Organic Rxns Flashcards by Bee Who

Alkane + X2

with heat or light

Alkyl halide + acid

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Alkene

with H2 and Pt/Pd/Ni

Alkane

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Acid + alcohol

with acid catalyst

Ester + water

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Isobutane + Br2

with heat or light

t-butyl bromide

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Alkene + HX

Mono-subst. alkyl halide

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Alkene + X2

Di-subst. alkyl halide

Subst. on different C’s

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Alkyne + 2HX

Di-subst. alkyl halide

Subst. on the same C

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Alkyne + 2X2

Tetra-subst. alkyl halide

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Allylic alkene

with NBS, light

Allylic bromide

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Alcohol + HX, PX3, etc.

R-X

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R-X

with I-

R-I + X-

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Unhindered substrate

with strong nucleophile

Sn2: Substitution with reversed chirality

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Carbocation-forming substrate

with weak nucleophile, stable LG (WB)

Sn1: Substitution with mixed chirality (sometimes rearrangements)

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Carbocation-forming substrate

with good ionizing solvent

E1: Zaitsev (MS) product (sometimes rearrangements)

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Anti-coplanar arrangement

with strong base

E2: Zaitsev (MS) product (cis or trans based on substrate)

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R-X + HO-

Sn: R-OH + X-

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R-X

with R’O or R’S

Sn: Williamson ether synthesis: R-O-R or R-S-R

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R-X

with excess :NH3

Sn: R-NH2 + NH4X

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R-X

with -CN

Sn: R-CN + X-

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R-C(trip)C-

with R’-X

Sn: R-C(trip)C-R’ + X-

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H-CR2-CR2-X

with KOH

E: R2C=CR2 + X-

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Br-CR2-CR2-BR

with KI

R2C=CR2 + I-Br + KBr

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R-X (not F) + Mg

in diethyl ether

Grignard: R-Mg-X

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R-X (not F) + 2Li

Organolithium: R-Li + LiX

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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

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

Benzene | with Br2 in CCl4

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

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)-

Organic Rxns Flashcards

(266 cards)