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SJU / Chemistry / CHEM 1130 / What is organolithium?

What is organolithium?

What is organolithium?

Description

School: St. John's University (NY)
Department: Chemistry
Course: Intro to Gen & Org Chem III
Professor: Covell
Term: Fall 2016
Tags: Organic Chemistry
Cost: 50
Name: Chemistry study guide for the exam on the 11/15/16
Description: These notes cover all the chapters that are going to be on our next exam on 11/15/16.
Uploaded: 11/10/2016
12 Pages 111 Views 1 Unlocks
Reviews


SOU


What is organolithium?



St

CHAR 10

) Study Sous

(onwards

Grigrard reagent R-x + mg

-

+

k-ng-x7.

up

Study

irbons attached to metals behave like Rosty

Study Sap

Both more conbons

nucleophilic

Study Soup

Organo lithiums R-X + 2 Li R-Li & Loxo7 R behomes like R:0


What does a grignard reaction mean?



Grignard reactions The basic grignard reaction with a carbonyl is shown below!

Ric-oi → R-¢-030 R-¢-00 HO - R-C-GH We also discuss several other topics like Where does christian religion come from?

ALCOI

YNTHESIS BY NUCLEOPHILIC ADDITIONS TO CARBONYI

GIROURS

IR

with

a


What is the reduction of carbonyl compound?



0

Ketone

Aldehyde

Formaldehyde

C

formaldehyde

Hot

O: Aldehyde

+ R .

Ketone

+ R

de

ESTER If you want to learn more check out What is the conjunctive normal form?

OH

R

+R-mgx

est R-mgx

ACIP CHLORIDO

one mol of Rmgx

nol gives alcohol.

gives ketones If you want to learn more check out Which hormones have nuclear receptors?

Mg x

/B-c-OH

R - B-c-of (B-mg x +

+ B-Max

,

D

P-o-o:

& CAPSHOT R-¢-B- Ba mg Don't forget about the age old question of What is the musical example used for theme and variation?

R-C-R

3° aleahal,

20 alaho

o alcohol

1

2

-0

70-r

D-O-01

R

1

H-O

IKETONE

s adysou

SESO

H-O-HR-C-R

cao.

H-0-4

IR-C-H

Too

Н

-С If you want to learn more check out What is the difference between arthritis and rheumatism?

and 2nd

-n-op-no

OH

-

Н

Study

Studio We also discuss several other topics like What do you mean by capital budgeting?

Sour

a) St

Soup

Addition to

Ethylone

Oxich

OH

C

H307

R- CH2 - CH2

R-mg x

R-CH2 - CH2

CH2 - CH2

Sup

Study Cup

Epoxide

REDUCTION

OF CARBONYL compoUNDS

Ř

OH (OR) (e)

-

-

-&-oh 1024

☆ H (R) Grignard's reagent

StudySoull

- NaBiL

Ketons

Aldenyde

2

10

Study Soup

o

converts comboxylic acids

to lo alcohols

LiAIHL

Alkanest

Alkenes.

brings it to 1° alwhols

Study

Raney Ni (works on any

kind of

double bond)

Soudy sou

THIOL PREPARATION -SH this group Named by adding this to alkane name

CHz-SH CH3 CH2 CH2 CH2 -SH methane thiol butanethiol

• Thiob are moll audic than alcohols

to because weakce bond in beth s-t cor of s is bigger than o 48 has moll bigger é- cloud for delicatization

Stud

& SYNTHESIS OF THIOLS

Thiols oxidation disulfide

reduction bonds

Sour

Stussy Soup S

Study Soup

Study

SOU

SE

se dySoup

CHAP

D

; loss of 2

up

Oxidation addition of Oor O2 ; X2 ; loss of H2 Reduction - addition of H2 (or H-) ; LOSS OF OXYGEN Neither - add or loss of H+ OH, H2O, HX

Studi

Study Soup

top 33cn

) Study Soup

H2sou

Nazir207 -

R-C-OM

soup

Naou

PCC

30 DONT

Sween/ome/

OXIDIZE

aldehya Ketone

an

I bettee for sensitive

becomes

Stu

and 20

ma

OXIDATION OF ALCOHOLS 1. Na2Cr2O7 2 Ketones.

1 Carboxylic acids 2) m nou in

kalboxylic acids

Aldedyces canboxylic 3) Na ou jo - Carboxylit auds.

Ketones 4) PCC

aldehydes 5) Sween H 20 Ketones 6) DMP Iso 30 cannot be oxidized ALLOHOL AS A NULIDOPHILE

weak nucleophile CROH)

• Al koxides (R-0-) strong nucleophile ALCOHOL AS A ELECTROPHILE

• weak eleemophile

• Protonation of Ho- makes it a good learning group,

can be done on & Substitution and Celimination

using tosylates (good leaving group) Dehydration of Allohals

Stud

Carboxylic

muona

I Rez 25 OH, OR, CY

OV

alcohol by

HOH

ALCOHOL -> AKKYL HALIDES y so

2002

R-ce

Pu2 Zn42

R-OHJ

- isol,

SOU

StudySoap

2) Puridine

R-Br

Bral

e

l

/ HI

R-I

Hor

) Stua, Soup

Stud

ALCOHOL - ETHER * Williamson Ether Synthesis

OOH + Nath Do Not Han You H2C - CH2 - Br o -CH2-C013

NaT

+ NaH

up

Study

Study Sou

auso Ether

StudySoup

peso. R-E-GR

StudySoup

R-o-c-R

& H2O

ALCOHOL ESTER * Fischee Esterification,

R-O-H & H-o-c-R

Aluchal Coubraglic and with acid chloride

R-O-H & a-c-R

Ester

C-c-

R

R

-0-C-R' Estes usou

Acid

Chloride

Alcohol

R H Acid chloride?

R-o-Neon

OsudySoup

Ront=0

0

OH

OH

OH

Study Soup

u

* INORGANIC

Intermediate ESTERS

Nitrate ester R-O-H)

[OH-P-OH

R-O-P-OM R-OH R-O-P-P-R OH Phosphate

ester, REACTION OF ALKOXID ES

Alloxides can be made using Na,K, NaH/THE

Important for Williamson Ether reaction.

R-0-H & Nath – R-ö & Nat +H2 t/

Alwheel

Williamson R-00 + R - C2 - - R-O-CH2 - RJ

Ethee

reaction Alkoxice Swo l' alkye halihe Ether sol

SUSQUE

Study Soup

Studio

SOU

St

CHAP-14

StudySoup

NamING ETHERS

IUPAC 1) The most complex 2) Name the small

3 CH2 Hiz- 82 C- CH2

CH2

alkyl group is the alkane name. group with o as alkoxy (Methoxy, ethoxy etc)

ro-CH2

Stud

Study Soup

Methoxycyclohexane

2-methyl-2-methoxypropane

1,2-epoxy-4-methylbyl cyclohexane

suas

NAMING EPOXIDES 1) detemine the longest chain. 2) Locate expoxy group 3) Arrange alphabetically.

Study Soup

MAKING EROXIDES ETHERS i) williamson Ether synthesis R-OH + NaH - R-6 +R-X Alcohol sinong

Study

R-O-R

Ether

Alxoxide

Alkyl Halide

base

) Sedy Soup

-

C-H

2) Alkoxymercuration - Demuuration reaction

-R NABHY

H.

7

ROH

-H

OR

x=CR & Hg (Ac), usou o Actig

OR

Ether

H

Alkene

Study Soup

REACTIONS OF ETHERS

• Cleavage of Ethers by HBr and HI

©

.

D

H

-Br

R-Bri

- Br

-

Goo + Bro

-

e

7 BY.

.

or + RO Ether

Alcohol

Alkyl

R-Br: +R-O-H. Alkyl halide

The process for phierols stops here!

hande

Soup

studySoup

12

Autoxidation

of Ethers.

SE

내국

CH3

CH3

OOH CH-o-c-CH3 +

CHE

ICH-o- of th3 excess O2

412 41

CH-o-o-c

CH3

CH3

Studio

SOUT

St

THIOETHERS R-S-R 1) syt Synthesized using williamson ethee by using a thiolate

ion as a nice instead of Alkoxide ion. 1. Sulfonium sults as Aly Alkylating agents.

Nuc & CSR

Studium

StudySOU

-

Nuc

-cu

Study Soup

-

& RAC R-C-0-4

C

COU

SYNTHESIS OF REPOXIDES

'c = c + R-d-o-0-H - Alkene peroxyacid

epoxide (MCPBA) * the most é rich double bond reacts of astee to

This is selective epoxiclation. 2) Halolydin cyclization (Inteenal SN 2)

carboxylic

acid form epoxides,

Studyso

OHS

-c-

OM

tix

epoxide.

a

in

polar solwent like

H2O.

Study

X @

Halchydin Base Ablahydrius ale fermed via addition of OPENING OF EPOXIDES 1) Via hydrohalic Acids. H

--- + HX - - -

HX

-

x-u

-X

#: 0

Study Sour

2) Via

ACID

AND BASES

H

H UN CH2 - C-Ć -

H -

CH2 - C - d

oup

Ole

Wy

05

ACID IS CATALYZE

TH3 -C- CH

JOH

4

vazh? te asto

он н

CH2-

c-c-H.

Sour

studySouz

-

OH

CH2-c-c-it

St

2

нон

H oH

The Grignaed and organolithium and attack a

reagents The regring

R to it

attack the least subs

opens up and form OH.

choose a

Studio

САР 15

av Soup

DIENES

Stud

CONJUGATED . one single bond

sepeating the double bonds

ISOLATED & two or more single bonds sepereativy

the double bonds stuar

CoMOLATED . No single bond.

seperating the double & bonds

StudySou

HEAT OR HYDROGENATION

Study Soup

tu

P STABILITY

& HEAT OF

HYDROGENATION

tudySoup

ZATIVE STABILITIES

hast stable

most stable Cumulated, taminal Internal Isoleta

diene

alkyne - Alkyne diene

tolated

diane

. Corrugated < diene

deceases

heat of hydrogenation POSITION

dy Soup

Theem

THE ALLYLIC

Kinetic

c=c

Allyric"

Position

Study Soup

Theino higher Ea

Kinetic lower Ea

THERMODYNAMIC AND KINETIC POSITIONS 1. 1,2 and 1,4 Additions.

+

H- Br

ud Cup

Bi.

no

H

a

(12) mono substituted

double bond 2° callocation

kinetic

ic

(least substituted &

results from most stable carbocation)

Sou

tudySoul

11,4)

disubstituted

double bond 1 carbocation

Theemodynamic

(most substitutos Cand results

furon least. stable cacbocation)

Study Soup

Studio

SOU

SE

StudySoup

A Allylic cations

Stability l ñ 2 carbocation

2 x 3 cacbocation 3° h most stable cacbocation.

Study up

StudySoup

*

ALLY LIC RADICE

Study Soup

RADICALS

> Study Soup

Ravlical stability i<2 <3 <l'allylic IA ALLYLIC BROMINATION

Low amount of Bre In the presence of light (hr)

Needs R-oo-R

Adds Br to the

rather than the

• NBS can be used to connel the amount of Brs

Br

allylic position double bond.

H-Br &

N-By

Bra &

CN-H.

low

concentration

) StudySoup

of Bra prevents the addition of HBr.

access the double bond. SN2 reaction of Allylic nalices are mou stable coz of

the resonance.

tudySoup

• SN2 reactions with organolithium Our selylic holiches and organelithin

of tesonce resonance.

wone stable becaen

Soup

StadySoup

SE

) Study Soup

Studio

CHAP -16

BENZENE

Study Soup

Studium

ANNULENES - hydrocarbous

with

alternating

double and single banels

[4] Annulene

[o Annulene

[8] cyclo

Annulene

AROMACZTY TEST:

dysou

Test

Aromatic

Antiaromatic

Non-Aromatic

Х

3) Planet

Planar

2) Hybridization

sp/sp

sp3

sp2/sp.

Study Soup

UN

4N+2

3) Hikles rule

4) Example

4-4N

6=4N+ 2

L3) Annulene [io ] Annulene

is non aromatic coz Aromatic isomers

of no planar shape are non aromatic, Y & Non alomatic

Study Soup

CYCLOPENTADIENYL

IONS

+ B

-

Ter= AROMATIC

4 π e not SOUP aromatic CYCLOHEPTATRIENZL

udy Soup

FONS

1 Study Soup

& & sp2

HT

H2O

che, spa

-AROMATIC

St

Studio

SOU

SE

CYCLOOCTATETRAENE DI ANION

+ K

+ 2K

O

8 Ten

=4N Alo Anti Aromatic

10 Te - AROMATIC

Study up

Study Soap

HETEROATOMS

) StudySoup

To Get

involved

- 6 Te

oup - 6 Te

- 6 T e

- Spe - AROMATIC

- blue -sp?

-AROMATIC

make it

Aromatic

- sp2 - AROMATIC

- sp2 - AROMATIC

) StudySoup

BASIC OR

NOT?

IN ENTH

N

Not basic

Basic

Not basic

Basic

or the love

pair takes part

in aromanity

DISUBSTITUTED

DIENES

meta

ortho

para

PHENYL

VS

BENZYL

Study Soup

OCH2 {

Sour

sudy Soup

SE

(

Phenye

Beneye

Studys up

Stud

ISSOU

AROMATICO SUBSTITUTION

LCHAP

17

ELEC TROPHILIC STEPI

+

Step 2

[ext basei D E + base

STEP 2

Stup

StudySoup

Study Soup

Argarin

Aicle, ou

77 LHNO3/H THREE WATS TO FORM CARBO ATIBMS

NO 200

Ha

OH

, Bf3 iudy

Clemmensen

Reduction.

.

a

, H2SO4

, HE

lo- ortho m-meta P- para

(12) (1,3) 11,4)

, ALUZ

1.

2ND GROUP

ADDITIONS

) StudySoup

DIRECTING

GROUP

ACTIVATING/ DEACTIVATING

Activating

Deactivation

- NO2

Activating Deactivating

m. o

op!

m

Deactivating Deactivating Deactivating

1

Study Soul

op

lo:

Activating

op

-a:

Study Soup

Deactivating

op

Activating

EXCEPTIONS

NH2

Study Soup

-OH

Activating

- S-OH Deactivating me

During the signa complex (there is a completion of octet at o and

s

adySoup

ome

Activating

PO

Iss op

Stud

SOUT

St

ENERGY DIAGRAMS

RTO

Mz Nor

NO2

NUZ

NO2

VH

POSITION

Sup

Study Soup

СН3

PARA

Studys

loszTION

H NO2

H

No2

H NO2

Study Typ

o

CH3

13° CH3

сна

CH3

ansour

7 Never 30

3) StudySoup

МЕТІЯ

H

+

Noz

I POSITION

NO2

NO2

20

) StudySoup

or tho and mila para y 3 Carbocation but

more stable because there is a chance in mela there is herec a 3 callocation.

NO2

NO2

2 stud

ho ipara

ortho

benene

НЕ

NU

su

YCH

meta

boncen

I the and para

Energy

VOUR

least enefy

StudySoup

Dettet

Activating groups. Stur prefer op because lowee

Cheegy than meta.

Deactivating groeps.

prefer neta z lower energy than

Study Soup

Stud Soup

op

Study Soup

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