Ch 17-21 Reactions

Forming Aniline from Benzene

add HNO3, H2SO4

reduction via h2 pd/c

Aniline to diazonium salt

NaNO2, HCl

Diazonium ion to ph-OH

H2O, heat

Diazonium N2+ ion to Ph-I

KI

Sandmeyer rxn (Turning diazonium ion to Ph-X)

KX, Cu2X2

Diazonium to Flourine-Ph

Heat, BF4-, salt

Forming Benzene from Diazonium

H2PO4

SnAR: THINK HALOGEN NEEDS NO2 to leave

replacing halogen in benzene via NO2

1) 1st step is RDS, niratrate

2) then add substituent, forms carbanion intermediate

3) substituted via aromaticity

BEST LG is F for SnAR

Benzyne intermediate Nucleophilic substitution

Benzyneeeee think NH222222 e=ii=2

so we have Ph-X, need KNH2/NH3 then turns to aniline + KX

NH2 deprotonate H from ring and pushes Br out…forms Benzyne, then NH3 attack and benzyne takes H from NH3, forms aniiline

Benzene vs X-Benzene to aniline

For just benzene use NO2 and then reduce to NH2

For X-Benzene u must use Benzyne intermediate, forms two products

Benzyne is highly reactive

the triple bond will condense to a double bond and form two bonds.

Ortho/para directing

highly activating to least: Resonance donating >Inductive withdrawing

strong -NH2, NHR, NHR2, OH, OR

moderate -NHOR, NHOAr, OOR, OOAr

weak- R,Ph

Benzene ring: Inductive only (donating)

Weakly deactivating: Inductive withdrawing> Resonance donating

-F, Cl, Br, I

Meta directing (most to least reactive)

Moderate deactivating: resonance=inductive all withdrawing

-CHO, COR(Ar), COOH

-COOR, CONH2 (or NR2)

Strongly deactivating: Inductive only withdrawing

-NO2, CN, SO3OH

-NH3+, NR3+, CF3, CCl3

formaldehyde (methanal)

acetaldehyde

ethanal

benzaldehyde

phenylmethanal

acetone

propanone

acetophenone

1-phenylethanone

priophenone

1-phenyl1-propanone

benzophenone

cyclopentanecarbaldehyde

propyl phenyl ketone

(IUPAC: 1-phenyl-1-butanone)

methyl ethyl ketone

(IUPAC: 2-butanone)

priority prefix

oic, al, one, ol, amine, thiol

priority suffix (lower than COOH)

formyl (CHO)

oxo (CO)

hydroxy (OH)

amino (NH2)

mercapto (SH)

alykne and catecholborane + H2O2, OH-

anti-markovnikov

OH on less sub

H on more sub

aldehyde formation

alkyne and PtCl, H2O, THF or HgSO4,H2SO4, H2O

adds OH on more sub

H on less sub

ketone formation

ozonolysis of alkenes

O3, CH3X

Periodate ion cleavage of alkenes

alkene to di-aldehydes

OSO4, THF then NaIO4, H2O

Oxidation of alcohols (C-OH to CHO)

CrO3, pyridine, CH2Cl2

or

PCC, CH2Cl2

adding carbonyls to benzene

RCOCl, AlCl2, H3O+

cyanohydrin formation

HCN + OH- (catalyst)

cyanohydrin rxns

acid catalyst—> alkene attached to CN

H2/Ni CN bond reduced to CH2-NH2

H3O+ or NaOH/H2O—> oxidized CN to COOH

Aldehyde + H2O

diol formation

reversible rxn

acidic conditions yield diol + H3O+

basic conditions yield diol+ OH-

carbonyl is more stable than diol

K= hydrate/carbonyl

larger K= EWG stabilized, higher EN away from C= more likely to form diol

CF3-(C=O)-CF3 1.2 x 106

smaller K= bulkier alkyl groups, more steric hinderence

CH3-(C=O)-CH3 0.0014

NaBH4, H2O in EtOH

mild reducing agent

CO or CHO to OH

NaBH4= Nahhh NOT others

LiAlH4, THF and H3O+

CO/CHO to OH

COOH to OH

COO to OH

LiAl= like ALLL

Protecting groups

Sia2(CH3)3Cl, trimethylsilyl

or Benzyl chloride

NADH, H+

1 CO reduction to OH

reverse is

NAD+, -H+

MnO2

selective oxidation of C-OH to CO

H2CrO4

Oxidation of primary C-OH to COOH

H2, Pt or Pd/C

CO to C-OH to CH2 (as added)

catalytic hydrogen

Zn(Hg)Cl, HCl

CO to CH2

clemmensen reduction

KMnO4, H2O heat

NR with ketones (2R carbons)

CrO3, H2O,RCOOH

NR with ketone

oxidizing agent limitations

They need H presence to oxidize into CO or COOH or CHO

RCO3H (triflouroperoxyacid)

Baeyer villager rxn

makes RCOR to RCOOR

ketone to ester

cycloketones to lactones (add O on more substituted side next to ketone)

alkene to anti mark OH

BH3, THF and H2O2,- OH

primary alcohol to aldehyde

cro3, py

or pcc

terminal alkyne to aldehyde

Sia2BH, THFor 9BBN or Catecolborane

in H2O2, OH-

adds =O to less sub side

terminal alkyne to ketone

H2O, H2SO4

in HgSo4

adds C=O to more sub side

adding mcpba to RCOR

makes ester near more sub side

silver mirror test/tollens Ag(NH3)2+ in water

confirms presence of CHO if positive

if positive, forms RCOOH + Ag+

if negative, no CHO

wolf kishner reduction

H2NNH2 turns C=O to C=NNH2

then KOH and heat turn C=NNH2 to CH2

acteal + H3O+

pinch to RC=O at quarternry spot and diol

Hemiacetal from CHO

ROH and TsOH

Hemiketal

TsOH and ROH

Hemiketal/hemiacteal to Acteal

ROH and TsOH

pTsOH

Para Toulene SO3H

Protecting agent

Ethylene glycol with acid

Ethylene dithiol with ZnCl2

Deprotecting

H3O+ heat for ethylene glycol

RA-Ni for dithiol (removes CO as well)

Process forming hemi acetal to acteal

Protonate CO to COH+

Attack with ROH to COH+ area to turn into COH

Deprotonate ROH+ to OR

Protonate OH to OH2+ so it can become LG

Attack with ROH and water leaves

Deprotonate ROH+ to OR and now u have acetal

Acetal Ketal reversal to OROH or CO

H3O+ heat

Vinyl ethers (double bond next to O)

Split retro style when they see H3O+

Vinyl ethers in ROH, H+

Replaces double bond with OR group

Protecting vinyl ethers

DHP in acid to THP to back to normal (protects cyclic O)

Remove via heat and hydronium

Protects alcohols and forms acetal (cyclic O and OR)

Aldoses

CHO

CH2OH

Ketoses

CH2OH

C=O

CH2OH

Naming sugars

B= up

A= down

D= 2nd last OH right (down)

L=2nd last OH left (up)

Pyran

6 member ring

Furan

5 member ring

Tollens Test

Positive is aldose

Negative is ketose

Imine

C=N

Enamine

C=C-N

maltose

a-1-4 linkage

lactose

b-1-4 linkage

sucrose

so weird

a-d,b-d

HNO3 to sugar

makes COOH from CHO

chemical rxns of sugars

NaBH4, H2O in EtOH to sugars

reduces CHO to CH2OH

Ag to sugars

Ag+ and COOH if aldose

NR if ketose

larger Keq

less steric hinderence

more EN group instead of H

Me3SiCl in NEt3

protects OH

deprotect via TBAF or F-

DHP in TsOH to THP

protects alcohol in esters to make acetals

acetal protection

Benzyl protection

NaH

PhCH2Cl or Br

alcohol protecting groups

ways to reduce CO to CH2

Zn/Hg HCl clemmensen

H2NNH2 KOH heat wolf kishner

diothiol ethylene, zncl2 then ra-ni

do not use wolf or clemmensen for ethers

due to acidic/basic conditions, use neutral conditions of ethylene dithiol

LDA in THF, -78deg

converts ketones to enolate ions

quick nitration through benzyne int via Cl2, FeCl3 then KNH2/NH3

forms aniline, but two isomers (m or p)

forming phenol from benzene

Cl2, AlCl3

NaOH, heat in water

deleterious in water and OH- (basic conditions)

wolf kishner reduction

NH2NH2

NaBH4 on amines

Reduces double bonds of C=N to NH2

oxime fully turns to NH2 (removes OH too)

NaBH3CN reductive amination

C=O to CNHR (single bond)

wittig rxn

ph3ph-R anion

in dmso

unstabilized product is cis+trans

stabilized product is trans

product is O=PPh3 and whatever the rest is (replace double bonds)

(Ch3)2ChS in LiBu

forms epoxides

sulfonium ylide epoxide formation

kinda like mcpba

hornemer emmons rxn

(Ch3O)3P anion

works like ylide

identical to ylide

cyclic oxime + h2so4, h2O heat

in cylce extension (N adds to ring)

rearrangement of oxime (acylic)

R-C=N-OH to RHN-C=O

needs acid and water

amide

N and =O in a molecule

Oate

name used when there’s an ester in a molecule