redox

TRANS​ ​05​ ​|​ ​CHEM​ ​31​ ​EXAM​ ​4​ ​|​ ​IMED​ ​2023  
 
Outline:  
I. How​ ​to​ ​determine​ ​which​ ​substances​ ​were​ ​reduced​ ​and​ ​which​ ​were​ ​oxidized 
II. Oxidation​ ​Reactions 
III. Reduction​ ​Reactions 
IV. Josh​ ​Aguasin’s​ ​Table​ ​(with​ ​slight​ ​changes) 
 
 
I. How​ ​to​ ​determine​ ​which​ ​substances​ ​were​ ​reduced​ ​and​ ​which​ ​were​ ​oxidized

Recall​ ​from​ ​Chem​ ​14​ ​that​ ​LEO​ ​the​ ​lion​ ​says​ ​GER.​ ​Oxidiation​ ​is​ ​when​ ​something​ ​loses​ ​electrons,​ ​and​ ​reduction
is​ ​when​ ​something​ ​gains​ ​electrons.​ ​A​ ​decrease​ ​(more​ ​negative​ ​result)​ ​in​ ​oxidation​ ​number​ ​means​ ​that
something​ ​was​ ​reduced,​ ​and​ ​an​ ​increase​ ​in​ ​oxidation​ ​number​ ​means​ ​that​ ​something​ ​was​ ​oxidized.

Oxidation​ ​Number​ ​=​ ​the​ ​charge​ ​of​ ​an​ ​atom​ ​would​ ​have​ ​if​ ​all​ ​its​ ​bonds​ ​were​ ​ionic.

Recall​ ​that​ ​in​ ​an​ ​ionic​ ​bond​ ​one​ ​atom​ ​gives​ ​off​ ​electrons​ ​and​ ​one​ ​atom​ ​accepts​ ​them.​ ​They​ ​are​ ​not​ ​shared
equally.​ ​In​ ​determining​ ​the​ ​oxidation​ ​number,​ ​we​ ​consider​ ​the​ ​more​ ​electronegative​ ​atom​ ​to​ ​be​ ​the​ ​one​ ​which
“accepts”​ ​electrons,​ ​and​ ​the​ ​less​ ​electronegative​ ​atom​ ​to​ ​be​ ​the​ ​one​ ​which​ ​“gives”​ ​electrons.​ ​If​ ​an​ ​atom​ ​is
bonded​ ​to​ ​an​ ​identical​ ​atom,​ ​that​ ​bond​ ​is​ ​not​ ​taken​ ​into​ ​account.

Example:​ ​Determine​ ​the​ ​oxidation​ ​numbers​ ​of​ ​C1​ ​in​ ​the​ ​following​ ​organic​ ​molecules.​ ​(Do​ ​you​ ​remember​ ​which
carbons​ ​should​ ​be​ ​C1​ ​based​ ​on​ ​nomenclature​ ​rules?​ ​:D)

1. C1​ ​is​ ​bonded​ ​once​ ​to​ ​oxygen,​ ​twice​ ​to​ ​hydrogen,​ ​and​ ​once​ ​to​ ​another​ ​carbon.​ ​If​ ​we​ ​imagine​ ​that​ ​all
these​ ​bonds​ ​were​ ​ionic,​ ​this​ ​carbon​ ​would​ ​lose​ ​one​ ​electron​ ​to​ ​oxygen,​ ​gain​ ​two​ ​electrons​ ​from​ ​the
two​ ​hydrogens,​ ​and​ ​not​ ​do​ ​anything​ ​with​ ​another​ ​carbon.​​ ​This​ ​is​ ​because​ ​oxygen​ ​has​ ​a​ ​higher
electronegativity​ ​than​ ​carbon,​ ​which​ ​has​ ​a​ ​higher​ ​electronegativity​ ​than​ ​hydrogen.​ ​A​ ​bond​ ​between​ ​two
carbons​ ​doesn’t​ ​change​ ​our​ ​oxidation​ ​number.​ ​If​ ​it​ ​loses​ ​an​ ​electron,​ ​its​ ​charge​ ​increases​ ​by​ ​1,​ ​and​ ​if​ ​it
gains​ ​an​ ​electron,​ ​its​ ​charge​ ​decreases​ ​by​ ​1.​ ​Therefore,​ ​the​ ​oxidation​ ​number​ ​of​ ​C1​ ​is​ (​ +1)​ ​+​ ​(-2)​ ​=​ ​-1
 2. C1​ ​is​ ​bonded​ ​thrice​ ​to​ ​oxygens,​ ​and​ ​once​ ​to​ ​carbon.​ ​It​ ​therefore​ ​has​ ​an​ ​oxidation​ ​number​ ​of​ + ​ 3​.
3. C1​ i​ s​ ​bonded​ ​twice​ ​to​ ​chlorine​ ​atoms,​ ​once​ ​to​ ​a​ ​hydrogen,​ ​and​ ​once​ ​to​ ​a​ ​carbon.​ ​Carbon​ ​is​ ​less
electronegative​ ​than​ ​halogens​ ​so​ ​it​ ​loses​ ​an​ ​electron​ ​from​ ​them.​ ​Its​ ​oxidation​ ​number​ ​is​ ​thus​​ ​(+2)​ ​+​ ​(-1)
=​ ​+1.
4. C1​ ​is​ ​bonded​ ​thrice​ ​to​ ​hydrogens.​ ​It​ ​thus​ ​has​ ​an​ ​oxidation​ ​number​ ​of​​ ​-3​.
5. C1​ ​is​ ​also​ ​bonded​ ​thrice​ ​to​ ​hydrogens.​ ​Its​ ​oxidation​ ​number​ ​is​ ​also​ -​ 3​.

Now,​ ​knowing​ ​that​ ​an​ ​oxidation​ ​involves​ ​an​ ​increase​ ​in​ ​oxidation​ ​number​,​ ​and​ ​knowing​ ​that​ ​a​ ​reduction
involves​ ​a​ ​decrease​ ​in​ ​oxidation​ ​number​,​ ​we​ ​can​ ​easily​ ​tell​ ​if​ ​a​ ​reaction​ ​is​ ​a​ ​reduction​ ​or​ ​an​ ​oxidation.

Source:​ ​masterorganicchemistry.com

The​ ​substance​ ​that​ ​was​ ​oxidized​ ​is​ ​called​ ​the​ ​reducing​ ​agent​​ ​because​ ​in​ ​getting​ ​oxidized​ ​it​ ​reduced
something​ ​else.
The​ ​substance​ ​that​ ​was​ ​reduced​ ​is​ ​called​ ​the​ ​oxidizing​ ​agent​​ ​because​ ​in​ ​getting​ ​reduced​ ​it​ ​oxidized
something​ ​else.
Furthermore,​ ​in​ ​general,​ ​in​ ​organic​ ​reactions,

Oxidation​ ​involves​ ​formation​ ​of​ ​C-O​ ​bonds,​ ​and​ ​loss​ ​of​ ​C-H​ ​bonds.
Reduction​ ​involves​ ​formation​ ​of​ ​C-H​ ​bonds,​ ​and​ ​loss​ ​of​ ​C-O​ ​bonds.
 NOTE:​ ​Removing​ ​C-O​ ​bonds​ ​is​ ​the​ ​most​ ​common​ ​thing​ ​done​ ​when​ ​you​ ​reduce,​ ​but​ ​you​ ​can​ ​also
reduce​ ​by​ ​breaking​ ​C-X​ ​(where​ ​X​ ​is​ ​a​ ​halogen)​ ​bonds,​ ​because​ ​X​ ​acts​ ​like​ ​O​ ​in​ ​that​ ​it​ ​is​ ​more
electronegative​ ​than​ ​carbon.

WARNING:​ ​Some​ ​extra​ ​stuff​ ​were​ ​added​ ​here​ ​to​ ​make​ ​the​ ​concepts​ ​more​ ​concrete​ ​and​ ​less​ ​abstract.​ ​These
will​ ​not​ ​be​ ​tested​ ​in​ ​the​ ​exam.
(example:​ ​some​ ​throwbacks​ ​to​ ​Bio​ ​22…​ ​testing​ ​testing​ ​blah​ ​blah,​ ​you’ll​ ​know​ ​naman​ ​kung​ ​‘di​ ​kasali,​ ​I​ ​will
specify​ ​naman​ ​if​ ​it’s​ ​not​ ​obvious)

II.​ ​Oxidation​ ​Reactions​ ​-​ ​form​ ​C-O​ ​bonds

Alkenes​ ​and​ ​Alkynes

1. Syn​ ​dihydroxylation
Reagents:​​ ​Cold​​ ​KMnO​4
Effect:​​ ​Turns​ ​double​ ​or​ ​triple​ ​bonds​ ​into​ ​-OH​ ​groups.​ ​For​ ​double​ ​bonds,​ ​two​ ​-OH​ ​groups​ ​are​ ​added.​ ​For
triple​ ​bonds,​ ​four​ ​-OH​ ​groups​ ​are​ ​added.
Extra​ ​info:​​ ​Syn​ ​addition​ ​of​ ​hydroxyl​ ​groups.

2. Ozonolysis
Reagents:
Alkenes:​ ​O​3​/DMS;​ ​DMS​ ​can​ ​be​ ​substituted​ ​for​ ​any​ ​reducing​ ​agent​ ​such​ ​as​ ​Zn/H​2​O
Alkynes:​ ​O​3​/H​2​O
Effect:​​ ​Cleaves​ ​alkenes​ ​into​ ​ketones​ ​(aldehydes​ ​if​ ​adjacent​ ​to​ ​a​ ​hydrogen),​ ​and​ ​alkynes​ ​into​ ​carboxylic
acids.
Extra​ ​info:​​ ​Terminal​ ​alkynes​ ​are​ ​cleaved​ ​into​ ​a​ ​carbon​ ​dioxide​ ​molecule.​ ​Carbon​ ​dioxide​ ​is​ ​the​ ​most
oxidized​ ​form​ ​of​ ​carbon​ ​(+4​ ​oxidation​ ​state).​ ​Hot​ ​KMnO4​ ​or​ ​H2​​ O​2​ ​ allows​
​ ​you​ ​to​ ​cleave​ ​into​ ​carboxylic
acids​ ​regardless​ ​of​ ​it​ ​being​ ​an​ ​alkene​ ​or​ ​an​ ​alkyne

Alcohols

1.​ ​Oxidation​ ​of​ ​Alcohols​ ​I

 Reagents:​​ ​Na​2​Cr​2​O​4​/KMnO​4​ [Sodium​
​ ​dichromate​ ​in​ ​acidic​ ​aqueous​ ​solution​ ​produces​ ​chromic​ ​acid
which​ ​is​ ​actually​ ​what​ ​is​ ​active​ ​here,​ ​after​ ​it​ ​forms.​ ​Might​ ​not​ ​be​ ​needed]
Effect:​​ ​Oxidizes​ ​the​ ​alpha-carbon​ ​of​ ​an​ ​alcohol​ ​[oxidation​ ​=​ ​removal​ ​of​ ​C-H​ ​and​ ​formation​ ​of​ ​C-O​ ​bond]
Extra​ ​notes:​​ ​A​ ​primary​ ​alcohol​ ​can​ ​be​ ​oxidized​ ​twice​​ ​because​ ​its​ ​alpha​ ​carbon​ ​contains​ ​two​ ​hydrogens,
forming​ ​a​ ​carboxylic​ ​acid​ ​as​ ​its​ ​final​ ​product​ ​[recall​ ​that​ ​oxidation​ ​involves​ ​removing​ ​C-H​ ​bonds​ ​and
forming​ ​C-O​ ​bonds]

Extra​ ​notes:​​ ​A​ ​secondary​ ​alcohol​ ​can​ ​only​ ​be​ ​oxidized​ ​once,​ ​forming​ ​a​ ​ketone​ ​as​ ​its​ ​final​ ​product​ ​(it
cannot​ ​be​ ​oxidized​ ​further​ ​after​ ​this​ ​kasi​ ​wala​ ​nang​ ​hydrogens​ ​to​ ​remove)

Extra​ ​notes:​​ ​a​ ​tertiary​ ​alcohol​ ​has​ ​no​ ​hydrogens​ ​to​ ​be​ ​oxidized​ ​so​ ​it​ ​doesn’t​ ​produce​ ​a​ ​reaction.

Extra​ ​notes:​​ ​KMnO​4​ ​​ ​is​ ​typically​ ​a​ ​weaker​ ​reagent​ ​than​ ​Na​2​Cr​2​O​4

2.​ ​Oxidation​ ​of​ ​Alcohols​ ​II

Reagents:​​ ​PCC​ ​(Pyridinium​ ​chlorochromate)​ ​[a​ ​milder​ ​version​ ​of​ ​chromic​ ​acid,​ ​this​ ​bit​ ​not​ ​needed]
Effect:​​ ​oxidizes​ ​the​ ​alpha-carbon​ ​of​ ​an​ ​alcohol,​ ​but​ ​doesn’t​ ​proceed​ ​to​ ​completion
Extra​ ​notes:​​ ​Recall​ ​that​ ​in​ ​the​ ​previous​ ​reaction,​ ​a​ ​primary​ ​alcohol​ ​was​ ​oxidized​ ​twice.​ ​In​ ​this​ ​case,​ ​it
doesn’t​ ​proceed​ ​to​ ​completion,​ ​and​ ​only​ ​oxidizes​ ​it​ ​once.​ ​It​ ​can​ ​control​ ​its​ ​oxidation​ ​because​ ​it’s​ ​a
milder​ ​version​ ​of​ ​chromic​ ​acid.

Extra​ ​notes:​​ ​Because​ ​a​ ​secondary​ ​alcohol​ ​can​ ​really​ ​only​ ​be​ ​oxidized​ ​once​ ​no​ ​matter​ ​what,​ ​it​ ​makes​ ​no
difference​ ​if​ ​you​ ​use​ ​PCC​ ​or​ ​if​ ​you​ ​use​ ​the​ ​reagents​ ​to​ ​produce​ ​chromic​ ​acid​ ​as​ ​described​ ​previously:
 Extra​ ​notes:​ ​It​ ​will​ ​also​ ​produce​ ​no​ ​reaction​ ​with​ ​a​ ​tertiary​ ​alcohol​ ​because​ ​there​ ​is​ ​nothing​ ​to​ ​oxidize
(no​ ​hydrogens)

3.​ ​Periodic​ ​cleavage

Reagents:​​ ​HIO​4​ [Anything​

​ ​which​ ​can​ ​dissociate​ ​to​ ​form​ ​IO​4​]
Effect:​​ ​Cleaves​ ​1,2-diols​ ​into​ ​two​ ​carbonyl​ ​compounds​ ​(may​ ​be​ ​a​ ​ketone​ ​or​ ​aldehyde​ ​depending​ ​on
position)

Extra​ ​notes:​​ ​Only​ ​works​ ​for​ ​1,2-diols​ ​[​vicinal​ ​diols​].​ ​Used​ ​to​ ​test​ ​for​ ​the​ ​presence​ ​of​ ​vicinal​ ​diols.​ ​The
hydroxyl​ ​groups​ ​do​ ​not​ ​have​ ​to​ ​be​ ​actually​ ​numbered​ ​1,2.​ ​It​ ​is​ ​only​ ​necessary​ ​for​ ​the​ ​alcohols​ ​to​ ​be
adjacent​ ​to​ ​each​ ​other.

Aldehydes​ ​-​ ​strong​ ​reducing​ ​agents​ ​because​ ​they​ ​have​ ​a​ ​C-H​ ​bond​ ​to​ ​be​ ​oxidized​ ​unlike​ ​ketones​ ​which​ ​have
no​ ​hydrogens,​ ​which​ ​is​ ​why​ ​the​ ​following​ ​are​ ​tests​ ​to​ ​distinguish​ ​the​ ​presence​ ​of​ ​aldehydes.
*Recall:​ ​Reducing​ ​agents​ ​are​ ​things​ ​that​ ​get​ ​oxidized​ ​(and​ ​therefore​ ​cause​ ​something​ ​else​ ​to​ ​be​ ​reduced)
while​ ​Oxidizing​ ​agents​ ​are​ ​things​ ​that​ ​get​ ​reduced​ ​(therefore​ ​causing​ ​something​ ​else​ ​to​ ​be​ ​oxidized)

1. Tollen’s​ ​Reaction

Reagents:​​ ​[Ag(NH2)2​ ​(Ag+​ ​in​ ​aqueous​ ​ammonia)

Effect:​​ ​Turns​ ​aldehydes​ ​into​ ​carboxylic​ ​acids
Extra​ ​notes:​​ ​Used​ ​to​ ​test​ ​for​ ​the​ ​presence​ ​of​ ​aldehydes​ ​because​ ​Tollen’s​ ​reaction​ ​produces​ ​silver​ ​as​ ​a
by-product.​ ​If​ ​carried​ ​out​ ​on​ ​a​ ​test​ ​tube,​ ​this​ ​silver​ ​forms​ ​a​ ​mirror,​ ​which​ ​is​ ​why​ ​it​ ​is​ ​also​ ​called​ ​the​ ​silver
mirror​ ​test​ ​[not​ ​part​ ​of​ ​the​ ​test​ ​but​ ​good​ ​to​ ​know​ ​and​ ​to​ ​remember​ ​why​ ​its​ ​Ag]
 2. Benedict’s​ ​Reaction

Reagents:​​ ​Cu​2+​​ ​in​ ​aqueous​ ​sodium​ ​citrate

Effect:​​ ​Turns​ ​aldehydes​ ​into​ ​carboxylate​ ​ions
Extra​ ​notes:​​ ​Tollen’s​ ​Reagents​ ​uses​ ​silver,​ ​while​ ​Benedict’s​ ​Reagents​ ​uses​ ​copper.​ ​The​ ​presence​ ​of
aldehydes​ ​is​ ​signalled​ ​by​ ​a​ ​reddish​ ​precipitate​ ​(cuprous​ ​oxide)

Extra​ ​notes:​​ ​Can​ ​also​ ​be​ ​used​ ​as​ ​a​ ​test​ ​for​ ​reducing​ ​sugars​​ ​(throwback​ ​to​ ​Bio​ ​22),​ ​so-named​ ​because
they​ ​reduce​ ​Benedict’s​ ​Reagent​ ​(Benedict’s​ ​Reagent​ ​oxidizes​ ​these​ ​sugars).​ ​These​ ​sugars​ h ​ ave​ ​an
aldehyde​ ​group​ ​which​ ​can​ ​be​ ​oxidized​ ​by​ ​Benedict’s​ ​Reagent​.​ ​In​ ​Bio​ ​22,​ ​we​ ​tested​ ​for​ ​the​ ​effectiveness
of​ ​salivary​ ​amylase​ ​to​ ​digest​ ​starch​ ​under​ ​different​ ​environments​ ​(remember​ ​how​ ​low​ ​pH​ ​or​ ​high​ ​heat
deactivate​ ​or​ ​denature​ ​amylase?).​ ​Amylase​ ​reacts​ ​with​ ​starch​ ​to​ ​form​ ​maltose​,​ ​a​ ​reducing​ ​sugar,​ ​and
the​ ​reddishness​ ​of​ ​each​ ​solution​ ​was​ ​compared​ ​to​ ​determine​ ​the​ ​solution​ ​which​ ​had​ ​the​ ​highest
maltose​ ​concentration,​ ​and​ ​thus​ ​had​ ​the​ ​best​ ​environment​ ​for​ ​amylase​ ​to​ ​react​ ​with​ ​starch.
OMG​ ​NOW​ ​I​ ​UNDERSTAND​ ​BIO

3. KMnO​4​ Test
​

Reagents:​​ ​KMnO​4
Effect:​​ ​Turns​ ​aldehydes​ ​into​ ​carboxylic​ ​acids
Extra​ ​notes:​​ ​Used​ ​to​ ​test​ ​for​ ​the​ ​presence​ ​of​ ​aldehydes,​ ​alkenes​ ​or​ ​phenols,​ ​turns​ ​yellow​ ​when​ ​positive

Side​ ​Chain​ ​Oxidation

Reagents:​​ ​KMnO​4​ ​or​ ​Na​2​Cr​2​O​7

 Effect:​​ ​oxidizes​ ​benzylic​ ​carbons​ ​(or​ ​any​ ​carbons​ ​adjacent​ ​to​ ​an​ ​aromatic​ ​ring)​ ​to​ ​give​ ​carboxylic​ ​acids
Extra​ ​notes:​​ ​As​ ​before,​ ​if​ ​there​ ​is​ ​nothing​ ​to​ ​oxidize,​ ​i.e.​ ​there​ ​are​ ​no​ ​C-H​ ​bonds​ ​to​ ​break,​ ​then​ ​no
reaction​ ​will​ ​occur.

III.​ ​Reduction​ ​Reactions​​ ​-​ ​form​ ​C-H​ ​bonds

Alkynes

1. Catalytic​ ​hydrogenation

Reagents​:​ ​H​2​,​ ​metal​ ​catalyst​ ​such​ ​as​ ​Pt,​ ​Pd,​ ​or​ ​Raney-Ni​ ​(finely​ ​dispersed​ ​nickel)
Effect​:​ ​converts​ ​an​ ​alkyne​ ​into​ ​an​ ​alkane

Extra​ ​notes​:​ ​Hydrogen​ ​is​ ​added​ ​via​ ​syn​ ​addition.

2. Reaction​ ​with​ ​Lindlar’s​ ​catalyst

Reagents​:​ ​H​2​,​ ​Lindlar’s​ ​catalyst​ ​(​palladium​ ​catalyst​ ​poisoned​ ​with​ ​traces​ ​of​ ​lead​ ​and​ ​quinoline)
Effect​:​ ​it​ ​can​ ​only​ ​reduce​ ​alkynes​ ​and​ ​always​ ​gives​ ​the​ c​ is​ ​alkene
 Extra​ ​notes:​​ ​It​ ​is​ ​mainly​ ​used​ ​to​ ​control​ ​the​ ​hydrogenation​ ​of​ ​alkynes​ ​and​ ​to​ ​prevent​ ​them​ ​from
“over-hydrogenating”​ ​to​ ​alkanes.

3. Dissolving​ ​metal​ ​reduction

Reagents:​​ ​Na​ ​in​ ​liquid​ ​NH​3

Effect:​​ ​Turns​ ​an​ ​alkyne​ ​into​ ​a​ ​trans​ ​alkene
Extra​ ​notes:​​ ​Doesn’t​ ​over-hydrogenate​ ​into​ ​alkanes,​ ​requires​ ​low​ ​temperatures,​ ​proceeds​ ​through​ ​a
free-radical​ ​mechanism​ ​(not​ ​needed​ ​for​ ​the​ ​exam).​ ​Anti​ ​addition​ ​which​ ​is​ ​why​ ​we​ ​have​ ​a​ ​trans​ ​alkene.

Alkenes

1. Catalytic​ ​hydrogenation

Reagents​:​ ​H​2​,​ ​metal​ ​catalyst​ ​such​ ​as​ ​Pt,​ ​Pd,​ ​or​ ​Raney-Ni​ ​(finely​ ​dispersed​ ​nickel)
Effect​:​ ​converts​ ​an​ ​alkene​ ​into​ ​an​ ​alkane
Extra​ ​notes​:​ ​Hydrogen​ ​is​ ​added​ ​via​ ​syn​ ​addition.​ ​Same​ ​as​ ​before.

Carbonyls​ ​-​ ​much​ ​like​ ​how​ ​a​ ​double​ ​bond​ ​can​ ​accept​ ​two​ ​hydrogens,​ ​a​ ​C=O​ ​bond​ ​can​ ​also​ ​accept​ ​two
hydrogens.​ ​One​ ​hydrogen​ ​gets​ ​attached​ ​to​ ​the​ ​carbon,​ ​and​ ​the​ ​other​ ​one​ ​gets​ ​attached​ ​to​ ​the​ ​O​ ​to​ ​become​ ​an
alcohol​ ​group.​ ​When​ ​we​ ​reduce​ ​carbonyls,​ ​this​ ​is​ ​what​ ​happens​ ​(most​ ​of​ ​the​ ​time).

1.
Reagents​:​ ​NaBH​4
Effect:​​ ​Reduces​ ​aldehydes,​ ​ketones
Extra​ ​notes:​​ ​Does​ ​this​ ​Reagents​ ​seem​ ​familiar?​ ​As​ ​seen​ ​in​ ​oxymercuration-demercuration,​ ​it​ ​can
actually​ ​also​ ​be​ ​used​ ​to​ ​replace​ ​the​ ​C-Hg​ ​bond​ ​with​ ​a​ ​C-H​ ​bond.​ ​[probably​ ​not​ ​needed​ ​for​ ​exam,​ ​just
good​ ​to​ ​know]
2.
Reagents​:​ ​LiAlH​4​ ​also​ ​known​ ​as​ ​LAH
Effect:​​ ​Reduces​ ​all​ ​carbonyls​ ​into​ ​hydroxyl​ ​groups.​ ​Amides​ ​have​ ​their​ ​carbonyl​ ​replaced​ ​by​ ​two
hydrogens.
Extra​ ​notes:​​ ​Exactly​ ​the​ ​same​ ​as​ ​NaBH​4​​ ​but​ ​stronger​ ​and​ ​more​ ​reactive,​ ​which​ ​is​ ​why​ ​it​ ​can​ ​reduce​ ​all
carbonyls.​ ​When​ ​reacting​ ​with​ ​esters,​ ​it​ ​produces​ t​ wo​​ ​alcohols.​ ​The​ ​added​ ​hydrogens​ ​are​ ​highlighted
in​ ​blue;​ ​the​ ​reductions​ ​work​ ​by​ ​producing​ ​an​ ​alcohol​ ​and​ ​then​ ​by​ ​expelling​ ​the​ ​C-O​ ​group

Extra​ ​notes:​​ ​For​ ​amides,​ ​carbonyls​ ​are​ ​removed​ ​and​ ​replaced​ ​with​ ​two​ ​hydrogens.
 Extra​ ​notes:​​ ​For​ ​acid​ ​anhydrides,​ ​an​ ​alcohol​ ​is​ ​formed​ ​from​ ​one​ ​half​ ​(separated​ ​by​ ​the​ ​single​ ​bond​ ​O)
and​ ​a​ ​carboxylic​ ​acid​ ​is​ ​formed​ ​from​ ​the​ ​other.

Extra​ ​notes:​​ ​Reducing​ ​anhydrides​ ​and​ ​acyl​ ​halides​ ​into​ ​alcohols​ ​is​ ​seldom​ ​used​ ​because​ ​anhydrides
and​ ​acyl​ ​halides​ ​are​ ​produced​ ​from​ ​carboxylic​ ​acids,​ ​which​ ​themselves​ ​already​ ​can​ ​be​ ​reduced​ ​directly
to​ ​acids​ ​(why​ ​waste​ ​time​ ​turning​ ​them​ ​into​ ​anhydrides​ ​and​ ​acyl​ ​halides​ ​pa?)​ ​[not​ ​needed​ ​for​ ​the​ ​exam]

3. Hydrogenation​ ​with​ ​Raney​ ​Nickel

Reagents:​​ ​H​2​ with​

​ ​Raney​ ​Nickel​ ​(finely​ ​dispersed​ ​nickel)
Effect​:​ ​Reduces​ ​ketones​ ​and​ ​aldehydes​ ​into​ ​alcohols
Extra​ ​notes:​​ ​Like​ ​catalytic​ ​hydrogenation,​ ​it​ ​can​ ​not​ ​limit​ ​its​ ​reduction​ ​and​ ​keeps​ ​on​ ​going​ ​until​ ​the
carbon​ ​is​ ​reduced​ ​into​ ​an​ ​alcohol.​ ​Lindlar’s​ ​catalyst​ ​can​ ​also​ ​be​ ​used​ ​here​​ ​to​ ​keep​ ​it​ ​in​ ​the​ ​aldehyde
stage.

Extra​ ​notes:​​ ​Like​ ​catalytic​ ​hydrogenation,​ ​it​ ​also​ ​adds​ ​across​ ​double​ ​bonds.​ ​If​ ​we​ ​were​ ​to​ ​only​ ​reduce
the​ ​carbonyl​ ​group​ ​we​ ​need​ ​to​ ​use​ ​something​ ​like​ ​NaBH​4​ instead.
​

Removal​ ​of​ ​carbonyl​ ​groups

1. Clemmensen​ ​Reduction

Reagents:​​ ​Zn(Hg),​ ​HCl,​ ​Heat

Effect:​​ ​Replaces​ ​a​ ​carbonyl​ ​with​ ​two​ ​hydrogen​ ​atoms
Extra​ ​notes:​​ ​We​ ​used​ ​this​ ​during​ ​the​ ​last​ ​exam​ ​after​ ​a​ ​Friedel-crafts​ ​acylation​ ​to​ ​produce​ ​an​ ​alkyl
substituent​ ​on​ ​a​ ​benzene​ ​ring.​ ​Its​ ​use​ ​is​ ​not​ ​limited​ ​to​ ​this​ ​however.
 2. Wolff-Kishner​ ​Reduction

Reagents:​​ ​NH2-NH2,​ ​OH,​ ​Heat

Effect:​​ ​Replaces​ ​a​ ​carbonyl​ ​with​ ​two​ ​hydrogen​ ​atoms
Extra​ ​notes:​​ ​Essentially​ ​the​ ​same​ ​as​ ​Clemmensen​ ​reductions,​ ​but​ ​take​ ​place​ ​in​ ​basic​ ​conditions.​ ​The
NH2-NH2​ ​actually​ ​converts​ ​the​ ​ketone​ ​into​ ​a​ ​hydrazone​ ​and​ ​isn’t​ ​part​ ​of​ ​the​ ​Wolff-Kishner​ ​reduction.
The​ ​actual​ ​reduction​ ​only​ ​refers​ ​to​ ​the​ ​hydrazones​ ​being​ ​reduced​ ​(source:​ ​Klein).

Reduction​ ​of​ ​nitro​ ​groups

Reagents:​​ ​Sn​ ​(or​ ​Fe,​ ​Zn,​ ​SnCl​2​),​ ​HCl​ ​(H​3​O​+​​ ​in​ ​any​ ​form)​ ​**​ ​Only​ ​Sn​ ​and​ ​HCl​ ​were​ ​written​ ​by​ ​sir,​ ​the​ ​rest
are​ ​from​ ​Klein.
Effect:​​ ​Replaces​ ​a​ ​nitro​ ​group​ ​with​ ​an​ ​amine​ ​group

Extra​ ​notes:​​ ​During​ ​the​ ​last​ ​exam,​ ​we​ ​actually​ ​used​ ​Fe​ ​or​ ​Zn,​ ​HCl​ ​to​ ​reduce​ ​NO​2​ to​ ​ ​NH​2​.​ ​I​ ​don’t​ ​know
why​ ​sir​ ​decided​ ​to​ ​emphasize​ ​Sn​ ​this​ ​time​ ​around​ ​however.​ ​Furthermore,​ ​the​ ​second​ ​step​ ​of​ ​adding
NaOH​ ​is​ ​not​ ​needed​ ​(sir​ ​didn’t​ ​mention​ ​it,​ ​and​ ​it​ ​is​ ​not​ ​used​ ​in​ ​Klein​ ​aside​ ​from​ ​this​ ​picture)
 IV.​ ​Josh​ ​Aguasin’s​ ​Table​ ​(with​ ​changes​ ​in​ ​red​)

Oxidation​ ​Reactions:
Alkenes​ ​and 
Alkynes 

Removes​ ​a​ ​pi 

● In​ ​alkynes,​ ​two​ ​covalent​ ​bonds 
bond​ ​and​ ​replaces 
Syn​ ​dihydroxylation  cold​ ​KMnO​4  are​ ​broken,​ ​so​ ​you​ ​end​ ​up​ ​with 
it​ ​with​ ​2​ ​OH 
4​ ​OH​ ​groups 
groups 
Alkene:​ ​cleaves 
● Alkene: 
into​ ​ketone 
O​3​/DMS  ● Using​ ​hot​ ​KMnO​4​​ ​or​ ​H​2​O​2​ allows 
​
Alkyne:​ ​cleaves 
[DMS​ ​or  you​ ​to​ ​cleave​ ​into​ ​carboxylic 
Ozonolysis  into​ ​carboxylic 
Zn/H​2​O]  acid​ ​(regardless​ ​of​ ​alkene​ ​or 
acid 
● Alkyne:  alkyne) 
Terminal​ ​Alkyne: 
O​3​,​ ​H​2​O 
becomes​ ​CO​2 
Alcohols 
 
Just​ ​accept​​ ​The​ ​number​ ​of​ ​available 
Na​2​Cr​2​O​7​​ ​or  C-H​ ​bonds​ ​to​ ​oxidize​ ​is​ ​the​ ​reason​ ​for 
KMnO​4  the​ ​following​ ​trends.​ ​These​ ​reagents 
oxidize​ ​till​ ​it​ ​can’t​ ​oxidize​ ​no​ ​more 

 
PCC​ ​(​Pyridinium
This​ ​reagent​ ​can​ ​control​ ​itself​ ​so​ ​it
chlorochromate)​, 
only​ ​half-oxidizes
CH​2​Cl​2 

 
Works​ ​as​ ​long​ ​as​ ​the​ ​OH​ ​groups​ ​are
Periodic​ ​cleavage  HIO​4 
adjacent

Aldehyde 
 Aldehyde​ ​to  ● Ag​ ​as​ ​a​ ​byproduct​ ​(forms​ ​a 
Tollens  [Ag(NH​2​)​2​]​+ 
carboxylic​ ​acid  silver​ ​mirror) 
● Cu​2​O​ ​as​ ​a​ ​byproduct​ ​(forms​ ​the 
Aldehyde​ ​to 
Benedicts  Cu​2+  red​ ​precipitate​ ​we​ ​observed​ ​in 
carboxylic​ ​acid 
Bio​ ​22) 
KMnO​4​​ ​or  Aldehyde​ ​to 
KMnO​4​ Test
​
Na​2​Cr​2​O7  carboxylic​ ​acid 
Side​ ​Chain 
Oxidation 
● Affects​ ​the​ ​hydrogens​ ​of​ ​the 
Side​ ​Chain  KMnO​4​​ ​or  Carbon​ ​becomes  α-carbon​​ ​of​ ​benzene​ ​or​ ​any 
Oxidation  Na​2​Cr​2​O7,​ ​heat  carboxylic​ ​acid  aromatic​ ​compound.​ ​If​ ​no 
hydrogens,​ ​no​ ​reaction 

Reduction​ ​reactions:

Alkyne 

● SYN​ ​addition. 
Catalytic  H​2  ● In​ ​the​ ​presence​ ​of​ ​a​ ​metal 
H,​ ​H 
Hydrogenation  Pt/Pd/Ni  catalyst 
● Reduces​ ​towards​ ​an​ ​alkane 

H​2  ● Reduces​ ​an​ ​alkyne​ ​to​ ​an​ ​alkene 

Lindlar’s​ ​Catalyst  Lindlar’s  H,​ ​H  ● Gets​ ​the​ ​Z-isomer​​ ​(kasi​ ​SYN 
Catalyst  addition) 

● Reduces​ ​an​ ​alkyne​ ​to​ ​an​ ​alkene 

Dissolving​ ​metal  Na 
H,​ ​H  ● Anti-addition;​ ​E-isomer 
reduction  liquid​ ​NH​3 
 

Alkene 

Catalytic  ● SYN​ ​addition. 

H​2 
Hydrogenation  H,​ ​H  ● In​ ​the​ ​presence​ ​of​ ​a​ ​metal 
Pt/Pd/Ni 
  catalyst 
 ● Reduces​ ​towards​ ​an​ ​alkane 
Carbonyls 

  ● Works​ ​with​ ​ketones​ ​and 

aldehydes 
NaBH​4 
● Basically​ ​just​ ​makes​ ​a​ ​=O​ ​into​ ​a 
  -OH 
 
● Can​ ​reduce​ ​any​ ​carbonyl 
● Acid​ a​ nhydride​ ​becomes​ ​two 
alcohols,​ ​the​ ​one​ ​shown​ ​in​ ​the 
LiAlH​4​​ ​(aka 
picture​ ​and​ ​a​ ​carboxylic​ ​acid 
LAH) 
(see​ ​trans​ ​for​ ​details) 
ether 
● Esters​ ​become​ ​two​ ​alcohols​ ​(see 
trans​ ​for​ ​details) 
● Stronger​ ​version​ ​of​ ​NaBH​4 
  
● Walang​ ​tinuro​ ​na​ ​mechanism​, 
  pero​ ​apparently​ ​Raney​ ​Ni​ ​has​ ​a 
lot​ ​of​ ​functions.  
● Just​ ​remove​ ​all​ ​C-X​ ​and​ ​replace 
Raney​ ​nickel 
Hydrogenation  with​ ​C-H​ ​and​ ​turn​ ​all​ ​C=O​ ​to 
(Raney​ ​Ni) 
with​ ​Raney​ ​Nickel  C-OH​ ​(as​ ​is​ ​done​ ​in​ ​all 
H​2 
reductions) 
According​ ​to​ ​sir: 
● Can​ ​reduce​ ​ketones​ ​&​ ​aldehydes 
● For​ ​alkanes​ ​&​ ​alkynes 
Removal​ ​of​ ​Carbonyl​ ​groups 

● Basically​ ​nawawala​ ​yung​ ​=O 

Clemmensen  Zn(Hg)  Replaces​ ​=O​ ​with 
● Same​ ​as​ t​ he​ ​previous​ ​exam 
Reduction  HCl,​ ​Heat  two​ ​-H 
● Acidic 
  
● Same​ ​shit,​ ​different​ ​reagents 
Wolff-Kishner  NH​2​-NH​2​,​ ​OH 
● Basic