ALCOHOLS. DIOLS AND THIOLS 365 On reaction with CH,OD. deuterium is trar from the alcohol to the oxygen of CH),CDOJB CH3)23- CH3 COD+ B[OCD(CH,)2I3 CH3 D-OCH OCH NabDa (CH3)2C=0 CHOD( CH3)2COD Acetol 2-Propanol-2-d-O-d (c) In this case NaBDa serves as a deuterium donor to carbon, and CD,oh is a proton(not deu erium) donor to oxygen. O NaBDa C6HSCH CD,OH C6HSCHOH Benzyl alcohol (d) Lithium aluminum deuteride is a deuterium donor to the carbonyl carbon of formaldehyde D一AD3 HC-OAID 3HCH (CH,O)Al H H On hydrolysis with D,O, the oxygen-aluminum bond is cleaved and DCH,Od is formed. Al(OCH, D)4 4DCH,OD+ Al(OD) 15.3 The acyl portion of the ester gives a primary alcohol on reduction. The alkyl group bonded to oxy gen may be primary, secondary, or tertiary and gives the corresponding alcohol L. LIA CH3CH, COCH(CH3) CH, CH, CH,OH HOCH(CH,)2 Isopropyl propanoate 1-Propanol 2-Propanol 15.4(b) Reaction with ethylene oxide results in the addition of a-CH, CH,OH unit to the grignard reagent. Cyclohexylmagnesium bromide (or chloride)is the appropriate reagent. CH CHOH t h,c--CH, nexymagnesum Ethylene oxide 2-Cyclohexylethano 15.5 Lithium aluminum hydride is the appropriate reagent for reducing carboxylic acids or esters to L. LiAIHa HOCCHCHCHCOH HOCH, CH, CHCH, CH,OH CH Back Forward Main Menu TOC Study Guide Toc Student OLC MHHE WebsiteALCOHOLS, DIOLS, AND THIOLS 365 On reaction with CH3OD, deuterium is transferred from the alcohol to the oxygen of [(CH3)2CDO]4B . Overall: (c) In this case NaBD4 serves as a deuterium donor to carbon, and CD3OH is a proton (not deu￾terium) donor to oxygen. (d) Lithium aluminum deuteride is a deuterium donor to the carbonyl carbon of formaldehyde. On hydrolysis with D2O, the oxygen–aluminum bond is cleaved and DCH2OD is formed. 15.3 The acyl portion of the ester gives a primary alcohol on reduction. The alkyl group bonded to oxy￾gen may be primary, secondary, or tertiary and gives the corresponding alcohol. 15.4 (b) Reaction with ethylene oxide results in the addition of a @CH2CH2OH unit to the Grignard reagent. Cyclohexylmagnesium bromide (or chloride) is the appropriate reagent. 15.5 Lithium aluminum hydride is the appropriate reagent for reducing carboxylic acids or esters to alcohols. 1. LiAlH4 2. H2O 3-Methyl-1,5-pentanedioic acid 3-Methyl-1,5-pentanediol HOCCH2CHCH2COH O O CH3 HOCH2CH2CHCH2CH2OH CH3 1. diethyl ether 2. H3O Cyclohexylmagnesium bromide MgBr 2-Cyclohexylethanol CH2CH2OH Ethylene oxide H2C CH2 O 1. LiAlH4 2. H2O CH3CH2CH2OH Isopropyl propanoate 2-Propanol 1-Propanol HOCH(CH3) CH3CH2COCH(CH3 2 )2 O 4D2O Methanol-d-O-d 4DCH2OD Al(OD)4 Al(OCH2D)4 HC H O D AlD3 HC H D OAlD3 (DCH2O)4Al 3HCH O NaBD4 CD3OH Benzaldehyde C6H5CH O Benzyl alcohol-1-d C6H5CHOH D NaBD4 CH3OD (CH3)2C (CH3)2COD Acetone 2-Propanol-2-d-O-d O D CH3COD CH3 D CH3C CH3 D O B[OCD(CH3)2]3 D OCH3 OCH3 B[OCD(CH3)2]3 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website