orgo 2 exam 2 reagents and when to use them

ozonolysis of alkenes

1) O3

2)DMS

OR Zn, H3O+

Periodate cleavage of alkenes

1) OsO4, ether and NaIO4, H2O

oxidation of primary alcohols

PCC

oxidation of secondary alcohol

PCC or CrO3, pyridine

Friedel-Crafts Acylation

1) ClCOR, AlCl3

2) H3O+

formation of cyanohydrin

HCN, OH- catalyst

** think that killing something with cyanide is basic af, so thats why this rxn takes place in basic conditions)

cyanohydrin to hydroxyamine

H2, Ni

cyanohydrin --> hydroxycarboxylic acid

NaOH/H2O OR H3O+

formation of gem-diol(hydrate)

H2O; H+ or OH-

reduction of aldehydes to primary alcohols

r1

option 1) NaBH4, H2O in EtOH

option 2)

1) LiAlH4, ether

2) H3O+

reduction of ketones to secondary alcohols

r2

option 1) NaBH4, H2O in EtOH

option 2)

1) LiAlH4, ether

2) H3O+

reduction of carbonyl by catalytic hydrogenation

H2, Pd/C

Clemmenson Reduction

Zn(Hg), HCl

*Think that it sounds like clementine and it is zesty to Zn(Hg) because you feel like u are on mercury with that zestiness*

oxidation of hydrate from aldehyde

1. KMnO4, OH-

2. H3O+

*KMnO4 sounds to cnty so its a fem queen and turns the CHO into a COOH**

oxidation of hydrate from ketone

NR

Baeyer-Villiger reaction, also cyclic ketone to lactone

RCO3H, MCPBA or other peracid

hemiacetal formation

Use acids like H2SO4, TsO4, HCl with 1 equivalent of ROH

acetal formation

Use acids like H2SO4, TsO4, HCl with 2 equivalents of ROH

acetal hydrolysis

add H3O+ and just protonate and deprotonate from there until you get to a hemi, and then a carbonyl and alcohol

vinyl ether to acetal

EtOH, H2SO4, acidic conditions

protection of OH using vinyl ether

use vinyl ether like DHP in basic conditions(like TsOH), add H3O+ and heat to hydrolyze acetal and get alcohol back

protection of C=O using thiol

use HS-(CH2)x - SH with ZnCL2, Et2), do reactions

hydrolyze product with HgCl2, CH3CN, H2O and CaCO3 to get carbonyl group back

C=O to CH2 via thioacetal

sh-(ch2)3-sh with ZnCl2 to form thioacetal

raney ni to hydrolyze thioacetal along with the corbonyl that once existed

cyclic hemiacetal

H+

open chain to pyranose

open chain to furanose

mutarotation

glycoside formation

acid catalyzed; product is acetal

formation of disaccharide

h2o removed

reduction of aldose

-NaBH4, H2O, EtOH; can also use H2/Ni

-alditol

reduction of ketose

-NaBH4, H2O, EtOH

forms 2 epimeric alditols

oxidation of reducing sugars

Fehling's: CuSO4(aq), potassium tartrate, NaOH heat

Tollen's:[Ag(NH3)2]+-OH

*reacts as open chain; acetals can't be reducing sugars

enediol rearrangement

OH- then H2O because oxidization of aldose drives equilibrium to the right

oxidation to form aldonic acids, which can exist as lactones

Br2, H2O in acidic conditions

oxidation to form aldaric acids

HNO3; both CHO and CH2OH at end are oxidized and can be meso

imine formation

R-NH3, H+

imine hydrolysis

H3O+

hydrazone formation

H2N-NH2, H+

oxime formation

HO-NH2

enamine formation

secondary amine, H+, water to deprotonate alpha hydrogen and change double bond from C=N to C=C after imine intermediate

hydrolysis of enamines

H3O+

Wolf-Kishner Reduction

H2N-NH2, KOH, heat

reduction of N-containing groups

R-NH2, NaBH3CN, EtOH, H2O, acidic conditions

enamines as nucleophiles

react with alkyl halides via sn2 to form iminium ions; iminium ions via hydrolysis to form alpha alkyl/acyl ubstituted aldehyde or ketone

reduction of enamine

tertiary amine formed; H2, Pd/C reduces alkene part

Wittig reaction

PPh3 + Cl-R --> phosphoylide(carbanion)

Horner Emmons Reaction

1. P(OMe)3; 2. NaOEt, EtOH

beckmann rearrangement

H2SO4, H2O and heat

oxidation of aldehydes/primary alcohols

H2CrO4 or Na2Cr2O7, H2SO4 or

1. Ag2O, NH3

2. H3O+

oxidation of primary alcohols

1. KMnO4/OH-

2. H3O+

oxidation of alkylbenzene containing benzylic hydrogens

1. KMnO4/OH-

2. H3O+

hydrolysis of nitriles

first get good leaving group on reactant

1. NaCN, DMF

2. H3O+ and heat

carboxylation of Grignard reagents

1. form grignard reagent with Mg in polar aprotic solvent

next

1. CO2

2. H3O+

formation of acid chloride

react SOCl2 with thionyl chloride, then Cl- ion, rearrange to form RCOCl

acid chloride to acid anhydride

-O-COR

acid chloride to ester

R-O- or ROH/pyr

acid chloride to amide

R-N^-H or excess R-NH2

acid chloride to carboxylic acid

H2O, pyr

acid chloride to carboxylate

N/A

ester to carboxylic acid(acid catalyzed ester hydrolysis)

H2O, HCl

saponification(ester to carboxylate)

1. OH, heat

2. acid workup

ester to different ester(transesterification)

R-O- or ROH/H+

ester to amide

R-N^-H or R-NH2/H+

anhydride to carboxylic acid

+H2O

anhydride to ester plus carboxylic acid

R-O- or ROH

anhydride to amide

R-N-H or excess R-NH2

amide to carboxylic acid

H3O+, heat

amide to carboxylate

OH-, heat

hydrolysis of nitriles(acid catalyzed)

H3O+

hydrolysis of nitriles(base catalyzed)

OH-

reduction reactions of acid chloride(RCOCL), ester(RCOOR), carboxylic acids(RCOOH)

1. LiAlH4, ether

2. H3O+

reduction of amide to amine

1. LiAlH4

2. H3O+

3. OH-

reduction to of acid chloride to aldehyde

Lithium tri(tertbutoxy)aluminum hybride

reduction to of ester to aldehyde

DIBALH and hydrolysis with H3O+

acid chloride addition elimination with organmetallic

R-MgX to form tertiary alcohols

R2CuLi to form ketones

ketones do not react with organocuprates

and acid workup

esters

RLi or R-MgX to form tertiary alcohol

formate esters with RLi and MgX to form secondary alcohols

and acid workup

tertiary amides

Grignard, polar aprotic and acid workup

nitriles

grignard and acid workup

Fischer esterification

ROH, H+

lactone formation

H-X, X-

or Br2/H2O in acidic conditions

formation of methyl ester

diazomethane, ether