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34 Cards in this Set
- Front
- Back
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dehydration of ROH
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alkenes
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oxidation of ROH
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ketones, aldehydes, acids
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substitution of ROH
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R-X halides
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reduction of ROH
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R-H alkanes
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esterification of ROH
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esters
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tosylation of R-OH
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R-OTs tosylate esters (good leaving groups)
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oxidation
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addition of O or O2, addition of X2, loss of H2
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reduction
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addition of H2 or H-, loss of O or O2, loss of X2
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neither oxidation nor reduction
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addition or loss of H+,H20, HX
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primary alkane oxidizes to...
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primary alcohol which oxidizes to an aldehyde which oxidizes to a carboxilic acid
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secondary alkane oxidizes to...
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secondary alcohol which oxidizes to a keytone
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tertiary alkane oxidizes to...
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tertiary alcohol which does not oxidize further.
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chromic acid reagen oxidation of secondary alcohol
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R-CH(OH)-R + Na2Cr2O7, H2SO4 --> R-C(=O)-R (keytone)
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chromate ester --> oxidation of carbinol carbon
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R-CH(OH)-R + OH-Cr(O2)-OH --> H20 removed, one molecule attached by remaining O --> R-C(=O)-R + O-Cr(=O)-OH (CrIV)
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oxidation of primary alcohol
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R-CH2-OH -[O]-> R-CH=O (aldehyde) -[O]-> R-C(=O)-OH (carboxilic acid)
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how to keep aldehyde from oxidation of primary alcohol
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primary alchohol + CrO3, pyridine, HCl, CH2Cl2 --> R-CH=O (aldehyde)
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primary OH + KMnO4 + H20
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carboxilic acid
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secondary OH + KMnO4 + H20
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keytone
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primary OH + 71% HNO3
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carboxilic acid
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secondary OH + 71% HNO3
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keytone
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dehydrogenation: secondary alcohol + CuO + heat
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R-C(=O)-R + H2
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Swern oxidation
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alcohol + DMSO + oxalyl chloride + (CH3CH2)3N: + CH2Cl2 --> ketone or aldehyde + dimethyl sulfide + gases
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alcohol as a nucleophile
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OH bonds break
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alcohol as an electrophile
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CO bonds break
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SN2 reactions of tosylate esters
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R must be primary or unhindered secondary
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R-OTs + OH-
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R-OH +OTs-
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R-OTs + -CN
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R-CN +OTs-
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R-OTs + Br-
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R-Br + OTs-
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R-OTs + R-O-
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R-O-R +OTs-
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R-OTs + :NH3
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R-NH3 +OTs-
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R-OTs + LAH
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R-H (alkane) + OTs-
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reducing alcohol
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R-OH +H2SO4 +heat --> alkene +H2 + Pt ---> alkane
R-OH + TsCl + pyridine --> R-O-Ts + LAH --> R |
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limits on use of hydrohalic acids with alcohols
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-poor yields o alkyl chlorides from primary and secondary alcohols.
-often leads to elimination. -intermediates prone to rearrangments -limited ability to make alkyl iodides |
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dehydration rules
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-usually by E1, rearrangments may occur.
-works best with 3* alcohol (rearrangements and poor yields in 1*) -the most high substituted alkene usually dominates -ease of dehydration 3>2>1 -rate limiting step is the formation of carbocation |
