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32.5.19: Chapter 19

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    Problem 19-1
    (a) 2-Methyl-3-pentanone
    (b) 3-Phenylpropanal
    (c) 2,6-Octanedione
    (d) trans-2-Methylcyclohexanecarbaldehyde
    (e) 4-Hexenal
    (f) cis-2,5-Dimethylcyclohexanone
    Problem 19-2
    (a) The structure of 3-methylbutanal. A four-carbon chain with an aldehyde group on the first carbon and a methyl group attached to the third carbon.
    (b) The structure of 4-chloro-2-pentanone. A five-carbon chain with a chlorine atom attached to the fourth carbon and a carbonyl group is on the second position.
    (c) The structure of phenylacetaldehyde. A benzene ring with the first carbon attached to C H 2 C H O group.
    (d) Cyclohexane ring in which one carbon has t-butyl (wedge) and H (dash) substituents, and two carbons away (clockwise) has C H O (wedge) and H (dash) groups.
    (e) The structure of 3-methyl-3-butenal. A four-carbon chain with a methyl group on the third carbon, sharing a double bond between the third and fourth carbons with aldehyde on first position.
    (f) A seven-carbon chain with a chloroethyl group attached to the second carbon by chloroethyl C 1, methyl attached to the fifth carbon, and aldehyde group attached to the first carbon.
    Problem 19-3
    (a) Dess–Martin periodinane
    (b) 1. O3; 2. Zn
    (c) DIBAH
    (d) 1. BH3, then H2O2, NaOH; 2. Dess–Martin periodinane
    Problem 19-4
    (a) HgSO4, H3O+
    (b) 1. CH3COCl, AlCl3; 2. Br2, FeBr3
    (c) 1. Mg; 2. CH3CHO; 3. H3O+; 4. CrO3
    (d) 1. BH3; 2. H2O2, NaOH; 3. CrO3
    Problem 19-6 The electron-withdrawing nitro group in p-nitrobenzaldehyde polarizes the carbonyl group.
    Problem 19-7 CCl3CH(OH)2
    Problem 19-8 Labeled water adds reversibly to the carbonyl group.
    Problem 19-9 The equilibrium is unfavorable for sterically hindered ketones.
    Problem 19-11 The steps are the exact reverse of the forward reaction shown in Figure 19.7.
    Problem 19-13
    (a) H2/Pd
    (b) N2H4, KOH
    (c) 1. H2/Pd; 2. N2H4, KOH
    Problem 19-14 The mechanism is identical to that between a ketone and 2 equivalents of a monoalcohol, shown in Figure 19.11.
    Problem 19-16
    (a) Cyclohexanone + (Ph)3P = CHCH3
    (b) Cyclohexanecarbaldehyde + (Ph)3P = CH2
    (c) Acetone + (Ph)3P = CHCH2CH2CH3
    (d) Acetone + (Ph)3P = CHPh
    (e) PhCOCH3 + (Ph)3P = CHPh
    (f) 2-Cyclohexenone + (Ph)3P = CH2
    Problem 19-18 Intramolecular Cannizzaro reaction
    Problem 19-19 Addition of the pro-R hydrogen of NADH takes place on the Re face of pyruvate.
    Problem 19-20 The −OH group adds to the Re face at C2, and −H adds to the Re face at C3, to yield (2R,3S)-isocitrate.
    Problem 19-22
    (a) 3-Buten-2-one + (CH3CH2CH2)2CuLi
    (b) 3-Methyl-2-cyclohexenone + (CH3)2CuLi
    (c) 4-tert-Butyl-2-cyclohexenone + (CH3CH2)2CuLi
    (d) Unsaturated ketone + (H2C = CH)2CuLi
    Problem 19-23 Look for appearance of either an alcohol or a saturated ketone in the product.
    Problem 19-24
    (a) 1715 cm−1
    (b) 1685 cm−1
    (c) 1750 cm−1
    (d) 1705 cm−1
    (e) 1715 cm−1
    (f) 1705 cm−1
    Problem 19-25
    (a) Different peaks due to McLafferty rearrangement
    (b) Different peaks due to α cleavage and McLafferty rearrangement
    (c) Different peaks due to McLafferty rearrangement
    Problem 19-26 IR: 1750 cm−1; MS: 140, 84

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