C11: Alcohol Reactions Flashcards
oxidation of alkane to carboxylic acid
alkane – 1 alcohol – aldehyde – carboxylic acid
oxidation of alkane to ketone
alkane – 2ndary alcohol – ketone
R-OH –_____–> alkenes
dehydration
R-OH –_____–> ketones, aldhydes, acids
oxidation
R-OH –_____–> R-X (halides)
substitution
R-OH –_____–> R-H (alkanes)
reduction
R-OH –_____–> R-O-C(=O)-R’ (esters)
esterification
R-OH –_____–> R-OTs (tosylate esters)
tosylation
R-OH –______–>–______–> R-O-R’ (ethers)
[1] form alkoxide [2] R’X
___ and ____ ____ are easily oxided
Primary, Secondary, Alcohols
oxidation of ____ alcohols gives ketones
secondary
oxidation of ____ alcohols gives aldehydes
primary
______ can be further oxidized to carboxylic acid
aldhydes
Primary alcohol + ______ = carboxylic acid
Chromic acid
HO-(O=)Cr(=O)-OH
Primary alcohol + ______ = stop at aldehyde
PCC. HCl. (Pyridine or dichloromethane)
Collins Reagent
Chromium Trioxide + Pyridine
CrO3 + (benzene ring with N replacing one carbon)
Jones Reagent
Chromic acid + Hydrosulfuric acid + acetone
CrO3 + H2SO4 + CH3-C(=O)-CH3
Bleach
Sodium hypochlorite
NaOCl
DMSO4, Swerns Reagent
dimethyl sulfoxide, oxalyl chloride and triethyl amine
CH3-(S=O)C-CH3 , (COCl)2
Secondary Alcohol oxidized to ketone by
Chromium Reagent: Chromic acid or PCC
Non Chromium Reagent: Bleach, Swern, DMP
Primary Alcohol oxidized to aldehyde by
Chromium Reagent: PCC
Non Chromium Reagent: Swern or DMP
Primary Alcohol oxidized to carboxylic acid by
Chromium Reagent: Chromic acid
Non Chromium Reagent: Bleach
R-OH + TsOH
alcohol + p-toluenesulfonic acid
R-O-Ts + H20 alkyl tosylate (p-toluenesulfonate ester) + water
Primary alcohol + TsCl/pyridine –______—>
nucleophile: - (substitution, OH replaced by nucleophile)
base: - (elimination, C=C formed)
____ displacement of tosylate ion, with inversion
SN2
R-OTs + -OH —> ????
R-OH + -OTs
alcohol
R-OTs + -C(triplebond)N —> ????
R-C(triplebond)N + -OTs
nitrile
R-OTs + Br- —> ????
R-Br + -OTs
alkyl halide
R-OTs + R’-O- —> ????
R-O-R’ + OTs
ether
R-OTs + :NH3 —> ????
R-NH3+/-OTs
amine salt
R-OTs + LiAlH4, LAH —> ????
R-H + -OTs
alkane
Tertiary alcohol + HBr –____–> ????
SN1, carbocation formed
Primary alcohol + HBr –____–> ????
SN2, no carbocation formed
HCl + ZnCl2 , does what
Lucas Reagent, replaces OH
___ and ____ alcohols react with Lucas reagent by SN1, a _____ reaction
secondary, tertiary, fast
___ and ____ alcohols react with Lucas reagent by SN2, a _____ reaction
methyl and primary, slow
Order of reactivity of alcohols with sulfuric acid
3>2>1
Chromic acid test distinguishes ____ from ____ by ____
tertiary from secondary and primary by color, tertiary stays orange, secondary and primary turn blue green
Lucas test distinguishes ___ from ___ by ____
Primary from secondary from tertiary by reaction rate
Primary - takes forever
Secondary - takes 1-5 min
Tertiary - takes less than a minute
Best reagents for converting primary alcohol to alkyl halide
Chloride: SOCl2
Bromide: PBr3 or HBr
Iodide: I2
Best reagents for converting secondary alcohol to alkyl halide
Chloride: SOCl2
Bromide: PBr3
Iodide: I2
Best reagents for converting tertiary alcohol to alkyl halide
Chloride: HCl
Bromide: HBr
Iodide: HI
acid dehydration of alcohol mechanism, works best with ____, follows _______ rule stating that the _____ substituted alkene will form
E1, tertiary and secondary, rearrangement may occur, Zaitsev rule, most
H3C-H2C-OH —______—> CH2=CH2
H2SO4, heat
H3C-H2C-OH —______—> H3C-H2C-O-CH2- _
H2SO4, no heat
_____ migration after carbocation formation of a _____ forms a _____
methyl , pinacol, pinacolone
alkene —______—> glycol —-______—> ketones and aldhydes
[1] OsO4/H202 [2] HIO4
alcohol + nitric acid
R-OH + H-O-N(=O)-O-
alkyl nitrate ester + water
R-O-N(=O)-O-
phosphoric acid + alcohol (up to x3)
[1] mono-R-phosphate
[2] di-R-phosphate
[3] tri-R-phosphate
Williamson Ether Synthesis (step 1)
Alcohol + Na(NaH or K) —> R-O- +Na + H2
Williamson Ether Synthesis (step 2)
alkoxide displaces the leaving group of a good SN2 substrate
R-O- + R’-CH2-X —> R-O-CH2-R’ + XNa
