Dolbier HW Solutions 552

Dolbier HW Solutions 552 - This synthesis is the one...

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( h ) In this exercise the two nitrogen substituents are differentiated; one is an amino nitrogen, the other an amide nitrogen. By keeping them differentiated they can be manipulated indepen- dently. Remove one amino group completely before deprotecting the other. Once the acetyl group has been removed by hydrolysis, the molecule is ready for introduction of the iodo substituent by way of a diazonium salt. ( i ) To convert the designated starting material to the indicated product, both the nitro group and the ester function must be reduced and a carbon nitrogen bond must be formed. Converting the starting material to an amide gives the necessary carbon nitrogen bond and has the advantage that amides can be reduced to amines by lithium aluminum hydride. The amide can be formed intramolecularly by reducing the nitro group to an amine, then heating to cause cyclization.
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Unformatted text preview: This synthesis is the one described in the chemical literature. Other routes are also possible, but the one shown is short and ef f cient. 22.42 Weakly basic nucleophiles react with a , b-unsaturated carbonyl compounds by conjugate addition. R 2 CCH 2 CR 9 O Y CHCR 9 R 2 C 1 O HY H 2 Ni heat CH 3 O CH 3 O CH 2 COCH 3 O 2 N O CH 3 O CH 3 O CH 2 COCH 3 H 2 N O CH 3 O CH 3 O O NH CH 3 O CH 3 O NH 1. LiAlH 4 2. H 2 O 1. HCl, H 2 O heat 2. HO 2 1. NaNO 2 , HCl, H 2 O 2. KI Br CF 3 NHCCH 3 O 2-Bromo-6-(trifluoromethyl)-acetanilide Br CF 3 NH 2 2-Bromo-6-(trifluoromethyl)-aniline (69%) Br CF 3 I 1-Bromo-2-iodo-3-(trifluoromethyl)benzene (87%) 1. NaNO 2 , H 1 , H 2 O 2. H 3 PO 2 4-Amino-2-bromo-6-(trifluoromethyl)acetanilide H 2 N Br CF 3 NHCCH 3 O 2-Bromo-6-(trifluoromethyl)-acetanilide (92%) Br CF 3 NHCCH 3 O 646 AMINES...
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