Organic Chemistry-Semester 1

Acid/Base

 

Electrophile/Nucleophile

 

 

Neutralized Substance (frequently HOH)

 

A + :B AB

Sn2

 

Alkane w/ Leaving Group (1°)

 to

Replaced Leaving Group

 

Nucleophile

 

   H                      H              H

C-C-L + :Nu →[ Nu-C-L ] → Nu-C-C + :L

   H                     CH              H 

 

Inversion

Sn1

 

Alkane w/ Leaving Group (2/3°)

to

Alkane w/ New Substituent (has E1 by-product)

Nu:

 

   C          C                    C 

C-C-L C-C + + :NuC-C-Nu

   C           C                   C

 

Racemate

E2

 

Alkane w/ Leaving Group (1/2°)

to

Alkene

Nu:

 

      H                                  H              H

H-C-C-L + :Nu → [Nu–H–C==C–L] → C=C

      H                                  H              H

E1

 

Alkane w/ Leaving Group (3°)

to

Alkene

Nu:

 

      C            C                                     C 

H-C-C-L →  H-C-C+ + :Nu → [ Nu–H–C==C ] →

      C            C                                     C

    C

C=C

    C

Dehydrohalogenation

 

Alkyl Halide

to

Alkene

Nu:

 

By E2/1

Acid Catalysed Dehydration

 

Alcohol (3º>2º>1º)

to

Alkene

Strong Acid

 

H adds to -OH

 

Proceeds as E1/2

Double Elimination

 

Vicinal Dihalide

to

Alkyne

 

Nu: (2eq)

 

2 repeated E2 reactions

Rearrangement

 

1º/2º Cation

 

 

3º Cation

 

An entire subsituent moves over to the 1º/2º cation to make more stable

Replacement

 

Terminal Alkyne

to

Terminal Alkynide

 

NaNH2, NH3, Li…

 

R-CΞC-H → R-CΞC:

Hydrogenation

 

Alkene

to

Alkane

 

H2, Pd/Ni

 

Double bond attacks H in H2

Hydrogenation

 

Alkyne

 

Syn Alkene

 

 OR

 

Anti Alkene

Ni2B, H2

OR

Li, EtNH2 (Radical)

 

 

Addition

 

Alkene

to

Alkyl Halide

HX

 

Double bond attacks H (adds to side w/ most H’s), creates a Cation, X- attacks.

;

;REARRANGEMENT can happen.

Acid Catalysed Hydration

;

Alkene

to

Alcohol

;

1)HA

2) OH

;

Double bond attacks H on Acid, then Conj. Base attacks cation.; OH attacks C with sulfonate.

Acid Catalysed Hydration

;

Alkene

to

Alcohol (3;/2;)

;

SA, H2O

;

Double bond attacks H on acid, forms cation.; H2O attacks cation.; Conjugate base deprotonates the O+ formed.

Oxymercuration/Demercuration

;

Alkene

to;

Alcohol (no rearrangement)

Hg(COOCH3)2 , THF (becomes Cation), H2O

;

Double bond attacks Hg, forms bond from both C’s.  Hydrogenation occurs. 

NaBH4, OH

H attacks C w/ Hg

 

 

Hydroboration

 

Alkene

to

Alkyl Borane

BH3

 

Double bond attacks B, kicks out an H

 

(occurs for each H)

Oxidation and Hydrolysis

 

Alkylborane

to

Alcohol

HOO, NaOH

 

Peroxide Ion attacks B, R attacks 1st O, forms ether.  Repeats 3 times.

 

OH attacks B, kicks out O-R, which attacks H on BOROH. 

Addition

 

Alkene

to

Vicinal Dihalide

Cl2, CCl4

 

C=C forms ring with a Cl, Cl attacks from other side

 

TRANS

Addition

 

Alkene

to

Halohydrin

X2, H2O

 

C=C forms ring with X, H2O goes through Hydration

Carbene Formation

 

Diazomethane (:CH2-NΞN:)

to

Carbene

 

N-C bond breaks and

:CH2 forms

Cyclopropane formation

 

Alkene

to

Cyclopropane

Carbene

 

Cyclic donation from double bond to carbene and vice versa.

Oxidation

 

Alkene

to

Diol (Syn)

1) OsO4, Pyradine 2)NaSO3/H2O

OR

KMnO4, OH, H2O

 

Double Bond attacks an O, an O attacks the other Carbon, and the H’s attack at O bonds.

Oxidative Cleavage

;

Alkene (alkyne)

to

Carboxylic Acid, CO2, or Ketone (carboxylic acid)

1) KMnO4, OH, H2O, heat 2)H3O+

;

Breaks double bond, adds a =O.

Oxonolysis

;

Alkene

;

1) O3, CH2Cl2 2);Zn, HOAc

Aldehyde/Ketone

;

Forms C-C;Ring

;; O-O-O

Which changes to a C-O-C Ring

;;;;;;;;;;;;;;;;;;;; O; O

Which breaks apart w/ Zn, HOAc

Addition

;

Alkyne

to

Dihaloalkene (trans)

Tetrahaloalkane

X2, CCl4

;

Adds 1/2 times depending on eq

(like addition to Alkene).

Addition

;

Alkyne

to

Haloalkene

HX (for Markovnikov)

;

HX and ROOR (for Anti-Markovnikov)

;

Addition

;

Haloalkene

to

Geminal Dihalide

HX

;

Adds Markovnikov, so adds X to C with other X.

Radical

;

Alkane

to

Alkyl Halide

X2, Light

;

Cl; abstracts the H, leaving a radical.; Cl; attacks the radical.

Anti-Markovnikovian Addition

;

Alkene

to

Alkyl Halide

HX, light, ROOR

;

RO; abstracts H from HX, X; attacks double bond, the radical C abstract and H from HX.

;

;

Substitution

;

Alcohol

to

Alkyl Halide

;

HX, PBr3, SOCl2 and pyradine

;

OH attacks either P or H, making a good leaving group.; X will then attack the C.

Intermolecular Dehydration

;

1; Alcohol

to

Ether

HA

;

R-OH ; R-OH2 ; [ROH–R–OH2] → ROR → ROR

                                        H

Williamson Synthesis

 

Alcohols

to

Ether

K or NaH and R’-L

 

R-OH → R-ONa/K → R-O-R’ (Na/K+ and L)

Alkoxymercuration/Demercuration

 

Alkene

to

Ether

1) Hg(OOCCF3)2, HO-R’

2) NaBH2, OH

 

 

Protecting Groups

 

Alcohol

to

Protected Ether

H2SO4, C=C(CH3)2

 OR

ClSi(CH3)2CH3, Imidiazole, DMF

(Bu4NF, THF to remove)

 

Use to get a base to attack a C rather than an H

Cleavage

 

Ether

to

Alkyl Halide and Alcohol

H-X

 

H adds to O, stablest cation forms (or X attacks-Mark)

     H 

  R-O-R’ → R-OH + R’+ or R’X

Formation of Epoxides

 

Alkene

to

Epoxide

Peroxyacid

 

Forms cyclic bond with OH from ROOH, also forms a carboxylic acid

Acid Catalysed Ring Opening

 

Epoxide

to

Akyl ____

Water or other Weak Acid

 

O attacks H from Acid, acid attacks C and OH breaks off to form an Alkyl whatever.

Base Catalysed Ring Opening

 

Epoxide

to

Alkyl______

Strong Base and NH4Cl

 

Base attacks the C, O breaks off, attacks a Hydrogen.

Reduction by Hydride Transfer

 

Carboxyl Group

to

Alcohol

1) LiAlH4, Et2O 2) H2SO4/H2O

or

BH4, H2O

 

Donates an H, Oattacks an H (or pushes out an OH)

Oxidation

 

Alcohol

to

Aldehyde (1°), Carboxylic Acid (1°), or Ketone

PCC, CH2Cl2

or

KMnO4, OH, H2O, heat, H3O+

or

CrO3 (HCrO4, Acetone), H2O (JONES REAGENT)

Organometal Formation

 

Alkyl Halide

to

Organometal

Mg or Li (Et2O, THF)

 

Replaces X

Acid/Base

 

(What can go WRONG)

 

Carboxyl group with an acidic H

to

Alkane

 

 

Organometallic attacks the H rather than the C with the =O

 

(Works with -OH, and CΞCH notably)

Grignard/Lithium Rxn

 

Carboxyl Group

to

Alcohol

Grignard/Organolithium Reagent or C≡C:, H3O+

 

R group on Organometallic attacks C with =O.

 Also works in Epoxides with C-O

 

Esters will act as a leaving group

Corey-Posner, Whiteside-House Synthesis

 

Alkyl Halide

to

Dialkyl cuprate

Li in Et2O and CuI

 

Li replaces X, Cu takes place of Li to get CuLi compound with 2 alkyl groups

Corey-Posner Whiteside-House Synthesis

(part deux)

 

Alkyl Halide

to

Alkane

Dialkyl Cuprate

 

Alkyl Group takes place of X

Allylic Substitution

 

Alkene with ≥1 branch

to

Halo-alkene

X2, Heat

also: NBS, hv, CCl4

 

X· Forms, abstracting an H and leaving a radical on an allylic carbon.  Through RESONANCE, many different placements of the X occur.

Diels-Alder Reaction

 

Diene (best if with edonating group)

to

Six-Membered Ring

Alkene with e withdrawing group (Electron Acceptor)

 

Resonance makes the donor/acceptor possible, number carbons along double bonds 1-4 and 5-6 to show bonds of ring.

 

***IN=UP, OUT=DOWN***

 

 

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