective
synthesis of amino acids.
Atomic orbital In quantum mechanics, a region associated with the electrons surrounding an atom.
Aufbau principle The assignment of electrons to atomic orbitals.
Axial bond A bond parallel to the principal molecular axis of, usually, a cycloalkane ring.
Azacydoalkane A saturated nitrogen heterocycle, such as azacyclohexane (piperidine), C5H„N.
Azide ion N3~, a nucleophile useful in introducing an amino group.
Azo group —N=N—, the functional group of several brilliantly colored dyes, the azobenzenes.
Backside displacement A concerted mechanism in which the nucleophile approaches from the side
opposite the leaving group (SN2 displacement, for example).
Baeyer-Villiger oxidation Addition of peroxycarboxylic acid to a ketone followed by rearrangement to
an ester.
Base (1) A proton acceptor; (2) the conjugate base of an acid; or (3) one of the four heterocyclic subunits
of a nucleic acid.
Benzene The aromatic compound C6H6, a remarkably stable conjugated cyclic system.
Benzoic acid An aromatic carboxylic acid, C6H5—COOH.
Benzyl C6H5CH2—, also called the phenylmethyl group—with a corresponding resonance-stabilized
benzylic radical. , _ __ _tl . .
Benzylic resonance Resonance stabilization of the phenylmethyl (benzyl) radical, C6H5CH2 • (also cation
and anion). . ,
Benzyne 1,2-Dehydrobenzene, a highly reactive intermediate, C6H4, with a bent triple bond.
Bimolecular reaction A process, usually second-order, in which two molecules participate in the transi-
Birch reduction Conversion of a benzene into a 1,4-cyclohexadiene through interaction with an alkali
Boot'conformotion An unstable cyclohexane structure, with carbons 1 and 4 tilted out of the plane in the
:r„d « -g„ ^
same direction. ., „
cleavage, or the energy released in forming that bond. • th t _ change would release
Bond length The separation between nuclei for maximum chemical bonding, in that a Chang
no further energy. , , ,. , .f /fnr pXamDle) the tetrahedral
Bond-angle strain Relative instability of a molecule due to distortion of (for exampl
carbon bond angle away from 109.5°. ^ bon chain and omitting
Bond-line notation Molecular representation using straight lines tor
all hydrogens attached to tetrahedral carbon atomSm , h drogenshave been replaced by an alkyl group.
Branched alkane An alkane in which one or more methylene hy g
Bridgehead carbon A carbon atom shared by two nnfcs. riosed-shell allotrope of carbon.
"Rnckvball." or C60, the most prevalent closed shell
Buckminsterfullerene "'Buckyball, or C,6o.
iarbamic acid RNH-COOH, an amide derivative of ith comm„„ name urethane.

larbamic ester RNH-COOR', an amide derivative of carbonic acid
•arbanion Negatively charged carbon.
•arbene R2C:, a highly reactive species; such as me 2^^ t0 cyclopropanes stereospeci ica
•arbenoid A reactive substance that, like a car
•arbocation Positively charged carbon.
-arbocydic compound A ring of only carbon atoms.. ^ ceiluiose.
-arbohydrate A saccharide, which may be a sug ,
x-Carbon The carbon adjacent to a carbonyl group.
520 • Glossary
13CNMR spectrometry NMR spectrometry used to reveal molecular structure by observation of nuclei
of the isotope carbon-13.
Carbonyl group C=0, the functional group characteristic of aldehydes, ketones, and, together with an
OH group, carboxylic acids.
Carboxamide The amide derivative of carboxylic acids.
Carboxylate An organic ester, or a salt of a carboxylic acid (see below).
Carboxylate salt The salt of a carboxylic acid, such as sodium formate, HCOCTNa+.
Carboxylic acid An organic molecule whose functional unit is —COOH, the carbonyl group in conjunction
with a hydroxy group.
Catalytic hydrogenation The addition of hydrogen to a double bond on the surface of a heterogenous
catalyst.
Cbz The phenylmethoxycarbonyl group, a protecting group in peptide synthesis.
Cellulose A polysaccharide of glucose linked at C4.
Chair conformation The most strain-free cyclohexane structure, with carbons 1 and 4 tilted out of the
plane in opposite directions.
Chemical shift The position of an NMR signal, related to molecular structure near the nucleus observed.
Chichibabin reaction Nucleophilic substitution of an amine group in pyridine, using sodium amide in
liquid ammonia.
Chiral molecule A compound that lacks reflection symmetry, and so exists as two nonsuperimposable
mirror-image enantiomers.
Chromic ester The chromium analog to an organic ester and an intermediate in the Cr(VI) oxidation of
alcohols.
Cis isomer A stereoisomer in which substituents are on the same face, or side, of a ring or a double bond—in
contrast to a trans isomer.
Claisen condensation Addition-elimination of ester enolates with esters, giving 0-dicarbonyl compounds.
Claisen rearrangement An electrocyclic reaction of 2-propenyloxybenzene, giving 2-(2-propenyl) phenol,
emmensen reduction Synthesis of an alkylbenzene by conversion of a carbonyl group to CH, in the
presence of HC1 and zinc.
S° j' tQr SOlid distillate of coal (having a residue called coke), a source of many aromatic compounds.
Codon The three-nucleotide sequence in RNA that selects an amino acid in protein biosynthesis
Common name A traditional name, often derived from the molecule's source or discoverer-in contrast
with systematic nomenclature.
Competition experiment An experiment comparing the relative reactivity of two substrates.
Complex sugar An oligomer or polymer of linked simple sugars.
rted/eaC,iTK •A reactifin WhiCh bondS break and new bonds form "in c°nc<*t>" or simultaneously,
condensation The joining of two molecules with elimination of water
C°char nSed '°rmUla MokCUlar rePresentat'on omitting all lone pairs and the bonds of the main carbon
n
COco"s0nal an°lySiS StUdy °f the thermodâm'c aad kinetic behavior of conformations or
C^"lleTconfomersôr0rctomer:trUCtUreS ^ "y ""*» ** b™ds' a>»

Conjugate acid The species HB+ derived from a base B.
Coniuqate base ^ The *7; P"Unsaturated carbonyl compound. See Michael addition.
con|ugare base The species A derived from an acid HA
CO"nXb™dldiene A StmCtUre With 'W0 d°Uble b°ndS eonjugation," or linked across a carbon-carbon
Constitutional'iscuners A Motecules t m T* " Wh'Ch Carbon a,oms rotate » <he same direction.
different order. Synonymous with structural isomm m°'eCUlar f0rmula but with the atoms eonnected in a
Coordination The supplying of an electron pair to an atom by a Lewis base
Cope rearrangement A concerted reaction of compounds containing 1,5-diene units.
Glossary • 521
Coulomb's law The mathematical law describing the force between electric charges, a main contribution
to chemical bonding.
Coupling The splitting of an NMR spectral peak by neighbors into more complex patterns.
Covalent bond A bond formed by the sharing of electrons between atoms—in contrast to an ionic bond.
Cracking The breaking of alkanes into smaller fragments, as in refining crude oil.
Cross-linkage The connection of two or more polymer chains; gives rubber its familiar hardness and
elasticity.
Crossed aldol condensation An aldol condensation of two different aldehydes or ketones.
Cyano group —CN, the functional group of the nitriles.
Cyanohydrin RR'C(CN)OH, the product of hydrogen cyanide addition to the carbonyl group.
Cyclic bromonium ion An intermediate in addition reactions, in which bromine bridges both carbons of
a double bond.
Cydoaddition An addition reaction, such as the Diels-Alder reaction, leading to a closed ring (the
"cycloadduct").
Cydoalkane An alkane whose carbons form a ring, also called a cyclic alkane or carbocycle.
Cydoalkanecarboxylic acid A saturated cyclic carboxylic acid.
Cydoalkanone The systematic name for a cyclic ketone.
Cytosine (C) One of the four bases in both DNA and RNA, a polyfunctional nitrogen heterocycle.
D, L sugars R, S configurations based on the highest-numbered stereocenter, with all natural sugars D.
DCC Dicyclohexylcarbodiimide, a dehydrating agent in peptide synthesis.
Deactivating group Substituents allowing only sluggish reaction, such as electron-withdrawing groups on
benzene undergoing electrophilic attack.
Decoupling Techniques that remove NMR coupling, such as proton decoupling and fast proton
exchange. , ,. . ._
Degenerate orbital Orbitals of equal energy, such as the three p orbitals, px, pv and Pz" ,
Degree of unsoturotion The sum of the number of rings and rr bonds in a molecule, determined from
the molecular formula.
Dehydration Elimination of a molecule of water. hvhrid
Derealization The distribution of electrons over several nuclei as in a re™a"êfheredit™ informa.
Deoxyribonucleic acid (DNA) The dimeric helix of uucleohde chains that cames heieditaiy
d SUTE increase in the local magnetic field or removal of electrons from a nucleus, causing a
Dextrorotatory^!molecule Ân enantiomer that rotates the plane of polarization clockwise as the viewer
Diamine'6 '^compound with two amine groups, such as l.~toe (putrescine).

Diastereomers Stereoisomers that are not mirror images o one a all possible stereo-
Diastereoselectivity Preference for a reaction to produce one stereoisome
isomers of a product. , t . „„11Mi:no nf axial substituents across a ring.

1/3-Diaxial interaction Transannular strain due to s eric crH9N?) a useful synthetic intermediate.
Diazo compound A diazoalkane, R2C=N2, such as iaz°™ j iv"ing az0 dyes.
Diazo coupling Electrophilic substitution with arenedi,azomum g ^^ nitrous d.

Diozonium ion R-N2+, a highly reactive product of the iwtfra F^ usjng cold „itrous ac,d.
Diozotizotion Synthesis of arenediazomum salts from en carbonyi groups adjacent to the same
H-Dicorbonyl compound A useful intermediate bearing two carbony
Cmonn condensation Intramolecular Claisen condition, P™™tow"taes, widt

Diels-Alder reoction Concerted [4 + 2] cycloaddition of dienes, ^^
two, to form cyclohexenes. including conjugated and nonconjugate ie

Diene A compound containing two double bonds, including conjug
as allenes.
522 • Glossary
Difunctional molecule A compound with two functional groups, subject to the characteristic reactivity
of both.
Dimer Linkage of two identical subunits, often the first stage in polymerization.
Dioic acid A dicarboxylic acid, such as propanedioic acid (malonic acid).
Disaccharide A substance combining two simple sugars, such as sucrose, which combines fructose and
glucose.
Disrotatory process A reaction, such as a ring closure, in which one carbon atom rotates clockwise, one
counterclockwise.
Dissociation The breaking of chemical bonds.
Disulfide A molecule containing a sulfur-sulfur linkage.
DMSO Dimethylsulfoxide, a useful polar aprotic solvent.
Double Claisen condensation Intermolecular followed by intramolecular Claisen condensation, giving
cyclic products.
E, Z system Naming rules for diastereomers with double bonds, assigning priority separately to substituents
on each carbon.
Eclipsed conformation An arrangement such that, in a view along the carbon axis, each hydrogen or
substituent group is aligned with one on the next carbon.
Edman degradation Peptide sequencing by stepwise hydrolysis of /V-terminal amino acids.
Electric dipole A separation of charges giving each end of a neutral species a partial positive or negative
charge.
Electrocyclic reaction A ring closure that involves cyclic movement of electrons.
Electron affinity (EA) The energy released when an electron attaches itself to an atom.
Electronegativity The ability to accept electrons, highest in the rightmost elements of the periodic table.
Electrophile A species (coded blue in this text) that tends to react with centers having unshared electron
pairs.
Electrophilic addition Addition to a double bond through attack by an electrophile followed by trapping
of the resulting carbocation by a nucleophile.
Electrophilic aromatic substitution Electrophilic attack on benzene in which hydrogen is replaced by
the electrophilic group. K J
Elemental analysis Determination of a chemical's empirical formula, and so the kinds and ratios of
elements present.
Elimination (E) A unimolecular (El) or bimolecular (E2) reaction in which atoms, such as a halide and a
hydrogen, are eliminated and it bonds form in their place.
Enamine A product of amine-carbonyl condensation having both a carbonârbon double bond and an
amino group.
Enantiomers Pairs of molecules that are nonsuperimposable mirror images
pmd" C,iVity PreferenCe ^ 3 reaC'i0n '° Pr°dUCe °ne °f ,he tW0 P°ssibIe enantiomers of a chiral
Entdo°anaexoUaddn« biCyCliC Pr°dUCttra"S With t0 the shOTter bridge-in contrast
Endo rule ^ Selectivity favoring the endo adduct in the Diels-Alder reaction
Endothermic reaction A reaction absorbing heat, giving a positive enthalpy change
n:ir
Enol
En —rjrformed upon—°f the

An alcohol containing a double bond
au — —<•
inIn^yisCreS,,AH°) ^ ^ °f 3 ""*» * <™ P™-a negative value indicating that
favoring the reaction's'progress^"86 °f " SyStSm l°Ward greater disPersal of energy—a positive value
Enzyme A catalyst found in living systems.
Epimers Diastereomers differing at only one stereocenter.
Glossary • 523
xide Common name for oxacyclopropane.

t uatorial bond A bond approximately perpendicular to the principal molecular axis.
Equilibrium The state of a reaction at which the concentrations of reactants and products no longer
change. 0
Ester In organic chemistry, a molecule whose functional group is —C—0—, oxygen singly bonded to a
carbonyl group.
Ester hydrolysis The reverse of esterification, leading to a carboxylic acid and an alcohol in the presence
of excess water.
Esterification The production of esters and water from alcohols and carboxylic acids in the presence of a
mineral acid catalyst.
Ether An organic molecule whose functional group is the alkoxy group, —OR.
Exact mass The precise mass of the peaks of mass spectra.
Excitation Discrete changes in the state of a molecule when it absorbs radiation.
Exo adduct A bicyclic product with substituents placed cis with respect to the shorter bridge—in contrast
to an endo adduct.
Exothermic reaction A reaction releasing heat, giving a negative enthalpy change.
Extended n system A molecule with more than two conjugated double bonds, such as benzene.
Fat An ester of long-chain carboxylic acids that is solid at room temperature—in contrast to liquid oils.
Fatty acid The carboxylic acid parts of fats and oils.
Fehling's test A chemical test for aldehydes by oxidation to a carboxylic acid and formation of cuprous
oxide, a red precipitate.
Finaerprint region The infrared spectrum between 600 and 1500 cm .
Fischer projection Representation of a configuration with horizontal lines for bonds pointed toward
viewer, vertical lines for bonds pointed away.
Fischer-Tropsch reaction Catalytic synthesis of hydrocarbons from synthesis gas_
Formaldehyde H2C=0, the parent aldehyde-the aldehyde corresponding to formic acid.
Formalin An aqueous solution of formaldehyde, a common disinfectant.
Formic acid HCOOH, the parent carboxylic acid.
p :
T« eTP Admass' spectrum show,ng the abundance of the chat— ft— of a
Alkylation and
Frontside displacement A (hypothetical) mechanism in wh.ch a nucleoph.le approa
side as the leaving group.
Fructose A ketohexose found in many fruits and honey. iwwhaii» r'
Fullerene A molecule containing a closed carbon shell, such as y . ^ molecule,s reactivity.
Functional group A group of atoms, also called a unctlon' d b, r tripiy bonded carbon or other
Functionalization The introduction of a functional group, such as doubly P
elements, into a molecule.
Furan C4H40, an aromatic heterocyclopentadiene.
Furanose A five-membered cyclic monosaccharide. atoms.
Fused ring A structure in which two rings share two a ja • • d ( hthalimide)
Gabriel synthesis Synthesis of a primary amine usi"S1'^ ênze adjacent carbon atoms are close—in
Gauche conformation A staggered arrangement such that groups on J
contrast to anti. . hvdrogens on the same carbon atom, such as te
Geminal coupling Coupling between nonequivalent hyd g
hydrogens at a double bond. onverns a
Geminal dial RC(OH)2R\ a carbonyl hydrate. function of temperature tha
Gibbs standard free energy change (AG )
reaction equilibrium.
524 • Glossary
Glucose An aldohexose, also called dextrose or grape sugar.

Glutathione A peptide that acts as an intracellular reducing agent.
Glycogen A huge branched polysaccharide of glucose, a store of energy in humans and animals.
Glycoside A sugar acetal, linking monosaccharides.
Glycosyl Sugar as a substituent bound at its anomeric carbon.
Gngnard reagent RMgX, an organomagnesium compound useful in synthesis.
Guanadine NH=C(NH2)NH—as a substituent, the guanadino group in amino acids like arginine
Guanine (G) One of the four bases in both DNA and RNA, a polyfunctional bicyclic nitrogen heterocycle.
Haloalkane An organic molecule whose functional group is a carbon-halogen bond.

Halogenation-dehydrohalogenation Synthesis of an alkyne through an alkenyl halide intermediate.
Hantzsch pyridine synthesis Condensation of two fi-dicarbonyl molecules, an aldehyde, and ammonia
to an aromatic ring.
Hashed-wedge line notation Molecular representation using hashed lines for bonds angled below the
page, wedges for bonds angled above it.
Haworth projection Representation of D-sugars with the anomeric carbon at the right and substituents
attached by vertical lines.
Heat of combustion (AH°comb) The heat released in combustion, or the burning of a molecule, a useful
measure of its stability.
Heck reaction Coupling reaction between alkenyl halides and alkenes to produce dienes, catalyzed by
metals such as Ni or Pd.
Hell-Vollhard-Zelinsky reaction Bromination of a carboxylic acid at the a-carbon catalyzed by trace
amounts of phosphorus.
Heme group The oxygen-carrying porphyrin substituent in the natural polypeptides myoglobin and
hemoglobin.
Hemiacetal HRC(OH)OR, the product of addition of an alcohol to aldehydes or ketones.
Hemiaminal HRC(NH2)OH, the nitrogen analog of a hemiacetal.
Heteroatom An element other than carbon, most frequently nitrogen or oxygen.
Heterocycle A cyclic molecule whose ring contains a heteroatom, or element other than carbon.
Heterogeneous catalyst A catalyst insoluble in the reaction solvent.
Heterolytic cleavage Dissociation in which the bonding electron pair is donated to one atom only-in
contrast to homolytic cleavage.
Hofmonn elimination Alkene synthesis from quaternary ammonium salts, used to determine the structure
or amines.
H<rfb°"n rearran9emen' Lossof the carbony' 8rouPfrom acarboxamide by halogenation in the presence
"t'lTeneT rU'e Regi°SdeCtivity Whereby E2 eliminution by a hindered base leads to the less stable terminal
^riec^S:be,Wee" ^ W8heSt ~ orbitals,
"zszss. fsszs* - -
Huckel's rule The rule that an aromatic annulene must contain An + 2 v electrons
dehors ^ ^ eIeCtr°"S fU1 d~ b« with one eiectron of the
Hybrid orbital An orbital formed from the mixing of atomic orbitals on a single atom
Hydration Addition of the components of water to a double bond
Hydrazine H2N—NH2.
HydrTde°ioen ZT™ *** ^ ^ " identif^S aldehydes and Atones.

Mydnde ,on [H.] , an anion of hydrogen possessing the helium electronic configuration.
Glossary • 525
... Rearrangement i n which a hydrogen i n a carbocation moves with its pair of bonding electrons
a neighboring positively charged carbon,
d oboration Addition of borane, BH3, to a double bond.
HJdroboration-oxidation A two-step addition of water to a double bond, with anti-Markovnikov
regioselectivity.
H^droqen An acidic hydrogen on the carbon next to a carbonyl group, the a-carbon.
Hydrogen bond A dipole-dipole attraction between a positively polarized hydrogen atom and an electro
negative atom.
Hydrogen (1H) NMR spectroscopy NMR spectroscopy used to reveal molecular structure near a hydro
gen nucleus.
Hydrogenation Addition of gaseous hydrogen (H2) to a double bond.
Hydrogenolysis Hydrogen addition with simultaneous bond breaking.
Hydrophilic Enhancing solubility in water.
Hydrophobic Insoluble in water.
Hydroxy group —OH, the functional group of the alcohols.
Hyperconjugation Derealization of a bonding electron pair into an empty or a partly empty atomic orbital,
stabilizing the structure.
Imidazole Diazacyclopentadiene, an aromatic heterocycle found in amino acids like histidine.

Imide The nitrogen analog of a cyclic anhydride, a ring in which two carbonyl carbons flank a nitrogen atom.
Imine An organic compound, also called a Schiff base, whose functional group is a carbon-nitrogen double
Iminium ion [R2N—CH2+ » R2N=CH2], the resonance-stabilized fragment left by loss of an alkyl group
from an amine in mass spectrometry.
Indole A benzpyrrole, or fused six- and five-membered aromatic rings with a nitrogen heteroatom.
Inductive effect The stabilizing of a charge by its transmission through a chain of atoms.
Infrared (IR) radiation Radiation just lower in energy than visible light, useful in spectroscopy for iden
tification of functional groups in organic molecules.
Infrared spectroscopy Determination of structure by assignment of vibrational excitations to specific
functional groups.
Initiation The initial step in a radical chain mechanism.
Intermediate A (typically) unobserved species formed on the pathway between reactants and products, as
described by the reaction mechanism. _
Intramolecular aldol condensation An aldol condensation between enolate ions and carbonyl group
in the same molecule. . ... -norc,\
Intramolecular esterification The production of lactones from hydroxy acids on treatment with mineral
acid catalyst. . . . „nll_j
Inversion Acid- or enzyme-driven decrease in the specific rotation of sucrose, giving a mixture ca e
invert SU23T *
Inversion of configuration A stereospecific reaction in which the reactant and product are of oppos
Ionic bond A bond formed by the transfer of electrons between atoms—in contrast to a covalent bond.
Ionization potential (IP) The energy needed to remove an electron from an atom.
Ipso substitution The displacement of a group other than hydrogen from an aromatic ring.
Isoalkane An alkane branched with a methyl substituent at C2. amino acid
Isoelectric point (pi) The isoelectric pH, at which the charge-neutralized form of an amino
Isomers Substances with the same molecular formula, such as constitutional 1Jom®rs.^ Stere°
Isoquinoline 2-Azanaphthalene, an unsaturated heterocycle of fused six"memb^ Chemistry to reflect
'UPAC rules Nomenclature adopted by the International Union of Pure and Applied Chemistry
a molecule's structure.
526 • Glossary
Kekule structure Representation using a line notation for bonding electrons, with lone pairs either shown
by dots or omitted.
Keto The carbonyl tautomer, which rapidly interconverts with its less stable enol form in the presence of
acid or base.
Ketone An organic molecule in which the carbonyl group, C=0, is bound to two carbon atoms.
Ketose A sugar based on ketones—so that a three-carbon chain would be a ketotriose, for example.
Kiliani-Fischer synthesis An older method for chain lengthening of sugars through a cyanohydrin
intermediate.
Kinetic control Conditions under which the major product of a reaction is the one that forms fastest.
Kolbe reaction Attack of the phenoxide ion on carbon dioxide, giving a 2-hydroxybenzoic acid.
Lactam A cyclic amide, or ring in which a carbonyl carbon is singly bonded to a nitrogen atom.
Lactone A cyclic ester, the product of intramolecular esterification.
Lactose The most abundant natural disaccharide, made of glucose and galactose units.
Leaving group The group of atoms (coded green in this text) displaced in a substitution reaction.
Leaving-group ability The ease with which a group can be displaced in a nucleophilic substitution,
related inversely to basicity.
Levorotatory molecule An enantiomer that rotates the plane of polarization counterclockwise as the
viewer faces the light.
Lewis structure Representation using dots to show valence electrons.
Lindlar's catalyst A special deactivated form of palladium, used in partial hydrogenation of alkynes to
form cis-alkenes.
Lipid A water-insoluble biomolecule made of waxes and fats.
Lipid bilayer A unimolecular sheet of phospholipids.
Lithium aluminum hydride LiAlH4, a reducing agent in many organic syntheses.
London forces Weak intermolecular forces between nonpolar molecules due to a correlation of electrons
as they approach.
Magnetic resonance imaging (MRI) A diagnostic tool that utilizes proton NMR to image the human body.
°|or resonance contributor The Lewis structures most nearly representative of the electron distribution
in a delocalized molecule.
Malonic ester synthesis Synthesis of either 2-substituted or 2,2-disubstituted carboxylic acids from diethyl
propanedioate (malonic ester).
Maltose A dimer of glucose with an acetal linkage.
Mannich base The free amine whose salts are produced in the Mannich reaction.
Marlrovr "i""*0" A'kylatio" of enols electrophilic iminium ions, giving (3-aminocarbonyl compounds.
ti^ carbon!° eCtlV1'^ m '° ^ » <='«><= ^
Masked acyl anion An acyl anion equivalent.
MmagnetirfleMme,ry Detem,inati°n °f StrUCtUre from the of molecular-ion fragments in a
^ên7rgTx:ia„dDrersition in mass °f carbonyi <=—dS a

"change huo prod^" ^ °f 3 reaCU°n' ^^ » Which ta—d*» then rapidly
Mercapto group The SH group.
Mela- (m-) Common-name prefix for 1,3-disubstaXSeT "S

"benzene^''"9 A'l0WinS Pred0minant1^ electrophilic substitution, like a tnfluoromethyl group on
Metallation The preparation of organometallic reagents.
Glossary • 527
, jhe highly reactive species H2C, the simplest carbene.

(lethy ene _CH2-, the basic unit of the alkanes.
Methylene S K ^ aqueQUS solution5 such as the cluster of long-chain alkali metal carboxylates
Micelle A sPne
inS0? Edition The conjugate addition of enolates to a,(S-unsaturated aldehydes and ketones.
J'^dClaisen condensation" Claisen condensation involving two different esters and often giving prod-
ja,"extinction coefficient (e) The reported peak height in a UV-visible spectrum, also called molar
aSlr'ion A radical cation, M+% formed by electron impact in a mass spectrometer,

unl ular orbital An orbital formed of overlapping atomic orbitals from different atoms,
rimer The repeated building block in a dimer, oligomer, or polymer.
Z r«horide A simple sugar, or carbonyl compound bearing at least two addmonal hydroxy groups.
Mutarotation Change in a sugar's optical rotation when it equilibrates with its anomer.
N11 rule The rule that N equivalent neighbors produce N + 1 spectral peaks in NMR owing to spin-spin
Naphthalene Two fused benzene rings, the simplest polycyclic benzenoid hydrocarbon.
Natural product A compound produced by living organisms.
Neoalkane A branched alkane in which C2 bears two methyl substituents. . . . .,
Newman projection Representation of an alkane along the carbon axis, so that the conformation is easily
Nitrile An organic molecule whose functional group is a carbon-nitrogen triple bond.

N-Nitrosamine R2N-N=0, the carcinogenic product of the reaction of a secondary amtne
Nitrosyl cation NO+, a resonance-stabilized electrophile derived from nitrous acid.

NMR spectrometry Determination of molecular structure from how nuclei absorb radiation in a magnetic
field (nuclear magnetic resonance). . Qrp «faot nn the
NMR time scole A limit to spectral resolution-peaks cannot be dist.ngu.shed if changes are fas. on
NoNdeR Tsurfate separating portions of a wave function with opposite arithmetic signs, indicating where an
electron is never found. , , , „ ,. ~wtrr.n<;
Nuclear core The nucleus of an atom together with all inner-shell electrons but not vale,ace el*
Nuclear magnetic resonance Characteristic excitations of a magnetic atomic nucleus ,n an external
magnetic field, causing it to "flip," or alter, its spin state. nrotein
Nudeic acid DNA or RNA, the nucleotide polymers that carry the genetic code
NuclMphile'lNu) A species (coded red in this text) bearing lone electron pairs and attacking positively
Nudeophilic aromatic substitution Ipso substitution, giving phenols anilines, or

Nudeophilic substitution A bimolecular (SN2) or unimolecular (SN1) reaction in
displaces a leaving group.
Nudeophilicity The reactivity of a nucleophile.
Nucleoside The sugar-base subunit of a nucleotide.
Nucleotide A phosphate-substituted nucleoside—a building block of DN or
Octet A group of eight electrons, as in the outermost shell of the noble gases afterTieliu lid
OH An ester 0f long-chain carboxylic acids that is liquid at room temperature-in contrast
f^ts
Oligomer ^ A molecule with a subunit repeated only a few times,the. ^"uâ^ral molecule, also called
Optical activity Rotation of the plane of polarization of incoming lig y
optical rotation.
528 • Glossary
Optical isomer A molecule, such as an enantiomer, that is optically active, or rotates the plane of polar
ization of incoming light.
Optical purity The percentage of optical activity observed relative to that of the pure enantiomer.
Organic molecules Carbon compounds (traditionally excepting C02 and compounds where carbon enters
solely in a CN subunit).
Organometallic reagent A compound in which the carbon atom of an organic group is bound to a metal
and so a source of nucleophilic carbon.
Ortho- (o-) Common-name prefix for 1,2- (adjacently) disubstituted benzenes.
Ortho and para directing Allowing ortho and para electrophilic substitution, like a methyl group on
benzene.
Oxacycloalkane A cyclic ether, or ring in which a carbon atom is replaced by oxygen.
Oxalic acid The common name of ethanedioic acid, the simplest dicarboxylic acid.
Oxidation The addition of electronegative atoms such as oxygen or the removal of hydrogen from a
molecule.
Oxime RR'C=NOH, a crystalline imine product used in identifying aldehydes and ketones.
Oxonium ion The conjugate acid of an alcohol.
Oxymercuration-demercuration Hydration of a double bond by addition of a mercuric salt and water,
then removal of mercury.
Ozonolysis Cleaving of an alkene ir bond leading to carbonyl compounds.
Paal-Knorr synthesis Synthesis of pyrrole by cyclization of a y-dicarbonyl compound.

Para- (p) Common-name prefix for 1,4-disubstituted benzenes.
Pauli exclusion principle The rule that no atomic orbital may be occupied by more than two electrons.
PCC Pyridinium chlorochromate, an oxidizing agent.
Penicillin An annulated P-lactam.
Peptide An oligomer of amino acids joined by amide linkages—a dipeptide, tripeptide, and so on.
Peptide bond The carboxylic acid-amine link in a peptide chain.
Peri fusion Angular fusion of benzenes, as in the three-ring system phenanthrene.
Pericychc reactions Electrocyclic and other reactions with a transition state having a cyclic array of
nuclei and electrons. J
Peroxide Any - system

- with two oxygens
jo directly
~"j joined by "
J"""-" "J a single bond.
ojiigic UU11U.
Peroxycarboxyhc acid RC03H, a carboxylic acid with an additional, electrophilic oxygen.
Phenol ^ The alcohol derived from benzene, formerly known as carbolic acid.
Phenoxide ion C6H5CT, the resonance-stabilized anion accounting for the acidity of phenol.
Phenoxy C6H50—, phenol as a substituent.
Phenyl Benzene as a substituent, the simplest aryl, C6H5—.
Phenylmethyl group C6H5CH2-, also called the benzyl group.
Phenylmethyl radical The resonance-stabilized benzylic radical C6HsCHr
Phenylosazone A J—l'- •• •
»yT"n, A d0UMe PhenyIhydraZ°"e "y carbonyl condensation of sugars with
r r
naturally occurring substance used for communication within a living species
Photosvnt'h*.ci« p'l" °! carboxyllc ac,ds and phosphoric acid, a component of cell membranes.
Photosynthesis Plant synthes.s of carbohydrates from carbon dioxide and water using energy fron
sunlight.
Pi (IT) bond A bond derived from overlap of parallel D orhitak a« in , x* J L, , ,
•tt .re* transition.: i . • oroitais, as in components of double and triple bonds.
1. . ?nS,t'°nS Excitation of electrons in ir orbitals by visible or UV radiation
Picric acid 2,4,6-Trinitrophenol, a highly explosive acid
Plane-polarized light Light whose electric field vectors lie in one nlan„ tk« i * ,
Polarimeter A device for measuring optical rotations P ' P °f Polar,zatlon-
Polarizability The capacity of an atom's electrons to respond to a changing electric field
Polarized bond A covalent bond between atoms of different .i /
electrons are not shared equally. different electronegativity, so that the bonding
Glossary • 529
po|ycyC|JC benzenoid hydrocarbon An extended IT system of fused rings, also called a polycyclic
aromatic hydrocarbon (PAH).
Polyethene A branched polymer with common name polyethylene, familiar as plastic storage bags and
containers.
afunctional compound A compound with many functional groups, such as a carbohydrate.
Polymer A molecule with a repeated subunit, such as polyethene and the other synthetic compounds listed
in Table 12-3.
Polymerization The synthesis of polymers.
Polypeptide An amino-acid polymer, such as a protein, with chains sometimes joined by disulfide badges.
Polysaccharide A polymeric complex sugar.
Polystyrene A polymer derived from ethenylbenzene (styrene).
PorDhvrin A cyclic molecule, such as a heme group, of four linked pyrrole units.
Potential energy diagram A graph of potential energy changes, as in a chemical reaction or rotation
about a carbon-carbon bond.
Z
tCSy attached to only one Cher carbon ate,
C structure amino-acid 'sequence in a peptide chain-in contrast to secondary stmcture, the
ProstaglandiI^ I PG)18 A potent hormonelike substance containing alcohol groups, alkene bonds, and car-
Protecting group A group that temporarily -f-"«^brous proteins in muscle,

Proteins Large natural polypeptides, such as globular proteins used as enzy
and hemoglobin. notorized hydrogens, and so available to interact with anionic

Protic solvent A solvent containing positively polanzed hy g
nucleophiles. .,
Pyranose A six-membered cyclic monosacc^ . heterocycle with a six-membered ring.
Pyridine C5H5N, an azabenzene, or
Pyrolysis The breaking of alkane bonds when a m
Pyrrole C4H5N, an aromatic heterocyclopentadiene.
. that make up electromagnetic radiation, each of energy dependent on
Quanta The discrete "packets that maxe p
wavelength. , M . tn fnnr other carbon atoms.
Quaternary carbon A carbon directly attached to f ^ six.membered rings-
Quinoline 1 -Azanaphthalene, an unsaturated fon0wing hydroxymethylation of P

hen°.
Quinomethone CHfi&P. an intermedtate pr (be„zoqu.none), a cychc dtketone.
Quinone The common name for denvattves of cyclohex
Racemic mixture A racemate, or 1.1 ml*'"^rate witb the enantiomer's mirroif1™^. ic cieavage.
Racemize To undergo racemization, or eq j d eiectron as a resu t o initiating further
Radical A fragment of a molecule possessmg^ generates radtcal fragments, mthatt g
Radical chain mechanism A eye e in

reaction until chain termination.
Raffinose A nonreducing trisacchan e. dispersed nickel. slowest step
Raney nickel (Ra-Ni) A catalyst J overall reaction rate because
Rate-determining step The step describing the progress o
in a sequence. ^ coordinate in a potential energy diagra
Reaction coordinate The hon ^ oxjdation t0 carboxyhc aci .
a reaction. nriftoble by Fehling's and Tollen
Reducing sugars Sugars identifiable y
530 • Glossary
Reduction The removal of electronegative atoms such as oxygen or the addition of hydrogen to a molecule
Reductive amination Amine synthesis by condensation with a carbonyl compound to an imine interme
diate, followed by reduction.
Reformate A new hydrocarbon created, or reformed, from an old one.
Regioselectivity The attack of a reagent preferentially at one of several possible centers.
Residue An amino acid as a peptide subunit.
Resolution The separation of enantiomers.
Resonance energy The stabilizing energy difference between delocalized and nondelocalized structures.
Resonance hybrid Representation of a molecule in which no one Lewis structure is correct, because
electrons are delocalized, or shared, over several nuclei.
Retro-Claisen condensation The reverse of Claisen condensation upon treatment of certain P-dicarbonvl
compounds with base.
Retrosynthetic analysis Planning a synthesis by reasoning backward from the desired product to precursors
by identifying bonds that may be constructed.
Reverse polarization The conversion of a carbon atom from an electrophilic center to a nucleophilic one
or vice versa.
Ribonucleic acid (RNA) The chains of nucleotides, arranged in codons, that govern protein biosynthesis.
Ribose An aldopentose, building block of the ribonucleic acids.
Ring strain The relative instability of smaller rings due to torsional and bond-angle strain.
Robinson annulation Michael addition followed by intramolecular aldol condensation, used in steroid
synthesis.
Rotamers Conformations or conformers.
Ruff degradation Chain shortening of sugars by oxidative decarboxylation.
Saccharides Sugars.
Sandmeyer reaction Decomposition of arenediazonium salts to haloarenes in the presence of cuprous salts
saturated compound A compound, such as an alkane, with only single bonds
Saytzev rule Regioselectivity whereby E2 elimination by a nonhindered base leads to the more stable
internal alkenes.
Seatom1ary Carb0" A" Sp3"hybridized Cetrahedral) carbon directly attached to exactly two other carbon
Se"
r"^s
S,rUC,Ure The f0ldinS Paltern of a PePtida chain in contrast to primary structure, the sequence
^selective ^ °f °"e °f SeVeraI P°ssible Pûcts, so that the reagent is said to be
^ketone h010"6 RR'C=N-NH-CONH

2, a crystalline imine product used in identifying aldehydes and
^Tosltthe '° '"h" * 3 — ^ » a<°™ — a"d

Sequencing Determination of a peptide's primary structure
cS shmredUCti0n the '°Cal magne,iC f,eld' 0r dona"°" of'*a nucleus, causing an upfield
siqmfMnbondbSThontSHj0inehd 'a *** 0r Se"UenCe of rcsite in a polypeptide,

sê bind m * m °rbi'alS
6CUlar aIig"ed in a cC'ncar manner, as in a carbon-carbon
Singlet A single sharp peak in an NMR spectrum electrons.
SkconfoZ!Ta,i0n A" a"an8ement °f methyl gr0"PS between the extremes of a staggered or echpsed
Specific rotation ,[„]) A standard value for the optical rotation of a chira, compound.
Glossary • 531
Spectrometer An instrument for recording spectra, by comparing radiation transmitted through a samnle
to a reference beam. b F
Spectrometry A tool for determining molecular structure from how molecules absorb radiation.
Spectrum (plural: spectra) A plot of intensity, showing peaks at wavelengths where a molecule absorbs
radiation.
Spin The intrinsic angular momentum of an electron, nucleus, or other quantum-mechanical object.
Spin-spin splitting Coupling, or the splitting of an NMR spectral peak by neighbors into more complex
patterns.
Staggered conformation An arrangement such that, in a view along the carbon axis, each hydrogen or
attached group is midway between two such groups on the next carbon.
Starch A polysaccharide of glucose with ot-acetal linkages.
Stereocenter A carbon connected to four different substituents, so that molecules possessing just one such
center are chiral.
Stereoisomers Molecules with the same atoms connected in the same order but arranged differently in space.
Stereoselectivity The predominance of one of several possible stereoisomers products.
Stereospecific reaction Transformation of a pure stereoisomer of starting material into a pure stereoisomer
of product.
Steric hindrance The repulsive interaction between atoms in close proximity, raising the molecule's energy.
Steroid A compound, such as a sex hormone or cholesterol, with three fused six-membered rings fused to
a five-membered ring.
Strecker synthesis Synthesis of amino acids through an imine intermediate using hydrogen cyanide and
ammonia.
Substitution A reaction, such as nucleophilic substitution, in which a group is replaced by atoms from a
reagent.
Substrate The species attacked in a reaction, such as the target of a nucleophile in nucleophilic
substitution.
Sucrose A disaccharide of glucose and fructose.
Sugar A saccharide, with empirical formula C„,(H20)„.
Sulfate A sulfur derivative based on the ion R0S03~.
Sulfonamide The product of reaction between a sulfonyl chloride and an amine, such as a sulfa drug.
Sulfonate A sulfur derivative based on the ion RS03~.
Sulfone A molecule of the form RS02R.
Sulfonic acid A molecule of the form RS03H.
Sulfonyl chloride An acid chloride of a sulfonic acid, RS02C1.
Sulfoxide A molecule of the form RSOR, such as the solvent DMSO.
Synthesis The making of molecules, with reagents, catalysts, and conditions chosen based on knowledge
of the mechanism.
Synthesis gas A pressurized mixture of carbon monoxide and hydrogen, useful starting material in hy ro-
carbon syntheses. .
Systematic nomenclature Nomenclature following IUPAC or Chemical Abstracts rules to reflect a mol
ecule's structure.
Tautomers Isomers differing by the shift of both a proton and a double bond, such as an alkenol and a
carbonyl compound. , , . . . 0 • _
C-Terminal amino acid The residue at the carboxy end of a peptide chain, placed to the right in drawing.
N-Terminal amino acid The residue at the amino end of a peptide chain, placed to t e e in
Terpene One of the (often fragrant) natural compounds made of isoprene, or five-car on, urn s.
Tertiary carbon An ,?p3-hybridized (tetrahedral) carbon directly attached to exact y t ee o
Tertiary structure Further coiling or aggregation of the secondary structure of a pepti e: caii . ^^
Tetrahedral intermediate An intermediate in addition-elimination ot a car oxy IC
its reactive carbon center.
Tetrahydrofuran (THF) Oxacyclopentane, a common solvent.
532 • Glossary
Thermal isomerization The interconversion of stereoisomers by heating, useful for measuring the strength
of a TT bond.
Thermodynamic control Conditions under which the most stable of several possible reaction products
forms to the greatest extent.
Thiacydoalkane A saturated sulfur heterocycle.
Thiazolium ion A five-membered ring with an acidic proton flanked by an NR group and a sulfur
heteroatom.
Thioacetal The sulfur analog of an acetal, which may be "desulfurized" by treatment with Raney nickel.
Thiol A sulfur analog of an alcohol, RSH.
Thiophene C4H4S, an aromatic heterocyclopentadiene.
Thymine (T) One of the four DNA bases, a polyfunctional nitrogen heterocycle.
Tollen's test A chemical test for aldehydes by oxidation to a carboxylic acid and formation of a mirrorlike
silver precipitate.
Toluene Common name of methylbenzene, C6H5CH3, a solvent.
Torsional strain Relative instability of a molecule due to the eclipsing of neighboring hydrogens.
Total synthesis The most efficient plan for obtaining a desired product, often by a series of reactions.
Trans isomer A stereoisomer in which substituents are on opposite sides of a ring or a double bond in
contrast to a cis isomer.
Transannular strain Relative instability of a molecule due to steric crowding of groups across a ring.
Transesterification Interconversion of esters by acid- or base-catalyzed reaction with alcohols.
Transition state The highest-energy point in a potential energy diagram between species in a process or
reaction.
Trivial name The common name of a molecule—in contrast with systematic nomenclature.
Twist-boat conformation A structure obtained by partial removal of the transannular strain in boat
cyclohexane.
Ubiquinone One of a series of quinones, collectively called coenzyme Q (CoQ), used in biological reduc
tions of oxygen.
Ultraviolet (UV) radiation Radiation just higher in energy than visible light, used to produce electronic
spectra.
Un.molecular reaction A first-order process, one whose rate is proportional to the concentration of one
species only.
Unsaturated compound A compound, such as an alkene, contaming double or triple bonds, and so able
to undergo additions.
Uracil (U) One of the four RNA bases, a polyfunctional nitrogen heterocycle.
Urea RNH—CO—NHR', an amide derivative of carbonic acid
U!xctotos SPeC,r°me,ry Determination of the ^ture unsaturated systems from electronic
Valence electrons Outer-shell electrons available to form a covalent bond
WbraHon^r«ci alton êech'eTleC,Ular m°'eCUles t0 as s°lids u"d U1uids-

'fr^ra ™ CharaCtenSUC eXC"a,10n 0f at0ms ab0Ul the b°"ds ba«ween them as they absorb
Vicinal coupling Coupling of nonequivalent hydrogens on adjacent carbon atoms in NMR

PVC. COmm°" "ame °f ethCnyI' CH2=CH~' " m « '"e repeated subunitof the polymer
VSEPR method The determining of molecular shapes by minimizing valence shell electron pair repulsions.
Wacker process The catalytic conversion of ethene into acetaldehyde
™'rZor :r~eCha"iCS' a ma,hematICal -d - "tost likely location

Wax An ester of long-chain carboxylic acids and long-chain alcohols.
Glo»*ary *533
Williamson ether synthesis Ss2 reaction of an alkoxide with a primary haloalkane or sulfonate evter
vieldins an ether.
WHtig reaction Nucleophilic attack of a phosphorus ylide on an aldehyde or ketone, leaving a carbon-
carbon double bond.
Wolff-Kishner reduction Tne decomposition of hydrazones in the presence of a base, used to deoxygenate
aldehvdes and ketones.
Woodward -Hoffman rules The stereochemistry of electrocyclic processes, based on the symmetry of
molecular ~ orbitals.
Xylene Common name of dimethylbenzene.
Ylide Most commonly a phosphorus ylide RHCPCQHOs. in which the heteroatom stabilizes a carbanion.
Zwitterion A dipolar ion or inner salt)—a structure that acts as both acid and base, such as an amino acid.

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24

Carbohydrates: Polyfunctional Compounds in Nature

Outline of the Chapter

24-4 through 24-8 Polyfunctional Chemistry of Sugars

24-9, 24-10 Step-by-Step Buildup and Degradation of Sugars

24-1 1, 24-12 Complex Sugars in Nature

Keys to the Chapter

24-1. Names and Structures of Carbohydrates

24-2 and 24-3. Conformations and Cyclic Forms of Sugars; Mutarotation

CH2OH CH2OH Will form a six-membered ring

By convention, the procedure for L-serieis sugar^ modified

being down and /3 being up.

For a pyranose (six-membered ring)

HOCH2 CHO HOCH2 CHO

24-4 though 24-8. Polyfunctional Chemistry of Sugars

24-9 and 24-10. Step-by-Step Buildup and Degradation of Sugars

24-11 and 24-12. Complex Sugars in Nature

(a) L-Glyceraldehyde; (b) D-erythrulose,

38. Make models if you need to.

(a) CHO (b) CH2OH

(C) CHO (d) CH2OH

(a) CH2OH H2C=0

(b) HC=0 HC02H

(c) CH2OH H2C=O

44. (a) (i) COOH (ii) COOH (Hi) CH2OH

CH2OH COOH CH2OH

CH2OH (iv) CH=NNHC6H5 (c) (i) COOH

*Same as D-erythrose phenylosazone.

45. (a) D-gulose (Figure 24-1); (b) L-allose (all OH's

46. Steps ,-4 are by— fo—

insteps*3 Mid fi^t 0 andVen N into better leaving groups.

(b) CH2OH CH2OH CH2OH

HO- -H NaBft, HO- -H HO- -H

H- -OH H- -OH H- -OH

CH2OH CH2OH CH2OH

(e) is HOCH2 Also with an acetal, not a hemiacetal, at CI.

HOCH2 CH2OH HOCH2 OCH3

of adjacent cis hydroxy groups, so these readily

HTO treatment produces a mole of C02

(iii) and (v) tell you that

Next, (iv) tells you that

CHO COOH COOH

inactive meso compound.

P„ OH (Three equatorial and

(c) 0.65 kcal mol 1 (Table 2-1)

Unravel each structure

part is trickier; use models if necessary

, , 1 j Redraw each one separately,

cture is shown below, with *e ^^

is just P-D-glucopyranose again,

CH2OH CH2OH CH2OH

.„ , „ —ivtnrp nf the two, and the reactions in (a) can

AM. ir1 TH OH H+- (d) ester of acid in (b): —COOCH, at

65. (a) CH3OH, H"

(d) CHO (e) CH2OH (f) CH2OH

H- -OH H- -OH H- -OH

(g) CH2OH CHO

66. First, D-glucuronic acid y-lactone is HO- -H 0

Solutions to Problems • 483

(a) NaBH4 (b) CH2OH (C) H Q OH

67 Follow along with the actual structure of D-lactose in Section 24-11.

This oxidation frees .he hydroxyl

Outline of the Chapter