Chemistry 2100
description
Transcript of Chemistry 2100
![Page 1: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/1.jpg)
Chemistry 2100
Lecture 5
![Page 2: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/2.jpg)
C
O
R'R
CO R'R
C
O
HR R CHO
![Page 3: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/3.jpg)
NomenclatureIUPAC names for aldehydes– To name an aldehyde, change the suffix -ee of
the parent alkane to -alal.– Because the carbonyl group of an aldehyde can
only be at the end of a parent chain and numbering must start with it as carbon-1, there is no need to use a number to locate the aldehyde group.
– For unsaturated aldehydesunsaturated aldehydes, indicate the presence of a carbon-carbon double bond by changing the ending of the parent alkane from -aneane to -enalenal. Numbering the carbon chain begins with the aldehyde carbonyl carbon. Show the location of the carbon-carbon double bond by the number of its first carbon.
![Page 4: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/4.jpg)
Nomenclature• The IUPAC system retains common
names for some aldehydes, including these three.
CHO
H
OCHO
OCH3
OHtrans-3-Phenyl-2-propenal
(Cinnamaldehyde; inoil of cinnamon)
Benzaldehyde(in almonds)
Vanillin(from vanilla
beans)
![Page 5: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/5.jpg)
NomenclatureIUPAC names for ketones.– The parent alkane is the longest chain
that contains the carbonyl group.– Indicate the presence of the carbonyl
group by changing the -aneane of the parent alkane -oneone.
– Number the parent chain from the direction that gives the carbonyl carbon the smaller number.
– The IUPAC retains the common name acetone for 2-propanone.O
Acetone 2-Methylcyclohexanone5-Methyl-3-hexanone
OO
12
34
56
12
![Page 6: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/6.jpg)
NomenclatureTo name an aldehyde or ketone that also contains an -OH (hydroxyl) or -NH2 (amino) group:– Number the parent chain to give the
carbonyl carbon the lower number.– Indicate an -OH substituent by hydroxy-hydroxy-,
and an -NH2 substituent by amino-amino-.
– Hydroxyl and amino substituents are numbered and alphabetized along with other substituents.
O
H
OOH
NH2
3-Hydroxy-4-methylpentanal 3-Amino-4-ethyl-2-hexanone
1345 12346
![Page 7: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/7.jpg)
Nomenclature
Common namesThe common name for an aldehyde is derived from the common name of the corresponding carboxylic acid. – Drop the word "acidacid" and change the suffix -icic or -
oicoic to -aldehyde.aldehyde.
• Name each alkyl or aryl group bonded to the carbonyl carbon as a separate word, followed by the word "ketoneketone”. Alkyl or aryl groups are generally listed in order of increasing molecular weight.O
CH3CH
O
CH3COH
Acetaldehyde Acetic acid Ethyl isopropyl ketoneMethyl ethyl ketone
OO
![Page 8: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/8.jpg)
Physical Properties
![Page 9: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/9.jpg)
Physical Properties
pentanebutanal2-butanone1-butanolpropanoic acid
Name Structural FormulaMolecular
Weight (amu)
72727274
74
367680
117
141
bp(°C)
CH3CH2 CH2CH2CH3CH3CH2 CH2CHO
CH3CH2 CH2CH2OHCH3CH2 COOH
CH3CH2 COCH3
diethyl ether 74 34CH3CH2 OCH2CH3
![Page 10: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/10.jpg)
Preparations
![Page 11: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/11.jpg)
(1°)
R HC
O
aldehyde
[O] [O]
H
O
C ORcarboxylic acid
(2°)
[O]
H
O
C ORcarboxylic acid
R
HO
C H
H R
HO
C
H
R'
ketone
R C
O
R'[O]
![Page 12: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/12.jpg)
(1°)
R HC
O
aldehyde
[O] [O]
H
O
C ORcarboxylic acid
(2°)
[O]
H
O
C ORcarboxylic acid
R
HO
C H
H R
HO
C
H
R'
ketone
R C
O
R'[O]
![Page 13: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/13.jpg)
(1°)
R HC
O
aldehyde
[O] [O]
H
O
C ORcarboxylic acid
(2°)
[O]
H
O
C ORcarboxylic acid
R
HO
C H
H R
HO
C
H
R'
ketone
R C
O
R'[O]
![Page 14: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/14.jpg)
(1°)
R HC
O
aldehyde
[O] [O]
H
O
C ORcarboxylic acid
(2°)
[O]
H
O
C ORcarboxylic acid
R
HO
C H
H R
HO
C
H
R'
ketone
R C
O
R'[O]
![Page 15: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/15.jpg)
(1°)
R HC
O
aldehyde
[O] [O]
H
O
C ORcarboxylic acid
(2°)
[O]
H
O
C ORcarboxylic acid
R
HO
C H
H R
HO
C
H
R'
ketone
R C
O
R'[O]
![Page 16: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/16.jpg)
Reactions
![Page 17: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/17.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 18: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/18.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 19: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/19.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 20: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/20.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 21: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/21.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 22: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/22.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 23: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/23.jpg)
C
O H
Z
O
C
H Z+
Z = C, H
![Page 24: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/24.jpg)
Z = C, H
C
O H
Z
O
C
H Z+
![Page 25: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/25.jpg)
C
O H
Z
O
C
Z = X, O, N
H Z+
![Page 26: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/26.jpg)
C
O H
Z
O
C
Z = X, O, N
OH
H Z+
![Page 27: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/27.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 28: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/28.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 29: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/29.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 30: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/30.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 31: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/31.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 32: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/32.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 33: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/33.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 34: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/34.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 35: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/35.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 36: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/36.jpg)
OC
H
CH3
+ OCH2 CH3H
dry HCl
orTsOH / C6H 6
H+
C
H
CH3 O
O CH2 CH3
H
hemiacetal (full) acetal
H2 O+C
H
CH3 O
O CH2 CH3
CH2 CH3
H+
(xs)HOCH 2CH 3
![Page 37: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/37.jpg)
H+
H+
H2 O
CH 3OH
ketal
+C
CH3
CH3 O
O CH3
CH3
hemiketal
C
CH3
CH3 O
O CH3
H
CH 3OHC
CH3
CH3
O
![Page 38: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/38.jpg)
H+
H+
H2 O
CH 3OH
ketal
+C
CH3
CH3 O
O CH3
CH3
hemiketal
C
CH3
CH3 O
O CH3
H
CH 3OHC
CH3
CH3
O
![Page 39: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/39.jpg)
H+
H+
H2 O
CH 3OH
ketal
+C
CH3
CH3 O
O CH3
CH3
hemiketal
C
CH3
CH3 O
O CH3
H
CH 3OHC
CH3
CH3
O(xs)
![Page 40: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/40.jpg)
H+
H+
H2 O
CH 3OH
ketal
+C
CH3
CH3 O
O CH3
CH3
hemiketal
C
CH3
CH3 O
O CH3
H
CH 3OHC
CH3
CH3
O(xs)
![Page 41: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/41.jpg)
H+
H+
H2 O
CH 3OH
ketal
+C
CH3
CH3 O
O CH3
CH3
hemiketal
C
CH3
CH3 O
O CH3
H
CH 3OHC
CH3
CH3
O(xs)
![Page 42: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/42.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
Cyclization
![Page 43: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/43.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
![Page 44: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/44.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
![Page 45: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/45.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
![Page 46: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/46.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
![Page 47: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/47.jpg)
OC
C
H
C
C
O
H
OH
O
C C
C C
H
![Page 48: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/48.jpg)
OH
O
C C
C C
H
C C
C
HO
C
C O
H
C O
C
CC
C
OH
H
![Page 49: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/49.jpg)
OH
O
C C
C C
H
C C
C
HO
C
C O
H
C O
C
CC
C
OH
H
![Page 50: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/50.jpg)
OH
O
C C
C C
H
C C
C
HO
C
C O
H
C O
C
CC
C
OH
H
![Page 51: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/51.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4
glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 52: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/52.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4
glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 53: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/53.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4
glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 54: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/54.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4
glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 55: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/55.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4
glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 56: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/56.jpg)
C
CH2OH
OHH
HO H
H OH
H O
H
H
O1
2
3
5
6
4
1
23
5
6
4 glucose
O
HO
OH
OH
H
O
CH2OH
H
![Page 57: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/57.jpg)
O
HO
OH
OH
H
O
CH2OH H
C
CH2OH
OHH
HO H
H OH
H O
H
H
O
1
23
5
6
4
1
2
3
5
6
4
1
23
5
6
4 glucose
O
HO
OH
OH
H
O
CH2OH
H
23
5
6
4
1
O
H
H
H
H
HO
HO
OHOH
CH2OH
H
-glucose
![Page 58: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/58.jpg)
Reduction• The carbonyl group of an aldehyde or
ketone is reduced to an -CHOH group by hydrogen in the presence of a transition-metal catalyst.– Reduction of an aldehyde gives a primary
alcohol.– Reduction a ketone gives a secondary
alcohol. H2
transition metal catalyst+H
O
PentanalOH
1-Pentanol
H2
transition metal catalyst
+O
Cyclopentanone
OH
Cyclopentanol
![Page 59: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/59.jpg)
Reduction
• Reduction by NaBH4 does not affect a carbon-carbon double bond or an aromatic ring.
HCO
1. NaBH4
2. H2O
CH2OH
Cinnamaldehyde Cinnamyl alcohol
O NaBH4O-
HH3O+ O-H
H
H - C O H C O - H3O+
H C O-H: +
Hydrideion
![Page 60: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/60.jpg)
Benedict
Tollens
O
O
RC
H
O
RC + Ag
0Ag(NH3)2 +
OH-
H2O Cu2O++ Cu
+2 (citrate)
H
O
RC
O
O
RC
H2O
OH-
![Page 61: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/61.jpg)
Keto-Enol Tautomerism
![Page 62: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/62.jpg)
'
H
CCCC C C
O
'
![Page 63: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/63.jpg)
'
H
CCCC C C
O
'
![Page 64: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/64.jpg)
'
H
CCCC C C
O
'
![Page 65: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/65.jpg)
'
H
CCCC C C
O
'
![Page 66: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/66.jpg)
'
H
CCCC C C
O
'
![Page 67: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/67.jpg)
'
H
CCCC C C
O
'
![Page 68: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/68.jpg)
'
H
CCCC C C
O
'
![Page 69: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/69.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 70: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/70.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 71: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/71.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 72: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/72.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 73: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/73.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 74: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/74.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 75: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/75.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
![Page 76: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/76.jpg)
"enolizable"
H
C
O
C
enol
keto
C
O
C
H
tautomers
![Page 77: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/77.jpg)
CH3 HC
O
CH2
?
![Page 78: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/78.jpg)
CH3 HC
O
CH2
H ?
![Page 79: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/79.jpg)
CH3 HC
O
CH
H CH3 HC
O
CH2
H H
![Page 80: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/80.jpg)
C
O
C CH3CH3
H
CH3
CH
O
C CH2CH3
CH3
H
CH
O
C CH3CH3
CH3
HH
H H
![Page 81: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/81.jpg)
C
O
C CH3CH3
H
CH3
CH
O
C CH2CH3
CH3
H
CH
O
C CH3CH3
CH3
HH
H H
H H
![Page 82: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/82.jpg)
C
O
C CH3CH3
H
CH3
CH
O
C CH2CH3
CH3
H
CH
O
C CH3CH3
CH3
HH
H H
H H
![Page 83: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/83.jpg)
C
O
C CH3CH3
H
CH3
CH
O
C CH2CH3
CH3
H
CH
O
C CH3CH3
CH3
HH
H H
H H
![Page 84: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/84.jpg)
CH3
O
OH
H
O
CH3OH
H
OH
CH3
OH
![Page 85: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/85.jpg)
CH3
O
OH
H
O
CH3OH
H
enediol
OH
CH3
OH
![Page 86: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/86.jpg)
CH3
O
OH
H
O
CH3OH
H
enediol
OH
CH3
OH
H
H
![Page 87: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/87.jpg)
CH3
O
OH
H
O
CH3OH
H
enediol
OH
CH3
OH
H
H
![Page 88: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/88.jpg)
CH3
O
OH
H
O
CH3OH
H
enediol
OH
CH3
OH
H
H
![Page 89: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/89.jpg)
O
O
O
CH OH
CH2 OH
HOH
O
O
HO OH
CH OH
CH2 OH
O
O
O
CH OH
CH2 OH
HOH
![Page 90: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/90.jpg)
O
O
O
CH OH
CH2 OH
HOH
O
O
HO OH
CH OH
CH2 OH
O
O
O
CH OH
CH2 OH
HOH
![Page 91: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/91.jpg)
O
O
O
CH OH
CH2 OH
HOH
O
O
HO OH
CH OH
CH2 OH
O
O
O
CH OH
CH2 OH
HOH
![Page 92: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/92.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 93: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/93.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 94: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/94.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 95: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/95.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 96: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/96.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 97: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/97.jpg)
glyceraldehyde
3-phosphate
OPO3-2
H
CH2
OH
HOC
Cketonize
enolize
enolize
ketonize
OPO3-2
C OH
CH
CH2
OH
enediol
OPO3
-2CH2
O
OHCH2
C
dihydroxyacetonephosphate
![Page 98: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/98.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 99: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/99.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 100: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/100.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 101: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/101.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 102: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/102.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 103: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/103.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 104: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/104.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 105: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/105.jpg)
fructose-6-phosphate
HHO
H OH
H OH
CH2O PO3-2
OH
O
CH2
enolize
ketonize
enediol
CH
OH
HHO
H OH
H OH
CH2O PO3-2
OH
glucose-6-phosphate
ketonize
enolize
HHO
H OH
H OH
CH2O PO3-2
OHH
CO H
![Page 106: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/106.jpg)
Carboxylic Acids
![Page 107: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/107.jpg)
Carboxylic Acids
• In this chapter, we study carboxylic acids, another class of organic compounds containing the carbonyl group.
• The functional group of a carboxylic acid is a carboxyl groupcarboxyl group, which can be represented in any one of three ways.
CO2HCOOHC-OHO
![Page 108: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/108.jpg)
Nomenclature
IUPAC names– For an acyclic carboxylic acid, take the
longest carbon chain that contains the carboxyl group as the parent alkane.
– Drop the final -ee from the name of the parent alkane and replace it by -oic acidoic acid.
– Number the chain beginning with the carbon of the carboxyl group.
– Because the carboxyl carbon is understood to be carbon 1, there is no need to give it a number.
![Page 109: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/109.jpg)
Nomenclature
– In these examples, the common name is given in parentheses.
– An -OH substituent is indicated by the prefix hydroxy-; an -NH2 substituent by the prefix amino-.
3-Methylbutanoic acid(Isovaleric acid)
Hexanoic acid(Caproic acid)
OH
O
OH
O1 1
63
OH
OOHH2N COOH
5-Hydroxyhexanoic acid
15
4-Aminobenzoic acid
![Page 110: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/110.jpg)
Nomenclature– To name a dicarboxylic acid, add the
suffix -dioic aciddioic acid to the name of the parent alkane that contains both carboxyl groups; thus, -aneane becomes -anedioic anedioic acidacid.
– The numbers of the carboxyl carbons are not indicated because they can be only at the ends of the chain.O
HOOH
O
Butanedioic acid(Succinic acid)
Ethanedioic acid(Oxalic acid)
Hexanedioic acid(Adipic acid)
Propanedioic acid(Malonic acid)
HO OH
O
OOH
O
OH
O
O
HO
O
HO
1 1
1 1
2 3
4 6OH
O
HO15
O
Pentanedioic acid(Glutaric acid)
![Page 111: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/111.jpg)
Nomenclature
CH3COOHHCOOH
CH3CH2COOHCH3(CH2)2COOHCH3(CH2)3COOHCH3(CH2)4COOHCH3(CH2)6COOHCH3(CH2)8COOHCH3(CH2)10COOHCH3(CH2)12COOHCH3(CH2)14COOHCH3(CH2)16COOHCH3(CH2)18COOH
DerivationCommon Name
IUPAC Name(acid)Structure
Greek: arachis, peanutGreek: stear, solid fatLatin: palma, palm treeGreek: myristikos, fragrantLatin: laurus, laurelLatin: caper, goatLatin: caper, goatLatin: caper, goatLatin: valere, to be strongLatin: butyrum, butterGreek: propion, first fatLatin: acetum, vinegarLatin: formica, ant
arachidicstearicpalmiticmyristiclauric
capriccapryliccaproicvalericbutyricpropionicaceticformic
eicosanoicoctadecanoichexadecanoictetradecanoicdodecanoicdecanoicoctanoichexanoicpentanoicbutanoicpropanoicethanoicmethanoic
![Page 112: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/112.jpg)
Nomenclature
For common names, use, the Greek letters alpha (), beta (), gamma (), and so forth to locate substituents.
C-C-C-C-OHO
OHH2N
O
OHOH
O
(-Aminobutyric acid; GABA)2-Hydroxypropanoic acid4-Aminobutanoic acid
4 3 2
1
4
1
2
(-Hydroxypropionic acid;lactic acid)
![Page 113: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/113.jpg)
Physical Properties
H3C C
O
O
H
CH3C
O
O
H- +
+ -
hydrogen bondingbetween two molecules
![Page 114: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/114.jpg)
Physical PropertiesCarboxylic acids are more soluble in water than are alcohols, ethers, aldehydes, and ketones of comparable molecular weight.
CH3COOHCH3CH2CH2OHCH3CH2CHO
CH3(CH2)2COOHCH3(CH2)3CH2OHCH3(CH2)3CHO
acetic acid
1-propanolpropanal
60.5
60.158.1
1189748
16388.1butanoic acid1-pentanol 88.1 137
103pentanal 86.1
Structure NameMolecularWeight
Boiling Point (°C)
Solubility(g/100 mL H2O)
infinite
infinite
16infinite
2.3slight
![Page 115: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/115.jpg)
larger Ka increased [H3O+] stronger acid
A– + H3O+
[HA][A–] [H3O+]
Ka =
HA + H2O
![Page 116: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/116.jpg)
larger Ka increased [H3O+] stronger acid
A– + H3O+
[HA][A–] [H3O+]
Ka =
HA + H2O
![Page 117: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/117.jpg)
increased [H3O+] stronger acid
A– + H3O+
[HA][A–] [H3O+]
larger Ka
Ka =
HA + H2O
![Page 118: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/118.jpg)
larger Ka increased [H3O+] stronger acid
A– + H3O+
[HA][A–] [H3O+]
Ka =
HA + H2O
![Page 119: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/119.jpg)
RCOOH + H2O RCOO– + H3O+
[RCOOH][RCOO–] [H3O+]
Ka =
![Page 120: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/120.jpg)
RCOOH + H2O RCOO– + H3O+
[RCOOH][RCOO–] [H3O+]
Ka =
![Page 121: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/121.jpg)
acids > phenols ~ thiols > water ~ alcohols
Ka % ionized [H3O+], M pH
~1 107 ~100 ~0.1 1.00
1.8 10–5 1.3 1.3 10–3 2.88
3.3 10–10 0.0036 3.6 10–6 5.44
2.5 10–11 0.0016 1.6 10–6 5.80
1.3 10–16 0.0001 1.0 10–7 7.00
HCl
HOAc
PhOH
EtSH
EtOH
HOH
Comparative acidities of 0.1 M aqueous solutions of representative acids HA
1.8 10–16 0.0001 1.0 10–7 7.00
![Page 122: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/122.jpg)
Fatty AcidsTable 18.3 The Most Abundant Fatty Acids in Animal Fats, Vegetable Oils, and Biological Membranes.
Unsaturated Fatty Acids
Saturated Fatty Acids
20:4
18:3
18:2
18:1
16:1
20:0
18:0
16:0
14:0
12:0
Carbon Atoms:Double Bonds*
Melting Point(°C)
Common NameStructure
-49
-11
-5
16
1
77
70
63
58
44
arachidonic acid
linolenic acid
linoleic acid
oleic acid
palmitoleic acid
arachidic acid
stearic acid
palmitic acid
myristic acid
lauric acid
CH3(CH2)1 2COOH
CH3(CH2)1 0COOH
CH3(CH2)1 4COOH
CH3(CH2)1 6COOH
CH3(CH2)1 8COOH
CH3(CH2)7 CH=CH(CH2 )7COOH
CH3(CH2)5 CH=CH(CH2 )7COOH
CH3(CH2)4 (CH=CHCH2 )2(CH2)6 COOH
CH3CH2 (CH=CHCH2 )3(CH2)6 COOH
CH3(CH2)4 (CH=CHCH2 )4(CH2)2 COOH
* The first number is the number of carbons in the fatty acid; the second is the number of carbon-carbon double bonds in its hydrocarbon chain.
![Page 123: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/123.jpg)
Fatty AcidsUnsaturated fatty acids generally have lower melting points than their saturated counterparts.
COOH
COOH
COOH
COOH
Stearic acid (18:0)(mp 70°C)
Oleic acid (18;1)(mp 16°C)
Linoleic acid (18:2)(mp-5°C)
Linolenic acid (18:3)(mp -11°C)
![Page 124: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/124.jpg)
Fatty AcidsSaturated fatty acids are solids at room temperature.– The regular nature of their hydrocarbon
chains allows them to pack together in such a way as to maximize interactions (by London dispersion forces) between their chains.
COOH
COOH
COOH
COOH
COOH
![Page 125: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/125.jpg)
Fatty Acids
In contrast, all unsaturated fatty acids are liquids at room temperature because the cis double bonds interrupt the regular packing of their hydrocarbon chains.
COOH
COOH
COOH
COOH
COOH
![Page 126: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/126.jpg)
Soaps
![Page 127: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/127.jpg)
Soaps
![Page 128: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/128.jpg)
Decarboxylation
• DecarboxylationDecarboxylation: The loss of CO2 from a carboxyl group.
• Almost all carboxylic acids, when heated to a very high temperature, will undergo thermal decarboxylation.
• Most carboxylic acids, however, are resistant to moderate heat and melt and even boil without undergoing decarboxylation.
• An exception is any carboxylic acid that has a carbonyl group on the carbon to the COOH group.
O
RCOH RH CO2decarboxylation +
high temperature
![Page 129: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/129.jpg)
Decarboxylation
• Decarboxylation of a -ketoacid.
• The mechanism of thermal decarboxylation involves (1) redistribution of electrons in a cyclic transition state followed by (2) keto-enol tautomerism.
OH
OO O
CO2Acetone3-Oxobutanoic acid
(Acetoacetic acid)
+warm
O OH
O
OH
C
O
O
OCO2
+
enol ofa ketone
(A cyclic six-membered transition state)
(1) (2)
![Page 130: Chemistry 2100](https://reader035.fdocuments.net/reader035/viewer/2022062309/56815338550346895dc15550/html5/thumbnails/130.jpg)
Decarboxylation• An important example of decarboxylation of
a -ketoacid in biochemistry occurs during the oxidation of foodstuffs in the tricarboxylic acid (TCA) cycle. Oxalosuccinic acid, one of the intermediates in this cycle, has a carbonyl group (in this case a ketone) to one of its three carboxyl groups.
COOHCOOH
O
HOOC COOH
O
HOOC CO2+
Oxalosuccinic acid
only this carboxyl has a C=O beta to it.
-Ketoglutaric acid