CH3CHCH2CH2CHCH3
(1)
(2)
O CH=CHCOOH CH3CH2CHCHCH2 C OH CH3 Br
(3)
NH2 COOH
(4)
(5)
(6)
NO2
S: (1) p-ethylbenzoic acid; (2) 2-ethylcyclohexanecarboxylic acid;
(3) 2,5-dimethylhexanedioic acid; (4) 3-phenylpropenoic acid (5) 4-bromo-3-methylhexanoic acid (6) 2-amino-5-nitrobenzoic acid
2-butanone acid
2-丁酮酸, β-丁酮酸
OH O CH3CH C OH
HO-CH-COOH CH2COOH
2-hydroxypropanoic acid
2-羟基丙酸, 乳酸(lactic acid) COOH
2-hydroxybutanedioic acid
2-羟基丁二酸, 苹果酸 (malic acid) 3,4,5-三羟基苯甲酸, 没食子酸(gallic acid)
S:
LiAlH4 COOH CH OH HCl 3 SOCl2 CH3 NaOH CH3I H3C H3C H3C H3C CH2OH O C－O－CH3 ＋ H2O O C－Cl ＋ HCl ＋SO2 O C－O－CH3
7
9-7 Preparation of the following compounds by using ethanoic acid with appropriate regents: (1) Ethanoyl chloride; (2) Ethanoic anhydride (3) Ethanamide
3
o-Hydroxybenzoic acid
9-4 Name each of the following carboxylic acids by IUPAC system O O O CH3CCH2 C OH HOOCCCH2CH2COOH
2-oxapentanedioic acid
2-氧代戊二酸, α-酮戊二酸
Ch9 Carboxylic acid
9-1 Draw the structure of each of the following carboxylic acids: CH3 (1) 4,4-Dimethylhexanoic acid (2) α,β-Dibromovaleric acid
(1) CH3CH2CCH2CH2COOH CH3 (2) CH3CH2CHCHCOOH Br Br
S:
CH3CH－CHCOOH OH CH3 (A) -H2O CH3－CH=C (B)
COOH CH3
O KMnO4 CH3COOH ＋ CH3－C－COOH (C)
I2 + OH-
HCI3 ＋ HOOC－COOH
Q1 Synthesize the following compounds. You can use all kinds of inorganic reagents.
HOOC
COOH OH
CH3CH2C-O-CHCH3 CH3
COOH ＋ H2O
(8)
β’γO ’ α’ β α
HOOC
O ＋ CO2
O
COOH
(9)* (3) CH3CHCH2COOH + PCl3 OH (10)* HO
COOH + NaHCO3
CH3CHCH2C Cl
HO
Cl
COONa+ ＋ CO2 ＋ H2O
S: A > C > D > E > B
(4) A. α-Ketopentanoic acid, B. β-ketopentanoic acid and C. γketopentanoic acid
S: A > B > C
11
9-11 N, N-Diethyl-m-toluamide is the active ingredient in many insect repellents. How might you synthesize it from m-bromotoluene?
CH3(CH2)4CO2-Na+ + H2O
(2) CH3CH2CH2CO2H + PCl3
O CH3CH2CH2C-Cl
O O + H OH CH C CH CH CH OH + CH3CH2CH2COCH3 + H2O (3) 3 3 2 2 heat
O CH3 + CH3CH2CHOH (4) CH3C-OH ?
4
3,4,5-trihydroxybenzoic acid
HO OH OH
9-5 Complete each of the following reactions by supplying the missing portion indicated by a question mark.
(1) CH3CH2CH2CH2CH2CO2H + NaOH
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
O O CH3COH + HOCCH3
CH3COOH SOCl2
P2O5
O O CH3COCCH3 + H2O
NH3 CH3CONH2 + NH4Cl
8
CH3COCl
9-8 Preparation of the following compounds by using butanoic acid. (1) 2-Aminobutanoic acid; (2) 2-Hydroxybutanoic acid; (3) 2-Ethylpropanedioic acid NH3
6
9-6 Predict the product of the reaction of p-methyl benzoic acid with each of the following reagents:
(1) LiAlH4 (3) SOCl2
(2) CH3OH,HCl (4) NaOH, then CH3I
OH (＋)
(2) Formic acid acetic acid propanal propanone
(3) o-Hydroxybenzaldehyde OH salicylic acid CHO salicylate OH
COOH OH COOEt
HCOOH CH3COOH CH3CH2CHO CH3－C－CH3 O
(1) (CH3)2C＝CH2 (2) HCHO, CH3CH2CH2CHO CH3CH2－C－COOH CH2OH
15
Ch10 Derivatives of RCOOH
H (5) H CCOOH CCOOH 300℃
H
+
H H
C C
O C C O
O CH3-C-OCHCH2CH3 CH3
O ＋ H2O
5
O O NaOH CH3CH2COH (6) CH3CH2CH2OH + CH3CH2CONa ? H + HOCH(CH3)2 H ? O
K2Cr ? 2O7
(7)
2
9-3 Draw the structure of each of the following carboxylic acids
(1) β-pentanone acid
O O CH3CH2CCH2 C OH
(2) β,γ-dihydroxybutytic acid
H2C－CH－ CH2COOH OH OH
O H3C C N(CH2CH3)2
S:
CH3
CH3 Mg MgBr
Br Ether
CH3 SOCl2 C－Cl O
① CO2 + H O ② 3
CH3
CH3 COOH
HN(C2H5)2 C－N(C2H5)2 O
12
9-12 Compound A (C5H8O4) is heated to lose readily water and obtain compound B (C5H6O3). B is refluxed with methanol to generate compound C and D, C is an isomer of D. Deduce possible structures of compounds A, B, C and D.
S: B > C >A > D > E
(2) A. Benzoic acid, B. o-nitrobenzoic acid, C. p-nitrobenzoic acid
S: B > C >A
(3) A. Oxalic acid, B. hexanedioic acid, C. propanedioic acid, D. butanedioic acid and E. pentanedioic acid
CH3CHCH2COOH O2N Cl (6)
COOH HOOC COOH
COOH
9-2 Name each of the following carboxylic acids by the IUPAC Nomenclature System:
CH3CH2 COOH
COOH CH2CH3
COOH
COOH
(3) 2,3-Dinitrobenzoic acid (4) 3-Methylcyclohexanecarboxylic acid (5)β-Chlorobutyric acid