Dolbier HW Solutions 497

Dolbier HW Solutions 497 - COCH 2 CH 3 O O 1-Bromobutane CH...

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21.21 ( a ) Recall that Grignard reagents are destroyed by reaction with proton donors. Ethyl acetoacetate is a stronger acid than water; it transfers a proton to a Grignard reagent. ( b ) Adding D 2 O and DCl to the reaction mixture leads to D 1 transfer to the a -carbon atom of ethyl acetoacetate. 21.22 ( a ) Ethyl octanoate undergoes a Claisen condensation to form a b -keto ester on being treated with sodium ethoxide. ( b ) Saponi f cation and decarboxylation of the b -keto ester yields a ketone. ( c ) On treatment with base, ethyl acetoacetate is converted to its enolate, which reacts as a nucle- ophile toward 1-bromobutane. ( d ) Alkylation of ethyl acetoacetate, followed by saponi f cation and decarboxylation, gives a ketone. The two steps constitute the acetoacetic ester synthesis. 2-Heptanone CH 3 CCH 2 CH 2 CH 2 CH 2 CH 3 O 1. NaOH, H 2 O 2. H 1 3. heat Ethyl 2-acetylhexanoate CH 3 CCHCOCH 2 CH 3 CH 2 CH 2 CH 2 CH 3 O O Ethyl acetoacetate CH 3 CCH 2
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Unformatted text preview: COCH 2 CH 3 O O 1-Bromobutane CH 3 CH 2 CH 2 CH 2 Br 1 NaOCH 2 CH 3 ethanol Ethyl 2-acetylhexanoate CH 3 CCHCOCH 2 CH 3 CH 2 CH 2 CH 2 CH 3 O O 2. H 1 3. heat 1. NaOH, H 2 O 8-Pentadecanone CH 3 (CH 2 ) 5 CH 2 CCH 2 (CH 2 ) 5 CH 3 O Ethyl 2-hexyl-3-oxodecanoate CH 3 (CH 2 ) 5 CH 2 CCHCOCH 2 CH 3 O O (CH 2 ) 5 CH 3 Ethyl octanoate CH 3 (CH 2 ) 5 CH 2 COCH 2 CH 3 O 2. H 1 1. NaOCH 2 CH 3 Ethyl 2-hexyl-3-oxodecanoate CH 3 (CH 2 ) 5 CH 2 CCHCOCH 2 CH 3 O O (CH 2 ) 5 CH 3 1 Deuterium oxide D 2 O Iodomagnesium salt of ethyl acetoacetate CH 3 CCHCOCH 2 CH 3 O O MgI Ethyl a-deuterioacetoacetate O CH 3 CCHCOCH 2 CH 3 O D DCl Methylmagnesium iodide Ethyl acetoacetate 1 CH 3 MgI Methane 1 CH 4 Iodomagnesium salt of ethyl acetoacetate CH 3 CCH 2 COCH 2 CH 3 O O CH 3 CCHCOCH 2 CH 3 O O MgI ESTER ENOLATES 591...
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