CSIR-JRF (NET), GATE

DRDO, BARC, IISC…...

LONG COURSE For CSIR-NET (JRF)-June-2017

U R
CHEMISTRY BY H. GAUR

GA
ORGANIC CHEMISTRY
H.
BY
NAMED REACTIONS
RY

SHEET-1
IST
E M

ACHARYA INSTITUTE
CH

1-K-4, M.N. Ext. KOTA

Contact: +91-8946891920
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BENZIL-BENZILIC ACID REARRANGEMENT:
* Exist in 1,2-Dicarbonyls
* Condition:
(i) OH –
+ -Hydroxy carboxylic acid
(ii) H 2O/H
1,2-Dicarbonyl
–
(i) OR
(ii) H 2O/H +
Ester of -Hydroxy carboxylic acid

* Driving force: Formation of carboxylate ion

* Attack of OH– or OR– : On the more electron defficient carbonyl group (>=O)

R
* >=O group on this, attack of OH– or OR– occur convert into –COOH or –COOR group while another carbonyl, convert into

U
alcoholic group (-OH).
OO OH
|| || |

GA
[O] (i) OH–
C6H5–CH–C–C6H5 C6H5–C–C–C6H5 C6H5–C–COOH
| || (ii) H2O/H + |
OH O Benzil C6H5
Benzoin (1,2-Diketone) Benzil acid
( Hydroxy Ketone) ( Hydroxy carboxylic acid)

H.
* Mechanism:
–
O O OO C6H5 C6H5
|| || | || | |
C6H5 –C–C–C6H5 + OH– C6H5–C–C–C6H5 HO–C–C–C6H5
Acid-base –
OOC–C–C6H5
| || | – reaction
|
BY
OH O O
Benzil H
Carboxylate ion

Acidification+
H 2O/H
RY

OH
|
C6H5–C–COOH
|
C6H5
IST

Benzilic acid

* Examples:

OO O O OH
|| || –
* || || – | *
M

(i) OH (i) OH
(1) CH3–C–C–H (ii) H+ CH3–CH–C–OH (2) C–C NO2 (ii) H
+ C–C–OH
* | || * | ||
OH O NO2 –R NO2 O
–I
E

NO2
CH

O O OH O
|| || (i) OH
– | ||
(3) CH3–C–C–CH3 + CH3–C–COOH (4) (i) OH
– OH
(ii) H /H2O | O +
(Ii) H /H2O O O
CH3 || C
O O
COOH
O –
OH
(i) OH
(5) +
(Ii) H /H2O COOH
O

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This reaction takes place through the following mechanism.
O O O
O
– || || ||
O C–OH C–O– C–OH
OH– H 2O/H
+

OH –
Acid-base
O O reaction OH OH
O

O COOH
–
K2Cr2O7 (i) OH
+
(6) (ii) H /H2O
O OH

R
O O OH

U
|| || (i) C2H5O
– |
(7) Ph–C–C–Ph + Ph–C–COOC2H5
(ii) H2O/H |

GA
Ph

O O OH
|| || – |
(i) OH
(8) CH3O C–C–C 6H 5 (ii) H O/H+ CH3O C–COOH
* 2 | *
+R C 6H 5

H.
O O OH
|| || – | *
(i) OH
(9) CH3 C–C–C 6H 5 (ii) H O/H+ CH3 C–COOH
* 2 |
+H C 6H 5
BY
O O OH
|| || – |
(i) OH
CH3 C–C CH3 C–COOH
* (ii) H2O/H+ *
(10) +H Cl
–I
Cl
RY

O O OH
|| || (i) OH– |
(11) Ph–CH2–C–C–Ph (ii) H2O/ H
+ Ph–CH2–C–COOH
* | *
Ph
O O OH
IST

|| || (i) OH– |
(12) HOOC–CH2–C–C–CH2–COOH (ii) H3O
+ HOOC–CH2–C–COOH
|
CH2–COOH
E M
CH

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SEMIBENZIL-BENZILIC ACID REARRANGEMENT:
* Exist in   L  Ketone
* Condition:
–
OH
Salt of carboxylic acid
L-Ketone
OR–
Ester
* Driving force: Formation of carboxlate ion.
* Attack of OH– or OR–  Always on the >=O group
* >=O group convert into –COO– or –COOR group

R
R2 R2
| – |
R1–C–C–R3 OH R3–C–COO–

U
|| | |
O L R1
Carboxylate ion
L-Ketone

GA
(As a salt of carboxylic acid)

*Mechanism:

R2 OH R2 R2 R2
| | | | |

H.
– –
R1–C–C–R3 OH R1–C––C–R3 R3–C––C–OH OH R3–C––C–O
–

|| | | | L– | || –H2O | ||
O L O– L R1 O R1 O
L-Ketone
BY
Questions:
Cl
–
OR
Ph N–R ?
Q.1
||
O
RY

Cl RO
OR–
| Cl – Ph
Sol. Ph N–R Ph–C–– N–R –Cl RO–C– N–R
|– ||
|| O
O O
IST

O O
Cl || Ph ||
|––C– |––C–OH
Q.2 –
OH Ans.
?
E M
CH

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CANNIZARO REACTION:
* Exist in aldehydes which does not have   H-atoms (Aromatic or Aliphatic)
* Condition:

Aldehyde OH– Alcohol + Salt of Acid

Via Disproportionation
(Without reaction
H-atom)
(Without   H- atom)
* Disproportionation reaction takes place (one molecule is reduced while another is oxidised)
* Hydride ion (H–) transfer occur

R
* Aldehyde molecule, on this attack of OH– occur convert into salt of acid while another aldehyde molecule convert into alcohol
O O

U
|| || HO–
H–C–H + H–C–H HCOO– + CH3OH
Formaldehyde Salt of Methanol

GA
formic acid

* Mechanism:

(A) At Low concentration of base:

H.
H
O O– C=O
|| – |
H
H–C–H OH H–C–H – HCOOH + CH3–O–
Acid-base
HCOO– + CH3OH
| H ion transfer Reaction
OH (Intermolecular)
BY
Rate  [ HCHO]2 [OH  ]  Third order kinetics

* At high Concentration of Base:

O O
–
O
– H O O
RY

|| | | =O || ||
– H2 O
– –
H–C–H OH H–C–H OH H–C–H H –
H–C–O + CH3–O
–
H–C–O + CH3OH
–
–H2O Slow R.D.S. –OH
| | Intramolecular
OH O– –
H ion transfer

Rate  [OH  ]2 [ HCHO]2 : Forth order kinetics

IST

* When in cannizaro reaction involve in two different types aldehyde molecules (without   H ) called cross cannizaro reation.
* When both aldehyde present within same molecule then cannizaro reaction is called internal cannizaro reaction or intramolecular
cannizaro reaction. (If both aldehydic group within molecule are different then this reaction also called internal cross cannizaro
M

or intramolecular cross cannizaro reaction)

E

* Cross Cannizaro Reaction:

CH

O O
|| || –
C6H5–C–H + H–C–H OH C6H5–CH2 –OH + HCOO–
+R
(OH– attack on the more electron defficient carbonyl)

* Internal cannizaro reaction:

OO OH
|| || OH– |
H–C–C–H H–C–COO–
1,2-Dialdehyde |
H
Mechanism operate as a benzil-benzilic acid rearrangement.
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* Internal Cross Cannizaro Reaction:
O O OH
|| || |
OH– CH –C–COO–
CH3–C–C–H 3
* | *
Keto aldehyde H

(OH– attack on the more electron defficient carbonyl)

* Mechanism operate as a benzil-benzilic acid rearrangement.

* Aldol As Well As Cannizaro Reaction:

HO OH
–
CH3–CHO + HCHO OH + HCOO–

R
Ethanal Methanal HO OH
(Excess) Pentaerythretol

U
Via three time aldol & one time cannizaro

GA
* Mechanism: Always first aldol after then cannizaro.

H H CH2–OH CH2–OH
| | HO OH
| OH – | – –
HCHO/OH CH –C–CHO HCHO/OH CH –C–CHO HCHO/OH
–
–
CH2–CHO + HCHO CH –CH–CHO | 2
| Aldol 2
Cannizaro + HCOO
Aldol | 2 Aldol | |
OH OH H OH CH2OH HO OH

H.
Example of Cannizaro Reaction:
COO– CH2OH
–
OH +
(1) –CHO + –CHO +
BY
(2) OH– –
Cl3C–CHO + HCHO Cl3C–COO + CH3OH
–I * *
Chloral
OH Side reaction
–
RY

CHCl3 + HCOO– (It also will be formed)

(Via halo form reaction)

*COO–
IST

|
–
–CHO + O2N– –CHO OH –CH2OH +
(3) *
–R |
NO2
M

–
CHO OH– COO CH2–OH
CHO CH2OH | | –
+ | –
OH– COOH COO COO
(4) (5) Salt due to basic
E

CHO COO– Not involve medium

CH

–
OH –
(6) Me3C–CHO + Me3C–CHO Me3C–CH 2–OH + Me3C–COO
CH3 CH3
O O OH | –
|
|| || –
| H3 C–C–CHO + H –C=O OH
H3C–C–CH2–OH+ HCOO–
OH C H –CH–COO– | | |
(7) C6H5–C–C–H
*
6 5
* (8) CH3 H CH3
Phenyl Glyoxal Mendilate ion Trimthyl Acetaldehyde Neo-Pentyl alcohol

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TISCHENKO REACTION:
* Exist in all aldehydes

* Condition:
Al(OC 2H5) 3
Aldehyde Ester
or Al2O3
or Na2[Fe(CO)4]

* It s extention of cannizaro reaction so during this reaction firstly formed alcohol & acid which react to each other & formed
product as a ester.
Al(OC2H5)3
CH3–CHO CH3–C–O–CH2–CH3
||

R
Acetaldehyde O Ethyl acetate
Al(OC2H5)3
CHO C–O–CH2

U
||
Benzeldehyde O
Benzylbenzoate

GA
H.
BY
RY
IST
E M
CH

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THE FAVORSKII REARRANGEMENT:
* Exist in α - halo ketones
* Condition:

OH– Acid
–
Halo Ketone OR Ester Product with Rearranged C-skeleton
–
NH2
Amide

But for cyclic   halo ketone

OH– Acid
–
OR Ester

R
Cyclic Halo keton Product with Ring Constraction
–NH2 –
Amide

U
* Gem-dihalo ketones & 1,3-dihaloketones always give ,  -unsaturated ester or acid as a cis alkene.
* ,  -Epoxy ketones alwas give   Hydroxy ester/acid.

GA
CH3
For * –COCH3 CH3
H
Product * –Cl –COOR
* CH3–C
||
O Cl

H.
–
OR
C6H5–CH2–C–CH2 –Cl C6H5–CH2–CH2–C–OR
|| ||
O O
Major
Mechanism:
BY
H
– OR–
CH CH2 CH CH2–Cl –Cl
– C6H5–CH––––CH2 C6H5–CH––––CH2
C6H5 OR – C6 H5
C Cl –ROH
C (a) (b)
|| || C C
O O ||
O O– OR
RY

(Cyclopropanone)
(Characteristic intermediate of this reaction)

(a) (b)
–
C6H5 –CH –CH2 –C–OR C6H5–CH–CH2–
||
IST

O COOR
More Stable Less Stable
H 2O/H + H2O/H +

C6 H5–CH2–CH2–C–OR C6H5–CH–C–OR
|| | ||
M

Major O CH3 O
Minor
E

* Similarly
CH

O COOR COOR
* Cl OR– * *
+
COOR COOR
Mechanism: O– OR –
(a) * H2O/H+ *
O O O (a) (b)
H * Cl – * Cl * COOR
OR– * OR– COOR
–ROH –
(b) * H2O/H+ *

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FAVORSKII AS WELL AS SEMIBENZIL-BENZILIC ACID REARRANGEMENT:

–
OD /D2 O COOD
O
Via semibenzil benzilic
acid rearrangement
D
OD–/D2 O (Favorskii product is more favoured)
Br COOD
Via Favorskii
rearrangment

When H in
O R3 Favorskii
|| | R1 is present
Normal

R
R1–C–C–R2
| When
Product
H in Semibenzil-Benzilic
Cl
R1 is absent acid rearrangment

U
Abnormal
OR
–
For semibenzil Product
benzilic acid

GA
rearrangement
(b)
–
O R3 O
| | (b)
R1–C–––C–R2 R1–C––C–R3
(a) | | Epoxide ring | |
OR Cl formation OR R2

H.
Abnormal
(a) Product
R3
|
RO–C–C–R2
|| |
O R1
BY
Normal Product

SETEROCHEMISTRY OF THE FAVORSKII REARRANGEMENT:

RY

* For favorskii in cyclic ketones: The presence of equitorial halogen at   position is must.
* If halogen present at axial position then favorskii does not take place.

O O O
||
IST

Cl
Cl
Cl
Only in the cyclic Less Stable
Halo kleton More Stable
Preferred conformer
M

for the favorskii

Q.1 Which one of the following compounds give the Favorskii rearrangement.
E

O O O O
CH

Cl
Cl Cl Cl Ans: Give
Ans: Not Give Ans: Not Give Ans: Not Give

CH3 CH3
O CH3
COCH3 CH3OC COCH3
Cl
CH3 Cl H H Cl
Cl Ans: Give Ans: Not Give Ans: Give
(B’coz of this compound Does not cyclic) (B’coz of Cl does not at position)

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Mechanism with stereochemistry:

O O
– –
OR
* H No Reaction (B’coz of does not possible back side attack)
–ROH
Cl Cl
–
O
O O O
–
– OR OR
–
* H Cl OR Cl Equitorial
–ROH attack

R
– H2 O/H+
COOR COOR

U
Major Major

GA
CH3 CH3
CH3 CH3 –
– Rotation H H OR
OH OR OH
–
* –ROH CH2
CH3 –CH || Cl
2
Cl Cl O O

H.
CH3 CH3 CH3
(b) H2O
H H H
(a)
ROOC – COOR
– (b) Less stable Minor
O
BY
OR
(a)

H CH3
CH3 CH3
H2O H
CH2
–
CH3 COOR
RY

COOR COOR
More stable Major

CH3 *COCH3 CH3

IST

OH Changes during the reaction

*Cl COOR
CH3
Cl
M

CH3 CH3
–
H OR ? H
E

Cl
Q. Ans: ROOC
O=C–CH3
CH3
CH

* FAVORSKII REARRANGEMENT IN GEM & 1,3-DIHALIDE:

H Br Br Br Br
O– COOR
O –
– O O –
OR OR
OR
Br Br

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 H
– –
* O –
O O O COOR
OR Br OR
–
Br
Br Br Br Br
Gem-dihalide
CH 3
CH 3
CH 3
Q. OR– Ans:
COCH3 ?
H COOR
H Cl
BrO H
| || ROOC

R
OR – C=C
Q. H3C–C–C–CH2–CH3 ? Ans:
| H3C CH3
Br

U
Cis-alkene
Gem-Dihalide (Always cis)

GA
* Duing this reaction always cis product obtain, reaction takes place as follows.
O O– OR
||
Br O C C CH3 CH3
| || – –
OR CH3–C–––CH–CH3 OR CH3––C–––CH–CH3 C=C
H3C–C–C–CH–CH3 |

H.
| | | ROOC H
Br
Br H Br (Ester)
Cis alkene

Br O Br H3C CH3
| || | OR
–
BY
Q. H3C–CH–C–CH–CH 3 ? Ans: C=C
H COOR
1,3-dihalide (Ester)
Cis alkene
(Always cis)
Gem-dihaloketone ( ,   dihalo)
and Always give ,  -unsaturated acids or ester
RY

1,3-Dihalo ketone (  ,  ' dihalo)

* During the reaction always cis product is obtained

O
IST

COOR
|| |
OR–
Q. R–CH–CH–C–CH2–R’ ? Ans: R–CH–CH–CH2 –R’
|
O OH
Epoxy ketone Hydroxy ester/acid
M

O
||
O O C
E

|| – || –
Sol. R–CH–CH–C–CH2–R’ OR OR–
–ROH R–CH–CH–C–CH–R’ R–CH–CH–––CH–R’ ROH–
–OR
CH

|–
O O O

O O– OR
||
O C COOR COOR
–
| – H2O
|
OR R–CH–CH–CH–R’ R–CH–CH–CH2–R’
R–CH–CH––––CH–R’ R–CH–CH–––CH–R’
| | |
OH OH OH
Hydroxy ester
* ,   Epoxy ketone always give  -Hydroxy ester or  -Hydroxy acid

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 O
|| –

Q. R–CH–S–CH–R’ OH ? Ans: R–CH=CH–R’

| || | –SO2
X O H
Halo Sulphone

O O
O O S
|| OH
– || –
Sol. R–CH–S–CH–R’ R–CH–S–CH–R’ R–CH–––CH–R’ R–CH=CH–R’
| || | –H2O | ||
X O H X O
Halo Sulphone
* This rearrangement is called ramberg backlund rearrangement.

U R
GA
H.
BY
RY
IST
E M
CH

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FAVORISKII REACTION:
* Exist in carbonyl compounds.
* The conversion of carbonyl compounds into 1,4-diol, usin acetylene & NaNH2 is called Favorskii reaction.

2R–CHO + 2NaNH2 + HC CH R–CH–C C–CH–R

| |
OH OH
1,4-diol
Mechanism:

2NH 2– – –
H–C C–H C C

R
–2NH3

U
H H
| | 2NH3
– –
R–C + C C + C–R R–CH––C C–CH–R –2NH2–
R–CH–C C–CH–R
|| || |– |– | |

GA
O O O O OH OH

* If electron with drawin group is present in alkyl group (R) then Rate of reaction is increase.

H.
BY
RY
IST
E M
CH

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CONDENSATION REACTIONS:
Basic
Substrate + Reagent   Product
* Reagent For Condensation Reaction:

CH2––––G Electron withdrawing group

|
H Reagent as a Nu–
–CHO
–COCH3
–COOR
–NO2
–CN etc.

CN

R
G
H–CH–COOEt H–CH
| , H–CH , CN R–C C–H ,
H–CH–COOEt G

U
Propane 1,3-dinitrile

COCH3

GA
COOEt H–CH
H–CH COOEt
COOEt H–HC H–C CH Malonic ester
Malonic ester AAE or B-keto ester

H.
.. COCH3
N H–CH R S
COCH3 C
N CH2–H H S
Acetyl Acetone
BY
RMgX, RLi, R2CuLi, R2Cd
SUBSTRATE FOR CONDENSATION REACTION:

[I] Substrate for Nucleophilic Attack in Nucleophilic Addition Reaction:

R–CH=C=O R–N=C=O
RY

= O (Aldehydes & Ketones) R–C N Isocyanate

Ketene
O

CH2=CH–––G (Involve in michael addition) R

Benzyne
IST

Epoxides

(II) Substracte for Nucleophilic Attack in Nucleophilic Substitution Reaction:

O |
| | || | ––C––COOR
Ph–CH2–X
M

R–X –C–C–C– |
C=C–CH 2–X | |
Alkyl halide Benzylic halides X X
Allylic halides
Halo ketones Halo ester
E

O O
|| O ||
R–C–G || EtO–C–OEt
CH

–OR, –X, –NH2, –OCOR

Acid derivative Cl–C–OEt Diethyl cabonate
Ester Acid Amide Anhydride
halide

(But very less reactive)

O O=C–OEt
|| | N
Cl–C–F O=C–OEt Pyridine

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IMPORTANT QUESTIONS:
CH3
CH3 (i) OH– C=
Q.1 C=O + + ? Ans.
CH3 (ii) H2O/H CH3
(iii)
* It is application of Knoevenagel reaction.
(i) NaNH
Q.2 R–C C–H (ii) HCHO2 ? Ans. R–C C–CH 2–OH
+
(iii) H2O/H

(i) 2equ.NaNH2 Pd-CaCO3/Quinoline OSO4

H–C C–H A B C
Q.3 (ii) 2equ. HCHO H2
(iii) H2O/H+

R
H H
C=C CH2–CH –CH–CH 2
| | | |

U
Ans: HO–CH2–C C–CH2–OH HO–CH2 CH2–OH OH OH OH OH
(B)
(A) (C)
Meso, Optically

GA
inactive, cis

1Equ. base (A)

O O R-X
Q.4 || ||
2Equ. base (B)
CH3–C–CH2 –C–OEt
R-X
AAE –

H.
OH /R–X OH–
(C) (D)
R–X

O O O O
O O || - || || ||
|| || CH3–C–C–C–OEt
CH2–C–CH–C–OEt
BY
Ans: CH3–C–CH–C–OEt |
| R R
R R (B) (D)
(A) & (C)
–
Q.5 H3C–CHO + CH3–NO2 OH ? Ans: CH 3–CH –CH2–NO 2
H2O |
OH
O
RY

|| (i) OH
–
H O/H
+
Q.6 CH3 –C–CH2–COOEt (A) 2 (B)
(ii) CH2–CH2–CH2
AAE | |
Br Br
IST

O Br Br
O | | O
|| – || - CH2–CH2–CH2 || OH
–
OH CH3–C–CH–COOEt
Ans. CH3–C–CH2 –COOEt CH3–C–CH–COOEt –
–H2 O –Br –H2O
CH2 CH2
Br CH2
M

O
O O O ||
|| – || || O O
H2O/H+ || || CH3
E

CH3–C–C–COOEt CH3–C–C–––C–OEt
CH2 –Br- OH H CH3–C–C––C–O H
CH2 –EtOH –CO2
(A) (B)
CH

Br CH2

Br O
S H S S
H (i) RLi RLi HgCl2
Q.7 C (A) (B) (C) Ans: C C
(ii) Br
H S Br S S (C)
(A) (B)
O O
S || ||
Q.8 R (i) RLi
C ? Ans: R–C–C–R
H S (ii) RCOCl Substrate for Benzil-
(iii) HgCl2 Benzilic acid Rearrangement

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STARK ENAMINE CONDENSATION:
* Enamine = Ene + Amine
* Preparation of Enamine:

H OH
H–CH2 .. | |
=O + HNR2 CH2–C–NR2 NR2
R | –H2O
R Enamine
H
| OH
..
O+HN N N
–H2 O
Enamine

R
* Enamine has two nucleophilic site; N &   C  atom of carbonyl but use only C–nucleophilic site
* Here following types of carbonys and 20 - Amineas are used:

U
O O O

GA
N N
,
N
H H H
* The reaction of Enamine with electrophile (E+) is called stark Enamine reaction. (or stark Enamine condensation)

+ O
.. ..
N N H2O E

H.
+
+E E

* In this reaction as a Electrophile, the following reagents can be used.

BY
O O R
O || ||
E + =O || CH2–C–R CH2–C–OR
R–C–Z | |
Cl Cl O
CH2–X O=C–OEt e– withdrawing group
| R–X CH 2=CH–CH 2–X
RY

O=C–OEt CH2=CH––G
CH2R
(i) O
? H
Q.1 Me (ii) R–CH2–X Ans:
N Me
(iii) H2O/HCl
IST

H Optically active

O
||
.. Me + Me +
N X Me
–
Me N Me N Me
.. + ||
Me –H2O || R–CH2–X CH2–R
Sol. Me
M

N –
H H
E

O
|| CH2–R
+
–H2O/H H +
CH

Me +
N Me
Optically
active H –
H
X
* This reaction is the example of enantioselective reaction.
* The important use of this reaction is as following reaction.
O O O O
|| || || ||
H E E
or or

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BENZOIN CONDENSATION REACTION:
* Exist in Aromatic carbonyls, ,   unsaturated carbonyls & Heterocyclic aromatic carbonyls (Mostly only in aldehydes)
C N
HCN/Base
=O
Aliphatic OH
carbonyls Cyanohydrine

HCN/Base
CHO No Cyanohydrine will be formed

H C N
Aromatic Me3SiCN
Carbonyl OH

R
Ph
Cyanohydrine

U
* Thus aromatic carbonyls does not give cyanohydrine with HCN, while formed cyanohydrine with Me3SiCN.

* In R.D.S., CN– attack on this carbonyl which is convert into more nucleophilic carbanion (C–) after the attack of CN– ion.

GA
This
|
carbonyl is maintain at the end of reaction. while another carbonyl convert into –CH–OH group.
* Rate  [C 6 H 5 CHO ]2 [CN  ]  Follow third order kinetics
Alc. KCN

H.
* 2C6H5–CHO Or Alc. NaCN C6H5–CH–C–C H
| || 6 5
Benzaldehyde OH O
Hydroxy ketone or
Benzoin
BY
Mechanism:
–
O Step-I O
|| | –
– R.D.S. Acid base –
H + CN C6H5–C–H C6H5–C–C N C6H5–C=C=N
Slow | Reaction | |
C N OH [A] OH
RY

O CN Step-II O– CN OH CN
|| | | | | |
C6H5–C + C–OH R.D.S. C6H5–C–––C–O–
–
C6H5–C–C–OH C6H5–CH–C–C6H5
| | Slow | | | | | ||
IST

H C6H5 H C6H5 H C6H5 OH O

[A] Benzoin

* Rate  [C6H5CHO]2[CN- ]  Follow third order kinetics

M

* KCN is used in the Benzoin condensation B’coz of

(i) It is a good nucleophile
E

(ii) It is a good leaving group

CH

(iii) It also increase the acidity of H-atom, attach on the carbonyl carbon
Examples of Benzoin Condensation Reaction:

alc. KCN
(1) + –CH–C–
CHO CHO | ||
O O O O
OH O
Furoin

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Important Points:
* Electron withdrawing group is present at o- or p-position of –CHO, then decrease the reaction rate due to decreasing
nucleophilicity of carbanion [A]. B’coz of in this condition step-II is hardly proceed.
* If electron donating group is present at o- or p-position of –CHO, then also rection rate decrease B’coz of in this condition
reactivity of aldehyde is decrease w.r.t. CN– attack in the step-I.
* Thus, electron withdrawing as well as electron donating both types of group at o- or p- position decrease the reaction rate.
* Generally, CN– attack on the that carbonyl which convert into more nucleophilic carbanion (have more electron charge
density) after the attack.

*CHO

R
CHO

(2) alc. KCN *

–CH–C– –CH3

U
+
| ||
OH O
CH3

GA
+H

H OH OH
CHO O OH
(3) CHO
alc.KCN
+ |
CHO CHO

H.
B’coz of OH
O aromatisation.
Convert into H OH OH
Convert into more Nu–
–
less Nu Carbanion
Carbanion –
So Cn attack
on this
BY
CHO
|
(4) 2 alc.KCN
No. Reaction
| * In ex.-4, step-II does not proceed b’coz of NO2 has strong
RY

NO2 electron withdrawing effect, so nucleophilicity of carbanion

is highly decrease
CHO
| * In ex.-5, step-I does not occur due to strong electron donating
effect of -N(CH3 )2
alc.KCN
IST

(5) 2 No. Reaction

|
N
CH3 CH3
E M
CH

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ACYLOIN CONDENSATION REACTION:
[O] [R]
Ph–C–C–Ph Ph–CH–C–Ph Ph–CH–CH–Ph
|| || | || | |
O O OH O OH OH
Benzil Benzoin Pinacol
Involve in Benizil-Benzilic Involve in Pinacol
acid rearrangement Pinacolone rearrangement
* Exist in Dibasic acid ester.
* Condition:
Akali Metal
Dibasic acid ester -Hydroxy Cyclic Ketone
In xylene

OEt

R
O OH
Na/xylene/ H 2O

U
O
OEt O
Dibasic acid ester Hydroxy Cyclic Ketone

GA
Mechanism:

O O–
O O– OH OH
OEt 2Na OEt 2Na 2H2O
– +
OEt –2Na+ OEt –2EtO –2Na
O O– O–H O

H.
O O–
1,2-Diketone -Hydroxy
Dibasic acid ester Cyclic Ketone
BY
RY
IST
E M
CH

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CLAISEN ESTER CONDENSATION REACTION:
* Takes palace in between to ester molecules.
* Presence of stronge base like C2H5O–, NH2– or OH–
O O O O
|| || – || ||
CH –C –OEt + CH –C–OEt OH CH –C –CH –C–OEt
* 3 3 3 2

Ethyl Acetate AAE

Mechanism:
–
H O O O
| || OH– – || |
CH2–C –OEt CH 2–C –OEt CH 2=C–OEt

R
O O O– O O O O O
|| || | || || || OH
– || – ||
CH3–C–OEt + CH2–C –OEt CH3–C–CH2–C–OEt CH3–C–CH–C–OEt CH3–C–CH–C–OEt

U
| |
OEt H

GA
O O
H3O
+ || ||
CH 3–C –CH2–C–OEt
AAE
* In order to shift the equilibrium in the forword direction, ester should have atleast 2  H  atom.

H.
CROSS CLAISEN ESTER CONDENSATION REACTION:
* If the reaction takes place in between two different ester molecules called Cross Claisen Ester Condensation
BY
React ion.
O
|| OH–
CH3–C–OEt + CH3–CH2–C–OEt A+ B + C + D
||
O Ethyl Propionate
Ethyl Acetate
RY

Here products are;

CH3–C–CH–C–OC2H5 CH3–CH2–C–CH2–C–OEt
CH3–C–CH2–C–OEt CH3–CH2–C–CH–C–OEt || | || || ||
|| || || | || O CH3 O O O
O O O CH3 O Cross product
IST

Cross product
(A) (B) (C) (D)

CLAISEN CONDENSATION REACTION:

* If the reaction takes place in between ester & Ketone, the reaction is known as claisen condensation reaction.
M

O H O O O
|| .. | || || ||
E

OH–
CH3 –C–OEt
.. + CH2–C– CH3–C–CH2–C–Ph
CH

* L.P. of electron is easily transfer compaire to   bond, so enolisation of ester does not occur, while the enolisation of ketone
is takes place.

CLAISEN REACTION OR CLAISEN-SCHMIDT REACTION:

* It is example of cross aldol condensation reaction.
Dil. OH–
Aromatic Carbonyl Compound + H-Containing Carbonyl Compound Unsaturated Compound
(Aldehyde or Ketone) (Aldehyde of Ketone)

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 H
| OH–
* C6H5–CHO + CH2–CHO C6H5–CH=CH–CHO
Cinamaldehyde
Mechanism:

OH– –
H–CH 2–CHO CH 2–CHO
–H2O
–H2O
C6H5–CH–CH2 –CHO –OH– C6H5–CH–CH–CHO –H2O C6H5–CH=CH–CHO
–
C6H5–C–H + CH2 –CHO
|| | | |
O O– OH H

EXAMPLE OF CLAISEN ESTER CONDENSATION / CLAISEN CONDENSATION/CLAISEN-SCHMIDT REACTION:

R
O O O O
|| || || ||

U
–
(i) OEt
(1) Ph–C–OEt + CH3–CH2–C–OEt (ii) HCl Ph–C–CH–C–OEt
|
CH3

GA
Ethyl 2-methyl-3-Phenyl
-3-Oxopropanoate

O O O O
|| || –
(i) OEt || ||
(2) EtO–C–OEt + CH3–C–OC2H5 EtO–C–CH2–C–OEt
(ii)H Cl
Diethyl Malonate

H.
O O O OO O
|| || || (i) OEt
– || || ||
(3) EtO–C–C–OEt + CH3–C–OEt EtO–C–C–CH 2–C–OEt
(ii) HCl
Diethyloxaloacetate
BY
H O O
CH2––O | (i) O
–
C || ||
2H5
| C=O + CH3–CH–COOC2H5 (ii) HCl HO–CH2–CH2–O–C–CH–C–OC2 H5
(4) CH2 ––O |
CH3
(2-Hydroxyethyl)ethyl- 2-methyl propanedioate
RY

H O O O
| || – || ||
(i) OEt
(5) CH2–C–CH3 + CH3–COOC2 H5 (ii) HCl CH3–C–CH2–C–CH3
Acetylacetone
IST

O O O
|| (i) OEt–
(6) + EtO–C–OEt
(ii) HCl
H C–OEt
||
O
M

H
H3C OH | CH3 OH
CH2 COOEt (i) OEt COOEt
E

(7) || + | || ||
O COOEt (ii) H3O+ O O
CH

_
O O O O O OH
|| HCl/H2O
+ H–C–OC2H5 NaH H
(8) H C–H C–H CHO CHO
|| |–
O O

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DIECKMANN CONDENSATION REACTION:
* Exist in dibasic acid ester.

Dieckmann Condensation
Intramolecular Intermolecular
OH
–
OH–
In Higher Dibasic In Lower Dibasic
Acid Ester Acid Ester

Product: Keto Ester Product: 1,4-Diketo Ester

Intramolecular Dieckmann Condensation reaction:

R
* Exist in higher Dibasic Acid Esters.

U
OEt COOEt
–
O OH

GA
O HCl/H2O C=O
OEt
Dibasic Acid Ester Keto-Ester
Mechanism:
* (Similar to Claisen Condensation)

H.
H
OEt – OEt COOEt
O OH –
O O–
BY
O O
C
OEt OEt OEt
Dibasic Acid Ester
COOEt COOEt COOEt
H –
RY

–
C=O OH C=O HCl C=O
H 2O

Intermolecular Dieckmann Condensation Reaction:

IST

* Exist in diester of succinic acid

O O
H || EtOOC ||
EtOOC
M

EtO CH2 –
CH OH
HCl/HOH
OEt CH COOEt
CH2 H COOEt ||
E

C O
||
O 1,4-Diketo Ester
CH

Diester of Succinic Acid

Mechanism:

EtOOC H EtOOC
OH– –
CH CH

CH2 OEt CH2 OEt

C C
|| ||
O O

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 O O
|| ||
C EtOOC C O
EtOOC EtO – HC CH2 H ||
– CH2 OH
CH | –
EtOOC 2OH
–

+ CH CH2 CH
OEt H C OEt COOEt COOEt
CH2 COOEt || || H
C O O
||
O

O COOEt
EtOOC – || + O
H3O
–
|| COOEt O

R
O COOEt
CH2=CH–COOEt (i) C2H5ONa/C2H5OH
Q.1 R–NH2 + CH 2=CH –COOEt (A) (B) (ii) HCl/H2O
(C)

U
.. Michael ..
Sol. R–NH–H + CH 2=CH–COOEt addition R–NH–CH2–CH2–COOEt CH2=CH–COOEt

GA
Michael addition
(A)

O
|| O
1C O 1|| COOEt
2 OEt || 2 6
CH2 H (i) OEt
–

| 6CH–C–OEt

H.
+
3 (ii) H 3O 3 5
CH2 4 5CH 4N
2
N | (C)
(B) R | R
Hetero Cyclic Keto Ester
BY
COOEt O
||
O
(i) H3O+
Q.2 (ii)
O ||
COOEt O
Cylohexane1,4-dione
RY
IST
E M
CH

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 STOBBE CONDENSATION REACTION:

H2 C–COOR EtO–Na+
=O + | =C–COOR
CH2–COOR Or Me3CO–Na+ |
Aromatic (Strong base) CH2–COOH
or Aliphatic Dialkyl Succinate
Unsaturated half ester
or
Unsaturated half acid
Mechanism:

H
| | | |

R
| –
––C + H–CH–COOR EtO –C–CH–COOR ––C –C––––C––COOR
|| | –EtOH | | 4 | ––––C–COOR
3| EtO
–
| |
O CH2 O– CH2 –OR– O 1 CH2 2 O CH2

U
–EtOH
RO–C C C
RO–C || ||
|| ||
O O O O

GA
Cyclic ester
or Lactone
or Butyro Lactone

=C–COOR + |
H2O/H
| –C=C–COOR

H.
CH2–COO– |
CH2–COOH
Unsaturated half ester
or
Unsaturated half acid
BY
Example of Stobbe Condensation reaction:
(1) C6H5–C=O CH2–COOEt Ph–C=C–COOEt
(i) NaH/EtOH/C6H6 | |
| + |
CH3 CH2–COOEt (ii) AcOH/H2O CH3 CH 2–COOH

O
RY

– +
||
(i) (CH3)3CO K /(CH3)3COH n-C11H23–C=C–C–OEt
(2) N-C11H23–CHO + CH2–COOEt | |
| (ii) HCl/C2H5 OH
CH2–COOEt H CH2–COOH
IST
E M
CH

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KNOEVENAGEL REACTION:
* When the aromatic aldehydes are treated with active methylene compound in the presence of base followed by Hydrolysis, ,  
unsaturated compound will be form.
COOEt
(i) OH–
Ar–CH=O + H2C (ii) H3O+ Ar–CH=CH–COOH
COOEt (ii i) Unsaturated acid
Mechanism:

COOEt COOEt
H–CH OH– –
–H2O
CH
COOEt COOEt

R
H COOEt COOEt COOEt COOEt
| – H2O

U
Ar–C + CH Ar–CH–CH Ar–CH–C –H2O
Ar–CH=C
|| | COOEt | | COOEt COOEt
COOEt O– OH H
O

GA
COOH
H2O/H+ Ar–CH=C Ar–CH=CH–COOH
–CO2
COOH -Unsaturated acid
Example of Knowledge Reaction:
COOEt –

H.
(i) OH
(i) Ph–CHO+ H2 C + Ph–CH=CH–COOH
(ii) H 3O
COOEt (iii) Cinnamic acid

COCH3 (i) OH
–

+ Ph–CH=CH–C–CH3
BY
(ii) Ph–CHO + H2C (ii) H3O ||
COOEt (iii) O
-Unsaturated Ketone
(Substrate for Michael addition)
RY
IST
E M
CH

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PARKIN REACTION:
Salt of acid that form anhydride

RCOONa -Unsaturated acid

Aromatic Aldehyde + Anhydride
(Generally) (with Atleast 2 H-atom)

O O |
| || || | H2C–COONa
|
Ar–CH= O + H2 C–C–O–C–CH2 Ar–CH=C–COOH
Replace by COOH group

O O
|| || CH 3COONa
* C6 H5CHO + CH3 –C–O–C–CH3 C6H5–CH=CH–COOH
Benzaldehyde Acetic Andhydride Cinnamic acid

R
Mechanism:
O O O O

U
|| || – – || ||
H–CH2–C–O–C–CH3 + CH3COO CH2–C –O–C–CH3 + CH3COOH

GA
–
O O O O CH3 O CH3
|| || || | | C6 H5 –CH C
–
C6H5–CH + CH2 –C–O–C–CH3 C6H5–CH OCOCH3
C=O | | O– |
| | CH2 O C6H5 –CH––CH–COO–
CH2 O C
|
|| H
C

H.
|| O
O
+
– H3O
CH3COOH C 6H 5 –CH=CH –COO C 6H 5–CH=CH –COOH
BY
Cinnamic Acid
* Anhydride should posses atleast 2 H-atoms. It’s characterisic of anhydride for this reaction.
EXAMPLE OF PERKIN REACTION (PERKIN CONDENSATION):
O O O
|| || || CH 3COONa
RY

(1) CH2 =CH–C –H + CH3 –C–O–C–CH 3 CH2=CH–CH=CH–COOH

Acryl aldehyde Acetic Anhydride
O O
|| || CH3COONa
(2) + CH3 –C–O–C–CH3 CH=CH–COOH
IST

CHO
O O

O CH–COOH
|| ||
C O O C
|| || CH3COONa
M

(3) O + CH3–C–O–C–CH3 O
C C
|| ||
O O
E

CH3COONa
(4) Ph–CH=CH–CHO + (CH3CO)2O Ph–CH=CH–CH=CH–COOH
CH

(5)   Acylamino acids can be used in place of acid anhydride in he Perkin reaction.

C6 H5–CH=O + H2 C – COOH CH3COONa Ph–CH=C––––C=O

| (CH3CO) 2O | |
H––N––C–CH3 N O
|| C
O |
-Acylamino acid CH3
Azlactone

This reaction specially known as Erlenmeyer Azlactone synthesis.

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Mechanism:

H2C–COOH H2C––––C=O H2C––––C=O Ph–CH=C––––––C=O

| | | Ac 2O | | | |
tautomerisation N OH PhCHO
H–N O –H2O N O N O
C C OH C C
| | | |
CH3 CH3 CH3 CH3
Azlactone

U R
GA
H.
BY
RY
IST
E M
CH

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ALDOL CONDENSATION REACTION:
* The carbonyl compounds having   H-atom undergoes self condensation reaction in the presence of dilute acid or base &
formed a   Hydroxy carbonyl compound (Aldol). This reaction is known as Aldol addition reaction.
* Which on heating loss one H2O molecule & give ,   unsaturated carbonyl compounds this is called condensation reaction.
* The aldol addition followed by dehydration of aldol is known as Aldol condensation reaction.

H +/OH – -Unsaturated carbonyl

-H containing carbonyls Hydroxy carbonyl –H2O
(dilute)
(Aldehyde or ketones) (Aldol)
Aldol addition
Condensation

R
Aldol Condensation Reaction

U
O O O
|| || ||
dilute acid
CH3 –C–H + CH3 –C–H or CH3 –CH–CH2–C–H CH3–CH=CH–CHO
| –H2O

GA
dil. base
OH -Unsaturated carbonyl
(Aldol)
Hydrox carbonyl
Mechanism:
(I) In Acidic Medium :

H.
O OH+ OH
|| || –H
+ |
CH2–C–H + H+ CH2–C–H CH2=C–H
| |
H H Enol
BY
OH+ O–H
|| |
CH3 –C–H + CH2=C–H CH3–CH–CH–CHO CH3–CH=CH–CHO
| | –H2O
Enol as a Nu– OH H Aldol -Unsaturated compound
RY

(II) In Basic Medium:

O O O–
|| – || |
CH2 –C–H + OH– CH2 –C–H CH2=C–H
| –H2O
H Enolate ion
IST

–
O O O O
|| – || | ||
CH3–C–H + CH2 –C–H CH3–CH–CH2–C–H H2O CH3–CH–CH–CHO CH3–CH=CH–CHO
Enolate as | | –H2O
– OH H Unsaturated carbonyl
a Nu
M

Aldol compound
* In acidic medium enol, while in the basic medium enolate ion is formed as a Nu–.

O H2 O
||
O
||
E

CH3 –CH=CH–C–H CH3–CH=O + CH3 –C–H

Product Starting meterial
CH

* Type of Aldol Condensation Reactions

Simple Cross

B/w Same Carbonyls B/w different Carbonyls

Structurally possible product always one. * B/w two diff. Aldehydes

* B/w two diff. Ketones
* B/w Aldehydes & Ketones

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* Between two different aldehydes

When both have When one have

H-atom H-atom

4-Product formed 2-Product formed

* Between Aldehyde & Ketone: Enolate form by the ketone

* Between two different ketones: Unfavourable Because of Enolate is a bulky Nu– as well as ketones are less reactive towards the
Nucleophilic addition reaction.

R
* When this reaction is carried out in Ketone yield is very poor due to
(i) Enol is a bulky Nucleophile, so increases steric repulsion.

U
(ii) Ketones are less reactive towards the the Nucleophilic addition reaction.

GA
Q.1 Identify the initial material of the given product.
(1) CH2=CH–CHO  HCHO + CH 3CHO
O O
1|| 1||
2 2 CH3
(2)  O 1,4-Diketone
3 3

H.
4 4

O O
1|| 1||
2 2 CH3
(3)  O 1,5-Diketone
BY
3 5 3
4 4 5

O O
1 1
2 67 2 7
O 6
(4) 
3 5 3 5 1,7-Diketone
RY

4 4
Intramolecular Aldol Condensation Reaction:
(I) In 1,4-Diketones:

H
IST

2 2 O
O 1 || 3 1
3 5 H 2O
4 3
1 OH– O O– OH
2 H 4
–H2O
O CH2– O
5 O
1,4-Diketone O OH
M

(II) In 1,5-Diketone:
O O O
E

5|| ||
H
||
O O 4 H2O
3 5 OH
– –
H O
CH

3 –H2O
2 4 6 1 It is reagent for Michael Addition
2 OH
1,5 Diketone H
(III) In 1,6-Diketone:

O H (A)
7 (i) OH
–

1 3 5 6
2 4 H (ii) H2O
O (B)
For B
1,6-Diketone

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 O O O
O 6||
4 H
7
5 5
3 H
4
OH –H2O
OH –H2O 1
2 1 Major 3 2
(A) (Not Cyclic Minor
(B)
Major Ketone, it is a Cyclic Minor
(More Stable) Alkene) (Less Stable)

(IV) In 1,7-Diketone:

R
O
O O 5 ||
1|| 3 5 7|| – 4 6
2 4 6 (i) OH

U
H
| (ii) H2 O 3 1
1,7-Diketone H (iii) 2
Major

GA
Cyclic Alkene
(Not Cyclic Ketone)
(V) In Cyclic Diketone:

H O O
O | O

H.
2 3 O 1 2 2 H
3 4 3 1
1 – 2 3
OH H2O
6 7
4 5 4 7 4 –H2O
5
O 5 6 O 5 –
6 O OH
1,6-Cyclic ketone
BY
Stereochemistry of Aldol Condensation:
–
C6H5 –CHO + CH3 –CHO OH C6H5–CH–CH–CHO C6H5–CH=CH–CHO
–H2O
| | Cinnamaldehyde
OH H
RY

cis trans
H H H CHO
C=C C=C
CHO
IST

Ph Ph H
Minor Major
Diastereoselectivity of the Aldol Condensation:
M

O OH
O O– ||
|| H |
OH– R–CHO R R
R R
CH3 (Erythro Form)
E

CH3 CH3
Anti-Diastereomer
E-Enolate
CH

(Give Anti Distereomers

as the major product)
O– OH
O | CH3
|| CH3 OH –

R R–CHO
R R R
H Z-Enolate
(Give Syn Distereomers CH3 (Threo Form)
as the major product) Syn-Diastereomer

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 O
||
Q.1 OH –
?
Ph–CHO

– –
O O O H OH
|| || ||
H
OH
–
Ph–CHO Ph
(Erythro)
Sol.
E-enolate
(Always)

R
* O O OH
|| O
CH3 | Ph-CHO
OH
–
CH3
Ph

U
H CH3
Z-enolate (only)
Bulky group, so increase Hindrance Syn-Diastereomer (only) (Threo)

GA
in E-enolate so that E-enolate is not form

DIRECTALDOL CONDENSATION REACTION:

* When cross aldol condensation is carrid out by the help fo LDA then this reaction known as directed aldol condensation
reaction.

H.
+ –
Li N

LDA
BY
* It is strong base but it is not a Nu– (Weak Nu–)
* Abstract more acidic   H -atom.
* But if acidity is same then, abstract less sterically Hindard   H -atom. because it is a bulky base.

O
O O ||
|| || – CH3–CHO
LDA CH2–CH2–C–CH–CH–CH3 (Aldol)
RY

* CH3–CH2–C–CH2–H CH3–CH2–C–CH2 | |
(Enolate formed by the Enolate ion H OH
Ketone)
–H2O
O
IST

||
CH3–CH2–C–CH=CH–CH3

O O O O
|| || – || ||
PhCHO
–C–CH3 LDA –C–CH=CH–Ph
M

* –C–CH2 –C–CH–CH–Ph
| | –H2O
Enolate ion H OH
E

O O
CH3 || CH3 ||
CH–Ph CHPh
O |
CH

CH3 LDA
|| Ph-CHO OH –H2O
H
* H
O
CH3 ||
NaH
PhCHO Ph–CH
|
OH

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 –
O O
CH3 || |
LDA CH3
–

O
* CH3 || More Stable Less Stable

–
O O
CH3 – || CH3 |

NaOH

Less Stable More Stable

* NaH is not used for reducing agent (Bad Reducing agent.)

R
Example of Aldol Condensation Reaction:
O O

U
|| – ||
(1) CH3–CHO + CH3 –C–CH3 (i) OH CH3–CH=CH–C–CH3
(ii)

GA
CH3
|
C CH3
CH H2 |
O Conc. H2SO4
H2 CH O –3H2O

H.
| || H3 C CH3
(2)
C C
O H CH CH3 Mesitylene
CH3 2

Acetone
BY
(3) O
O O || O
CH3 || Dry CH3 || CH3–C–CH3 CH3 || CH3
=O + H2CH–C–CH3 =CH–C–CH H2 =CH–C–CH=
CH3 HCl CH Mesityl Oxide
Acetone 3 CH3 Phorone CH3
RY

Conc. H2SO4
Mesitylene
Acetone
Dry HCl
Mesityloxide Acetone Phorone
O O
IST

|| H D || D
(4) OD–/D2O
D D
M

H O
Et Racemisation
–
OD/DO
(5) 2
will be takes place
E

CH3 R e.e. zero

–
OD
CH

Et Et –
O O
–

Me R Me R

D–OD

* Racemisation will be take place

* Enantiomeric Axis (e.e.) - Zero
* Rate of Duterium exchange & rate of Racemisation will be same

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 H O
Et
OH– Racemic mixture
(6) e.e. Zero
CH3 R

O
3 ||5 3
2 4 6 2
CH3 4
(7) 1 OH– 1 5
6 –H2O
O O O
OH

(8) CH2OH OH
| OH
CH3–CHO + HCHO OH– HCHO + HCOO–
HOCH2–C–CHO

R
(Excess) | Cross Cannizaro
CH2OH OH Salt of formic acid
OH
(Via 3 times aldol) Pentaerythretol

U
–
(9) 2CH –CHO OH nCH3CHO
3
Conc. CH3–CH=CH–CHO CH3(–CH=CH)n+1–CHO

GA
Rasin

–
OH –
HCHO + HCHO CH3OH + CHOO
(10) (Conc.) Cannizaro reaction

H.
Ba(OH)2
Soln. Aldol condensation
(Baryta) exceptional case
BY
OH OH OH OH OH OH
| Ba(OH)2 1|
2| 3 | 4 | 5 |
H–C–CHO H––C––C––C––C––C––CHO
| 4HCHO | | | | |
H H H H H H
Formose
RY
IST
E M
CH

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