Useful Reagent Spreadsheat PDF

Preview

Summary

Spreadsheet of useful reagents utilized throughout the semester....

Description

Reagent

Name of Reaction

EtONa/EtOH (small base)

Dehydrohalogenation of alkyl halides

t-BuOk/t-BuOH (bulky base)

Dehydrohalogenation of alkyl halides

+

+

H2SO4 or H3PO4 (H /H3O ) (strong acid + heat)

Acid-catalyzed dehydration of alcohols (↑conc. acid for 1◦, weaker for 2◦,3◦)

Type of Reaction

Starting Material

Elimination (NH2 takes β H and bumps off α halogen) Substitution (NH2 removes terminal H, leaves open δ+) Addition – syn addition across double or triple bond Addition – anti across triple bond Addition – syn across triple bond

Alkane or Alkene (alkanes need 2 equivalents of NH2) Terminal Alkyne

Substituted Alkyne

Alkene or alkyne

Alkane

Alkyne

Trans-Alkene

Alkyne

Syn-Alkene Alkane w/ H & X (racemic)

Protinate –OH group, leaves as H2O

Alkane Alkyl Halide (Anti coplanar T.S. preferred) Alkane Alkyl Halide (Anti coplanar T.S. preferred) Alkane with –OH group

NaNH2 (NH2-) (Very strong base)

Synthesis of alkene

NaNH2/XX-Br (NH2 has higher pka than acetylene, can remove its H)

Synthesis of terminal alkyne H

H2/Pt,Pd,Ni,Rh[(C6H5)3P]3Cl

Hydrogenation of alkenes/alkynes

Li,Na in EtNH2 or NH3

Hydrogenation of alkynes

H2/ Ni2B (P-2), Pd/CaCO3/quinoline

Hydrogenation of alkynes

HI, HBr, HCl, HF (HX/X-)

Hydrogen Halides to Alkenes

Markovnikov Addition

Alkene

HBr in presence of peroxides (ROOR)

Hydrogen Halides to Alkenes

Anit-Markovnikov Addition

Alkene

Conc. H2SO4 (cold)

Sulfuric Acid to Alkenes

Markovnikov Addition

Alkene

B2H6 or BH3:THF

Hydroboration

R3B→H2O2, aq. NaOH

Oxidation and hydrolysis of alkylboranes

Markovnikov Addition then substitution Markovnikov Addition w/ rearrangement of Markovnikov addition w/o rearrangement Markovnikov addition w/o rearrangement ending in ether Anti-Markovnikov hydration of double bond Anti-Markovniov addition of BH3 to double bond Anti-Markovnikov addition of water to alkene

R3B→CH3CO2H + Heat

Protonolysis of alkylboranes

Syn Substitution

Cl2 or Br2 / in CCl4 (non-nucleophilic solvents)

Bromine and chlorine to alkene

Cl2 or Br2 / in aq. Solution

Halohydrin formation (haloalcohol)

:CH2N≡N + Heat or Light [:CH2]

Reactions with Carbenes

Conc. H2SO4 (cold) then H2O (hot) +

Alcohol from Alkyl Hydrogen Sulfates

+

H2SO4 or H3PO4 [H /H3O ] + H2O (warm and dilute) (1) Hg(OAc)2/THF-H2O (2) NaBH4, –OH(1) Hg(O2CCF3)2/THF-R-OH (2) NaBH4, –OH(1) BH3:THF (2) H2O2, –OH-

Acid-catalyzed hydration Oxymercuration-demercuration Solvomercuration-demercuration Hydroboration-Oxidation

Final Product Alkene [More substituted alkene – Zaitsev’s Rule] Alkene [Less substituted alkene – Hofmann’s rule] Alkene with double bond between α and β carbons Alkene (with 1 eq. NH2) Alkyne (with 2 eq. NH2)

Elimination (Best with E2) [hydrogen on β C removed] Elimination (Best with E2) [hydrogen on β C removed] Elimination (1◦=E2) (2◦,3◦=E1)

Anti-addition of halogen across double bond Anti-addition of halogen and OH group across double bond Addition to double bond to form cyclic ring

Alkane w/ H bonded to C atom with fewest H atoms Alkane (alkyl hydrogen sulfate)

Alkene

Alkane (alcohol)

Alkene

Alkane (alcohol)

Alkene

Alkane (alcohol)

Alkene

Ether

Alkene

Alcohol (syn)

Alkene

Trialkylborane [syn] (boron attaches to least sub. C)

Alkylborane

Alkane (alcohol)

Alkylborane Alkene Alkene Alkene

Alkylborane with replaced substituent Alkane or cycloalkane Trans vicinal dihalide Alkane (major = halohydrin, minor = vic-dihalide) Cycloalkane

t-BuOK/CHCl3 or t-BuOK/CHBr3 CH2I2/Zn(Cu) in diethyl either (1) cold dilute (1) OsO4, pyridine KMnO4 (2) NaHSO3/H2O (2) –OH-, H2O (1) KMnO4, –OH-, + Heat (2) H3O+ (1) O3, CH2Cl2, -78◦ (2) Me2S Cl2 or Br2 in CCl4 (look at # of mols) -

HX (HI, HBr, HCl, HF) [X ] “HBr”/CH3COBr/alumina/CH2Cl2 HBr/peroxides [ROOR] R-C≡C-R→ R-C≡C-R→

(1) O3 (2) HOAc (acetic acid) (1) KMnO4, OH(2) H3O+

Dihalocarbenes (will maintain original cis/trans formation) Carbenoid addition (will maintain original cis/trans formation)

Alkane syn 1,2-Diol

Double bond cut in half (gives 1

Alkene

Ozonolysis

Double bond cut in half (puts an

Bromine and chlorine to alkyne (can add twice depending on # of equivalents)

Anti-addition of halogen across double bond Markovnikov addition of HX across double bond Markovnikov addition of Br with good yield Anti-Markovnikov addition of HBr across double bond Cleavage at triple bond and 2 formed carboxylic acids Cleavage at triple bond and 2 formed carboxylic acids Halogen homolytically splits adds via SN1 Halogen homolytically splits adds via SN1 Bromine radicals can be initiated by peroxides Anti-Markovnikov addition of Br radical across double bond Radical is formed and chains are built that are enormous Cations are formed that act like radicals Anions are formed that act like radicals The alcohols unshared electron initiates the reaction Allows for a desired configuration at oxygen The H is removed from the oxygen and it adds an R group The H is removed from the oxygen and it adds an R group

Addition of hydrogen halides to alkynes (watch #of mols) Addition of HBr facilitated with CH3COBr Addition of HBr in presence of peroxides Oxidative cleavage of alkynes Oxidative cleavage of alkynes

Br2/ROOR

Halogenation through radicals

HBr/ROOR

Addition of hydrogen bromide to alkene

ROOR

Radical Polymerization

BF3/H2O

Acid-catalyzed polymerizations

NaR, NaOR

Alkane or Cycloalkane

Oxidative cleavage of double bond

Halogenation through radicals

R-OH in H2SO4

Alkene or cycloalkene Alkene

Br2/hν

MeSO2 (Ms-) or Ts- or CF3SO2 (Tf-)

Alkane or cycloalkane w/ X2 added stereospecifically

Syn addition of –OH (1,2diols)

Halogenation through radicals

PBr3 or SOCl2

Alkene or cycloalkene

Syn 1,2-Dihydroxylation

Cl2/hν

NaNH2/NH3

Addition of :CX2 (if R groups are trans, they will stay trans) Addition of CH2 group to form cycloalkane

Base-catalyzed polymerizations Alkyl bromide and alkyl chloride addition Tosylates, Mesylates, and Triflates used as leaving groups Dehydration of a primary alcohol to form an ether Williamson Ether Synthesis

double bond to the C and 1 single bond to O-)

O at the end of both new double bonds)

Alkene Alkyne Alkyne

Two alkenes w/ at least 1 double bond to O in each Two alkenes w/ double bonds to O Alkene w/ 1 mol equivalent Alkane w/ 2 mol equivalent Alkene w/ 1 mol equivalent Alkane w/ 2 mol equivalent

Alkyne

Alkene

Alkyne

Alkene (E) and (Z)

Alkyne

Alkene (carboxylic acid)

Alkyne

Alkene (carboxylic acid)

Alkane or Alkene

Chloroalkane

Alkane or Alkene

Bromoalkane (selective)

Alkane or Alkene

Haloalkane

Alkene Alkene

Bromoalkane (AntiMarkovnikov) Polymer (normally massive)

Alkene

Cationic alkane chains

Alkene

Anionic alkane chains

Alcohol

Alkyl halide

Alcohol

Alkane

Alcohol

Ether

Alcohol (Preferably Me, 1◦)

Ether

(1) Hg(O2CCF3)2, t-BuOH (2) NaBH4, HOH2SO4/isobutylene

Alkoxymercuration-Demercuration Primary alcohol converted to t-Butyl ether (t-Butyl protecting group)

TBSCL/TBS

Silyl ether protecting group

ROR → HBr

Dialkyl ether reacting with acid to form oxonium salt

ROR → 2 HBr (strong acid)

Cleavage of ethers

MCPBA Epoxide → H3O+ (acid) Epoxide → OR- (base) +

MCPBA/H , H2O

Epoxidation (syn addition of O at double bond forming C-O-C ring) Acid-catalyzed ring opening of epoxide (more sub. Carbon) Base-catalyzed ring opening of epoxide (less sub. Carbon) Anti 1, 2-Dihydroxylation (cis will be enantiomers, trans will be meso)

Mercury adds and alcohol adds, removed an ROR left H is removed and t-Butyl group added at O H is removed and added at O, removed and left with ROR H atom is added to a lone pair on the oxygen atom Two SN1 reactions on same oxygen, O leaves as H2O An oxygen atom is added at double bond. Forms ring. H is removed from acid and H2O molecule attacks at (+) OR- attacks a C and lone pair on O pulls in an H Alkene is turned into a epoxide then anti addit. of OH

Alkene

Ether at double bond

Alcohol (primary)

t-Butyl Ether

Alcohol (primary)

Protected ether

Ether (dialkyl-diethyl)

Oxonium Salt

Ether

R-X

Alkene

Epoxide (cyclic ether)

Epoxide Epoxide Alkene then Epoxide

Diol (-OH groups add on both C from ring) RO- adds on a C and an H is added on O 1, 2-Diol...