Organic Chemistry Reactions and Reagents

Alkene + X₂

addition of 2 X atoms across the double bond.

and enantiomer

Markvovnikov: N/A

ANTI-stereochemistry

NO rearrangement.

Alkene + X₂ + H₂O

addition of X and OH atoms across the double bond.

and enantiomer

Markvovnikov

ANTI-stereochemistry

NO rearrangement.

Alkene + H₂ + metal (Pt or Pd or Ni)

addition of 2 H atoms across the double bond.

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

Alkene (1) H-OR + Hg(OAc)₂ (2) NaBH₄

addition of OR and H atoms across the double bond.

Markvovnikov

stereochemistry:N/A

NO rearrangement.

Alkene (1) BH₃ * THF (2) HO-OH + NaOH

addition of OH and H atoms across the double bond.

and enantiomer

ANTI-Markvovnikov

SYN-stereochemistry

NO rearrangement.

Alkene (1) H₂O + Hg(OAc)₂ (2) NaBH₄

addition of OH and H atoms across the double bond.

Markvovnikov

stereochemistry: N/A

NO rearrangement.

Alkene + H₂O + H⁺ catalyst

addition of 2 OH atoms across the double bond.

Markvovnikov

stereochemistry: N/A

YES rearrangement.

Alkene + H-Br + RO-OR (peroxides)

addition of X and H atoms across the double bond.

ANTI-Markvovnikov

stereochemistry: N/A

NO rearrangement.

Alkene + H-X

addition of X and H atoms across the double bond.

Markvovnikov

stereochemistry: N/A

YES rearrangement.

Alkene + ROOOH (peroxyacid)

addition of an O atom across the double bond, forming epoxide ring.

and enantiomer

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

most electron-rich double bond reacts faster, so selective epoxidation is possible

Alkene + ROOOH (peroxyacid) + H⁺ catalyst + H₂O

addition of OH and H atoms across the double bond.

and enantiomer

Markvovnikov: N/A

ANTI-stereochemistry

NO rearrangement.

Alkene +mCPBA + CCl₄

addition of an O atom across the double bond to form and epoxide ring.

and enantiomer

Alkene +CHBr₃ + KOH + H₂O

addition of CBr₂ across the double bond forming a new cyclopropane.

and enantiomer

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

Alkene + CH₂I₂ + Zn + CuCl

addition of CH₂ across the double bond forming a new cyclopropane ring. Simmons-Smith reaction.

and enantiomer

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

Alkene (1) O₃ + -78^.C (2) (CH₃)₂S

breaks double bond and adds 2 O atoms doubled bonded to each end. produces ketones and aldehydes

Markvovnikov: N/A

stereochemistry: N/A

NO rearrangement.

Alkene + KMnO₄ + H₂O + heat

breaks double bond and adds 2 O atoms double bonded to each end. If carbon in double bond had a H bonded to it that H becomes an OH. produces ketones and carboxylic acids.

Markvovnikov: N/A

stereochemistry: N/A

NO rearrangement.

Alkene + KMnO₄ + HO^-_(aq)

addition of 2 OH atoms across the double bond.

and enantiomer

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

Alkene + OsO₄ + H₂O₂

addition of 2 OH atoms across the double bond.

and enantiomer

Markvovnikov: N/A

SYN-stereochemistry

NO rearrangement.

Na⁺ H-S^- (sodium hydrosulfide) + R-X

produces R-SH (a thiol)

made with S_n2 generally so 1* alkyl halides work best

Epoxide (1) R-MgX (grignard) + ether (2) H₃O⁺

breaks open epoxide ring. Carbon now not bonded to the O bonds to R. Carbon still bonded to the O is now bonded to an OH. Produces alcohols

Markvovnikov: N/A

stereochemistry: N/A

Conjugated diene (buta-1,3-diene) + HBr

Break one double bond, add H and Br. Produces a 1,2-addition product and a 1,4-addition product.

1,2 is a kinetic product (low temp) cuz it’s faster

1,4 is a thermodynamic product (high temp) cuz the carbocation intermediate is more stable

R-X (R= aryl or vinyl) + base (ex: NaOH) + R’-B-(OH)₂ (or R’-B-(OR’’)₂ + Pd catalyst

Produces R-R’ + B(OH)₃ + NaX. Way to couple alkyl groups.

Suzuki Reaction

R-X (R=aryl or vinyl, X=Br or I) + =-R’ (double bond then single bond to R’) + Pd catalysts + base (ex: Et₃N)

Produces R-=-R’ (R single bonded then double bond then R’) + Et₃N⁺H X^-. Way to couple alkyl groups. Bond is formed at least substituted end of the alkene.

Heck Reaction

R’-X + R₂CuLi (lithium dialkylcuprate)

Produces R-R’ + R-Cu + Li-X. Way to couple alkyl groups.

Also called an organocopper reagent or a Gilman reagent.

R₂C=O (carbonyl compound) (1) R’-MgX (grignard) + ether (2) H₃O⁺

Produces R’-R₂-C-OH (alcohol). Way to add an alkyl group and turn compound into an alcohol.

R-X + 2 Li

Produces R-Li (organolithium) + Li^+-X. Organolithiums react like Grignards

R-X + Mg + ether

Produces R-Mg-X (grignard reagent). For identity of X: I is most reactive and F does not react.

R-OH + SOCl₂ + pyridine (base)

Produces R-Cl (alkyl halide). inversion of stereochemistry due to reaction mechanism being S_N2.

R-OH + SOCl₂

Produces R-Cl + SO₂ + HCl_(g). Retention of stereochemistry due to reaction mechanism being S_N1.

alcohol + acid catalyst (H₂SO₄ or H₃PO₄) + heat

Produces an alkene + H₂O.

YES rearrangements

Alkene + NBS + hv

Addition of Br at allylic position (carbon next to carbon in dobule bond).

YES rearrangements (Br still adds to the allylic carbon)

Alkene + Br₂ + hv

Addition of Br at allylic position (carbon next to carbon in dobule bond).

CR₂H-CR’₂X (alkyl halide) + Na^+-OCH₃ + CH₃OH (alcohol)

Produces alkene. E2 elimination of H and X. no intermediate.

CR₂H-CR’₂X (alkyl halide) + CH₃OH (alcohol)

Produces alkene. E1 elimination of H and X. carbocation intermediate.

Vicinal dihalide (CHRX-CHR’X) + KOH + 200 ^.C

Produces alkyne (R-C≡C-R’).

Favors internal alkyne.

R-C≡C-H (terminal alkyne) + NaNH₂

Produces R-C≡C:^-

R-C≡C-H (terminal alkyne) (1) NaNH₂ (2) R’₂C=O (carbonyl) (3) H₂O

Produces R-C≡C-CR’₂OH. Adds R-C≡C:^- to carbonyl, which is turned into an alcohol.

R-C≡C-H (terminal alkyne) (1) NaNH₂ (2) R’CH₂X

Produces R-C≡C-CH₂R’. Combines alkyne and alkyl halide with the elimination of a H and X.

R-C≡C-H (terminal alkyne) + H₂ + metal (Pt or Pd or Ni)

addition of 4 H atoms across the triple bond.

completely hydrogenates (can’t stop with a double bond)

also applies to internal alkynes

R-C≡C-H (terminal alkyne) + H₂ + Lindlar’s catalyst

addition of 2 H atoms across triple bond, producing an alkene.

with internal alkynes reaction produces a CIS-alkene

R-C≡C-H (terminal alkyne) + Na + NH₃

addition of 2 H across triple bond, producing an alkene.

with internal alkyne reaction produces TRANS-alkene

R-C≡C-H (terminal alkyne) + (1) X₂ + (2) X₂ (X = Cl or Br)

First addition of X₂ adds 2 X across triple bond, producing an alkene

Second addition of X₂ adds another 2 X across the double bond, producing an alkane.

for internal alkynes reaction produces TRANS-alkene

R-C≡C-H (terminal alkyne) + (1) O₃ + -78^.C + (2) H₂O

breaks triple bond completely, adding a double bonded O and an OH to each end. produces carboxylic acids.

also applies to internal alkynes

R-C≡C-H (terminal alkyne) + KMnO₄ + H₂O

breaks triple bond completely, adds a double bonded O to each end and an OH to carbon bonded to an R group and another double bonded O to the carbon bonded to H. produces carboxylic acids and CO₂

also applies to internal alkynes

R-C≡C-H (terminal alkyne) + (1) R₂BH + (2) NaOH + H₂O₂

adds 2 H and one double bonded O across triple bond.

via enol intermediate

ANTI-Markovnikov

also applies to internal alkynes

R-C≡C-H (terminal alkyne) + H₂O + Hg²⁺ + H₂SO₄

adds 2 H and one double bonded O across triple bond.

via enol intermediate

YES Markovnikov

also applies to internal alkynes

R-C≡C-H (terminal alkyne) + (1) H-X + (2) H-X (X = Cl or Br)

first addition of HX adds H and X across the triple bond. producing an alkene.

second addition of HX adds another H and X across the double bond. producing an alkane.

YES Markvoknikov

with internal alkynes, produces a TRANS-alkene

R-C≡C-H (terminal alkyne) + H-Br + ROOR

adds Br and H across triple bond. producing alkene

ANTI-Markovnikov

produces a mix of CIS and TRANS isomers

⌬-OH (phenols) + R-OH + HF

addition of R to para and ortho positions.

hydroxy group stabilizes sigma complex so highly reactive.

use weak Friedel-Crafts catalysts to avoid over alkyl/acylation

(m)CH₃-⌬-OH (meta CH₃) + Na₂Cr₂O₇ + H₂SO₄

addition of double bonded O to para position. loss of aromaticity. produces quinones (conjugated 1,4-diketones)

⌬-CH₂-Br + R-OH + heat

removal of Br and addition of -OR to CH₂ side chain. produces benzyl alkyl ethers.

Via S_N2 mechanism

(ortho)Br-⌬-CH₂Br + NaCN + acetone

addition of -CN to CH₂ side chain, and elimination of Br from CH₂ side chain

via S_N2 mechanism

(p)NO₂-⌬-CH₂Br + NaOCH₃ + CH₃OH

addition of -OCH₃ to -CH₂ side chain, elimination of Br from -CH₂ side chain

via S_N2 mechanism

⌬-CH₂CH₃ + Br₂ (or NBS) + hv

addition of Br to alpha carbon on side chain (-CH₂ or the one directly bonded to the benzene ring). elimination of one H.

benzylic position is the most reactive and Br₂ only reacts there. Cl₂ is not as selective so it produces mixtures.

(m)H₂C=CH-⌬-COCH₃ + Na₂Cr₂O₇ + H₂SO₄ + heat

complete oxidation of side chains. ketone (-COCH₃) and alkene (-CH=CH₂) turned into carboxylic acids (-COOH). produces benzoic acids

(p)R’- + (o)NO₂ -⌬-R + (1) KMnO₄ + -OH + H₂O +100^.C + (2) H⁺

oxidation of alkyl side chains. both R and R’ turn into carboxylic acids (-COOH). produces benzoic acid

⌬-OCH₃ (benzene with electron-donating group) + Li + NH₃/THF + R-OH

benzene ring reduced to nonconjugated 1,4-cycloheaxadiene. the electron-donating group is NOT reduced

Birch Reduction

⌬-COOH (benzene with electron-withdrawing group) + Na + NH₃ + ROH

benzene ring reduced to nonconjugated 1,4-cycloheaxadiene. the electron-withdrawing group IS reduced, turning into -COO^-

Birch Reduction

⌬ + Na or Li + NaNH_{3 (l)} + ROH

aromatic ring reduced to a nonconjugated 1,4-cyclohexadiene.

Birch Reduction

⌬ + 3H₂ + 1000 psi + Pt, Pd, Ni, Ru, or Rh

Ring is completely reduced and is now a cyclohexANE

⌬ + 3Cl₂ + heat + pressure (or hv)

chlorination of entire ring. breaking double bonds and resulting in a cyclohexANE.

first Cl₂ addition is difficult, but next two add rapidly

(p)CH₃-⌬-Br + Na^+-NH₂ (strong base) + NH₃ + 33^.C

An elimination-addition reaction with an H being taken, then Br leaving resulting in the formation of a triple bond “benzyne”, -NH₂ attacks the triple bond, and H⁺ is added. Para and meta additions of NH₂

NO electron-withdrawing groups on the ring

(p,o) NO₂-⌬-Cl + 2NH₃ + heat + pressure

addition-elimination reaction where Cl is eliminated and NH₂ is added

electron-withdrawing groups activate ring for reaction

(CO + HCl + AlCl₃/CuCl) (happens first the adds to…) ⌬

Produces ⌬-CH=O (benzaldehyde). first reaction forms H-C⁺=O cation.

only way to add formyl group via a Fiedel-Crafts reaction

Gatterman-Koch Formylation

⌬-CR=O + Zn(Hg) + aq. HCl

Produces ⌬-R

Clemmensen Reduction

⌬ + RCOCl (acyl halide) + AlCl₃

Produces ⌬-CR=O + HCl.

acyl benzene (phenyl ketone) is less reactive than benzene

Friedel-Crafts Acylation

⌬ + R-Cl + AlCl₃

produces (p and m) R-⌬-R + ⌬-R + tri-R-benzenes + benzenes

multiple alkylations with Friedel-Crafts alkylations

⌬ + R-X (X = Cl, Br, I) + Lewis Acid (AlCl₃, FeBr₃, etc.)

produces ⌬-R + H-X, alkyl halide reacts with lewis acid to produce carbocation that is the electrophile.

YES Rearrangements

reaction fails if benzene has a substituent more deactivating than halogens

alkylbenzene is more reactive so polyalkylation occurs

(m) NO₂-⌬-OCH₃ + SO₃ + H₂SO₄

produces (p and o) SO₂H- + (m) NO₂-⌬-OCH₃, directing effects of NO₂ and OCH₃ oppose each other so more powerful activating group has dominant effect.

One of the ortho positions does not see additions because it is crowded by both the -OCH₃ and the -NO₂ right next to it

(m) CH₃-⌬-CH₃ + HNO₃ + H₂SO₄

Produces (p and o) NO₂- + (m) CH₃-⌬-CH₃

two places are ortho to one CH₃ and para to another. there is another position that is ortho to both CH₃ but it it hindered

⌬-Cl + HNO₃ + H₂SO₄

produces (o and p) NO₂-⌬-Cl

halogens are deactivators and ortho para directors

⌬-NO₂ + HNO₃ + 100^.C + H₂SO₄

produces (m) NO₂-⌬-NO₂. much slower than with benzene

⌬-NH₂ + 3 Br₂ + H₂O + NaHCO₃

produces (p,o,o) 3Br-⌬-NH₂ + 3HBr, adds Br to all 3 para and ortho positions

⌬-OCH₃ + 3Br₂ + H₂O

produces (p,o,o) 3Br-⌬-OCH₃ + 3HBr, adds Br to all 3 para and ortho positions

⌬-CH₃ + HNO₃ + H₂SO₄

produces (o and p) NO₂-⌬-CH₃, adds -NO₂ to ortho or para positions

methyl group is an activator and ortho para directing

reacts faster than benzene

⌬-SO₃H + H₂O + H⁺ + heat

produces ⌬ + H₂SO₄

desulfonation reaction

⌬ + SO₃ + H₂SO₄

produces ⌬-SO₃H (benzenesulfonic acid)

(p) R-⌬-NO₂ + Zn, Sn, or Fe + aq. HCL

produces (p) R-⌬-NH₂ reduced the nitro group on the benzene

⌬ + HNO₃ + H₂SO₄

produces ⌬-NO₂ + H₂O

forms a nitronium ion (O=N⁺=O) first

⌬ + ½ I₂ + HNO₃

produces ⌬-I + NO₂ + H₂O

⌬ + Cl₂ + AlCl₃ (or FeCl₃)

produces ⌬-Cl + HCl

⌬ + Br₂ + FeBr₃ + CCl₄

produces ⌬-Br + HBr

FeBr₃ is a strong Lewis acid catalyst

forms a Br₂^.FeBr₃ intermediate which is a stronger nucleophile than Br₂

=-= (diene, electron-rich, in C shape) + HWC=CH₂ (dienophile, electron-poor) + heat

produces cyclohexene ring with single bond formed between C’s at end of diene with C’s on dienophile double bond. Only double bond left is where single bond in diene used to be.

Diene must be in S-CIS conformation

dienophile comes in from under diene so…

if R groups are at end of diene and pointing in they will be dashed line in product

if R groups are facing toward diene in dienophile they will be dashed line in product

R-CHOH-R’ (alcohol) + DMSO + (COCl)₂ + Et₃N + CH₂Cl + -60^.C

produces R-CO-R (ketone or aldehyde)

1* alcohols oxidize to aldehydes

2* alcohols oxidize to ketones

Swern Oxidation

R-CHOH-R’ (2* alcohol) + NaOCl + HOAc

produces R-CO-R’ (ketone) + H₂O + NaCl

R-CHOH-R’ (alcohol) + CrO₃^.pyridine^.HCl (PCC) + CH₂Cl₂

produces R-CO-R’ (aldehyde or ketone)

1* alcohols oxidize to aldehydes

2* alcohols oxidize to ketones

R-CHOH-H (1* alcohol) + Na₂Cr₂O₇ + H₂SO₄

produces R-COOH (carboxylic acids)

the chromic acid reagent os too strong to stop at aldehyde

R-CHOH-R’ (2* alcohol) + Na₂Cr₂O₇ (sodium dichromate) (or CrO₃, chromium trioxide)+ H₂O + 2H₂SO₄

produces R-CO-R’ (ketone)

formation of chromic acid happens first, and then the chromic acid reacts with the alcohol to form chromate ester, which is then eliminated along with the H attached to the carbon

R₂C=O (ketone or aldehyde) + (1) LiAlH₄ (LAH) + (2) H₃O⁺

produces R₂-CH-OH (alcohol)

R₂C=O (ketone or aldehyde) + NaBH₄ + R’OH

produces R₂-C-OH (alcohol)

only in the presence of an acid or an ester

CANNOT reacts with esters or carboxylic acids

R₂C=O (ketone or aldehyde) + (1) R’-MgX (grignard) + ether + (2) H₃O⁺ or H₂O

produces R’-CR₂-OH (alcohol)

R-C≡C:^- + R₂C=O (ketone or aldehyde) + H₃O⁺

produces R-C≡C-CR’₂-OH (acetylenic alcohol)

R’-COCl (acid chloride) + (1) 2R-MgX (grignard) + ether solvent + (2) H₃O⁺

produces R’-CR₂-OH (alcohol)

HAVE to have 2 eq. of reagent

-C=O- (carbonyl) + H₂ + Raney Ni

produces -CHOH- (alcohol)

Raney Ni is more reactive than Pd or Pt catalysts

will also reduce any double or triple bonds in the molecule

R-COOR (ester or carboxylic acid) + (1) LiAlH₄ (LAH) + (2) H₃O⁺

produces R-CH₂-OH (1* alcohol)

mechanism is similar to a Grignard attack on esters

R’-COOR” (ester) + (1) 2R-MgX (grignard) + ether solvent + (2) H₂O⁺

produces R’-CR₂-OH (alcohol)

R-CH₂-OH (1* or 2* alcohol) + DMP reagent (Dess-Martin Periodinane)

Produces R-CH=O (aldehyde or ketone) + reduced DMP + 2HOAc

1* alcohols oxidizes to aldehydes

2* alcohols oxidize to ketones

R-OH + TsCl + pyridine

produces Tosylate esters (R-OTs)

the -OTs group is a good leaving group

can then be used in a substitution or elimination reaction

CH₃-CH₂OH (alcohol) + (1) H₂SO₄ + (2) H₂ + Pt

produces CH₃-CH₃ (alkane)

first step dehydrates and forms alkene (lose -OH and -H), second step adds 2 H across double bond

R-OH + (1) TsCl + pyridine + (2) LiAlH₄

produces an alkane, reduced alcohol