Orgo Chem Reactions

As many reactions from Orgo Chem 1 and 2 as possible

tertiary alkane in Br2, light/peroxide

Radical Bromination - Br is added to the carbon with the least amount of hydrogens

Nitrile - 1) LiAlH4, 2) H2O

1. removes the triple bond between C & N, turns to double-H - H- attacks C and N-/Li+ circle each other

2. H20 Protonates the N -- Final Product is NH2 attached to the original carbon

ketone - 1. LiAlH4/diethyl ether or NaBH4, 2. H2O

reduces double-bonded Oxygen to an OH group- secondary alcohol

carboxylic acid - 1. LiAlH4/diethyl ethe, 2. H2O

reduces to primary alcohol - only reagent strong enough to reduce acid this far

alkene - H2SO4, H2O

Hydates/reduces double bond to single bond - OH adds to most substituted carbon of double bond, and H adds to less substituted carbon (Markovinkov) — acid catalyzed reduction of alkene

alkene - 1. B2H6, diglyme, 2. H2O2, H2O

reduces double bond - OH adds to less substituted carbon, H adds to more substituted carbon (Anti-markovnikov) — hydroboration oxidation of alkene

Primary halide - NaOH, H2O, heat

eliminates halide, creates a double bond starting at halide carbon - E2 mechanism — hydrolysis of primary alkyl halides

formaldehyde - 1. CH3MgBr, THF or diethyl ether, 2. H2SO4, H2O

Primary alcohol - ethanol — Grignard reagent + carbonyl

aldehyde [RC(O)H] - 1. R’MgBr, THF or diethyl ether, 2. H2SO4, H2O

secondary alcohol [RC(OH)R’] — Grignard reagent + carbonyl

ketone [RC(O)R] - 1. R’MgBr, THF or diethyl ether, 2. H2SO4, H2O

tertiary alcohol - [RC(OH)RR’] — Grignard reagent + carbonyl

ester [RC(O)OR’] - 1. 2R"MgBr, THF or diethyl ether, 2. H2SO4, H2O

tertiary alcohol [RC(OH)R'R”] -- Grignard reagent + carbonyl

aldehyde - 1. NaBH4 or LiAlH4/diethyl ether, 2. H2O

reduces double bonded Oxygen to OH group -- primary alcohol -- does not affect normal C=C bonds

alkene - H2, Pt

reduces double bond -- does not affect carbonyls -- anti-addition of H's

alkene and aldehyde (one compound) - 2H2, Pt

reduces all double bonds (on C and O); protonates O to make OH group

ester - 1. LiAlH4, diethyl ether, 2. H2O

reduce down to primary alcohol - only reagent strong enough to do this with an ester

carboxylic acid - NaBH4, CH3OH

deprotonates carboxylic acid, just removes H of OH bond - does not affect carbonyl

ester - NaBH4, CH3OH

No reaction - reagent is not strong enough to affect the ester

epoxide - 1. RMgBr, THF or diethyl ether, 2. H2SO4, H2O

primary alcohol - Grignard reagent - epoxide carbons + added R group

epoxide - 1. LiAlH4, diethyl ether or THF, 2. H2O

primary alcohol - no R group added to epoxide carbons

two carbonyls groups attached to one another -- NaBH4, CH3OH

vicinal diols - normally from ketones or aldehydes

alkene - OsO4 (cat), (CH3)COOH, (CH3)COH, KOH

syn-diol formation from alkenes (cis) — if not cycloalkene, a previous cis bond alkene can twist and form a trans diol compound

alkene - 1. CH3COOOH, 2. H2SO4, H2O/NaOH, H2O

1. epoxide forms on double bond

2. epoxide reduces to trans vicinal diols

tertiary alcohol - acidic halogen

halogen replaces alcohol group through Sn1

primary alcohol - acidic halogen

halogen replaces alcohol group through Sn2 - inverts stereochem

primary alcohol - SOCl2, Pyridine

Cl replaces OH groups - Sn2 - inverts stereochem

secondary alcohol - PBr3

Br replaces OH group - Sn2 - inverts stereochem

secondary halide - NaOR, CH3OH

replaces halogen with OR group to form an ether - Sn2 - inverts stereochem

tertiary alcohol - H2SO4, heat

eliminates OH group and forms a C=C bond - E1

secondary alcohol - MsCl/TsCl, Pyridine

adds methanesulfonyl chloride group on O or toulenesulfonyl chloride group on O - Sn2 but NO stereochem inversion

2 mols primary alcohol - H2SO4, heat

forms an ether starting from OH - condensation reaction

4 or 5 carbon diol w primary OHs on opposite sides - H2SO4, heat

forms a furan (4 carbons) or a cyclohexane with one O instead of a C (5 carbons) - intramolecular cyclic reactions - condensation reaction

carboxylic acid and primary alcohol - H2O4 (cat)

forms an ester and H2O - reversible - Fischer Esterfication

primary alcohol and ketone w a halide as one of the R groups - pyridine

forms an ester with pyridinium ion OR HCl byproduct

primary alcohol and acid anhydride - H2SO4, heat

forms an ester and carboxylic acid by product

secondary alcohol - Na2Cr2O7, H2SO4, H2O, (CH3COCH3)

ketone and H2Cr2O4 formed - (peroxide adidition is Jones reagent - not necessary)

primary alcohol - Na2Cr2O7, H2SO4, H2O

forms carboxylic acid from OH, acidic conditions - strong oxidizer

primary alcohol - KMnO4, KOH, H2O

forms carboxylic acid, then deprotonates OH group to form an O- and K+ - from prim OH in basic conditions - strong oxidizer

secondary alcohol - KMnO4, KOH, H2O

ketone forms - basic conditions - strong oxidizer

secondary alcohol - KMnO4, KOH, H2O, heat

carboxylic acid forms but OH deprotonates to form O- and K+ - from sec OH in basic conditions - strong oxidizer

aldehyde - Na2Cr2O7, H2SO4, H2O

carboxylic acid forms from carbonyl in acidic conditions - strong oxidizer

aldehyde - KMnO4, KOH, H2O

carboxylic acid forms then deprotonates to form O- and K+ from carbonyl in basic conditions - strong oxidizer

primary alcohol - Pyridinium chlorochromate, DCM

aldehyde forms - mild oxidizer —- PCC

primary alcohol - 2 Pyridinium dichromate, DCM

aldehyde forms - mild oxidizer —- PDC

secondary alcohol - Pyridinium chlorochromate, DCM

ketone forms - mild oxidizer - PCC

secondary alcohol - 2 Pyridinium dichromate, DCM

ketone forms - mild oxidizer - PDC

primary alcohol - 1. (CH3)2SO, (COCl)2, CH2Cl2, -50 Celsius, 2.(CH3CH2)3N

aldehyde forms - weak oxidizer

secondary alcohol - 1. (CH3)2SO, (COCl)2, CH2Cl2, -50 Celsius, 2.(CH3CH2)3N

aldehyde forms - weak oxidizer (NOT ketone)

benzylic carbon - Na2Cr2O7, H2SO4, H2O, heat

carboxylic acid forms on benzene ring - acidic conditions - strong oxidizer

vicinal diols - HIO4

forms two separated aldehydes, HIO3, and H2O - oxidative cleavage of vicinal diols

alkene - 1. O3, 2. Zn, H2O

splits double bond and puts an aldehyde on both carbons - reducing conditions

alkene - 1. O3, 2. Zn, H2O2

splits double bond and puts a carboxylic acid on both carbons - oxidizing conditions

primary halide - NaSH, ethanol

replaces halogen with SH - Sn2 - inverts stereochem

halide (primary, secondary, or benzylic) - NaSR, THF

replaces halogen with SR group - inverts stereochem

2RSH - I2

R-S-S-R and HI

2RSH - O2

R-S-S-R (no byproduct)

R-S-S-R - NaBH4, H2O

2SRH - cleavage/reduction

benzene with NO2, X, and X’ in 1,2,3 positions - NaOR

adds ether at ortho or para positions to NO2, replacing a halogen as a good leaving group

primary halide - 2Li in THF or diethyl ether

R-Li and Li-X forms

primary halide - Mg in THF or diethyl ether

R-MgX

O=C=O - 1. RMgBr, THF or diethyl ether, 2. H2SO4, H2O

forms carboxylic acid - grignard reaction

CH2I2 and Zn - O(CH2CH3)2, Cu

ICH2ZnI - or Zn(Cu)CH2I2 — Simmons Smith Reagent

cis alkene - ICH2ZnI - or Zn(Cu)CH2I2, O(CH2CH3)2

cis cyclopropane formed on double bond

trans alkene - ICH2ZnI - or Zn(Cu)CH2I2, O(CH2CH3)2

trans cyclopropane formed on double bond

H2C=N+=N- — heat or UV

singlet state carbene, N=N, triple state carbene (intersystem crossing)

high conc. cis alkene - CH2N2, heat (carbene), cyclohexane

cis cyclopropane on double bond (100% same stereochem) - fast rxn

low conc. cis alkene - CH2N2, heat (carbene), cyclohexane

cis and trans cyclopropane on double bond (racemic mixture of all stereoisomers) - slow rxn

cis alkene - CHCl3 (dichlorocarbene), NaOCH3

cis cyclopropane on double bond with Cl’s replacing H’s on the “tip” of the cyclopropane (the added carbon) - basic conditions

trans alkene - CHCl3 (dichlorocarbene), NaOCH3

trans cyclopropane on double bond with Cl’s replacing the H’s on the “tip” of the cyclopropane (the added carbon) - basic conditions

2 RLi + CuI - diethyl ether

R_Cu-_R (Li+) - Gilman Reagent

sp2 carbon or primary halide - CuLi(R)2, diethyl ether

1 of the R groups replaces primary halogen/leaving group and the other stays with the Cu + LiX — substitution rxn

secondary or tertiary halides - CuLi(R)2, diethyl ether

eliminates halogen and forms double bond - RCu and RH + LiX byproducts

(multiple) alkenes + H2 - (Ph3P)3RhCl, benzene

only reduces least substituted C-C bonds, i.e. ones with primary carbons — carbonyls unaffected

double alkene - A=B and C=D (often one right above one another) — Grubbs Catalyst

alkenes will come together/overlap (in like a square) to form one double bond with an ethene as a byproduct —

A=C (on o.g. compound(s) connecting them together) and B=D - own product by itself

Primary alcohol - 1. DMSO or COCl2, 2. Et3N (triethylamine)

Reduces to an aldehyde - mild oxidizing reagent

primary halide - NaF, benzene, crown ether

F replaces benzene - crown ether makes Sn2 rxns faster - makes a better nucleophile of the salt by holding the positive ion in its senter and letting the anion float around until it bonds

primary alcohol with 4 to 5 carbons then a primary halide - NaH

Hydride with deprotonate the alcohol enough to encourage intramolecular cyclic reactions to form a ketone, but only if there is an excellent leaving group on the other end

primary alcohol with 4 to 5 carbons then a primary halide - NaOH

will form intramolecular cyclic reaction to form ketone but competes with Sn2 to form a diol instead of cyclic ketone

primary thiol with 4 to 5 carbons then a primary halide -NaOH

will form intramolecular cyclic reaction to create a cyclic sulfide but comes with Sn2 to substitute leaving group with an OH

alkene - ROH, H2SO4

Markovnikov addition of hydrogen and RO— group to reduce the double bond

alkene - Br2, ROH

trans addition of Br on less substituted carbon and RO— group to more substituted carbon to reduce double bond - trans vicinal halohydrin

RX in Cation+ -OR*, R*OH

R*—OR - general formula for Williamson Ether Synthesis

Methyl and primary alkyl halide with primary or secondary salt alkoxide

substitution reaction -OR replaces halogen (Williamson Ether Synthesis)

Secondary and tertiary alkyl halide and primary or secondary salt alkoxide

elimination reaction - major Zaitsev’s product, minor Hoffman product (Williamson Ether Synthesis)

primary, secondary, and tertiary alkyl halide and tertiary salt alkoxide

elimination reaction - major Zaitsev’s product, minor Hoffman product (Williamson Ether Synthesis) - methyl is only exception

methyl halide and tertiary salt alkoxide

substitution reaction - OR replaces halogen (Williamson Ether Synthesis) - exception

ether - O2

hydroxyl peroxide (OOH) group added to one of the carbons closest to the original oxygen - through radical formation

ether - 2HI or 2HBr, heat

cleaves ether on both sides of O, with halogen ending the carbon chain where it originally attached to the O - H2O byproduct

cis alkene - CH3COOOH (peroxyacetic acid), or PhCOOOH, or m-ClPHCOOOH (MCPBA)

cis epoxide formation over double bond - stereochem of functional group remains the same

trans alkene - CH3COOOH (peroxyacetic acid), or PhCOOOH, or m-ClPHCOOOH (MCPBA)

trans epoxide formation over double bond -stereochem of functional groups remains the same

alkene with OH and halogen trans to each other on bond - NaOH, H2O

epoxide formation over double bond, halogen and H of alcohol group leaves, stereochem of any other functional groups remains the same

epoxide - 1. LiAlH4, diethyl ether, 2. H2O

breaks open bond on least substituted carbon, and alcohol forms on more substituted carbon (opp side of bond break) w O of epoxide - no other R groups added

epoxide - NH3, H2O

breaks open epoxide on the least substituted carbon, adds NH2 group to this carbon, adds alcohol group to the more substituted carbon w O of epoxide, stereochem of other functional groups remains the same

epoxide - NaOR, H2O

breaks open epoxide on least substituted carbon, adds OR group to this carbon, adds OH group to more substitited carbon w O of the epoxide, stereochem of other functional groups remains the same

epoxide - NaN3, H2O

breaks open epoxide on least substituted carbon, adds N3 group to this carbon, adds OH group to more substitited carbon w O of the epoxide, stereochem of other functional groups remains the same

epoxide - HOR, H2SO4

breaks open epoxide at most substituted carbon, adds OR group at this carbon, adds OH at least substituted carbon with O of epoxide, stereochem of other functional groups remains the same

epoxide - H2SO4, H2O

breaks open epoxide at most substituted carbon, adds an OH group to this carbon, adds another OH group to least substituted carbon using the O of the epoxide, stereochem of other functional groups remains the same

epoxide - HX

breaks open epoxide at most substituted carbon, adds X at this carbon, adds OH to least substituted carbon w O of epoxide, stereochem of other functional groups remains the same

R-SH - KOH, H2O

R—S- +K

R—S- + K + R’—X

R—S—R’ + K+X-

R-S-R - NaIO4, H2O, or 1mol H2O2

RSOR (sulfoxide) - oxidation