Reagent by Kuldeep Sir

REAGENTS CLASS NOTES BY KULDEEP GARG
FOR CSIR NET /GATE/IIT JAM
by-KULDEEP GARG (KD SIR) ASF & UNACADEMY

1
CONTACT DETAIL- kuldeep.npl16a@acsir.res.in
REAGENTS
(LECTURE-1)
Reactant Product
Reagent is an attacking species which can be solvent, catalyst (eg. Wilkinson catalyst),
reactant itself (one group in the reactant can attack on other group within the reactant) or
other formula species, that attacks on the reactant.
Classification of Reagents
1. Reagents which can perform reduction( reducing reagent). (Upto lecture-13)

2. Reagents which can perform oxidation (oxidising reagent).
3. Organometallic catalyst. ( Ye catalyst oxidation, reduction ka kaam to krte hi hain sath m
coupling reaction bhi krte hain eg. Heck reaction)
by-KULDEEP GARG (KD SIR) ASF & UNACADEMY 2
Reduction based reagents ( Reducing Reagents)
Reduction can be done by following ways:
1. Addition of hydrogen
2. Accecpting electron
3. Removal of oxygen
1. Hydrogen donor based reagents

These are of two types:
(i) Hydride ( H- ) donor
Nucleophilic hydride donor : Li+ [AlH4 ]- , Na+[BH4]-
Directly releases H- ions.
Electrophilic hydride donor : AlH3 , BH3
First accepts electrons( acts as Lewis acid ), then releases H- ions.
(ii) H2 molecule donor
Mostly, reagents have tetrahedral geometry.
by-KULDEEP GARG (KD SIR) ASF &

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UNACADEMY
Nucleophilic hydride donor
Derivatives
Li+ [AlH4 ]- Na+[BH4]-
Li+ [AlH (O-tBu)3 ]- Li+[BH4]-
Li+ [AlH (OEt)3 ]- Zn[BH4]2
Na+[BH3 CN]-
NaBH4 . CeCl3 (selective reagent)
M[BHR3] where R can be any bulky group. Such compounds are called as selectrides.
When sodium metal is attached, it is called as N- Selectride.
When potassium metal is attached, it is called as K- Selectride.
When lithium metal is attached, it is called as L- Selectride.
Electrophilic hydride donor
Derivatives
AlH3 : DIBAL-H (derivative of AlH3 )
BH3 : B2H6 , 9BBN

(ii) H2 molecule donor
H2 / Metal / Base
(Pd/Pt/Ni/Cu) (Charcoal/BaSo4 (Rosenmund)/CaCO3 (Lindlar)/PtO2 /
N2H2)
H2 /PtO2 : Adams Catalyst

H2 /N2H2
2. Electron donor based reagents

These are of three types:
(i) Metal dissolving agent ( eg. Birch reduction Na/liq.NH3 , other derivatives are
K/liq.NH3 , Li/ liq.NH3 )
(ii) Na/Xylene ( Acylon condensation), Mg/Xylene, Ti/Xylene (Mcmurry coupling)
The above three reagents are used in radical coupling reaction.
Na/Xylene ,Mg/Xylene are used in Pinacol synthesis.
(iii) Zn/AcOH ( ye electron dene k sath sath bond bhi tod deta h i.e. clevage reduction)
3. Oxygen based/ out reagent
Hydrazine based Thioacetal based
N2H4 – Wolf Kishner Reduction SH-CH2 - CH2 – SH/Raney Ni
(other derivatives : H2N-NH-Ts)

Nucleophilic hydride donor
Li[AlH4 ] M[BH4]
Al-H B-H
According to polarizibility B kam polarize hoga to H pe
Al zyada polarize hoga to H pe kam partial negative charge
zyda partial negative charge generate generate hoga
Hoga
Al-H bond H2O m se H nikal leta h Poor Nucleophile

Poor base
Li[AlH4 ] ko ghulne k liye polar solvent Selectivity high
to chahiye but aprotic hona chahiye For this polar protic solvent can be
taki H na mil jaye. Isliye Li[AlH4 ] ki used
reaction polar aproticesolvent m karai
jati h (eg. THF, OEt2 ).
Hence, Li[AlH4 ] is highly reactive and
strong nucleophile. by-KULDEEP GARG (KD SIR) ASF &
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UNACADEMY
H- comes from polar species so attacks on polar species.
On these substrates, it gives nucleophilic addition reaction.
On these substrates, it gives substitution reaction.

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UNACADEMY
Order of partial positive charge on carbonyl carbon
Li[AlH4 ] will reduce all the above given substrates while Na [BH4] will reduce only
aldehyde and ketone from the above given substrates.
Mechanism for Aldehyde/ Ketone with Li[AlH4 ]

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UNACADEMY
Mechanism for Aldehyde/ Ketone with Na[BH4 ] /EtOH
Oxygen of carbonyl group interact with both polar protic solvent and metal. Hence,
partial positive charge on carbonyl carbon increases.
Use of polar protic solvent is that we don’t addtionally require water at the end of
reaction
Order of +M - effect

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UNACADEMY
Order of polarizibility
Zn2+ > Li+ > Na+
Greater the polarizibility of metal, more electrophilic the carbonyl carbon will be.
Zn[BH4]2 behaves like Li[AlH4 ] but the advantage is that we won’t require to add
water separately and we can carry out this reaction in polar protic solvent.
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UNACADEMY
REAGENTS
(LECTURE- 2)
Question 1:
Jab pehle ester ho ar reaction k baad firse ester bn jaye to iss process ko transesterification
kehte hain
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UNACADEMY
 Now in reactions we will discuss number of hydride ions used , partial reduction,
complete reduction.
Acyl Halide
Number of hydride ions used in partial reduction = 1

Number of hydride ions used in complete reduction = 2
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UNACADEMY
Aldehyde/ Ketone
 Only 1 hydride ion is consumed to do complete reduction of aldehyde and ketone.
 Aldehyde converts into primary alcohol and ketone converts into secondary alcohol.

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UNACADEMY
Ester
 For partial reduction ester requires 1 hydride ion.
 For complete reduction ester requires 2 hydride ions.
 Agar ester me Li+ [AlH4 ]- dala hua hai to reaction kabhi partial reduction pe nhi
rukegi. Hamesha completer reduction krke alcohol hi banega.

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UNACADEMY
Acid
 Li[AlH4 ] H2O ka hydrogen to chhorta ni h to acid ka hydrogen to zarur lega.
 For partial reduction 2 hydride ions are required.
 For complete reduction 3 hydride ions are required.

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UNACADEMY
Amide
 Hydride ions required to convert amide to amine are 2.

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Question 2:
 Agar 5 ya 6 membered ring bn rahi ho to aage ester bnega.

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Question 3:
 Number of hydride ions required in the reaction using Li[AlH4 ] =3

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UNACADEMY
Question 4:

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UNACADEMY
Selectivity
Selectivity are of following types:
1. Chemoselectivity (kon mara gya means reagent kispe jake attack krega like
aldehyde/ ketone/ ester/acid)
2. Regioselectivity (kahan mara gya)
Dono hi case m carbonyl marega ye to pata h but 1,4 attck

hoga ya 1,2 attack hoga , this is regioselectivity
3. Stereoselectivity (kaise mara gya)

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UNACADEMY
Selectivity
Li[AlH4 ] Na[BH4]
1. Li[AlH (O-tBu)3 ]
2. Li[AlH (OEt)3 ] Derivatives Selectrides
Na[BH3 CN] M[BH(s-Bu)3]
(CN- is an EWG, it reduces the M=Na/K/Li
reagent’s reducing power,
increases selectivity )
NaBH(OAc)3
NaBH4 . CeCl3

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UNACADEMY
Li[AlH(O-tBu)3 ]
 It has mono hydrogen.
 O-Al-H Yahan hydride achhe se ion bnke ni nikl paa raha because oxygen
electronegative h to electron density ko apni trf kheechega to hydride ion ko stable
kr raha h isliye hydrogen easily electron leke ni nikl paega. Hence, reducing power of
Li[AlH (O-tBu)3 ] has reduced as compared to Li[AlH4 ]
 Li[AlH (O-tBu)3 ] reduces the above given compounds in the given order.
 Li[AlH (O-tBu)3 ] reduces acyl halide partially to form aldehyde.
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UNACADEMY
 Since Pd being toxic and expensive in Rosenmund reduction, alternatively we use
Li[AlH (O-tBu)3 ]

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UNACADEMY
Question 5:
Question 6:

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UNACADEMY
Li[AlH (OEt)3 ]
 Its is useful in partial reduction of amide and partial reduction of nitrile.
Mechanism:

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Question 7:

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Question 8:

Mechanism of reduction of RCN

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UNACADEMY
Derivatives of Na[BH4]
1. Na[BH3 CN]
 It does the reaction in acidic medium.
 When pH is less than 4, it reduces aldehyde and ketone.

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UNACADEMY
 In normal conditions Na[BH3 CN] converts iminium ion into amine.
 Electronegativity of N+ > O . Therefore, carbon attached with N+ will have higher partial
positive charge than the carbon attached with O.

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UNACADEMY
Question 9:

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UNACADEMY
Question 10:

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UNACADEMY
REAGENTS
(LECTURE-3)
2. NaBH(OAc)3
 It has 1 hydride to give and does selective reduction.
 It is selective for ketone and aldehyde. Agar aldehyde ar ketone m se dekha jaye to sirf
aldehyde ko reduce krega.

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UNACADEMY
Question 11:

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UNACADEMY
3. NaBH4 . CeCl3
 This reagent is selective for ketone over aldehyde.
 In actual, this reagent is NaBH4 . CeCl3 .nH2O CH(OMe)3

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UNACADEMY
 Agar double bond carbonyl group k sath conjugation m h to Na[BH4]/ Li[AlH4 ] carbonyl
k sath double bond ka bhi reduction kr denge.
 Agar double bond carbonyl group se isolated h to Na[BH4]/ Li[AlH4 ] sirf carbonyl group
ka reduction krenge double bond ka ni.

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UNACADEMY
 Above given reaction m agar conjugated double bond ka reduction hone se bachana h
to wo kaam NaBH4 . CeCl3 krta h.

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UNACADEMY
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UNACADEMY
Selectrides
M[BH(s-Bu)3] where M=Na+ /K+ /Li+
 Agar α,β- unsaturated carbonyl compound me β – position pe H hai to selectride attack
krega double bond pe. Ar agar β – position pe H ni hokr koi R group laga h to selectride
attack krega carbonyl carbon pe . This is so because sec- butyl group is bulky and does
not want any type of hinderence.

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UNACADEMY
Mechanism:

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UNACADEMY
Question 12:

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UNACADEMY
Electrophilic hydride donor
9BBN : Derivative of BH3
DIBAL-H (Di isobutyl aluminium hydride) : Derivative of AlH3
BH3
Mechanism:
 Attack of hydride ion on carbonyl carbon depends on how fast oxygen of carbonyl
group donates its electron to BH3
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UNACADEMY
BH3 does BH3 reacts moderately BH3 sabse zyada acid
not react ar amide se react krega
because +M effect ki
wajh O ki l.p. donate
krne ki tendency
increase ho gyi
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UNACADEMY
 Solvents used with BH3 are THF / :SMe2
 BH3 sabse fast acid ar amide pe react krta.

 Following reactions occur in presence of BH3
Amide Amine
Acid Alcohol ( primary)
Ester Alcohol ( primary)
Ketone Alcohol (secondary)

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UNACADEMY
Question 13:
Question 14:

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Question 15:
I and II are position isomers

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UNACADEMY
Question 16:

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UNACADEMY
REAGENTS
(LECTURE-4)
DIBAL-H (Di isobutyl aluminium hydride)
 Bulky group increase krne se selectivity increase hoti h. Ar yahan chemoselectivity

increase hogi.
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UNACADEMY
1. DIBAL-H is best suitable for ester.
 It reduces ester first and then ketone.

 In case of BH3, electrophilicity of BH3 is quite high so it reduces acid and amide fast. But
in case of DIBAL-H, by introducing bulky group , its electrophilicity is reduced. So, it is
best for reducing ester.
 For reducing ketone reagent should have good nucleophilicity.
 DIBAL-H k sath ham kabi H2O solvent ka use ni krte because DIBAL-H , H2O k oxygen se
lone pair leke khud ko deactivate kr lega ar fir reaction ni karega. To ham solvent aisa
choose krenge jispe lone pair na ho , for example, hexane, CH2Cl2 (DCM).
 This reaction is temperature based reaction or temperature controlled reaction.
 DIBAL-H bahot reactive hota h isliye ham reaction ko -78°C pe krwate hain.

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UNACADEMY
Mechanism:

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UNACADEMY
 Agar likh k de k 2 eq. of DIBAL-H to ester se alcohol banaenge otherwise 1 eq. se to
ester se aldehyde hi bnega.
 Ester ki reaction DIBAL-H k sath room temperature pe krwaenge to bhi alcohol banega
because room temperature pe reaction controlled ni rehti. Pr DIBAL-H lagenge 2
equivalent hi.

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UNACADEMY
2. DIBAL-H is best at converting lactone to lactol.
 Hemiacetal ki cyclic for ko hi Lactol kehte hain.

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UNACADEMY
Mechanism of convertion of Lactone to Lactol using DIBAL-H:

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UNACADEMY
3. DIBAL-H does the partial reduction of CN
Mechanism:

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UNACADEMY
Question 17:
 Kahin 5- membered ya 6- membered ring bnti dikh rahi ho to wahan intra molecular
reaction krwa do
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UNACADEMY
Question 18:

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UNACADEMY
4. Reaction of DIBAL-H with α,β – unsaturated ketones
Summary of DIBAL-H:
Ester Aldehyde
Lactone Lactol
R-CN Aldehyde
α,β –usaturated Alcohol
ketone
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UNACADEMY
Question 19: (CSIR-NET)
Ye product inme se kin reagent m se milega?

(I) Li[AlH4 ] (II) Na[BH4] (III) NaBH4 . CeCl3 (IV) DIBAL-H
(a) Only (I) (b) (III) &(IV) (c) (II) & (III) (d)(I) & (II)
Ans: (b)

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Question 20:

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Exception of DIBAL-H ( Just remember it)
Vinylic Ester Alcohol

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UNACADEMY
9- BBN ( 9- Bora Bicyclo Nonane)
 Generally, 9BBN ka use ham ketone / aldehyde k reduction k liye ni krte because rate of
reaction slow hoti h .
 9 BBN ka usually use double pe addtion l liye use hota h as a reduction.

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UNACADEMY
Stereoselectivity of Hydride based reduction
 Always diastereomers because ek carbon ka bond ni todenge , ek hi carbon ka bond

tutega to ek carbon ka configuration same ae ek carbon ka configuration change.
Hence, diastereom ers and selectivity is known as diastereoselctivity. 64
by-KULDEEP GARG (KD SIR) ASF & UNACADEMY
Example:
 The configuration of already present chiral carbon remains same but the configuration
of newly formed chiral carbon is different in both the products formed. Hence, the
products are diastereomers.
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UNACADEMY
Stage -1 (SHORTCUT)
LAS / LSM
(shortcut – I) (shortcut – II)
L= Large group L= Large group
A= Anti-periplaner(wrt carbonyl) S= Syn- periplaner(wrt carbonyl)
S= Small group ki trf se attack M= Medium group ki trf se attack

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UNACADEMY
Example:
 In the above example Ph is the large group and is syn- periplaner to carbonyl. Applying
LSM shortcut, hydride (H- ) will attack from the same stereo as of medium group (here -
CH3) is the medium group. Hence, in major product stereo of –H and -CH3 are same.
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UNACADEMY
Question 21:
Question 22:

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UNACADEMY
REAGENTS
(LECTURE-5)
We will discuss diastereoselectivity in the the following molecules
Acyclic Monocyclic Fused Ring Bridged

molecule Ring Ring
No Hetero Halogen
Hetero atom present
atom present on the
on on the adjacent
adjacent adjacent carbon
carbon carbon (Dipolar
(Falkin (Chelate/ Model)
Ahn Non-Chelate
Model) Model) by-KULDEEP GARG (KD SIR) ASF &
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UNACADEMY
Acyclic Molecule
1. When no hetero atom is present on the adjacent carbon (Falkin Ahn Model)
 Now conceptually we will understand this via Falkin Anh Model.

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UNACADEMY
Falkin Ahn Model
 It comes from MOT.
 First draw the molecule in Newman’s projection.

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UNACADEMY
 Now attack of nucleophile will be from the small group side and at an angle of 107°
from the carbonyl. This is so because according to MOT empty π* orbital of carbonyl
forms 107° angle with carbonyl bond due to s & p character. This angle is known as
Burgi –Dunitz angle .

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UNACADEMY
 Now we have to convert obtained product from Newman’s projection to Sawhorse
projection
Ab according to question jo b groups on the plane pe hain unko horizontal line pe line
pe lana h

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UNACADEMY
 Jis view se molecule ko pehle dekh rahe the waise hi dekhenge. Iss view se R group left
me dikh raha tha to abi bhi Newman se Fisher me convert krne k liye R group ko left me
rakha hai. Ph pe right pehle center wale line se right side tha to abhi bhi right side rakha
hai. Jo above the palne hai unko above the palne lagao ar jo below the lane hain unko
below the plane lagao.

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UNACADEMY
Complexity in the above explained same example due to stereo

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UNACADEMY
 Uper wale example originally hamre pass nucleophile ke attack krwane ka correct
orientation ni hain. Carbonyl se 107° angle pe ethyl group hain ar small group 60° angle
pe hain jo ki nucleouphlie ke attack ke liye correct orientation ni hain.
 Isliye ham peeche wale carbon ko single bond ke around aise rotate krenge ke jisse Ph
group to carbonyl ke perpendicular hi rahe but small group 107° pe aajaye carbonyl se.
Aisa krne ke liye hamko 180° pe single bond ke arorund rotate krna pada. Tab nucleophile
ke attack krne ka correct orientation bna.

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UNACADEMY
Example:
 Ab iss uper wale example me small group to 107° pr hain but Ph group ( large group )
perpendicular ni hai carbonyl se. To ye bhi nucleophile ke attack krne ki correct
orientation ni hai. Isliye ham peeche wale carbon ko left side me 60° pe single bond ke
around rotate krenge tab correct orientation
by-KULDEEP aaega.
GARG (KD SIR) ASF &
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UNACADEMY
Example:
 Idher ham LSM lagaenge. Large group (-Ph) syn hai carbonyl ke to medium group ( -Et
group ) ki side se nucleophile (-R group) attack krega. To -R group above the palne
aaega ar fir –OH below the plane ho jaega.

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UNACADEMY
Example:
 Jab hame large above the plane mil jaye to large group rotate krke on the plane le
aaenge ar fir shortcut laga denge.
 Idher ham LAS lagaenge . Large group(-Ph) is anti to the carbonyl group to nucleophile
small group ki side se attack krega. Isliye hydride will be below the plane and –OH will
be above the plane.
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UNACADEMY
Question 22:
Which of the following products is major?
Ans: Product (A)

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UNACADEMY
2. When hetero atom is present on the adjacent carbon (Chelate or Non-Chelate Model)
 Hetero atom attached to the α- carbon may be O/N/P/S
 Agar aisi condition ho to kuchh metals k sath chelate model lgta h ar kuchh metals k
sath non-chelate model lagta h .

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UNACADEMY
Metals for Chelate Model (Case-I) Metals for Non-Chelate Model (Case-II)
Mg+2 Li
Mn+2 Na
Zn+2 K
Cu+2 Cs
Ti+4
Ce+3
Al+3
Trick: Manglo Mnzn Cuti Ce

Note:
Li reducing reagent ar organometallic reagent m non-chelating model dega. Pr kuchh
reagents k sath ye chelating model dega.

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UNACADEMY
Case-I (Chelate model)
L P S S
Lone Pair Sabse Saste
Lone Pair Syn h to Small group ki trf se attack hoga
Case-II ( Non-Chelate model)

L P S M
Lone Pair Sabse Mehenge
Lone Pair Syn h to Medium group ki trf se attack hoga
OR
L P A S
Lone Pair Anti h to Small group ki trf se attack hoga

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UNACADEMY
Question 23:

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UNACADEMY
Question 24:

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UNACADEMY
REAGENTS
(LECTURE-6)
Question 25:
What will be the major product for the given reagents?

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UNACADEMY
LiBH4 ZnBH4
(a) I I
(b) II II
(c) I II
(d) II I
Ans: (c)
Note:
Agar reagent m do metal hain ar usme se ek chelating h ar ek non chelating to ham
chelating ko priority denge ar question solve chelating ko consider krke karenge.
Example: LiAlH4 me Li non-chelating metal h ar Al chelating metal to LiAlH4 chelating ki
trh behave krega

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UNACADEMY
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UNACADEMY
Chelate Model

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UNACADEMY
Non-Chelate Model
 Here hydride is from LiBH4

 Ham yahan R group ko rotate krke left m le gye right m ni because jab ham question m
diye hue product se match krte hain to R wahan left side m h.

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UNACADEMY
Question 26:
What will be the major product for the given reagents?
Ans: For EtLi (II) and for EtMgBr (I)

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UNACADEMY
Question 27: (Homework)
Ans: Iss question m Ce+3 ki wajh se chelate model lagega
 Chelate model m pehle 5-membered ring bn rahi thi pr iss example m 6-membered ring
bn rahi h to ar bhi achha h.
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UNACADEMY
Question 28: (Homework)
Ans: Yahan chelate model lagega because of Zn+2

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UNACADEMY
REAGENTS
(LECTURE-7)
Stereochemistry in Ring compounds
1. Bridge compounds

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UNACADEMY
 Such rings have two faces: Exo face and Endo face.
 Nucleophile wahan se attack krega jahan less hinderence ho. Abi iss above given ring m
exo face less hindered h to nucleophile attack exo face se krega.
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UNACADEMY
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UNACADEMY
 Ab yahan exo face pe methyl group ki wajah se hinderence create ho gyi to ab
nucleophile exo face se attack ni karega ar endo face se attack krega.
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UNACADEMY
Question 29: (JAM)
Note:
MCPBA : forms epoxy group
OsO4 : forms syn- diol
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UNACADEMY
 Jidher ki trf se MCPBA attack krega ussi side epoxy group lagega. Ar jidher ki trf se OsO4
attack krega ussi side –OH group lagenge.

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UNACADEMY
2. Fused ring compounds
Cis :
 These rings have two faces : Convex face and Concave face.
 Attack of nucleophile will be from covex face in such ring. In other words attack of
nucleophile will be from same side as of these H untill and unless t-Bu jaisa bulky group na
aaye .
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UNACADEMY
Example:

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UNACADEMY
Question 30:

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UNACADEMY
Question 31: (GATE)
 Iss question me NaBH4 . CeCl3 aldehyde pe attack krega ya ketone pe krega ya double
bond pe krega, ye h chemoselectivity.

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UNACADEMY
Question 32: (Clayden)
Question 33:

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Question 34:
Question 35:

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UNACADEMY
 LDA : bulky base which abstracts less hindered acidic hydrogen.
 Enolate form is more stable than ketone form because oxygen more electronegative h
to negative charge ko sustain kr skta h.
6-Membered Fused Ring (DECALINE)

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UNACADEMY
Trans :
 Ab iss case m nucleophile kahan se attack krega uske liye cyclohexane ki stability wala
concept laga do (bulky group on the equitorial side).
Ham product ko dekh k bataenge k which one is more stable. Agar nucleophile bulky h
to nuleophile ko equitorial se laenge ar agar –OH bulky h –OH ko equitorial pe rakh
denge.
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UNACADEMY
Example:
 Ab trans decaline ka uper wala face alag h ar neeche wala face alag h. Uper wale face se
-CH3 ka repulsion zyada h ar neeche wale se -CH3 ka repulsion kam h. To ab attack
chhote wale group ki side se hoga. H- jo aaega wo below the plane H ki trf se aaega. Ab
ya product ki stability matter ni krti, yahan –OH above the plane jaega.
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UNACADEMY
3. Monocyclic compounds
 Nucleophile carbonyl se 107° k angle attack krega.
 Nucleophile neeche se attack krega to neeche wale H k sath eclipsed form m aajaega ar
torsional stain generate hoga. Agar nucleophile uper se attack krega to 1,3 diaxial
interaction hoga.
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UNACADEMY
 Agar ring pe hydrogen lage hain to uss case m ye dono strain equal hote hain.
 Ab nucleophile to dono trf se fas gya to iss case m nucleophile ka attack product pe
depend ho jaega. Agar nucleophile bulky h to nuleophile ko equitorial se laenge ar agar
–OH bulky h –OH ko equitorial pe rakh denge.
Example:
 Iss case m hydride chhota h to ar –OH bda h to ham –OH ko equitorial pe rakhna pasand
krenge. Isliye hydride ko axial side se attack kraenge taki OH equitorial pe aa jaye.
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UNACADEMY
Example:
 Iss case m nucleophile bulky h ar –OH chhota h to yahan nucleophile equitorial side se
attack krega ar –OH fir axialpe jaega.
Note:
 Till Lec-7 reduction vio hydride donar has been completed from next lecture reduction
via hydrogen (H2 ) donar will begin.
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UNACADEMY
REAGENTS
(LECTURE-8)
Difference between hydride donar and hydrogen (H2 )donar
 In reduction via hydride donar one hydrogen comes from the reducing reagent and the
other hydrogen comes from the solvent.
 In reduction via hydrogen donar, solvent ka koi role ni hoga H2 seeda donate hoga. Dono
hydrogen reagent se hi jaenge.
H2
R-CHO
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UNACADEMY
H2 – based Reagents
H2 (gas) Diimide
H2 being in gaseous H-N=N-H
form is not easy to This is easy to handle
handle. in comparison to H2
Isme dono hydrogen Isme dono hydrogen

ek hi jagh se aaenge alag alag jagh se aaenge

114
UNACADEMY
H2 – Donar
 Iske sath problem ye h k ye hota h vapour phase m to isko sabse pehle ki surface pe
adsorb karana padega. Isliye isse metal surface pe adsorb karaya jata h .
 H2 metal pe adsorb hone k baad substrate se react krti h ar iss reaction k baad hame
metal wapis mil jaati h. Hence, metals in this reaction are catalyst and this reaction is
called catalytic hydrogenation.
 Metals used as catalyst are: Rh, Ru, Pd, Pt, Ni, Ir. (Trick : Rah me rukawat padti hai
patni se )
These metals are expensive. We use the powdered form of these metals ar iss powder
ko b kisi ar metal base pe chipkaya jata h.
The metal base can be activated carbon( called as charcoal),CaCO3 , BaSO4 , Al2O3
 Reagent wala part hmko solid phase m milta h ar jispe reaction krwate hain ham
(subtrate) wo hame liquid phase m milta h. Agar phase alag alag hote hain to aise hi
catalytic reduction ko ham Heterogeneous catalytic reduction.

115
UNACADEMY
H2 – Donar
H2 – Heterogeneous H2 – Homogeneous
H2 / Pd / C Iss case m metal pehle complex
Pt BaSO4 banata h ar complex bna k wo
Rh CaCO3 solution form(liquid phase)
Ni Al2O3 m aa jata h.
Ru Eg: Wilkinson catalyst
Ir Ab jisse reaction krwana h wo b
Iss case m metal ya to powdered liquid phase m h ar hamara
form m use hota ar agar iss m reagent bhi liquid phase m aa
dikkat aati h to metal oxide k form gya h. Hence, homogeneous
m use hota h. Eg: PtO2 catalysis.

116
UNACADEMY
 Metal oxide jab ham use krte hain for heterogeneous catalysis to usme hame base lene
ki zarurat ni padti
Eg: PtO2 / H2 : Adams’ Catalyst
Heterogeneous Catalyst
Oxide based catalyst : PtO2 / H2 : Adams’ Catalyst
Metal based catalyst : H2 / Pd/ C : Sbse sasta to ye wala catalyst h but iski selectivity weak
h.
 To selectivity strong krne k liye ya to metal change kr do ya base change kr do.
Eg: H2 / Pd/ CaCO3 : Lindlar’s Catalyst
H2 / Pd/ BaSO4 : Rosenmund Catalyst
H2 / Rh/ Al2O3 : Thermoplastic H2 donar catalyst ( ye reaction high temp pe
karai ja skti h )

117
UNACADEMY
Note :
Kisi bhi catalyst ke bare me kya kya janna hai wo points me neeche diya hai
1. Introduction ( jo uper ki slide me diya hua hai)
2. Mechanism
3. Chemoselectivity ( means molecule me agar double bond hai ya ketone hai ya triple
bond hai ya aldehyde hai ya acida hai ya NO2 hai ya cyanide ai , ye sab present hain to
inme se sabse pehle react kispe karega catalyst, this is called chemoselectivity. Agar kisi
molecule me do double bond hain ar dono alag alag type ke hain means koi extra
substituted hai koi less substituted hain to kis double bond ka reduction hoga, ye bhi
chemoselectivity hai ).
4. Stereoselectivity ( means product kya banenge?, cis banenge ya trans banenge,
selectivity kya hogi , racemic mixture banege )
5. Controlled reation ( alkyne ke reduction se suppose alkane ban raha hai pr hame alkane
ni chahiye ar alkene tak hi reaction rokni hai, to ye reaction controlled reaction hogi)
6. Hydrogenolysis (kabi kabi hydrogenation na hoke hydrogenolysis ho jata hai.
Hydrogenolysis me C aur O ka bond tut jata
by-KULDEEP GARG hai ar ASF
(KD SIR) dono
& trf H jud jata hai)
118
UNACADEMY
Mechanism of Heterogeneous Catalyst:
 Ham pure metal ni lete because C-metal bond bahot strong bn jaega to fir
hydrogenation ni ho paega.
 Jab alkene detach hota h metal surface se to sath m H ko leke jata h jisse hydrogenation
hota h.

119
UNACADEMY
Isomerism of alkene using heterogeneous catalyst
 Ye jo red box m jo H hai wo already substrate m tha ar kabi kabi metal iss H ko le leta h
ar fir isomerism of alkene takes place.

120
UNACADEMY
H2 / Pd/ C
Chemoselectivity:
Reactivity order:
Sabse pehle 3 means 2 means 3 means

ye reduce tripple bond double bond tripple bond
Hoga between between between
two carbon two carbon C and N
121
UNACADEMY
Example:
 H2 / Pd/ C ke case me reaction controlled ho ni pati isliye reaction (I) ko krwane k liye
ham use krte hain Rosenmund catalyst.
 H2 / Pd/ C k case m uncontrolled reaction hi hoti h i.e. (II)

122
UNACADEMY
Question 36:

123
UNACADEMY
Question 37:

124
UNACADEMY
Question 38:

125
UNACADEMY
Question 39:

126
UNACADEMY
Stereoselectivity:
 Agar double bond ek se zyada hain to less substituted pe pehle attack hoga ar syn-
product milega.
 Cis- alkene pr agar syn-hydrogenation hoga to meso compound milega.

127
UNACADEMY
Shortcut :
C A R T S R
Cis Anti Racemic Trans Syn Racemic
 Iss shortcut se product banae k liye koi do ko different krenge ar ek ko same rakhenge
128
UNACADEMY
REAGENTS
(LECTURE-9)
Example:

129
UNACADEMY
Cis  D2 syn addition We get optical inactive products from them
Trans  D2 syn addition ( enantiomeric excess =0)
 Meso compound ki enantiomeric excess=0 due to internal compansation.

 Racemic mixture ki enantiomeric excess=0 due to external compansation.
 Racemic mixture ko racemization k through compound ko separate krke optically active
banaya ja skta h but aise meso compund m possible ni h .
Note:
 Agar fischer form m longest carbon chain ko vertically rakh k, do same groups jinko ham
add kr rahe hain wo same side aa jaye to compound ko Erythro bolenge ar do same
groups jinko ham add kr rahe hain wo different side pe aa jayen to uss compound ko
Threo bolenge.
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UNACADEMY
 Erythro and Threo are always optically active.
Shortcut :
Z S E Z A T
Z-alkene Syn Erythro Anti Threo
E S T E A E
E-alkene Syn Threo Anti Erythro
131
UNACADEMY
132
UNACADEMY
Cyclic Molecules
 H2 will attack from the less hindered side. Here, -CH3 group is above the plane so the
less hindered side will be below the plane. H2 will attack from below the plane.
 Cyclic compounds will be
(i) Bridge cyclic
(ii) Fused cyclic
(iii) Monocyclic
133
UNACADEMY
Bridged Molecules
 Here, attack from above side due to less hinderence. From lower side attack can not be
done because cavity is more hindered.

134
UNACADEMY
 Since upper side has been bloked by –CH3 group, so , attack will be from lower side.

135
UNACADEMY
Question 40:

136
UNACADEMY
Question 41:
 Agar 1 eq. ni diya hoga to excess m consider krenge H2 /Pd/ C ko ar dono alkene ka
reduction hoga fir.
Priority order of reduction of alkene:
Mono substituted > di substituted > tri substituted > tetra substituted
137
UNACADEMY
Question 42:
Question 43:

138
UNACADEMY
Question 44:
 Agar fused ring carbon k adjacent carbon pe koi polar group(-OH/-NH2/-OR/-NR2 )aa jata
h to metal usse attach ho jata h ar adduct bna leta h. Isliye H ka attack polar group ki
stereo ki side se hota h.
 Agar do polar group lage hain ar dono ki stereo different h to attack krte time dekhenge k
kon zyada polar h ar kiski side se less hinderence h.
139
UNACADEMY
Monocyclic Molecules
 Exo double bond pe pehle attack hota h as compared to endo.
Question 45:

140
UNACADEMY
Question 46:
Question 47:

141
UNACADEMY
Selective Catalytic Reduction
1. Lindlar Catalyst
 H2 / Pd/ CaCO3 + Pb(OAc)2
BaCO3 (poison)
Poison grts attached to the metal. Because of this metal can not bind to as many
hydrogen as it used to. Therefore, due to less hydrogen metal becomes selective to
donate hydrogen.
Jab tak alkyne h to metal alkene ko H ni dega.
 Alkene ko H dene k liye metal ko ek particular orientation m aana hoga because uske
pass 1 hi p-orbital empty h whereas alkyne has 2 empty p-orbitals so metal can easily
donate H in any orientation.
That is why metal selectively reduce alkyne.
 Formation of Z-alkene takes place.

142
UNACADEMY
Alkene Alkyne
Yahan 1 p-orbital khali h to metal Yahan 2 p-orbitl khali hain to metal
ko H dene k liye ek particular kii b orientaion m aaega fir b alkyne
orientation m aana hoga. Isliye metal ko tehelte hue H de jaega kyun k kisi
ko alkyne k comparsion m alkene ko orientation m metal aaega to usse
H dena difficult h. Khali p-orbital milenge.

143
UNACADEMY
REAGENTS
(LECTURE-10)
 Aisa ni h k Lindlar Catalyst alkene ko ni kr sakta reduce but alkyne k samne alkene ko ni
krta.

144
UNACADEMY
Question 48:
Question 49: (JAM 2019)

Which the following will remain optically active?
(a) Only 1 (b)Only 2 (c) Both (d)None of these

145
UNACADEMY
Ans: (a)

146
UNACADEMY
Question 50:
Note:
 Sometimes in question directly Lindlar Catalyst is not mentioned instead 1eq. H2 /Pd/ C
is written , which also means we have to form product according to Lindlar Catalyst.

147
UNACADEMY
Question 51:
Priority order of reduction of alkene by Lindlar Catalyst or 1 eq. H2 /Pd/ C :

Mono substituted > di substituted > tri substituted > tetra substituted

148
UNACADEMY
Question 52:
Question 53:

149
UNACADEMY
Difference between Wilkinson catalyst and Lindlar Catalyst
Jab kaam dono ek jaisa k rahe hain to difference kya h dono m?
Difference dono m ye h k Wilkinson Catalyst to homogeneous catalyst h ar Lindlar
Catalyst heterogeneous catalyst h.
Note:
 Agar cis alkene ar trans alkene dono present hain to sabse pehle reduction cis alkene ka
hoga.

150
UNACADEMY
Heterogenous Catalyst
Hydrogenation Hyrogenolysis
Isme π- bond ki breaking hoti h Isme σ-bond breaking hoti h
C=O C-O R-X R-H + X-H
H H C-O C-H + O-H
C=C C-C
HH

151
UNACADEMY
Order of reduction using particular metal
Pt (Adams’ catalyst) : C=O > C=C > Hydrogenolysis > Aromatic
Pd : C=C > Hydrogenolysis > C=O
Rh : C=O > C=C > Aromatic
Raney Ni : C-S > Aromatic (at high temperature)
Hyrogenolysis
 For hydrogenolysis compound m Benzyl group ar Propargyl group zarur hona chahiye.
where X = -OH, -OR, -NH2 , -NR2 , -NHR, -SH, -SR.

152
UNACADEMY
 Benzene ka electron cloud metal se bind ho jata h. That is why σ-bond breaks.
Note:
 Ham mostly har jagh hydrogenolysis m Pd ka use isliye kr rahe hain because
hydrogenolusis krne k liye Pd ka sabse rate fast h.
153
UNACADEMY
Question 54:
Question 55:

154
UNACADEMY
Question 56:
Question 57:

155
UNACADEMY
Example:
 Carbamic acid is quite unstable and easily removes CO2

156
UNACADEMY
 -CBz group is h used to protect -NH2 group while the reaction of amino acid.

157
UNACADEMY
Note:
 Reagent A ek aisa reagent h jo teeno groups se react kr skta h i.e. -NH2 , -COOH , -X pe
hamko chahiye k wo sirf group X se hi react kre . Isliye ham -NH2 ar -COOH ko mask kr
dene CBz and Bn se. Uske liye ham following reaction follow krenge.
Y= reagent A se reaction k baad X convert ho gya Y me.

158
UNACADEMY
REAGENTS
(LECTURE-11)
Homogeneous Catalyst
 Ham wo homogeneous catalyst padh rhe hain jo hydrogen tranfer k kaam aate hain.
(i) Wilkinson Catalyst. [Rh (PPh3)3Cl]
(ii) Crabtree Catalyst. [Ir(COD)P(Cy)3 Py] PF6

159
UNACADEMY
 Hetrogeneous catalysis me metal jispe H chipka rahe the wo solid phase m tha ar
compound hamara tha liquid phase me to dono phase alag alag hone ki wajh se rate of
reaction tha wo bahot zyada slow tha.
 Homogeneous catalysis me jo catalyst hota h wo soluble hota h to catalyst bhi same
phase m ar reaction bhi same phase m. Isliye rate of reaction fast hoti h. Hence,
hoogeneous catalyst are better than heterogeneous catalyst.
Homogeneous Catalyst Heterogeneous Catalyst
(H2 /Pd/ C )
(i) Syn addition hydrogen (i) Both syn and trans addition of H
(ii) No hydrogenolysis ( sirf ek hi jag (ii) Yahan har jah hi mil ja raha tha
hydrogenolysis hota h jahan weak hydrogenolysis
conjugation hota h )
(iii) NO2 ko NO2 m hi rehne deta h (iii) Ye NO2 ko NH2 m convert kr deta h
(iv) Selectivity high h ( stereoselectivity (iv) Selectivity low hai.
bhi high hai)
(v) Less catalyst required (v) More catalyst required.
160
UNACADEMY
Homogeneous Catalyst
 Catalyst kaam krta rehta pr uski activity h wo dheere dheere waek hoti rehti h ar ek
time aisa hota h jab catalyst kaam ni krta to usko side hata dete hain.
To agar ham ek catalyst daalen to ye catalyst kitne compound ko ya kitne baar reaction
cyclic m ghum skta h. Isse turn over number( TON) kehte hain.
 Jiss catalyst ka turn over number jitna zyada hota h, uss catalyst ko utna achha mana
jata hai.
NOTE:
Ek hota h enzyme ka TON ar TOF( Turn over frequrncy) and ye kinetics based hote hain .
Ek hota h catalyst ka TON ar TOF pr ye kinetics based ni hoti.
Turn Over Number

Turn over frequency = = Ek minute m aapko kitna product
Time mil raha hain wo hota h TOF
161
UNACADEMY
Example:
Works on isolated double bond Works on conjugated double bond

selectively
Example:

162
UNACADEMY
Wilkinson Catalyst Crabtree Catalyst
(i) Syn addition on alkene (i) Syn addition on alkene
(ii) Inn alkene ke liye wilkinson (ii) Inn alkene k liye crabtree
catalyst best hai . catalyst best hai..

163
UNACADEMY
Wilkinson Catalyst Crabtree Catalyst
(iii) Iss catalyst m pehle H2 ka addition (iii) Crabtree catalyst me sabse pehla step
hota h to catalyst pehle se ar b zyada hota h reductive elimination, COD
bulky bn jata h (Wilkinson catalyst group leave krke chala jata h. Jiski wajh
pehle hi kafi bulky hota h) to wo ye catalyst chhota ho jata h. To ye
chahta h k aisi alkene se judun jo hindered alkene se b jud skta h .
less hindered ho. Ye catalyst pehle alkene se judta h fir H
hydrogen se judta h.

164
UNACADEMY
Question 58:
 Ye reaction crabtree catalyst ar wilkinson catalyst dono ki presence m ho skti h but

wilkinson k case m slow hogi ar crabtree k case m fast hogi. Ham wilkinson ko isliye bhi
lete hain kyun k wilkinson catalyst sasta hota h crabtree catalyst se.

165
UNACADEMY
Order of rate of reaction using Wilkinson catalyst
Question 59:

166
UNACADEMY
Note:
 In question 59 we used already discussed shortcuts for syn addition i.e. CSM, TSR, CAR,
TAM.
Question 60:

167
UNACADEMY
Stereoselective nature of Wilkinson catalyst and Crabtree catalyst
 Dono Wilkinson catalyst and Crabtree catalyst bahot hi stereoselctive hain.
 H wahan se attack krega jis side polar group hoga because metal polar group k sath bond
banata h ar reactivity ko fast krta h.
Question 61:
Which will be the major product formed in the following reaction ?

168
UNACADEMY
(a) (i) (b) (ii) (c) Both (d) None of these
Ans: (b)
Note:
 Reactivity m exo alkene ko priority di jaegi than endo alkene. Aisa ni h endo pe attack ni
krega pr jab dono alkene hongi to pehle exo pe attack krega Wilkinson catalyst.
Decarbonylation of Aldehyde by Wilkinson catalyst

169
UNACADEMY
 Ye double bond conjugation m hai to isko to Wilkinson catalyst reduce krega ni.
 Decarbonylation ke baad Wilkinson catalyst catalyst ni rehta , reagent bn jata hai kyun
conjugated double bond ka to kuchh kr ni skta ye to ye apna ek PPh3 ko tod deta h ar
apne sath carbonyl >C=O ko laga leta h ar catalyst ko khatam kr deta.
 Ham Wilkinson catalyst se ko decarbonylation k liye isliye use ni krte because ham bina
baat itna mehenga Rh catalyst decarbonylation m waste krna pasand ni krte.

170
UNACADEMY
REAGENTS
(LECTURE-12)
Electron donar based Reagents

 Electron dene ki kabiliyat metal m hoti hai.
 Agar hamko metal se electron lena hain to metal aisa hona chahiye jo solvent me jake
easily dissolve ho jaye. To electron dene me sirf metal ka role ni hota solvent ka bhi hota
hai.
 Metal ko electron dene k liye apna electron kisi k pass reserve krke bhi rkhna hota h ar
khud ko stablize bhi krna hota hain . To metal k liye ye kaam solvent krta hai.
 Solvent ka kaam badh gya,ek to usse metal ka electron reserve rakhna h ar metal k sath
bond bna k usko apne phase m rakhna hai. Issi k basis pe iss trh k reduction ko kehte hain
dissolving metal reduction.

171
UNACADEMY
Metals ( jo electron transfer ka kam krenge)
Alkali metals Li/Na/K
Alkaline Earth metals Ca/ Mg
Some transition metal Zn/Ti (ye hamne experimentally dekha
tha k kon kon se TM hain)
Only 1 p-block metal Al
Note:
F-block metals ni lete because size bahot bada ho jata h ar wo easily dissolve ni hote.
Ham metals hi wo lenge yahan jo easily dissolve ho jaye.
Solvents
 Solvents are of two types:
(i) Protic Solvent : NH3 , H2O, HCl, EtOH
(ii) Aprotic Solvent: Xylene
172
UNACADEMY
Combinations of Metals and Solvent
Na/ liq. NH3 Na/Xylene Zn/HCl
K/ liq. NH3 Mg/Xylene Zn-Hg/ HCl
Li/ liq. NH3 Al/Xylene
Ti/Xylene
Ti hamesha ion form m paya jata hai( TiCl3 ki form m) mtlb
electron pehle diye baitha hai. To iske pass wapis electron aane
k liye Na ko isle sath liya jata hai.
To actually ye TiCl3 + K / Xylene hota hai.
Note:
Metals jaise Mg, Al bahot reactive hain. Ek baar m 1 se zyada electron de dete hain pr
chahiye 1 hi electron , to inki reactivity ko block krne k liye inke sath amalgum banaya
jata h. To exam aise bhi likha aa sakta h : Mg-Hg/Xylene , Al-Hg/Xylene
173
UNACADEMY
Na/K/Li /liq. NH3 (BIRCH REDUCTION)
It does the reduction of
Aromatic Heterocyclic Conjugated Enone Alkyne

Ring Ring Diene
Inke derivative
(EWG/EDG)ka
bhi reduction
karega
174
UNACADEMY
Pinacol –Pinacolone Rearrangement
Na/Xylene
K/Xylene + Ketone/ Aldehyde Pinacol
Mg/Xylene
Al/Xylene

175
UNACADEMY
Acyloin Condensation
Na/Xylene
Ester Acyloin
(α-hydroxy ketone)

176
UNACADEMY
McMurry Coupling

177
UNACADEMY
Oxygen/ Halogen removal based Reagents
 Iss reduction ko krne k liye ham Zn lete hain ya kuchh case m Birch reduction bhi yahi
kaam krta h. To ye group removal ka kaam krte hain pr group α- pisotion pe laga hona
chahiye.

178
UNACADEMY
BIRCH REDUCTION
Metal/ Solvent => Solvent kisi bhi reaction k liye hand to hand ready kiya jata h
Na/ liq. NH3 Jab tak iska colour blue hai means ham reaction k liye ready hain
Agar iska blue colour

disappear ho jata h
mtlb iss solution ko bne
kafi time ho gya h.
179
UNACADEMY
 Na ko jab ham NH3 me dissolve krte hain to ye apne ek electron ko NH3 k beech rakh
deta hain. Isse hota ye hai k NH3 ka jo H+ hai wo iss electron ko stabilize krta hai. Ar ye
stabilize krta h -33°C pe krta hai.
 Agar ye temperature thoda zyada ho jaye to iss electron ko NH2 le jaega ar NH2- bna ke
apne m se H2 nikal dega . Ar fir ye reaction electron transfer na reh k hydride transfer bn
jaegi.
NH2- + ½ H2
Iss NH2- bnne ki wajh se blue colour disappear ho jata h. Isliye ham freshly prepared
solvent lete hain.
 Hamko iss solvent (liq. NH3 ) ke sath m co-solvent lena padta hai because liq. NH3 to
electron deke aa jata h to ab negative charge generate ho gya reactant pe, to cosolvent
ka kaam hota h reactant ko H+ deke negative charge balance krta hai.
 Kahin kahin ye co-solvent na leke alkyl group le lete hain taki wo negative ko balance kr
ske.

180
UNACADEMY
Birch Reduction on Aromatic Ring
Mechanism:

181
UNACADEMY
Substituted Benzene:
 First condition ki bhi do condition bn skti hain

182
UNACADEMY
 Alkylation wale case me (A) wala zyada stable hota h to wahi major product deta h. Pr
last m birch reaction tak (A) and (B) dono se same product aaenge pr birch reduction k
baad jo aap karaoge to product change ho skte hain wo major ar minor me change ho
skte hain.
183
UNACADEMY
Shortcut:
W D D P
W = Electron Withdrawing Group D = Electron Donating Group
D = Double bond DoorDoor P = Double bond Pass Pass

184
UNACADEMY
Mechanism:

185
UNACADEMY
Summary
EDG = -OH/ -OMe/ -C / -NHR/ -SH/ - PR2 /-CH3 / -Et/ -t-Bu

EWG = -COOH/ - CONR2 / - CONH2

186
UNACADEMY
Note:
 -CHO (Aldehyde) ar -COOR(Ester) me special dhyan rakhna hota h. Dikhne m to EWG
jain but jaise hi ye metal k electron ko dekhte hain to aromatic ring se pehle khud
electron leke baith jate hain ar dono hi –CH2O- ban jate hain
 Ab ye –CH2O- electron donating group bn gya to birch reduction ab EDG ke according

hoga. Hence, we will consider that -CHO (Aldehyde) ar -COOR(Ester) will act as EDG.
187
UNACADEMY
Example:

188
UNACADEMY
Question 62:
What will be the product formed in the following reaction?
Ans: (c)
-OCH3 and -CH3 are EDG to dono ko double bond pass chahiye.

189
UNACADEMY
Question 63:
Ans: (c)
-OCH3 and -CH3 are EDG to dono ko double bond pass chahiye.
190
UNACADEMY
Question 64:
Ans:

191
UNACADEMY
Question 65:
Ans: (c)
-OCH3 EDG hai to double bond iske pass hoga ar –COOH EWG hai to double bond isse
dur hoga.

192
UNACADEMY
Question 66:
Ans: (a)
-OCH3 EDG hai to double bond iske pass hoga ar –COOH EWG hai to double bond isse
dur hoga.
193
UNACADEMY
Question 67:
Ans: (a)
Yahan product jo banega wo EWG ke hisab se bnega. EDG khush ho na ho EWG zarur
khush rehna chahiye. Because EWG ki wajh se charge stabilization ka zyada frk padta hai
rather than EDG ki wajh se destabilization ka. (reason GOC se aata h )
194
UNACADEMY
Question 68:
Ans:

195
UNACADEMY
Question 69:
More substituted alkene bn jaegi.

Question 70:
Dono ring ka reduction ho jaega ar more substituted alkene bn jaegi.

196
UNACADEMY
Question 71:
Ans: Yahan metal apna electron uss ring ko dega jiske pass electron deficiency hai. Jiske
pass already EDG wahan to electron khud hi zyada honge to metala wahan apna
electron ni dega. Hence, electron deficient ring ka reduction hoga. (iska explaination
MOT se atta h )

197
UNACADEMY
REAGENTS
(LECTURE-13)
Naphthalene and its derivatives

Question 72:
Agar hmko ek ring ka reduction karan h to which among the following is best possible?
Ans: (c)
Because atleast ek ring m to aromaticity reh rahi h .
198
UNACADEMY
Note:
 Agar naphthalene ki dono ring ka reduction karan hoga to neeche diya hua product
bnega

199
UNACADEMY
Question 73:
Ans:
 Electron deficient ring ka reduction hoga ar dusri ring ki aromaticity retain rahegi.
200
UNACADEMY
Question 74:
Ans:
 Furan, Thiophene, Pyrrole , inn sab k products aise hi banenge.

201
UNACADEMY
Question 75:
Ans:

202
UNACADEMY
Question 76:
Ans:
 Negative charge jo aaega wo more EN atom pe rehna pasand krega means N pe kyun k N
ke l.p. to use hi ni ho rahe to negative charge
by-KULDEEP N SIR)
GARG (KD pe ASF
rehna
& pasand karega.
203
UNACADEMY
Birch Reduction followed by other reactions
Other reactions
(a) Alkylation
(b) Hydrolysis
(c) Ozonolysis
(d) Epoxidation
(e) Dihydroxylation
(f) Hydrogenation
(g) Hydroboration

204
UNACADEMY
Birch reduction followed by Alkylation

205
UNACADEMY
Question 77:
Ans:

206
UNACADEMY
Question 78:
Ans:

207
UNACADEMY
Question 79:
Ans:

208
UNACADEMY
Birch reduction followed by Hydrolysis in presence of acid
Question 80:
Ans:

209
UNACADEMY
 Jaisi uper wali reactin m α-H wali condition agar aisi same condition kahin ar aajaye in
acidic medium to seeda enone bna do.

210
UNACADEMY
Question 81:
Ans:

211
UNACADEMY
Question 82:
Ans:

212
UNACADEMY
Birch reduction followed by Alkylation and then by Hydrolysis in presence of acid
Question 83:
Ans:

213
UNACADEMY
Birch reduction followed by Ozonolysis
Ozonolysis
Shortcut:
 Ozonolysis me double bond tod ke dono trf oxygen laga dete hain.
 Ozonolysis uss dobule bond pe hogi jispe electron density zyada hogi kyun oxidation ho
raha mtlb electron ko jana h to electron wahin se jaega jahan pehle se electron density
zyada hogi.

214
UNACADEMY
Question 84:
Ans:
 The intramolecular reaction in product B ni hogi kyun wo 7-membered ring banaega ar 7-

membered ring stable ni hoti hai. Isliye reaction product B pe hi ruk jaega aage
cyclization ni hoga. by-KULDEEP GARG (KD SIR) ASF &
215
UNACADEMY
Birch reduction followed by Epoxidation
 Here, we will do epoxidation by mCPBA (meta chloro per benzoic acid)
 Epoxidation more electron density wale double bond pe hoga.
 Epoxidation ki stereochemistry ham tab padhenge jab oxidation padhenge.
Example:

216
UNACADEMY
Question 85:
Ans:

217
UNACADEMY
Birch reduction followed by Hydroxylation
 Isme 2 –OH group judenge ar 2 –OH groups ko jodne ka kaam OsO4 bahot achhe se krta
h.
 OsO4 syn-addtion krwata h –OH groups ka.
 Di-ol uss double bond pe banega jispe electron density zyada hogi.
Example:

218
UNACADEMY
Birch reduction followed by Catalytic Hydrogenation
Question 86:
Ans:
 Wilkinson catalyst will attack on less hindered site.

219
UNACADEMY
Question 87:
Ans:
 In hydroboration addition of BH2 and H is syn.

 Agar ham product A pe hydroboration krwa den to hydroboration less hindered double
bond pe hoga because ye ek reduction
by-KULDEEPprocess hai.ASF( According
GARG (KD SIR) & to Markovnikov’s Rule)
220
UNACADEMY
Na/K/Li /liq. NH3 (BIRCH REDUCTION)
It does the reduction of
Aromatic Heterocyclic Conjugated Enone Alkyne

Ring Ring Diene
Inke derivative
(EWG/EDG)ka
bhi reduction
karega
221
UNACADEMY
 So, till now we have completed the aromatic ring .
 Hmko enone mil raha tha jab ham aromatic ring ka birch reduction karane k baad
hydrolysis kra rahe the. Ab ham hydrolysed product pe firse birch reduction krwaenge.
Birch Reduction on Enone
Question 88:

222
UNACADEMY
Ans:
Agar protonation k liye H+ / H3O + / NH4Cl me se koi ek bhi diya hua h to O- H+ ko accept kr
lega. Ar agar protonation step ni di hui hai to enolate apni enolate form m hi reh jaega ar
fir yahan se enolate chemistry start hogi.

223
UNACADEMY
Mechanism of Birch reduction on Enone

224
UNACADEMY
Shortcut:
1. Birch Reduction
Enone Ketone (This happens 2 H are
provided to Enone)
2. Birch Reduction
Enone Enolate (This happens 1H is
provided to Enone)
225
UNACADEMY
Question 89:
Ans:

226
UNACADEMY
Question 90:
Ans:
 Step 1 me OH- C-1 se H lega because yahin

by-KULDEEP GARGse
(KDcyclized
SIR) ASF & product possible hai.
227
UNACADEMY
Question 91:
TMS = Tetra methyl silane

Birch Reduction on Diene

228
UNACADEMY
Birch Reduction on Alkyne
Birch Reduction
Alkyne Trans Alkene
Note:

229
UNACADEMY
Question 92:
Ans:
 Si pe positive charge zyada stabilized hoga in comparison to C. Isliye Si is hard center and
C is soft center. by-KULDEEP GARG (KD SIR) ASF &
230
UNACADEMY
REAGENTS
(LECTURE-14)
Oxidation based reagents ( Oxidizing Reagents)
 Oxidation me 3 cheez hoti hai
(i) Addition of oxygen
(ii) Removal of Hydrogen
(iii) Removal of electron
 Ham basically oxygen ko 4 jagh add krte hain.
(i) Oxidation of alcohol
(ii) Oxidation of alkene
(iii) Oxidation of ketone
(iv) Oxidation of aromatic hydrocarbon

231
UNACADEMY
Oxidation of Alcohol
 Alcohol ko ham 2 trh se change krte hain : ek to metal ka use krke ar ek non-metal ka use
krke.
Metal/ Non-metal
Alcohol Aldehyde / Ketone
Acid
 Metal wahi oxidation karenge jinka oxidation state high hoga.
John’s (in acidic medium)

Collins (in basic medium)
Metal Cr PDC (increases chemoselectivity)
PCC (in buffer)
Sarett Oxidation
232
UNACADEMY
Metal Mn MnO2
Metal Ru TPAPR (Tetra propyl ammonia per ruthanate)
Metal Ag Fetizon’s Reagent (Ag2CO3)
Metal Ce CAN (Cerric Ammonium nitrate)
TPAPR (Tetra propyl ammonia

by-KULDEEP GARG (KDper ruthanate)
SIR) ASF &
233
UNACADEMY
Swern Oxidation (CoCl2 /DMSO /NEt3 )
Non Metal TEMPO (tetramethylpiperidine oxyl )
DMP
IBX
Oxidation of Alkene
1. Epoxidation
2. Formation of Diol

234
UNACADEMY
3. Ozonolysis
4. Formation of allylic alcohol
5. Formation of ketone

235
UNACADEMY
1. Epoxidation
Epoxidation 3 tareeke se hota h:
In presence In presence In presence

of acid of alcohol of peroxide
mCPBA t-BuOOH + Metal H2O2 + NaOH
CH3CO3H DMDO
CF3CO3H

236
UNACADEMY
2. Formation of Diol
Reagents
1. OsO4
2. KMnO4
3. Prevost Reagent (forms Trans diol) (Reaction carried in presence of Ag)
4. Woodward Reagent (forms Cis diol) (Reaction carried in H2O)

237
UNACADEMY
3. Ozonolysis
Alkene ka ozonolysis krne ki kai sari conditions hoti hain

1. O3 + H2O2
2. O3 + DMS
3. O3 + Zn
4. O3 + In and NaBH4

238
UNACADEMY
4. Formation of allylic alcohol
Reagent
SeO2 with t-BuOH

239
UNACADEMY
Oxidation of Ketone
Ketone to Ester
Baeyer Villiger Oxidation
Ketone Ester
Ketone to Alcohol

240
UNACADEMY
Ketone to Acid
Haloform reaction
Ketone Acid
Oxidation of Aromatic Hydrocarbon

241
UNACADEMY
Alcohol to Aldehyde / Acid /Ketone

242
UNACADEMY
243
UNACADEMY
Metal based oxidising Reagents
John’s Collins PCC PDC Sarett

Reagent Reagent (mild Oxidation
(strong (mild oxidizing
oxidizing oxidizing reagent)
reagent) reagent)
CrO3 /K2Cr2O7/ CrO3/Pyridine/ CrO3/Pyridine

H2Cr2O7 CrO3/Pyridine HCl Cr2O7/Pyridine/
+ aq. H2SO4 /CH2Cl2 HCl
+ Acetone

244
UNACADEMY
PCC ( Pyridinium Chloro Chromate)

245
UNACADEMY
John’s Reagent
 It is strong oxidizing reagent.
 Its converts alcohol to acid or ketone.
 Primary alcohol Acid
 Secondary alcohol Ketone

246
UNACADEMY
Drawback of John’s Reagent
 There is no chemoselectivity.
Ye dono –OH ko oxidize kr dega.

 Acid sensitive group ko ye maar dalta hai ye reagent means unko bhi oxidize kr deta hai.
-OTMS ek protecting group hi arby-KULDEEP

ye acid se tut
GARG (KDta hai.
SIR) To ye acid sensitive group hai.
ASF &
247
UNACADEMY
Epoxide is also acid sensitive group

248
UNACADEMY
REAGENTS
(LECTURE-15)
Question 93:
Ans:

249
UNACADEMY
Question 94:
 Agar β- keto acid ki condition hogi to wahan se –CO2 niklegi because of heating.
 80°C pe –CO2 nikl jati hai to agar usse uper ka temperature de rakha ho John’s reagent ke
sath to –CO2 nikal do.

250
UNACADEMY
Question 95:
Question 96:

251
UNACADEMY
Question 97:
Collins Reagent
CrO3/ Pyridine /CH2Cl2
 This reaction is in basic medium so the acid sensitive groups remain intact.
 It is a mild oxidizing reagent.
Primary alcohol Aldehyde
Secondary alcohol Ketone

252
UNACADEMY
Drawback of Collins Reagent
 There is no chemoselectivtiy.
Question 98:
Question 99:

253
UNACADEMY
PCC ( Pyridinium Chloro Chromate)
CrO3/Pyridine/HCl
 It is mild oxidizing agent.

 It reacts with acid sensitive groups.
 Agar buffer solution le len sodium acetate ka to ye acid sensitive group ke sath react ni
krega.

 There is no chemoselectivity.
254
UNACADEMY
Question 100:
 In case of PCC + Buffer , no side reaction is possible.

255
UNACADEMY
Question 101:

256
UNACADEMY
Question 102:

257
UNACADEMY
Question 103:
Question 104:

258
UNACADEMY
Ans: Agar ketone ar aldehyde dono groups present hain molecule me to wittig reaction
pehle aldehyde pe hogi.
Note:
Wittig reaction me agar stable ylide hai (EWG laga hua hai) to E-alkene banegi. Agar ylide
unstable hai(EDG group laga hua hai) to Z-alkene banegi.
259
UNACADEMY
Question 105:
Ans:

260
UNACADEMY
Examples:

261
UNACADEMY
Question 106:

262
UNACADEMY
Ans: (b)
Iss reaction me buffer to liya ni hai ar iss reaction me acid present hain ar uska conjugate
base bhi present hai.

263
UNACADEMY
Question 107:

264
UNACADEMY
REAGENTS
(LECTURE-16)
Babler Reaction
 Issme ek concept aaega Sigmatropic ka.
 Sigmatropic wo reactions hoti hain jo heat/ photochemical (light ) ki presence me ho jati
hain.
 Jahan se bond tut ta hai wahan se numbering start krte hain.

 Uper wale case me 1-1 ke beech ka bond tut raha hai 1-3 ke beech ka bond ban raha hai
to isko kehte hain 1,3- sigmatropic .
265
UNACADEMY
 Jiske beech me bond bn raha hai uske naam pe reaction jani jati hai. Isliye neeche wale
case reaction ko bolenge 3,3- sigmatropic.
 Babler reaction me pehle 3,3 sigmatropic milega fir oxidation milega.

 Abhi tak ham ye padh rahe the ke 3° - alcohol ka oxidation ni hota but iss reaction ki khas
baat yahi hai ke ye chalaki se 3° - alcohol ka oxidation kr deta hai.
 Iss reaction (Babler reaction ) ke zaruri hai allylic tertiary alcohol.
266
UNACADEMY
 Iss reaction me first step heat hai ar second step me PCC dala hai. But exam me aisa bhi
ho sakta hian ke heat likh ke na de sirf PCC likhe ke de, to hamko assume krna hain PCC
ke sath reaction heat ki presence me ho rahi hai.
 Ye reaction most of the students ko 1,3-sigmatropic lagti because ye dikhne me 1,3-shift
ki trh lagti hai but actually me hoti ni hai 1,3 – shift. Ye reaction 3,3- sigmatropic se
complete hoti hai.

267
UNACADEMY
Note:
 Agar koi bhi tertiary allylic alcohol hoga to aise reaction complete krenge.
 PCC ka wahi role hain

 Uper wali reaction me jo product bna hai usme aage reaction proceed krwa dete hai
exam me koi ar reagent daal ke. For example: Gillman’s Reagent daal ke 1,4 addition krwa
dete hain ya RLi daal ke 1,2 adition krwa dete hain.
268
UNACADEMY
Explaination of how Babler oxidation is 3,3 sigmatropic + its mechanism
 Reaction acidic medium me ho rahi hai isliye structure (I) me –OH aaya.
 Product me oxygen chromate se aata hai (shown by labeling in the mechanism).
269
UNACADEMY
Question 108:
Ans:

270
UNACADEMY
Question 109:
Ans:

271
UNACADEMY
Question 110:
Ans:

272
UNACADEMY
Question 111:
Ans: Step 1 is nucleophilic addition reaction ( Grignard reagent : 1,2- addition)

273
UNACADEMY
Question 112:
Ans:

274
UNACADEMY
Question 113:
Ans:

275
UNACADEMY
PDC (Pyridinium Dichromate)
 Its is mild oxidising reagent.
 Mild oxidizing reagent means primary alcohol aldehyde tak hi oxidize hoga.
 Iss reagent ki selectivity solvent dependent hoti hai. Ye reagent acid bhi dega but uske
liye hmko solvent dependent hona padega.
 Generally abi tak ham reaction DCM solvent me karate aa rahe the.
PDC –DCM
PDC –DMF
Primary alcohol Acid
 PDC , DMF ki presence me overoxidation ka kaam krta hain but DCM ki presence me mild
oxidation ka kaam krta hai.
 Secondary alcohol pe solvent kaby-KULDEEP
koi effect ni (KD
GARG hai.SIR) ASF & 276
UNACADEMY
Question 114:
Question 115:

277
UNACADEMY
Solvent Based Reagents
1. DMSO
 DMSO solvent bhi hai, reagent bhi hai.
 Isske sath 2 reactions hoti hain
Swern Oxidation Moffet Oxidation

DMSO DMSO
DMSO ke sath [COCl]2 DMSO ke sath DCC
(dicyclohexylcarbodiimide)
Base (:NEt3), temp. (-60°C) Acid (NH4Cl/H2O or H3PO4 )

Room temperature
Agar base use ni krenge to substitution
product milega.
278
UNACADEMY
Swern Oxidation
Reagent used : DMSO + [COCl]2 + base (strong/bulky base) e.g. :NEt3
 This reaction is very exothermic to iss reaction ko very low temperature pe karaya jata
hai.
Question 116:

279
UNACADEMY
Very Important Note:
 Agar reaction me base(:NEt3 ) ni daala ar temperature - 60°C ki jagh 0°C likha hai tab iss
case me hame swern oxidation ni milega, Swern substitution milega. Ar Swern
substitution product hamko neeche likhi reaction ke corresponding milega.

280
UNACADEMY
Mechanism of Swern Oxidation
 Oxygen ar chlorine ki wajh se carbonyl carbon pe partial positive charge generate ho raha
hai.
 Structure (I) me oxygen ne apna charge shi9ft kr diya to wo charge sulfur pe aagya .
 Structure (II) ne partial positive charge stabilize hai chlorine ke partial negative charge ki
wajh se. Structure (II) active ar stable species hai. Pehle structure (I) me wo active
species ni thi to Cl- ne attack kr diya tha.

281
UNACADEMY
 Structure (III) me do positive charge ek sath reh ni skte to H ne apne electrons chhor diye.
 Structure (IV) ke baad agar base present hai to H remove hoga ar agar base precent ni h
to Cl- attack krega CH2 pr.

282
UNACADEMY
Example:

283
UNACADEMY
Question 117:
Ans: Wittig reaction pehle aldehyde pe hogi.

284
UNACADEMY
REAGENTS
(LECTURE-17)
Moffet Oxidation
 Yahan DMSO use hota ar sath me DCC (dicyclohexylcarbodiimide) use hota h jabki Swern
oxidation me [COCl]2 use krte hain DMSO k sath.
 Swern Oxidation basic medium me ho rahi thi to uska ye drawback tha ke agar pehle se
koi acidic H present hai to usske sat reaction ho jaegi. But Moffet oxidation acidic
medium me hoti hai . Acids used are NH4Cl/H2O or H3PO4 . Both the acids give the
same result.
 Reagent used in Moffet Oxidation: DMSO/ DCC /H+
 Moffet Oxidation me product same banenge jaise Swern Oxidation me bante the.
285
UNACADEMY
Mechanism of Moffet Oxidation
 Lone pair of N will take H+ , then electronegativity of N will increase and partial positive
charge will generate on C. After that the lone pair of O of DMSO will attack on C with
partial positive charge.
 Structure (I) me positive charge pehle O pe hi bnta hai pr fir S pe shift ho jata hai because
positive charge less electronegative atom pe rehna pasand krta hai.

286
UNACADEMY
 Species (II) will act as base for species (III). To yahan kabi substitution dekhne ko ni
milega.

287
UNACADEMY
Note:
 John’s reagent, Collins reagent, PCC, PDC, Swern oxidation , Moffet oxidation, ye sab
primary alcohol ko ar secondary ko same treat krte hain . Koi selectivity ni hai to dono ka
oxidation kr dete hain.
 Tab do reagent samne aaye jinki chemoselectivity dekhi gyi and those reagents are
1. Fetizon’s Reagent
2. TEMPO (Tetramethylpiperidinyl oxyl)
Fetizon’s Reagent
Reagent: Ag2CO3 + Celite (SiO2)
 Ag2CO3 adsorb ni ho pata hai solvent me to isliye ham Ag2CO3 ko Celite me daalte hain.
Celite ki layer Ag2CO3 adsorb ho jata hai.
 Fetizon’s reagent pehle secorndary alcohol ka oxidation krta hai fir primary alcohol ka
krta hain.
288
UNACADEMY
 Aisa ni hai k primary alcohol ka oxidation ni krta . Agar reaction m secondary alcohol hai
to uska oxidation krega. Agar secondary alcohol hai hi ni reaction me, sirf primary
alcohol hai reaction me to primary alcohol ka oxidation kr dega ar major product fir
obviously primary alcohol se hi aaega. Agar do trh ke alcohol hain to major product
secondary alcohol se aaega.
Order of oxidation
Benzylic - Allylic -OH > 2° alcohol > 1° alcohol
Waise benzylic ar allylic ki priority almost same hoti hai but agar compare krna hi pad
jaye to benzylic –OH ko priority denge in comparison to allylic -OH


289
UNACADEMY
Example:

290
UNACADEMY
Question 118:
Question 119:

291
UNACADEMY
Very Important point to remember about Fetizon’s reagent
1,4- diol Fetizon’s Reagent

1,5- diol Lactone
1,6- diol
Question 120:

292
UNACADEMY
Ans: Ab ya secondary alcohol to hai ni to primary alcohol hi oxidize hoga wo bhi ek hi ar badi
mushkil se.
Note:
In example just before Q-118, we did not form lactone in presence of Fetizon’s reagent
because by the attack of –OH on ketone, a 4- membered ring would form which is
unstable.
293
UNACADEMY
Question 121:
Question 122:

294
UNACADEMY
Question 123: (CSIR-PYQ)
Ans:

295
UNACADEMY
Question 124:
Ans: Allyic alcohol will oxidize first.
 Product formed is now ready to give Diels Alder reaction.

296
UNACADEMY
Question 125:
Which of the following is the correct option?
Ans: Allyic alcohol will oxidize first. Correct option : (D)

297
UNACADEMY
TEMPO (Tetramethylpiperidinyl oxyl)
Order of oxidation
Benzylic - Allylic -OH > 1° alcohol > 2° alcohol
Reagent

298
UNACADEMY
Example:

299
UNACADEMY
REAGENTS
(LECTURE-18)
MnO2 (Oxidizing Agent)
Primary Alcohol Aldehyde

Secondary Alcohol Ketone
 Agar kisi molecule me sirf ar sirf primary ya secondary alcohol hai (no double bond in
conjugation) to usko oxidize krne k liye hame 10 mol MnO2 lagenge ar reaction high
temperature pe hogi. Agar allylic ya benzylic alcohol hai to bas 1 mol MnO2 lagega ar
reaction room temperature pe hogi. Therefore, MnO2 is chemoselective to allylic and
benzylic alcohol.
Allylic Primary Alcohol Aldehyde
300
UNACADEMY
Benzylic Primary Alcohol Aldehyde

301
UNACADEMY
Question 126:
Question 127:

302
UNACADEMY
Question 128: (IIT JAM)
Question 129:

303
UNACADEMY
Ans:
 Yr jo pehle se MnO2 reactione me pade hain ye Benzoin condensation ni hone denge.

Question 130:

304
UNACADEMY
Ans:

305
UNACADEMY
MnO2 SeO2
It oxidizes allylic and benzylic alcohol. It works on allylic and bezylic position
(carbon ).
Allylic carbon pe alcohol lagata hai ar
benzylic carbon pe ye carbonyl group lagata
hai.
Note: SeO2 is toxic and white crystalline
solid.
SeO2 (Oxidizing Agent)
Example:

306
UNACADEMY
Example:
Selectivity of SeO2
 Selectivity always comes from expertimental properties.
Order of oxidation
2° allylic carbon > 1° allylic carbon

307
UNACADEMY
 SeO2 converts the carbon which is at α – position to carbonyl into carbonyl group.
Example:
Yahan abhi koi selectivity ni hai to dono me se koi bhi α-carbon oxidize kr denge ham.
Example:
Ab yahan 2° α-carbon oxidize hoga.

308
UNACADEMY
Question 131:
Question 132:

309
UNACADEMY
Question 133:
Question 134:
Bridge head pe ni lagega- CO because 5 bond to banaega ni C. To ar kahin jagh bachti ni .

310
UNACADEMY
Question 135:
Ans:
SeO2 carbonyl ussi side lagaega jahan alkene zyada stable hogi.
Tautomerism krke dekhna hai alkene ki stabliblity ke liye.

311
UNACADEMY
Question 136:

312
UNACADEMY
Question 137:
 Structure (I) pe SeO2 ki reaction bahot fast hoti hai because reaction se pehle ye non-
aromatic hota hai ar reaction ke baad structure (II) quasi aromatic ban jata hai.
 Quasi aromatic is more stable than non-aromatic.

313
UNACADEMY
 Quasi aromatic bnne ke case me structure ko benzylic ki trh treat kiya jaega na ki allylic ki
trh.

314
UNACADEMY
Rule 1 : Order of oxidation 2° allylic/benzylic carbon > 1° allylic/benzylic carbon
Allylic carbon Alcohol
Benzylic carbon Ketone
Rule 2 : Jiss ring me strain zyada hoga, ussi ring me oxidation hoga.
Example:
 Ye red dot wale sare carbon secondary carbon hain to kisi ka bhi oxidation ho sakta hai.
Pr oxidation ussi carbon ka hoga jiss ring me strain hoga.
Rule 3 : Jahan more alkylation hoga wahan oxidation hoga.

Rule 4 : Hamesha E-alkene banegi. by-KULDEEP GARG (KD SIR) ASF &
315
UNACADEMY
Question 138:
Which of the following will be the correct major product?
Ans: Yahan hamesha E-alkene banegi.

 Iss question ko solve krne k liye hamne dekha k kaha more alkyl groups hain. To oxidation
wahin hoge. Iske sath sath hamari E- alkene banni chahiye.
Correct option : (C)

316
UNACADEMY
Summary of Rules of Oxidation by SeO2
Rule 1 : 2° > 1°
Rule 2 : Strained ring > non-strained ring
Rule 3 : More alkylated > less alkylated
Rule 4 : E-alkene will be formed (always)
Order to apply these rules

Rule 3 > Rule 1 > Rule 2

317
UNACADEMY
Question 139:
Ans:

318
UNACADEMY
Question 140:
Which of the following is the major product?
Ans:
Correct option : (D)

319
UNACADEMY
Question 141:
 Iss question me jo uper wala double bond hai uspe allylic group attached hai but hamne
kaha tha k hamko more alkylated groups wali side dekhni .
320
UNACADEMY
Question 142:
Which of the following is the major product?
Ans: Correct option : (C)

 Yahan pehle E- alkene ni, 2° carbon ko pehle priority denge (as per rules). Ar jo always E
likha hai wo tab hai jab ar baki ki sari priority check kr li hain.

321
UNACADEMY
Question 143:
Ans:

322
UNACADEMY
REAGENTS
(LECTURE-19)
 Abi tak ham oxidation krwa rahe the carbonyl ka ya alcohol ka. Aaj ham double bond
break krenge ar uska oxidation hoga.
 Carbon - carbon double bond todne ke do tareeke hain.

323
UNACADEMY
Oxidation of double bond
Case 1: Breaking of C=C completely
This is done by 2 reagents
1. Ozonolysis (O3)
OsO4 + NaIO4
2. Luminx Reagent
KMnO4 + NaIO4
 Luminx Reagent me do reagent aa jate hain jo uper likhe hain.

 Agar sirf OsO4 dalenge double bond pe wo diol banaega. Agar sath me NaIO4 daal denge
to double completely.

324
UNACADEMY
Ozonolysis
Note:
 O3 jab kisi double bond pe jata hai to ek reaction mechanism follow krke ye banata hai
first ozonide. Ar ye jo reaction mechanism hai ye pericylic se aati hai. Pericyclic me ye
reaction dipolar cycloaddition reaction hoti hai .
 First ozonide me fir kuchh rearrangements honge ar kuchh products banenge. Inn
products me apas me fir dipolar cycloaddition reaction hogi ar firse kuchh products
banenge. by-KULDEEP GARG (KD SIR) ASF &
325
UNACADEMY
 Ab inn products pe secondary reagents(jo O3 ke sath reagents liya hai) act krega.
 Secondary reagents can be Me2S, Zn/H2O, H2O2 , NaBH4 , LiAlH4

326
UNACADEMY
Mechanism

327
UNACADEMY
 Me2S, Zn/H2O ke sath to reaction yahin ruk jaegi.
 H2O2 ke case me agar products ketone hain to reaction yahin ruk jaegi ar agar aldehyde
hai to usse acid bna ke chhorega.

328
UNACADEMY
Example:
Example:
Example:

329
UNACADEMY
OZONOLYSIS kahan sabse fast hoga
 Pericyclic reaction electron ki periphery hoti hain.
 Ozonolysis electron rich species pe hogi ya more nucleophile double bond pe hogi.
Alkene ka HOMO lena hoga ar HOMO me electron rich species chahiye hoti hai.
Order of Ozonolysis ( kon fast hoga )

330
UNACADEMY
Example:
Inn teeno double bond me se sabse pehle ozonolysis c pe hoga then b pe then a
c>b>a
Question 144: (NAT type question)

How many different types of products will be formed in the following reaction?

331
UNACADEMY
Ans: 4 products will be obtained.
Question 145:

332
UNACADEMY
Question 146:

333
UNACADEMY
Question 147:
Question 148:

334
UNACADEMY
Question 149: (NAT type question)
How many different types of products will be formed in the following reaction?
Ans: Correct option : (B) Iss me product dono resonation structures se aaega.

335
UNACADEMY
Therefore, total different types of compounds are 3.
Total number of species = 6

336
UNACADEMY
Luminx Reagent
OsO4 + NaIO4 KMnO4 + NaIO4

Yahan to wahi products milenge jo Yahan alkene ke oxidation se
ozonolysis me milte hain. following set of products milenge
Acid + Acid
Acid + Ketone
Ketone + Ketone
Hamko yahan acid iskiye mil raha
hai kyun reaction me jo aldehyde
bna hoga wo acid me convert ho
gya.

337
UNACADEMY
Question 150:

338
UNACADEMY
Question 151:
Following reaction kis kis reagent se possible hai?
Ans: Correct options : (a), (b) and (c)

339
UNACADEMY
Question 152:
Following reaction kis kis reagent se possible hai?
Ans: Correct options : (a) and (d)

340
UNACADEMY
Dihydroxylation on Double bond (alkene)
 Ab inn diol ki geometry cis bhi ho skti ar trans ar ye depend krta hai k reagent kya dalte
hain.
 Regents are:
(a) OsO4 + NMO simple reagent
OsO4 + NMO + TMEDA Iss reagent se selectivity ar increase ho jaegi
Ye reagent cis geometry to dega hi. Isse zyada selectivity increase krne k liye following
reagent use krte hain. Ab cis ke sath sath dono groups above the plane honge ya below
the plane uske liye OsO4 ke sath following reagents use honge.
(DHQD) 2PHAL in presence of [Fe(CN)6]3- (ye –OH above the plane dega)
OsO4
3-
(DHQ) 2PHAL in presence of [Fe(CN)
by-KULDEEP GARG 6]& ( ye –OH below the plane dega)
(KD SIR) ASF
341
UNACADEMY
(b) KMnO4 +OH- Ye bhi diol deta h pr selectivity achhi ni hai isliye use krna pasand ni
krte
(c) Prevost Reagent Ag k sath hota hai to costly hota hai ar stereoselective hota hai.
(d) Woodward Reagent Stereoselective hota hai.
OsO4 + NMO
Mechanism

342
UNACADEMY
What is NMO and why is it used?
 NMO : N-Methylmorpholine N-oxide
 NMO is used as co-oxidant.
 OsO4 strong oxidizing reagent hai ye achchi baat hai but ye harmful hai. Oxidation me ye
apni 2 oxygen alkene ko dene ke baad jo bachta hai wo waste hai ar wo environment me
jaega to harm krega.
 NMO ka waise oxidation me koi kaam ni hai but ye OsO4 ko regenerate krta hai ani
oxygen deke
 OsO4 NMO ki absence me as a catalyst ni work krta. OsO4 works as a catalyst in presence
of NMO.

343
UNACADEMY
Itne part ko dekhen to reaction pericyclic dikhti hai to
alkene electron rich honi chahiye because ye apna
HOMO use kregi.
Hence, OsO4 will react with electron rich species.
 Electron rich species dekhne ke baad OsO4 less hindered side se attack krega. Agar bahot
bulky group ( example : t- Bu group) na laga hua ho to steric hinderence α-position ki
dekhenge ar syn diol banaega.
 OsO4 itna strong hai k α,β- unsaturated ketone ko bhi diol bna deta hai.

344
UNACADEMY
Question 153:
 We obtain this reaction mixture.
 Issi reaction mixture se bachne ke liye OsO4 / NMO me do reagent mila diye jate hain
1. (DHQD) 2PHAL ( iss reagent se –OH above the plane jate hain)
2. (DHQ) 2PHAL ( iss reagent se –OH below the plane jate hain)

345
UNACADEMY
Question 154: (Application of attack from less hindered side)
Question 155: (Application of attack from less hindered side)

346
UNACADEMY
Question 156: (Important )

347
UNACADEMY
Question 158:
Question 159:

348
UNACADEMY
Question 160:

349
UNACADEMY
TMEDA
 Ye OsO4 ki -OH ke sath H-bonding kre ke OsO4 ki orientation change kr deta hai.

350
UNACADEMY
 OsO4 waise tetradhedral hai ar jab TMEDA iske sath bidentate banata hai to iski
geometry change krke octahedtral bna deta hai.

351
UNACADEMY
Question 161:
 Coming –OH ki stereo chemistry α- position wale group decide krte hain.
Question 162:

352
UNACADEMY
 t-Bu group ke case me ye t-Bu TMEDA ko H- bonding ni krne dega to TMEDA dalne ka koi
benefit ni hoga. Isliye TMEDA tab daalte hain jab t-Bu jaise bulky group na hon.

353
UNACADEMY
REAGENTS
(LECTURE-20)
Bayer Reagent
1. KMnO4 + 1% dil. KOH (in cold water )
(alkaline solution) Bayer Reagent (confirms C=C)
2. KMnO4 conc. (in hot water )
 Bayer Reagent unsaturation test deta hai. KMnO4 (+7 O.S.) ka colour purple hota hai ar
jab ye double bond ke sath react krta hai to MnO2 (+4 O.S.) banata hai ar uska colour
brown hota hai .
KMnO4
Alkane Purple colour
KMnO4
Alkene Brown colour
354
UNACADEMY
 Kisi bhi alkene pe KMnO4 ki mechanism same hoti hai just like OsO4 . Bas difference OsO4
toxic hota hai ar KMnO4 toxic ni hota hai.
 KMnO4 ke sath dikkat ye hain ke MnO4 khud apne aap me polar hai , KOH bhi polar hai ar
H2O bhi polar hai pr compound hamara non polar to ab mix kaise hoga. To uske liye ham
use krte hain phase transfer catalyst jo polar and non polar ko bind krke rakhta hai.
 Ye phase transfer catalyst arrow pe likh ke de bhi sakta hai ar ni bhi.

355
UNACADEMY
Example:
Using CAR shortcut sys addition.
Double bond will convert into dihydroxylation.
Example:
Triple bond will convert into diketone.

356
UNACADEMY
Hot concentrated alkaline KMnO4
 Hot concentrated alkaline KMnO4 ko agar alkene pe daal denge to C=C completely break
hoga. Yahan ek bond tutega to ek O lagega ar jab dusra bond lagega to ek ar O lagega.
 Jab concentrated alkaline KMnO4 hota hai to ye HCOOH (formic acid)ko bhi oxidize kr
deta hai.

357
UNACADEMY
Question 164:
 Ar jahan formic acid mil jaye, usse CO2 and H2O me convert kr do.

358
UNACADEMY
Woodwords Prevost
cis diol trans diol
Solvent used is water (H2O) Here non- aquous solvent is used

(CCl4 )
CCl4 ke baad workup karate hain.
Note:

359
UNACADEMY
Mechanism of Woodwards
 Yahan I2 me se jo ek I niklega usko Ag ( from CH3COOAg ) leke jaega as AgI and will leave
CH3COO-

360
UNACADEMY
Question 165:
 OsO4 ke case me OsO4 khud jake judta hai ar O deta hai from less hindered side. But
Woodwords ke case me pehle I2 judta hai to –OH fir I2 ke opposite side se judta hai.

361
UNACADEMY
Mechanism of Prevost
 Isme water solvent to hota ni hai.

362
UNACADEMY
Question 166 :
 Trans attack ke liye CH3COO- (a) position pe below the plane se attack karega. Because O
pe negative banega to (a) position wale carbon pe positive charge banega ar –CH3 uss
positive charge ko balance karega. To CH3COO- (a) position wale carbon pe below the
plane attack krega.
363
UNACADEMY
Question 167 :

364
UNACADEMY
Question 168:

365
UNACADEMY
Question 169 :
Ans: Yahan 2 possibilities hain OsO4 ke sath product banne ki pr banega konsa ye decide
krna hain.

366
UNACADEMY
 OsO4 ke case me possibility 1 se product banega because possibility 2 me axial position
pe –OH hone se -CH3 ke sath interaction hoga.

367
UNACADEMY
Question 170 :
 Product yahi banega chahe kitna hi stable ho ya kitna hi unstable ho.

368
UNACADEMY
Cleavage of Glycol bond
 Glycol bond ka cleavage means following bonds ko todna.
 Agar koi alcohol hai to convert hoga carbonyl me; Agar carbonyl ko tod rahe ho to
convert hoga acid me ; agar acid ko tod rahe ho to convert hoga CO2 + H2O
Alcohol Carbonyl Acid CO2 + H2O

369
UNACADEMY
 Attack krne wali species (jo glycol cleavage krenge ) following hain
1. HIO4
2. NaIO4
3. H5IO6
4. LTA (Lead tetra Acetate) Pb(OAc) 4
Question 171 :
Following product will form from which reagents?

370
UNACADEMY
Ans:

371
UNACADEMY
Question 172 :
Question 173 :

372
UNACADEMY
Ans:
 Agar ek ar equivalent diya hota to Formic acid convert ho jata CO2 + H2O me

373
UNACADEMY
Question 174 :

374
UNACADEMY
Question 175:

375
UNACADEMY
Stereochemistry of Cyclohexane and Decaline
 Jitna zyada ring flipping, rate utna hi fast hoga.(HIO4 ke sath )
 No ring flipping means inert for HIO4 ( mtlb HIO4 ke sath reaction ni dega)
Question 176:
Following compounds me se konse compound me glycolysis ka rate fast hoga?

376
UNACADEMY
Ans:
 Ring flipping ka mtlb dono ek dusre ke sath reversible hon but yahan equitorial wala
zyada stable ho gya ar inn dono compounds ki energy me bahot differnce aa gya. To
reversible ni hain ye dono.
 Ring flipping ka ye bilkul mtlb ni hota hai ke ek compound jaldi se jake stable compound
banke baith jaye.
 Rate of reaction will be fast in (b)

377
UNACADEMY
Question 177:

378
UNACADEMY
Question 178:
Ans: Trans decaline me flipping ni hoti. Cis decaline me hi hoti hai flipping.

379
UNACADEMY
Note:
HIO4 Jo compounds water soluble hote

NaIO4 hain unke sath inki reaction krwate hain.
Pb(OAc) 4 Jio compounds organic substance me soluble hote hain unki reaction iske
sath krwate hain.

380
UNACADEMY

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REAGENTS CLASS NOTES BY KULDEEP GARG

FOR CSIR NET /GATE/IIT JAM

by-KULDEEP GARG (KD SIR) ASF & UNACADEMY

1. Reagents which can perform reduction( reducing reagent). (Upto lecture-13)

1. Hydrogen donor based reagents

Mostly, reagents have tetrahedral geometry.

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF & UNACADEMY 4

H2 /PtO2 : Adams Catalyst

2. Electron donor based reagents

by-KULDEEP GARG (KD SIR) ASF & UNACADEMY 6

Al-H bond H2O m se H nikal leta h Poor Nucleophile

On these substrates, it gives nucleophilic addition reaction.

On these substrates, it gives substitution reaction.

by-KULDEEP GARG (KD SIR) ASF & UNACADEMY 9

by-KULDEEP GARG (KD SIR) ASF &

Number of hydride ions used in partial reduction = 1

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

 Agar 5 ya 6 membered ring bn rahi ho to aage ester bnega.

by-KULDEEP GARG (KD SIR) ASF &

 Number of hydride ions required in the reaction using Li[AlH4 ] =3

by-KULDEEP GARG (KD SIR) ASF &

Dono hi case m carbonyl marega ye to pata h but 1,4 attck

3. Stereoselectivity (kaise mara gya)

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF & UNACADEMY 29

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

 BH3 sabse fast acid ar amide pe react krta.

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

I and II are position isomers

by-KULDEEP GARG (KD SIR) ASF &

 Bulky group increase krne se selectivity increase hoti h. Ar yahan chemoselectivity

 It reduces ester first and then ketone.

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

by-KULDEEP GARG (KD SIR) ASF &

 Hemiacetal ki cyclic for ko hi Lactol kehte hain.

by-KULDEEP GARG (KD SIR) ASF &