Term
| why alcohols are important |
|
Definition
| because thehydroxy group is easily converted to almosdt any other functional group |
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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|
Term
name that reaction
[image] |
|
Definition
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Term
|
Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
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Definition
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Definition
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Term
|
Definition
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|
Term
| OCHEM definition of oxidation |
|
Definition
| adding an oxidizing agent
-O, O2
-X2 (halogens)
-etc.
OR losing H2 |
|
|
Term
| OCHEM definition of reduction |
|
Definition
| adding reducing agent
-H2
-H-
-NaBH4
-etc.
OR loss of
-O, O2
-X2 (halogens) |
|
|
Term
| when an organic rxn is neither oxidation nor reduction |
|
Definition
| adding or losing
-H+
--OH, H2O
-HX, etc. |
|
|
Term
| how to tell whether or not an organic redox rxn has occurred |
|
Definition
| by counting the number of C-O bonds on that C |
|
|
Term
| what an organic redox rxn usually does |
|
Definition
| converts C-H bonds to C-O bonds |
|
|
Term
| chart of organic oxidation and reduction |
|
Definition
|
|
Term
|
Definition
| unspecified oxidizing agent |
|
|
Term
| oxidixing alcohols often results in... |
|
Definition
-ketones
-aldehydes
-carboxylic acids |
|
|
Term
| some oxidizing agents that are used to oxidize alcohols |
|
Definition
-chromium oxides
-permangenate
-nitric acid
-sodium hypochlorite (NaOCl) |
|
|
Term
| what all the oxidizing agents used have in common |
|
Definition
-they have an element in a high oxidation state bonded to oxygen
-they follow similar mechanisms |
|
|
Term
| high (oxidized) oxidation state |
|
Definition
|
|
Term
| low (reduced) oxidation state |
|
Definition
|
|
Term
| when the chromic acid reagent (H2CrO4) is used to oxidize secondary alcohols |
|
Definition
| when less hazardous reagents, such as NaOCl (household bleach) fail to deliver a good yield |
|
|
Term
| how a chromate ester is formed |
|
Definition
|
|
Term
| how the chromate ester is eliminated and the carbinol atom is oxidized |
|
Definition
|
|
Term
|
Definition
|
|
Term
| NaOCl (sodium hypochlorite) can serve as a more selective oxidizing agent, especially when used with... |
|
Definition
|
|
Term
|
Definition
TEMPO
this is a stable free radical that can catalyze many oxidation rxns |
|
|
Term
|
Definition
[image]
this is a stable free radical that can catalyze many oxidation rxns |
|
|
Term
|
Definition
|
|
Term
| NaOCl with the right amount of TEMPO oxidizes primary alcohols to aldehydes, but what happens it there's excess TEMPO? |
|
Definition
| it oxidizes primary alcohols to carboxylic acids |
|
|
Term
|
Definition
|
|
Term
|
Definition
| pyridinium chlorochromate |
|
|
Term
|
Definition
| PCC (pyridinium chlorochromate) |
|
|
Term
| PCC (pyridinium chlorochromate) |
|
Definition
|
|
Term
|
Definition
|
|
Term
| why tertiary alcohols are more resistant to oxidation |
|
Definition
| because they have no H atoms on the carbnol C |
|
|
Term
| how tertiary alcohols are oxidized |
|
Definition
| by breaking of C-C bonds under severe conditions |
|
|
Term
| the type of alcohols that can't be oxidized by chromic acid nor PCC |
|
Definition
|
|
Term
|
Definition
| uses dimethyl sulfoxide (DMSO) to oxidize alcohols to form ketones and aldehydes |
|
|
Term
|
Definition
| dimethyl sulfoxide (DMSO) |
|
|
Term
| dimethyl sulfoxide (DMSO) |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
| Dess-Martin periodinane (DMP) reagent |
|
|
Term
| oxidation using the DMP reagent |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| why methanol is more toxic than ethanol |
|
Definition
| because it gets converted to formaldehyde, then to formic acid, both more toxic than methanol itself |
|
|
Term
| why alcohols are such vers\atile chemical intermediates |
|
Definition
| because they can function as both nucleophiles and electrophiles |
|
|
Term
| alcohol reacting as a weak nucleophile |
|
Definition
|
|
Term
| how alcohol is converted to a strong nucleophile |
|
Definition
by forming its alkoxide ion
[image] |
|
|
Term
| the bond that's broken when an alcohol reacts as a nucleophile |
|
Definition
|
|
Term
| the bond that's broken when alcohol reacts as an electrophile |
|
Definition
|
|
Term
| why alcohol is a weak electrophile |
|
Definition
| because the hydroxy (-OH) group is a poor leaving group |
|
|
Term
| how to convert an alcohol to an electrophile that's compatible with basic nucleophiles |
|
Definition
| by converting it to an alkyl halide or making its tosylate ester |
|
|
Term
|
Definition
| the product of condensation of an alcohol with p-toluenesulfonic acid (TsOH) |
|
|
Term
| converting an alcohol to an alkyl tosylate |
|
Definition
|
|
Term
|
Definition
|
|
Term
| substitution with a tosylate ester |
|
Definition
|
|
Term
| elimination with a tosylate ester |
|
Definition
|
|
Term
|
Definition
|
|
Term
| how a tosylate ester (ROTs) is formed |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| why the reduction of alcohols to alkanes is not common |
|
Definition
| because it removes a functional group |
|
|
Term
|
Definition
|
|
Term
the process described here
[image] |
|
Definition
|
|
Term
| how an alcohol is reduced |
|
Definition
|
|
Term
| another way to reduce an alcohol |
|
Definition
|
|
Term
| how tertiary alcohols become alkyl halides |
|
Definition
| the hydroxy (-OH) group gets protonated, then it gets replaced by the halide (X-)
the mechanis is SN1 or SN2 |
|
|
Term
| why the SN2 mechanism is more favorable for converting primary alcohols to alkyl bromides |
|
Definition
| because the a primary carbocation is unstable |
|
|
Term
| the mechanism used in converting a primary alcohol to an alkyl bromide |
|
Definition
|
|
Term
| the mechanism used in converting a secondary alcohol to an alkyl bromide |
|
Definition
|
|
Term
| the mechanism used in converting a tertiary alcohol to an alkyl bromide |
|
Definition
|
|
Term
| a catalyst that's sometimes needed for reactions of primary and secondary alcohols with HCl |
|
Definition
|
|
Term
| the role of ZnCl2 in reactions of primary alcohols with HCl |
|
Definition
| coordinates with the oxygen of that alcohol, but it coordinates more strongly than a proton does. |
|
|
Term
| the mechanism used for rxns of secondary alcohols with HCl |
|
Definition
|
|
Term
| the mechanism used for rxns of tertiary alcohols with HCl |
|
Definition
|
|
Term
| mechanism for the rxn of a secondary or tertiary alcohol with ZnCl2 |
|
Definition
|
|
Term
| mechanism for the rxn of a primary alcohol with ZnCl2 |
|
Definition
|
|
Term
| how the Lucas reagent (ZnCl2) helps distinguish among primary, secondary, and tertiary alcohols |
|
Definition
| by reacting with each at predictable rates |
|
|
Term
| how the Lucas test is done |
|
Definition
| by putting Lucas reagent (ZnCl2) into an unknown water-soluble alcohol and watching how quickly the second (water insoluble) phase forms |
|
|
Term
| the alcohols that react fastest with the Lucas reagent (ZnCl2) |
|
Definition
|
|
Term
| the alcohols that react slowest with the Lucas reagent (ZnCl2) |
|
Definition
|
|
Term
| Are ketones water soluble? |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| 4 limitations of the uses of hydrohalic acids with alcohols |
|
Definition
1: poor yields of alkyl chlorides from primary and secondary alcohols
2: eliminations
3: rearrangements
4: limited ability to make alkyl iodides |
|
|
Term
| some commercially available phosphorus halides that can be used to convert alcohols to alkyl halides |
|
Definition
|
|
Term
| some useful reactions of phosphorus halides with alcohols |
|
Definition
|
|
Term
| the type of alcohol phosphorus halides react poorly with |
|
Definition
|
|
Term
| are phosphorus halides nucleophiles or electrophiles? |
|
Definition
|
|
Term
| mechanism for the reaction of an alcohol with PBr3 |
|
Definition
|
|
Term
| mechanism for the rxn of an alcohol with thionyl chloride |
|
Definition
|
|
Term
|
Definition
|
|
Term
| the solvent used when using thionyl chloride ([image]) |
|
Definition
|
|
Term
| the type of chloride used when converting primary alcohols to alkyl halides |
|
Definition
|
|
Term
| the type of bromide used when converting primary alcohols to alkyl halides |
|
Definition
| PBr3 or HBr
(HBr works only in selected cases) |
|
|
Term
| the type of iodide used when converting primary alcohols to alkyl halides |
|
Definition
| P/I2
that is,
2P + 3I2 <--> 2PI3 |
|
|
Term
| the type of chloride used when converting secondary alcohols to alkyl halides |
|
Definition
| SOCl2 (SN1 mechanism)
PCl3 or PCl5 (SN2 mechanism) |
|
|
Term
| the type of bromide used when converting secondary alcohols to alkyl halides |
|
Definition
|
|
Term
| the type of iodide used when converting secondary alcohols to alkyl halides |
|
Definition
| P/I2
that is,
2P + 3I2 <--> 2PI3
this works only in selected cases |
|
|
Term
| the type of chloride used when converting tertiary alcohols to alkyl halides |
|
Definition
|
|
Term
| the type of bromide used when converting tertiary alcohols to alkyl halides |
|
Definition
|
|
Term
| the type of iodide used when converting tertiary alcohols to alkyl halides |
|
Definition
HI
this works only in selected cases |
|
|
Term
| the mechanism by which the Lucas reagent (ZnCl2) reacts with primary alcohols |
|
Definition
|
|
Term
| the mechanism by which the Lucas reagent (ZnCl2) reacts with secondary alcohols |
|
Definition
|
|
Term
| the mechanism by which the Lucas reagent (ZnCl2) reacts with tertiary alcohols |
|
Definition
|
|
Term
| the mechanism by which HBr reacts with primary alcohols |
|
Definition
|
|
Term
| the mechanism by which HBr reacts with secondary alcohols |
|
Definition
|
|
Term
| the mechanism by which HBr reacts with tertiary alcohols |
|
Definition
|
|
Term
| the mechanism by which phosphorus trihalides react with primary alcohols |
|
Definition
| form a leaving group, then SN2 |
|
|
Term
| the mechanism by which phosphorus trihalides react with secondary alcohols |
|
Definition
| form a leaving group, then SN2 |
|
|
Term
| the mechanism by which phosphorus trihalides react with tertiary alcohols |
|
Definition
| they react very poorly with tertiary alcohols, but form a leaving group, then SN2 |
|
|
Term
| mechanism by which thionyl chloride (SOCl2) reacts with alcohol |
|
Definition
| resembles Sn1, but retains stereochemistry because the halide is delivered by the leaving group |
|
|
Term
| why reactions with thionyl chloride (SOCl2) retain stereochemistry |
|
Definition
| because the halide is delivered by the leaving group |
|
|
Term
| the mechanism by which alcohol dehydration takes place |
|
Definition
|
|
Term
| rxn energy diagram for dehydration of an alcohol |
|
Definition
|
|
Term
| the rate-limiting step for dehydration of an alcohol |
|
Definition
| the formation of a carbocation |
|
|
Term
| why the formation of a carbocation is the rate-limiting step of dehydration of an alcohol |
|
Definition
| because tertiary carbocations form more easily, and therefore quicker, than secondary, and secondary more than tertiary |
|
|
Term
| why tertiary alcohols are more easily dehydrated than secondary and secondary more easily than primary |
|
Definition
| because of the ease of forming the carbocation (tertiary easier than secondary easier than primary) |
|
|
Term
| why dehydration is not a good method for converting primary alcohols into alkenes |
|
Definition
| because the rxn conditions must be severe and the frequent occurrence of rearrangement |
|
|
Term
| dehydration of a primary alcohol |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| bimolecular condensation / bimolecular dehydration |
|
Definition
| when a protonated primary alcohol is attacked by another molecule of that alcohol and undergoes an SN2 displacement |
|
|
Term
|
Definition
| rxn that joins 2 or more molecules, often at the expense of a small molecule like water |
|
|
Term
| the mechanism that occurs when an alcohol is dehydrated to give an alkene |
|
Definition
elimination; this is unimolecular
[image] |
|
|
Term
| the mechanism that occurs when bimolecular condensation of alcohol occurs |
|
Definition
|
|
Term
| which has a more positive change in entropy (ΔS)? elimination or substitution? |
|
Definition
|
|
Term
| Gibbs free energy equation |
|
Definition
|
|
Term
|
Definition
| change in Gibbs free energy or "available energy"
Δ = TΔStotal |
|
|
Term
|
Definition
| change in enthalpy
ΔH = TΔSsurr |
|
|
Term
|
Definition
|
|
Term
|
Definition
| entropy change
ΔS = TΔSsystem |
|
|
Term
| the temperature at which dehydration of alcohols is favored over substitution |
|
Definition
|
|
Term
| the temperature at which substitution of alcohols is favored over dehydration |
|
Definition
|
|
Term
| electrons move from ______ to ______ |
|
Definition
| nucleophile (electron donor) and electrophile (electron acceptor), respectively |
|
|
Term
| some reactions diols undergo that depend on 2 adjacent -OH groups |
|
Definition
-pinacol rearrangement
-cleavage by periodic acid |
|
|
Term
|
Definition
|
|
Term
| mechanism for pinacol rearrangement |
|
Definition
|
|
Term
| when periodic acid cleaves a bond between 2 C atoms |
|
Definition
| only when there's a free _OH group on each C |
|
|
Term
| periodic acid cleavage of glycols |
|
Definition
|
|
Term
| how to produce an alkoxide salt |
|
Definition
by deprotonating an alcohol using an active metal, like Na or K
[image] |
|
|
Term
| reactivity of Na and K with alcohols, most reactive to least reactive |
|
Definition
| methyl > primary > secondary > tertiary |
|
|
Term
| reagent that's often used when an alcohol reacts slowly with both Na and K |
|
Definition
| sodium hydride (NaH), usually in THF |
|
|
Term
| Williamson ether synthesis |
|
Definition
| an SN2 displacement in which an alcohol attacks a primary alkyl halide or tosylate to form an ether |
|
|
Term
| what usually happens when you try to do Williamson ether synthesis with a secondary or tertiary alkyl halide or tosylate? |
|
Definition
|
|
Term
| most important method for making ethers |
|
Definition
| Williamson ether synthesis |
|
|
Term
| mechanism for Williamson ether synthesis |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| the mechanism by which alcohol dehydration takes place |
|
Definition
|
|
Term
| rxn energy diagram for dehydration of an alcohol |
|
Definition
|
|
Term
| the rate-limiting step for dehydration of an alcohol |
|
Definition
| the formation of a carbocation |
|
|
Term
| why the formation of a carbocation is the rate-limiting step of dehydration of an alcohol |
|
Definition
| because tertiary carbocations form more easily, and therefore quicker, than secondary, and secondary more than tertiary |
|
|
Term
| why tertiary alcohols are more easily dehydrated than secondary and secondary more easily than primary |
|
Definition
| because of the ease of forming the carbocation (tertiary easier than secondary easier than primary) |
|
|
Term
| why dehydration is not a good method for converting primary alcohols into alkenes |
|
Definition
| because the rxn conditions must be severe and the frequent occurrence of rearrangement |
|
|
Term
| dehydration of a primary alcohol |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
| bimolecular condensation / bimolecular dehydration |
|
Definition
| when a protonated primary alcohol is attacked by another molecule of that alcohol and undergoes an SN2 displacement |
|
|
Term
|
Definition
| rxn that joins 2 or more molecules, often at the expense of a small molecule like water |
|
|
Term
| the mechanism that occurs when an alcohol is dehydrated to give an alkene |
|
Definition
elimination; this is unimolecular
[image] |
|
|
Term
| the mechanism that occurs when bimolecular condensation of alcohol occurs |
|
Definition
|
|
Term
| which has a more positive change in entropy (ΔS)? elimination or substitution? |
|
Definition
|
|
Term
| Gibbs free energy equation |
|
Definition
|
|
Term
|
Definition
| change in Gibbs free energy or "available energy"
Δ = TΔStotal |
|
|
Term
|
Definition
| change in enthalpy
ΔH = TΔSsurr |
|
|
Term
|
Definition
|
|
Term
|
Definition
| entropy change
ΔS = TΔSsystem |
|
|
Term
| the temperature at which dehydration of alcohols is favored over substitution |
|
Definition
|
|
Term
| the temperature at which substitution of alcohols is favored over dehydration |
|
Definition
|
|
Term
| electrons move from ______ to ______ |
|
Definition
| nucleophile (electron donor) and electrophile (electron acceptor), respectively |
|
|
Term
| some reactions diols undergo that depend on 2 adjacent -OH groups |
|
Definition
-pinacol rearrangement
-cleavage by periodic acid |
|
|
Term
|
Definition
|
|
Term
| mechanism for pinacol rearrangement |
|
Definition
|
|
Term
| when periodic acid cleaves a bond between 2 C atoms |
|
Definition
| only when there's a free _OH group on each C |
|
|
Term
| periodic acid cleavage of glycols |
|
Definition
|
|
Term
| how to produce an alkoxide salt |
|
Definition
by deprotonating an alcohol using an active metal, like Na or K
[image] |
|
|
Term
| reactivity of Na and K with alcohols, most reactive to least reactive |
|
Definition
| methyl > primary > secondary > tertiary |
|
|
Term
| reagent that's often used when an alcohol reacts slowly with both Na and K |
|
Definition
| sodium hydride (NaH), usually in THF |
|
|
Term
| Williamson ether synthesis |
|
Definition
| an SN2 displacement in which an alcohol attacks a primary alkyl halide or tosylate to form an ether |
|
|
Term
| what usually happens when you try to do Williamson ether synthesis with a secondary or tertiary alkyl halide or tosylate? |
|
Definition
|
|
Term
| most important method for making ethers |
|
Definition
| Williamson ether synthesis |
|
|
Term
| mechanism for Williamson ether synthesis |
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
Term
|
Definition
|
|
