Organic Rxns Flashcards
Alkane + X2
with heat or light
Alkyl halide + acid
Alkene
with H2 and Pt/Pd/Ni
Alkane
Acid + alcohol
with acid catalyst
Ester + water
Isobutane + Br2
with heat or light
t-butyl bromide
Alkene + HX
Mono-subst. alkyl halide
Alkene + X2
Di-subst. alkyl halide
Subst. on different C’s
Alkyne + 2HX
Di-subst. alkyl halide
Subst. on the same C
Alkyne + 2X2
Tetra-subst. alkyl halide
Allylic alkene
with NBS, light
Allylic bromide
Alcohol + HX, PX3, etc.
R-X
R-X
with I-
R-I + X-
Unhindered substrate
with strong nucleophile
Sn2: Substitution with reversed chirality
Carbocation-forming substrate
with weak nucleophile, stable LG (WB)
Sn1: Substitution with mixed chirality (sometimes rearrangements)
Carbocation-forming substrate
with good ionizing solvent
E1: Zaitsev (MS) product (sometimes rearrangements)
Anti-coplanar arrangement
with strong base
E2: Zaitsev (MS) product (cis or trans based on substrate)
R-X + HO-
Sn: R-OH + X-
R-X
with R’O or R’S
Sn: Williamson ether synthesis: R-O-R or R-S-R
R-X
with excess :NH3
Sn: R-NH2 + NH4X
R-X
with -CN
Sn: R-CN + X-
R-C(trip)C-
with R’-X
Sn: R-C(trip)C-R’ + X-
H-CR2-CR2-X
with KOH
E: R2C=CR2 + X-
Br-CR2-CR2-BR
with KI
R2C=CR2 + I-Br + KBr
R-X (not F) + Mg
in diethyl ether
Grignard: R-Mg-X
R-X (not F) + 2Li
Organolithium: R-Li + LiX
R-X
(1) Mg or Li
(2) H2O
Reduction: R-H
Vicinal dibromide
with NaI in acetone
E2: Alkene
Alcohol
with strong acid catalyst and heat
E1: Zaitsev alkene
Long chain alkane
with heat, catalyst
Catalytic cracking: alkanes and alkenes
Alkane
with heat, catalyst
Alkene + H2
Alkyl halide
with base, heat
Alkene + HX
C-C-N-(CH3)3
with Ag2O, heat
Hoffmann/Cope elimination: Hoffman alkene + :N(CH3)3
Alkyne
H2, Pd/BaSO4 in quinoline
Reduction: cis alkene
Alkyne
with Na, NH3
Reduction: trans alkene
R’-C=O-R
with Ph3P=CHR’’
Wittig: R’C=CHR’‘-R + Ph3P=O
Alkene
with water and acid
Alcohol
Alkene
with X2
Oxidation: Vicinal dihalide
Alkene
with HOX
Oxidation: Neighboring halo/alcohol
Alkene
with HOOH
Oxidation: Vicinal diol
Alkene
with HX
Alkyl halide
Alkene
with O2
Oxidative cleavage: 2 carbonyls
Alkene
with O
Epoxidation: CCO triangle
Alkene
with CH2
Cyclopropane
Alkene
with HBr, HOOH, heat
Anti-Markovnikov (LS) bromination product
Alkene
with Hg(OAc)2, water
then NaBH4
Oxymercuration/demercuration: Markovnikov alcohol
Alkene
with BH3+THF
then HOOH, -OH
Hydroboration: Anti-Markovnikov alcohol
Alkene
with X2
Anti alkyl halide
Alkene
with X2 in water
Anti halohydrin (Markovnikov)
Diazomethane
with heat/UV
Carbene formation: H-:C-H (methylene)
Halogenated molecule
with base
Halogenated carbene
Epoxide
with strong acid
Epoxide opening: anti 1,2-diol (glycol)
Alkene
with OsO4 + H2O2
Syn dihydroxylation: syn 1,2-diol
Alkene
with KMnO4 + base
Syn dihydroxylation: syn 1,2-diol
Alkene
with conc. KMnO4
Oxidative cleavage: Acids and maybe CO2
Alkene
O3, then Zn or dimethyl sulfide
Oxidative cleavage: Ketones and aldehydes
Alkene
with BF3
Cationic polymerization: Addition polymer
Alkenes
with metal catalyst
Olefin metathesis: new alkenes
2 methanes
Heat
Acetylene + 3H2
Acetylide + R-X
Sn2: R-C(3)C-R’ + X-
Acetylide + carbonyl
Sn: R-C(3)-OH
Vicinal or geminal dihalide
with VERY strong base
Alkyne + 2HX
Alkyne
with H2 and Pt/Pd/Ni
Alkane
Alkyne
with Lindlar’s (Pd) catalyst
cis alkene
Alkyne
with e- from Na in liquid NH3
trans alkene
Alkyne + X2
cis and trans alkenes
Alkyne + HX
Markovnikov alkene –> geminal alkyl dihalide
Alkyne + HX + ROOR
Antimarkovnikov alkene
Alkyne with Hg(II) then acid
Enol –> ketone
Alkyne
with Sia2BH then HOOH
Antimarkovnikov enol –> ketone or aldehyde
Alkyne
with cold, dilute KMnO4
alpha-ketones (vicinal carbonyls)
Terminal alkyne
with cold, dilute KMnO4
ketone + neighboring COOH
Alkyne
with hot KMnO4
carboxylic acids
Terminal alkyne
with hot KMnO4
carboxylic acid + CO2 gas
Alkyne
with ozone
carboxylic acids
CO + 2H
with catalyst in hi T, hi P
Methanol
Glucose
with yeast enzymes
Fermentation: Ethanol + 2CO2
Ethene and water
with catalyst in hi T, hi P
Ethanol
Propylene and water
with catalyst in hi T, hi P
Propan-2-ol
Alcohol
with Na or K in NaH
Alkoxide and H gas
Terminal alkyne
with NaNH2
Sodium acetylide + NH3
Formaldehyde
with OMR
Primary alcohol
Aldehyde
with OMR
Secondary alcohol
Ketone
with OMR
Tertiary alcohol
Acid chloride or ester
with 2 OMR
Tertiary alcohol (with two R1’s)
Ethylene oxide (CCO triangle) with OMR
Primary alcohol
Water
with OMR
R-H and LiOH/XMgOH
Ketone or aldehyde
with NaBH4 or LAH
Secondary or primary alcohol (need to use NaBH4 to preserve acids or esters)
Carbonyl
with H2 and Raney Ni
Alcohol
NaHS
with unhindered R-X
R-SH (thiol) + NaX
Pri/sec alcohol
with chromic acid
Carboxylic acid/ ketone
Pri/sec alcohol
with PCC in CH2Cl2
Aldehyde/ ketone
Collins reagent
PCC
Jones reagent
Chromic acid
Pri/sec alcohol
with nitric acid
Carboxylic acid/ ketone
Pri/sec alcohol
with KMnO4
Carboxylic acid/ ketone
Pri/sec alcohol with Swern (DMSO)
Aldehyde/ ketone
Pri/sec alcohol with DMP (iodine)
Aldehyde/ ketone
Pri/sec alcohol
with NaOCl
Carboxylic acid/ ketone
Alcohol
with TsCl in pyridine
Tosylate ester
Alcohol
1) TsCl in pyridine
(2) LAH/NaBH4 (X-
Alkane (alkyl halide)
Alcohol
with HX
Alkyl halide (rearr.)
3/2/1 alcohol
with HBr in water
Sn1/1/2: Alkyl bromide (rearr.)
3/2 alcohol
with Lucas reagent (HCl and ZnCl2)
Fast Sn1: Alkyl chloride (rearr.)
Primary alcohol
with Lucas reagent (HCl and ZnCl2)
Slow Sn2 Alkyl chloride
1/2 Alcohol
with PXn or P/I2
Alkyl halide (NO rearr.)
Alcohol
with SOCl2
Alkyl halide + SO2 + HCl (g’s)
1/2 alcohols to alkyl chlorides
SOCl2
Tertiary alcohols to alkyl halides
HX
1/2 alcohols to alkyl bromides
PBr3
1/2 alcohols to alkyl iodide
P/I2
Alcohol
with acid catalyst
E1: Alkene (rearr.)
Alcohol
with acid
(Subst. reaction)
Ether
Diol
with acid
Pinacol rearrangement: ketone
1,2-diol
with periodic acid
Ketones and aldehydes (like ozone)
Alcohol
with acid
Ester and water
Alcohol
with acid halide
Ester and HX
Alkoxide
with unhindered R’X
Williamson Ether Synthesis: R-O-R’ + X-
R-OH
with Na/K/NaH then R’-X
Williamson Ether Synthesis: R-O-R’ + X-
Alkene
with ROH and Hg(OAc)2
then NaBH4
Ether
2 primary R-OH
with H+
R-O-R
R-O-R’
with excess HX (Br, I)
R-X + R’-X (or phenol)
Ether
with O2
Hydroperoxide + dialkyl peroxide
Thiol
with -OH
Thiolate ion
Sulfide
witih HOOH in acetic acid
Sulfoxide then sulfone
Alkene with peroxyacid (MCPBA or MMPP)
Epoxide + acid
Alkene stereochem retained
Alkene
X2 in H2O
Markovnikov halohydrin
attack on MS carbon
Halohydrin
with base
Epoxide (or cyclic ether) + X-
Epoxide
with aqueous acid
Sn2: anti glycol
attack MS carbon
Alkene
with aqueous peroxyacid
Glycol
Epoxide
with alcohol
Sn2: anti alkoxy alcohol
Epoxide
with HX
Halohydrin, then vicinal dihalide
Epoxide
with -OH
Sn2: Anti glycol
attack unhindered C
Epoxide
with alkoxide
Sn2: anti alkoxy alcohol
Epoxide
with amine
Sn2: anti alcohol amine
Epoxide
with OMR
Alcohol; least hindered C is attacked
Conjugated diene
with HX
1,2 and 1,4 addition products (Markovnikov)
Alkene
with conc. Br2
Saturated vicinal dibromide
Alkene
with trace NBS, light
Allylic bromide
Diene
with electron-poor alkene
Diels-Alder: Cyclohexene ring
Diene
with electron-poor alkyne
Diels Alder: Cyclohexa-1,4-diene ring
Benzene
with KMnO4
NR
Benzene
with Br2 in CCl4
NR
Benzene
with Br2 and FeBr3
Ph-Br
Reagent to brominate benzene?
FeBr3
Reagent to chlorinate benzene?
AlCl3
Reagent to iodinate benzene?
I2 and HNO3
Benzene
with HNO3 in H2SO4
Ph-NO2 via NO2+
Ph-NO2
with Zn, Sn, or Fe in HCl
Ph-NH2
Benzene
with SO3 in H2SO4
Ph-SO2OH
Water
with SO3
H2SO4
Ph-SO3H
with water
Benzene + H2SO4
Benzene
with R-X (+ Lewis acid catalyst)
Friedel-Crafts: Ph-R + H-X
often polyalkylation
Alkene
with HF
Carbocation
Alcohol
with BF3
Carbocation (no O)
Benzene with acyl (acid) halide
Ph-C(=O)-R (monosubst.)
Reagent to get acylated product to alkylated product?
Zn(Hg) in aqueous HCl
Benzene
with CO, HCl, CuCl, AlCl3
Gatterman-Koch: Aryl aldehydes
EWG-Aryl
with Nuc
Ortho/para substitution
Aromatic ring
with strong base, hi T
Substitution via benzyne
4 pi donors (EAS)
NH2, OH, OR, NCHOCH3
O/P Directing
Activating
2 sigma donors (EAS)
R, Ph
O/P Directing
Activating
Halogens are… (EAS)
O/P Directing
Deactivating
4 Carbonyls (EAS)
Ketone, acid, aldehyde, ester
Meta directors
Deactivating
4 strong electrophiles (EAS)
SO3H, C(trip)N, NO2, N+R3
Meta directors
Deactivating
2 R-Li
with CuI
R2CuLi + LiI
R’-X
with R2CuLi
R’-R + R-Cu + LiX
R-X + Alkene-R’
with Pd catalyst, base
Heck reaction:
R-C=C-R’ at LS end
usually trans
Aryl/vinyl-X + boron reagent
with Pd catalyst, base
Suzuki coupling:
R-R’, stereochem of reagent is preserved
Alkene/alkyne with B(OR)2
Alkane/alkene with B(OR)2 at LS end
Benzene
with Na or Li in liq NH3 with ROH
Birch reduction:
cyclohexa-1,4-diene
via radical
Phenol
with chromic acid
QUinone: 1,4-diketone
Phenol
with CO2
Salicylic acid (1,2 acid alcohol on ring)
HC(=O)H
with water
CH2(OH)2
Carboxylic acid
with 2 R-Li
Ketone
Nitrile
with (1) OM and (2) Acid
Ketone
Nitrole
with (1) DIBAL-H and (2) Acid
Aldehyde
Carboxylic acid
with SOCl2
Acid chloride
Acid chloride with LiAlH(OtBu)3
Aldehyde
Acid or acid chloride or ester
with LAH
Primary alcohol
Ester
with cold DIBAL-H then water
Aldehyde
Acid chloride
with R2CuLi
Ketone
R2C=O
with -CN
R2C(OH)(CN)
R2C=O
with H2N-Z
R2C=N-Z
R2C=O
with 2 R’-OH
R2C(OR’)2
R2C=O
with diol
Cyclic acetal!
Aldehyde
with any [O]
Acid
Aldehyde
with Ag2O
Tollens test: Acid– selective!
Aldehydes and ketones with NaBH(OAc)3
Acids and ketones
R2C=O with Zn(Hg) in HCl
Clemmensen reduction: R2CH2
R2C=O
with (1) H2NNH2 then (2) KOH
Wolff-Kishner reduction: R2CH2
R’NH2
with RCOCl
RCONHR’
Reagent to exhaustively methylate amines?
MeI
NH4OH
with heat
Hoffman elimination: alkene + amine + water
Reagent used to convert NH4I to NH4OH?
Ag2O, H2O
Amine
with (1) excess CH3I then (2) Ag2O, H2O
Hoffman elimination: alkene (Hoffman product)
Secondary amine
with HOOH
Hydroxylamine
Tertiary amine
with HOOH
Amine oxide (R3N-O)
Amine oxide
Cope elimination: syn, Hoffman alkene
Primary amine
with NaNO2
R-N+(trip)N –> N2 and C+’s
Secondary amine
with NaNO2
R2NN=O
Ar
with HNO3 in H2SO4
Ar-NO2
Ar-NO2
with Fe, HCl then OH
Ar-NH2
Ar-NH2
with NaNO2 in HCl
Ar-N(+)(trip)N
Ar-N(+)(trip)N + what = Ar-OH?
H3O+, warm
Ar-N(+)(trip)N + what = Ar-Cl?
CuCl
Ar-N(+)(trip)N + what = Ar-Br?
CuBr
Ar-N(+)(trip)N + what = Ar-C(trip)N
CuCN
Ar-N(+)(trip)N + what = Ar-F
HBF4
Ar-N(+)(trip)N + what = Ar-I
KI
Ar-N(+)(trip)N + what = Ar-H
H3PO2
Ar-N(+)(trip)N + what = Ar-N=N=Ar’
H-Ar’
x-ary amine
with (1) carbonyl then (2) hydride
(x+1)-ary amine
Amine
with acid chloride
Amide
Amine
with (1) acid chloride then (2) hydride
Alkylated amine via amine
primary alkyl group
Ammonia
with halide or tosylate
Sn2: primary amine
Protected NH3
with RX then H2NNH2
Gabriel amine synthesis: R-NH2
R-X/Ts; primary or secondary
with (1) N3- then (2) H- or H2/Pd
RNH2
R-X/TS; primary or secondary
with (1) -CN then (2) H- or H2/Pd
R-CH2-NH2
Three things that change R-NO2 to R-NH2:
1) H2/cat
2) H+/met
3) H-
Methanol + CO
with Rh catalyst
CH3COOH
Toluene
with strong [O]
Benzoic acid
Methyl ketone
with X2 in base
R-COO- + HCX3
R-COOH with CH2N2 (diazomethane)
Methyl ester + N2
Carboxylic acid + amine
with heat
Amide
Carboxylic acid
with LAH
Primary alcohol (other C=O's reduced)
Carboxylic acid
with boron reagent
Primary alcohol (other C=O's unaffected)
How to make an acid an aldehyde?
Convert to acid chloride, then treat with LiAlH(OtBu)3
Acid
with SOCl2 or (COCL)2
Acid chloride + gas
How to make an acid an ester?
Convert to acid chloride, then react with alcohol
How to make an acid an amide (not heat)?
Convert to acid chloride, then react with amine
Nitrile
with water in acid
Primary amide then carboxylic acid
Carboxylic acid
with ammonia, heat
Primary amide
Primary amide
with POCl3
Nitrile
How to make a nitrile from an acid?
First ammonia and heat, then POCl3
Acid chloride to acid anhydride with…?
Carboxylic acid
Acid chloride to ester with…?
Alcohol
Acid chloride to amide with…?
Ammonia/amines (excess or with base)
Frequent product of acid chloride interconversion?
HCl
Acid anhydride to ester with…?
Alcohol (1 acid unit = LG)
Acid anhydride to amide with…?
Ammonia/amines
RCOOR’
with excess R’‘-OH
Transesterification:
RCOOR’’ + R’-OH
Ester
with excess water
Carboxylic acid and alcohol
Ester
with hydroxide
Saponification:
Carboxylate and alcohol
What can LAH reduce to alcohols?
Acids, acid chlorides, anhydrides, and esters
What can LAH reduce to amines?
Amides and nitriles
Acid chloride or ester
with 2 OMR
Tertiary alkoxide
Nitrile reduction via OMR?
OMR gives imine; acid hydrolysis gives ketone
Hydroxy acid
Cyclic ester (lactone) and water
Amino acid
Cyclic amide (lactam) and water
CO2
with water
H2CO3
Ketone or aldehyde
with secondary amine
Enamine (N equivalent of enol)
Iminium (+N=C) salt
with acid
Ketone
Ketone
with X2 in base
alpha-haloketone
multiple halogenations
Ketone
with X2 in acid
alpha-haloketone
can stop at monohalogenation
Aldehyde
with X2 in water
Carboxylic acid + 2HX
HVZ reaction
Carboxylic acid with Br2/PBr3 to bromo acyl bromide. Add reagent to give alpha bromo acid or other derivative.
Aldol condensation
Carbonyl C of one ket/ald reacts with alpha C of another to give aldol, which can dehydrate to unsaturated ket/ald
Claisen ester condensation
Two esters combine to give a beta-keto ester
Dieckmann condensation
Internal Claisen condensation of diester to form ring
Malonic ester synthesis
Makes substituted derivatives of acetic acid
Acetoacetic ester synthesis
Makes substituted derivatives of acetone
Michael addition
Nucleophilic 1,4-addition by doubly stabilized carbanion to beta carbon of conjugated system
Robinson annulation
Intramolecular aldol condensation of delta-diketone to form a 6-membered ring; dehydration gives alkene
Polyamide (nylon) building blocks
-NH-Y-NH-(C=O)-Z-(C=O)-
Polyester building blocks
-O-Y-O-(C=O)-Z-(C=O)-
Polycarbonate building blocks
-O-Y-O-(C=O)-
C=O from XCOX
Polyurethane building blocks
-O-Y-O-(C=O)-(NH)-Z-(NH)-(C=O)-
