APPENDIX

3
TYPICAL ALIPHATIC
AROMATIC AND
CONVERSIONS
LASCENT OF SERIES
The conversion of an
organic compound into its higher
pthe.series. In these conversions, the length of the homologue is called ascent of series or stepping
carbon
carbonatoms at a time. For this chain is increased by adding one or
a By Wurtz reaction (i) purpose, one or more of the following reactions are used :
more
Through
Wurtz reaction is especially used for cyanide (-C= N) group (ii) Through Grignard
Pcions are used for other classes of ascent of series of hydrocarbons while reaction
In allthese reactions, the organic compounds. cyanide and Grignard
te given compound is first starting material an alkyl halide. Therefore, to bring about
is
oi the above three converted into its corresponding alkyl halide these conversions,
reactions. For example, which is then subjected to any one
() Conversion of alower
alkane, RH toa higher alkane, R-R through
Wurtz reaction.
Br,/hv Na/Dry ether
R H RBr
-HBr RR
Alkane Alkyl bromide (Wurtz reaction)
Alkane
Unsymmetrical alkanes are, however, best prepared by Corey-House reaction, i.e.,
Li/ether Cul
R-Br R-Li R-Br
-LiBr -LiI
Dry ether
R,CuLi R-R'
Alkyl bromide Alkyllithium Lithium dialkylcuprate
) Conversion of alower alcohol, ROH toahigher alcohol,
RCH,OH through cyanide method.
ROH P+ly R-I
Alc. KCN
’ RCN
LiAlH, HONO

Alcohol or Plg A or Na/alcohol RCH,NH, (NaNO, +dil. HCI) RCH,OH

Alkyl Alkyl (Reduction) 1° Amine
Higher alcohol
iodide cyanide

(üü)
ConverPBrsion of alower alcohol, ROH to a higher alcohol, RCH,OH through Grignard reaction.
ROH R-Br Mg
R-MgBr
HCHO
[RCH,OMgBr]
H*H,0
’ RCH,0H
Alcohol Alkyl
in dry ether
Grignard Addition product Higher alcohol
bromide reagent

A/51
 A/52 PRADEEP'S NEW
COURSE
1. Methane to Ethane
EXAMPLES ON ASCENT OF SERIES THROUCH
WURTZ REACTION/COREY-HOUSE REACTION CHEMISTRY (XI) VoLN
Ch. light Na/ether
CH, CH,CI
Methane
-HCI
Methyl chloride
(Wurtz reaction) CH,CH,
2. Ethane to n-Butane Ethane
Br,/hv Nalether
CH,-CH, CH,CH,Br
Ethane
-HBr
Bthyl Bromide
(Wurtz reaction) CH-CH,n-ButaneCH,CH,
3. Propene to 2, 3-dimethylbutane
HBr CH, Nalether CH, CH,
CH,CH =CH, CH,-CH-Br
Propene
4. Ethane topropane
(Mark. addition)
2-Bromopropane
(Wurtz reaction)
CH,2,-3CH-CH--CH,
-Dimethylbutane
Cl,, hv L/ether
CH,CH,
Ethane
-HCI CH,CH,CI -LiCl CH,CH,Li
Cul
-LiI (CHHCH,),CLi
Ethyl Chloride Ethyllithium Lithium diethylcuprate
CH,Br, dry ether
(Corey-House reaction ) CH,CH,CH,
EXAMPLES ON ASCENT OF SERIES THROUGH CYANIDE METHOD Propane
1. Methanol into ethanol (CBSE 2007 ; Hr. Board 2010; Assam Board 2012)
CH,OH
P+l2 KCN
-KI CH,CN Na/C,H,OH CH,CH,NH, -Ng,-H,0 CHHCH,0H
HONO

Methanol
or Pl CH! (Reduction)
Methyl iodide Acetonitrile Ethylamine Ethanol
H*H,0 LiAlH, or B,H/ether
Alternatively, CH,CN (Hydrolysis )
CHHCOOH ’ CH,CH,OH
Acetonitrile Acetic acid
(Reduction)
Ethanol
2. Methyl iodide into eth
ethyl iodide
KCN Na/C,H;OH
CH,I - KI ’ CH,CN (Reduction) CH,CH,NH,
-Ng,-H,0 CH,CH,OH
HONO
P"h,
or Pl,
CH,CH,I
Methyl iodide Acetonitrile Ethylamine Bthanol Ethyl iodide

3. Methanamine to ethanamine (Methylamlnei ethylamine) (Chhatlsgarh Board 2012)

HONO P+y KCN NaC,H,OH
CH,NH, -N,-H,0 CH,OH or Pl, CH,l - KI 7 CH,CN (Reduction)
CH,CH,NH,
Methanamine Methanol Methyl iodide Acetonitile Ethanamine

4. Formie acidto acetic acid

LiAIH /ether KCN H*H,0 CH,C0OH
HCOOH CH,OH or Pi, CHyI - KI
’ CH,CN (Hydroysis) Acetic acid
(Reduction)
Formic acid Methyl alcohol Methyl iodide
 ALIPHATIC AND AROMATIC CONVERSIONS
Bthanoicacid to propanoic acid (Acetic A/53
5 acid to propionic acid)
LiAlH,/ether
P+l,
CH;COOH
(Reduction) CH,CH,OH or Pla CH, CH,1
KCN
H*H,0
Bthanoicacd Ethanol - KI CH,CH,CN
(Aceticacia)
Bthyl iodide Propionitrile (Hydrolysis)
(Ethyl cyanide)

CH,CH,COOH
Propanoic acid
(Propionic acid)
pVAMPLES ON ASCENT OF SERIES THROUGH GRIGNARD
MethanolI to ethanol (Methyl alcohol to ethyl alcohol) REACTION
(HP Board 2011 ; Assam Board 2012)
P+l, Mg/ether HCHO
CH,OH or Pla CH,I CH,Mgl (Grignard reaction) [CH,CH,OMgl]
Methanol Methyl iodide Methylmag. iodide Addition product
H*H,0
(Hydrolysis)
CH,CH,OH
Ethanol
2. Methanol to 1-propanol (Methyl alcohol to n-propyl alcohol )

CH,OH
PBS Mg/ether CH,-CH,/ether
or P+ Br, CH,Br CH,MgBr (Grignard reaction)
Methanol Methyl bromide Methyl mag. bromide
H*H,0
[CH,CH,CH,OMgBr) (Hydrolysis)
CH,CH,CH,OH
Addition product 1-Propanol

3. Methanol to 2-propanol (Methyl alcohol to isopropyl alcohol)

OMgl
P+1, Mg/ether CH,CHO
CH,OH CH,-I ’ CH,Mgl CH,a-CHCH,
or Pl, (Grignard reaction) Addition product
Methanol Methyl Iodide Methylmag. iodide
OH
HH,0
(Hydrolysis )
CH,-CH-CH,
2-Propanol

Bhanol to l-propanol (Ethyl alcoholto n-propyl alcohol)

Mglether HCHO
PBr
CH,CH,MgBr
CH,Ethanol
CH,OH or P+ B,
CH,CH,Br
Ethyl bromide Ethylmag. bromide
(Grignard reaction)

H*H,0
[CH,CH,CH,OMgBr] ’ CH,CH,CH,OH
Addition product 1-Propanol
 A/54 PRADEEP S
NEW
CoURSEC
5. Ethanol to 2-propanol
CHEMISTRY(CBSE(XI) 20svOLI
S
S
cH,NHOO,cr PCcyCH,CI, CH,MgBr
CH,CH,OH (Controlled oxidation)
CH,CHO
(Grignard reaction) OMgBr
Ethanol Acetaldehyde

H*H,O
CH,Addi-CtiH-on -productCH,
OH

6. Ethanol to 1-butanol (Ethyl alcohol to n-butyl alcohol )

-Mg(OH)Br
CH,2-Propanol
-CH--CH,
PBr, Mg/ether
CH,CH,OH
Ethanol
or P + Br CH,CH,Br
Ethylbromide
CH,CH,MgBr H,-CH,/ether
(Grignard reaction)
Ethylmag. bromide

[CH,CH,CH,CH,OMgBr] H*H,0 ’ CH;CH,CH,CH,0H

Addition product 1-Butanol

7. Methanal to ethanal (Formaldehyde to

to acetaldenyae)

CH,MgBr H*H,O Cu/573 K

H-C--H [CH,CH,OMgBr] ’ CH,CH,OH + CH,-C-H
Ethyl alcoholor CsH_NHCHO,Cr, Ethanal
Methanal Addition product
H,CI,
II. DESCENT OF SERIES
stepping
The conversion of an organic compound into lower homologue is called descent of series oratom
carbon at a
down the series. In these conversions, the length of the carbon chain is decreased by one
time by any one of the following two methods :
soda-lime (CaO + aOH)
) By heating sodium salt of a fatty acid (decarbOxylation ) with
(iü) Hofmann degradation of amides or Hofmann bromamide reaction.

EXAMPLES ON DESCENT OF SERIES BY HEATING SODIUM

SALT OF A FATTY ACID WITH SODA-LIME (CaO + NaOH)
1. Ethane to methane
Cl,/hv Aq. KOH K,CHO,/H,SO4 CH,COOH
CH,CH, -HCI CH,CH,CI (Hydrolysis) CH,CH,0H (Oxidation) Aceticacid
Ethane Ethyl chloride Ethanol
CaO + NaOH, A ’ CH,
NaOH
CH COONa (Decarboxylation) Methane
-H,0 Sod. acetate (CBSE 2007)

2. Acetaldehyde to methane
CaO + NaOH, A CH4
CH,CHO K,C,0,/H,s04 CH,COOH
NaOH
CH,COONa (Decarboxylation) Methane
(Oxidation)
Acetic acid
-H,0 Sod, acetate
Acetaldehyde
2PICA
PHATICAND AROMATIC CONVERSIONS A/55
BPropanetoethane

Cl,/hv Alc. KOH, A

CH,CH,CH; -HC) CHCH,CH,CI CH,CHCICH, -HCI
’ CH,CH = CH,
Propane 1-Chloropropane 2-Chloropropane Propene

(1:1 mixture)

(() B,H6 K,Cr,0,/H,SO4 NaOH

(ii) H,0,-NaOH
CH,CH,CH,OH (Oxidation)
’ CH,CH,C0OH -H,0 CH,CH,COONa
(Hydroboration-oxidation) 1-Propanl Sod. propanoate
Propanoic acid
CaO + NaOH, A
CH,CH3
-Na,COs
(Decarboxylation) Ethane

REACTION
EXAMPLES ON DESCENT OF SERIES BY HOFMANN BROMAMIDE
few examples are:
This method is easier and most of the conversions are achieved via this route. A
1. Ethanol into methanol or Ethyl alcohol to methyl alcohol
K,Cr,0,H,So4
CH,COOH NH3 CH,COONH
Heat
CH,CONHz
CH,CH,0H (Oxidation) -H,0 Acetamide
Acetic acid Ammonium acetate
Ethanol
Br, /KOH HONO
CH,NH, ’ CH,0H
(Hofnann -Ny, -H,0
bromanide Methanamine Methanol
reaction)

2. Ethyl iodide into methyl iodide

Aq. KOH K,Cr,0,H,so4 NH
CH;CH,OH CH,COOH ’ CH,COONH4
CH,CH,I (Hydrolysis)
Ethano1
(Oxidation) Acetic acid Amm. acetate
Ethyl iodide
A

CH-CONH
Br,/KOH HONO
CH,NH, -N,, -H,0’ CH,OH P+l2,
or PI
CH,I
-H0 Acetamide (Hofmann bromamide reaction)
Methylamide Methanol Methyl iodide

Ethanamine to methanamine (Ethylamine into methylamine)

(HP Board 2011;
Chhatisgarh Board 2012)
(Assam Board 2012)
or Acetic acid to methylamine
K,Cr,0,/H,SO4 NH,
HONO CH,COOH
CH,Ethanamine
CH,NH, -Nz. -H,0
CH,CH,0H
Ethanol
(Oxidation)
Acetic acid

Br,/KOH
CH,COONH, CH,CONH, (Hofmann bromamide reaction)
CH,NH,
-H,0 Acetamide Methanamine
Amm. acetate

4. Acetice acid to (CBSE 2007)

methylamine
Included in conversion 3above.
 PRADEEP'S NEW COURSE
A/56
CHEMISTRY XIl) VOLN
into formaldehyde
5.Acetaldehyde NH,
K,Cr,0,/H,So4 CH,COOH CH,COONH, -H,0 CHCONH,
CH,CHO (Oxidation) Acetic acid Amm. acetate
Acetamide
Acetaldehyde HONO Cu
Br,/KOH CH,OH
CH,NH, -N,, -H,0 S73 K HCHO
(Hofnann bromamide reaction) Methyl alcohol
Methylamine
(Propionic acid to acetic acid) Formaldehyde
6. Propanoic acid to ethanoic acid Br,/KOH
Heat
NHg CH,CH,COONH4 -H,0 CH,CH,CONH, (Hofmann
CH,CH,COOH Propionamide bromamide reaction)
Amm. propionate
Propanoic acid K,Cc,0,/H;s04
HONO
CH,CH,OH (Oxidation) CH,COOH
CH,CH,NH, -N,,-H,o Ethanol Ethanoic acid
Ethylamine
(CBSE 2012)
7. Ethyi cyanide to ethanoic acid
H*H,0 CH,CH,C0OH
CH,CH,CN (Hydrolysis) Propanoic acid
Ethylcyanide above.
ethanoic acid as explained in conversion 6
acid to
Nowconvert propanoic page A/67.
Alternatively, refer to conversion 18,
isopropyl alcohol
8.Propionic acid to to ethyl alcohol as given in conversion 6
above.
propionic acid
()First convert as follows :
convert ethyl alcoholto isopropyl alcohol OH
(ii)Now OMgl
CH,MgBr CH,-CH CH, H*H,O CH,-CH CH,
Cu
’ CH,CHO -Mg(OH)Br Isopropylalcohol
CH,CH,OH 573K dry ether Addition product
Acetaldehyde
Ethylalcohol
acetamide K,Cr,0, +H,S04
9. Propionamide into HONO
Br,/KOH CH,CH,0H (Oxidation)
CH,CH,CONH,
’ CH,CHzNH2 -N,, -H,0 Ethanol
(Hofmann bromamide)
reaction
Ethylamine
Propionamide
NH CH;CONH,
CH,COOH CH,COONHÊ -H,0 Acetamide
Amm. acetate
Acetic acid

ALIPHATIC CONVERSIONS
CONVERSIONS
TYPE L. TWOSTEP
1. Acetylene into acetic acid O,, Manganese acetate
H,0, Dil. H,SO4 CH,COOH
CH = CH
HgSO4,333 K
CH,CHO or K,Cr,0, + H,SO4 Acetic acid
Acetylene Acetaldehyde
2. Acetylene to ethanol
H,0, Dil. H,SO4 NaBH4
CH =CH CHCHO in ether
CH,CH,OH
HgSO4, 333 K Ethanol
Acetylene Acetaldehyde
 ALPHATIC AND AROMATIC CONVERSIONS A/57
PCAL J&K Board 2011)
Aceticacidto acetaldehyde
A
3 H, +Pd/BaSO, +S
PCls
CH,COOH CH,COCI CH,CHO
-POCI,, -HCI (Rosenmund reduction)
Acetyl chloride Acetaldehyde
Aceticacid (J&K Board 2011)
Acete acid to acetone
4 CH
CacO, CH,CO0 CCa
Dry distil C=0
CH,COOH -CacO, CH,
Acetic acid -c0,. H,0 CH,C00 Acetone
Cal. acetate

3-pentanone
B Propionic acid to
CH,CH,C00,
CH,CH,COOH -c0, -H,0 CH,CH,CO0
Propionic acid
CaCO3

Cal. propionate
Ca
Drydistil
-Cc0, CHCH, CH,CHC=0
3-Pentanone

formaldehyde
6.Formic acid to HCOO Drydistil H
CaCO, Ca
HCOOH
-c0,. -H,0 HCO0 -CacO,
Formic acid Formaldehyde
Cal. formate

7. 1-Propanol to 2-bromopropane
Conc. H,SO
HBr
CH,-CH--CH,
CH,CH =CH, (Mark. addition)
CH,CH,CH,OH 433-443K Br
(Dehydration) Propene
1-Propanol 2-Bromopropane

8.2-Propanol to 1-bromopropane
HBr, peroxide
OH Conc. H,SO44 CH,CH =CH CHHCH,CH, Br
Anti-Mark. adàn.) 1-Bromopropene
CH,-CH-CH, 433-443 K
Propene
(Dehydration)
2-Propanol (ethanoic acid)
to acetic acid
9 Methyl bromide (bromomethane) () Solid CO, CH,COOH
Mg/ether CH,MgBr (ii) H*H,0 Acetic acid
CH Br Methylmag. bromide
Methyl bromide H*H,0
Alc, KCN, A CH,C= N CH,COOH
(Hydrolysis) Acetic acid
Alternatively, CH -Br -KBr Acetonitrile
Methyl bromide
As discussedin
0. Methanol to acetic acid conversion 9 above CH,COOH
P+ Br, CH -Br Acetic acid
CH,OH or PBr Methyl bromide
Methanol
chloride
11. n-Propylamine from ethylAlc. KCN, CH,CH,CN
LiAlH4
CH,CH,CH,NH,
in ether
CH,CH,CI n-Propylamine
Ethyl cyanide
Bthyl chloride
A/58 PRADEEPS NEW coURSE CHEMISTRY (XiI)VOLn
12. Ethylene to acetylene
Br, NaNH,/iq, NH,, 196 K
CH, = CH, BrCH, CH,Br CH= CH
CC1, Ethylene dibromide (Dehydrobromination )
Ethylene Acetylene
13. Propylene to propyne
Brn NaNH,liq NH,, 196 K
CH CH=CH, CCl, CH CHBr CH,Br (Dehydrobromination)
CH,-C= CH
Propylene Propylene dibromide Propyne
14. Acetylene into propyne
NaNH,, iq NH, CH,I
CH = CH CH = C Nat
-Nal
CH,-C= CH
196 K
Acetylene Sod. acetylide Propyne
15. Propyne to 2-butyne
NaNH,, lig NH, CH,I
CH,-C= CH 196 K
CH,C=C-Nat -Nal’ CH,-C=C-CH,
Propyne Sod. propynide 2-Butyne
16. Acetylene (or methyl iodide to 2-butyne)
CH = CH
NaNH,/lig. NH,
’ NatCaCNat 2CH,I
196 K -2Nal CH, C=C--CH,
Acetylene Disodium acetylide 2-Butyne
17. Ethane into ethylene
CI,/hv Alc. KOH, A
CH CH -HCI CH CH,CI -HCI
’ CH, = CH,
Ethane Ethyl chloride Ethylene
(Dehydrochlorination )
18. Methyl bromide to ethylamine
Alc. KCN LiAlH, dry ether
CH, -Br -KBr CH,CN CH,CH,NH,
Methyl bromide Methyl cyanide (Reduction)
Ethylamine

19. Propane into propylene or propene. As discussed in conversion 3, page A/54.

20. Ethane to diethyl ether

Cl,/hy Dry Ag,0
CH CH, -HC]
’ CH,CH,CI ’ CH,CH 0 CH,CH,
-2 AgCl
Ethane Ethyl chloride Diethyl ether
21. Ethyl alcohol to diethyl ether
CH,CH,ONa
CH,CH,OH CH;CH, -I -Nal CH,CH, o CH,CH,
Ethyl alcohol Ethyl iodide (Williamson synthesis) Diethyl ether
PICAL AuGANDDAROMATIC CONVERSIONS A/59
Acetaldehyde to lactic acid (2-hydroxypropanoic acid) (CBSE 2013)
2.
H H
HCN
’ CH,-C-CN
H*H,0 CH,-C COOH
CH,-C =0
(Hydrolysis)
Acetaldehyde OH OH
Acetaldehyde Lactic acid
cyanohydrin 2-Hydroxypropanoic acid

3 Ethanol to 1, 1-dichloroethane
+

CçH,NHCHO,Cr (PCC) PCl; CH,-CH

CH,CH,OH ’ CH CHO -POCI, -2 HCI CI
Ethanol
CH,Clh Ethanal
1, 1-Dichloroethane
(CBSE 2007)
24. Propene to isopropyl alcohol or propan-2-0l OH
Br
Aq. KOH, A
HBr ’ CH,-CH-CH,
CH,CH =CH, CH,-CH-CH, -KBr
(Mark. addn.) (Hydrolysis) Isopropyl alcohol
Propene Isopropyl bromide
H,0, boil
Conc. H,SO4
CH,-CH CH, CH,-CH-CH,
Alternatively, CH,CH =CH, (Mark. addn.) -H,SO4 OH
Propene oSo,H Propan-2-ol
Isopropyl hydrogen sulphate
(CBSE (Foreign) 2017)
25. Propene to Acetone
one of the two methods discussesd in Conversion in24 and
Convert propene to propan-2-ol by any
then convert prop-2-ol to propanone as follows :
CgH, NHC0,Cl(PCC)
CH,-CH-CH, CH,-C-CH,
CH,Cl,
OH Acetone
Propan-2-ol

26. Propionic acid to lactic acid OH

Br
Aq. NaOH, A
Br,,Red P CH,-CH-COOH CH,-CH-COOH
(Hydrolysis )
CH CHCOOH (H.V.Z. reaction) a-Bromopropionic acid
Lactic acid
Propionic acid
27. Ethyne to 3-hydroxybutanal
+H,0 CH-CHO
CH =CH
Dil. H,SO4, HgSO4, 333 K Bthanal
Ethyne
OH
Dil. NaOH
CH,-CH--CH,-CHO
CHCHO + H CH, CHO (Aldol condensation)
3-Hydroxybutanal
Ethanal (2 molecules)
 PRADEEP'S NEW COURSEE
BA/60 CHEMISTRY(XII) VOLI
28. Ethanol to 3-hydroxybutanal (NCERT, CBSE 2009)
OH
Cu/573 K Dil. NaOH
CH,CHO
CH,CH,OH
Ethanol
or PCCICH,Cl, Ethanal
(Aldol condensation)
CH,3-Hydroxybutanal
CH-CH,CHo
(NCERT; CBSE 2010, CBSE (D) 2017, CBSE
29. Propanone to propene (OD) 2017)
OH
NaBH,. CH,OH Conc. H,SO4, 443 K
CH,-C-CH, CH,-CH-CH, ’ CH CH =CH,
(Reduction) (Dehydration)
Propanone 2-Propanol Propene
30. Propanal to butanone
OH
() CH,MgBr K,Cr,o,H,S04
CH,CH,CHO (ü) H,0* CH,CH,-CH-CH, or
PCCICH,C,
CH,CH,C-CH,
Butan-2-ol Butanone
Propanal (Oxidation)

31. Propanoic acid to propenoic acid

Br
Br,/red P KOH (alc), A
CH,-CH-COOH CH, = CH-COOH
CH,CH,COOH H.V.Z. reaction (Dehydrobromination)
2-Bromopropanoic acid Propenoic acid
Propanoic acid
(Acrylic acid)
32. Hept-1-ene to heptanal
() B,H/ether PCCICH,Clh CH,(CH)CHO
CH,(CH)4CH = CH, CH,(CH,)4CH,CH,OH
(ü) H,0,NaOH Heptan-1-ol Heptanal
Hept-1-ene
33. Hept-1-ene to heptanoic acid
() KMnO4/KOH, A
()B,Hg/ether
CH,(CH,),CH = CH, CH(CH,),CH,CH,OH (ü) Dil. H,so4
() H,0,NaOH Heptan-1-ol
Hept-1-ene CH,(CH),CH,COOH
Heptanoicacid

34. ,2-Dichloroethane to 1, 1-dichloroethane

Alc. KOH, A HCI
CICH,CH,CI CH, = CHCI CH, CHCI,
-HCI Mark. addn.
1, 1-Dichloroethane
1,2-Dichloroethane Vinyl chloride
(CBSE 2010, 2013)
35. Ethanal to but-2-enal
OH
Dil. NaOH
CH,-C-H+ HCH,-C-H CH,-CH-CH,CHO
Ethanal (2 molecules) (Aldol condensation)
3-Hydroxybutanal

CHCH = CH CHO
-H,0(Dehydration) But-2-enal
 A/61
ALIPHATIC AND AROMATIC CONVERsIONS 2-ethanediol
YPIC
2-Ethanediol (ethylene glycol) from ethanol (ethyl alcohol) or ethanol to 1,
B6. ,
CH, Conc. H,SO4 Cold dil. alk. KMnO4 CH,OH
CH,OH
433-443 K
(Dehydration) CH, (Baeyer's reagent) H,OH
1, 2-Ethanediol
Ethanol Ethylene (Hr. Board 2012)
|2-Bromopropane to 1-bromopropane
37.
Br HBr, peroxide
Alc. KOH, A CH,CH,CH,Br
CH,-CH-CH, CHCH=CH, (Anti-Mark. addn.)
(-HBr) 1-Bromopropane
2-Bromopropane Propene (Hr. Board 2011l)

38. 1-Bromopropane to 2-bromopropane

Alc. KOH, A
HBr CH,-CH-CH,
CH,CH,CH, Br CH -CH=CH, (Mark.addn.)
(-HBr) Br
1-Bromopropane Propene
2-Bromopropane

3-chlorobutanoic acid
39. 2-Chlorobutanoic acid to
C1 HCI
Alc. KOH, A CH,CH = CH-C-OH (4,4-Addition)
-CH-COOH
CH,CH, -KCI, -H,0
(Dehydrochlorination) But-2-en-1-oic acid
2-Chlorobutanoic acid
C1
Ci OH Tautomerises CH,-CH-CH, -COOH
CH,CH-CH = (-OH
3-Chlorobutanoic acid

40. Etiyl cyanide to ethylamine

Dissolve in conc. HCI or Br,-NaOH
H,SO, and then pour in H,0 CH,CH,-C-NH, CH,CH,NH2
(Hofnann bromamide
CH,CH,CN (Partial hydrolysis) Propionamide
reaction Ethylamine
Ethyl cyanide (Jharkhand Board 2011)
Acetone to mesitylene
41. (Calcum acetate to mesitylene or
CH3
CH C00, CH3 Conc. H2SO4
Dry distil CC=0
3 Ca
3 -3H,0
-3CaCOs
CH3 HC CH3
CHCO0 Acetone
Mesitylene
Cal. acetate

42. Benzal chlorde to cdnnamaldehyde ) (CH-CO),0, CH,COONa

433-453K
Dil. NaOH CçHCH= CHCHO
’ CGHCHO (ü)H*H,0
CHLCHCLy 2 NaCl, -H,0 Benzaldehyde (Perkin condensation) Cinnamaldehyde
Benzal chloride
(Bihar Board 2011)
|43. Ethanol into n-butane
Na, dry ether
P/Br, CH,CH,Br -2 NaBr
CH,CH,CH,CH,
CH,CH,OH
Ethanol
Bromoethane (Wurtz reaction)
n-Butane
 A/62 PRADEEP'S NEW COURSE CHEMISTRY (XII) vOLN
44. Acetic acid to ethane (J&K Board 2011)
NaOH Kolbe's
CH,COOH ’ CH,COONa ’ CHy CH,
Acetic acid
-H,0 Electrolytic method
Sod. acetate Ethane
TYPE IIL. THREE-STEP CONVERSIONS
1. Nitromethane to dimethylamine
Sn/HCI CHCl,, alc. KOH, A NaC,H,OH
CH,NO, (Reduction) CH,NH, (Carbylamine reaction)
CH,NC
(Reduction) CH,NHCH,
Nitromethane Methylamine Methyl Dimethylamine
isocyanide
2. Methane to acetic acid
Br,lhv Alc. KCN, A H*H,0
CH -HBr CH,Br -KBr CH,CN (Hydrolysis)
CH,COOH
Methane Methyl bromide Acetonitrile Acetic acid
|3. Ethylene to succinic acid
CH, Br, CH,Br 2 KCN CH,CN H*/H,0 CH,COOH
CH, CCl, CH,Br -2 KBr
CH,CN (Hydrolysis) CH,COOH
Ethylene Ethylene Butane-1, 4-dinitrile Succinic acid
dibromide
4. Ethylene to oxalicacid
CH, Br CH,Br Alc. KOH, A CH Cold dil. alk. KMn0, COOH
CH, CCI, CH,Br -2HBr CH (H,0+ 0) COOH
(Dehydrobromination) (Baeyer's reagent)
Ethylene Ethylene Acetylene Oxalicacid
dibromide

5. Ethylene to 3-hydroxypropanoie acid (p-hydroxypropionic acid)

CH, Oz, Ag CH, KCN CH,OH H*H,0 CH,OH
CH, 573 K
CH, CH,CN (Hydrolysis)
CH,COOH
Ethylene Ethylene oxide
Ethylene cyanohydrin 3-Hydroxypropanoic acid
6. Acetaldehyde to acetone (ethanal to propanone)

CH,CHO
K,Cyo,/H,s0, Ca(OH)2 Dry distillation
(Oxidation)
CH,COOH -H,0
’ (CH,CO0),Ca
-CacO,
CH,-C-CH,
Acetaldehyde Aceticacid Cal, acetate Acetone

OH
CH,MgBr
OMgBr H*H,0
Alternatively, CH,CHO dry ether
CH,-CH-CH, -Mg(OH)Br
CH,-CH--CH,
Acetaldehyde Addition product Isopropyl alcohol

Cu/573K
CH,-C-CH,
or K,Cr,0,/H,SO, Acetone
(Oxidation)
 A/63
TPICAL
ALIPHATIC AND AROMATIC CONVERSIONS
Ethanolto acetone (CBSE 2007, 2008 , Jharkhand Board 2011)
Z As discussed
K,Cr,0,/H,S04
CH,CH,OH (Oxidation)
CH,COOH in conversion CH,COCH,
Acetic acid 6above Acetone
Ethanol

acid
Eormic acid to oxalic
NaOH 633 K
COONa Dil. HCI COOH
HCOOH HCOONa COONa -2NaCl COOH
-H,0 -H,
Formic acid Sod. formate Oxalic acid
Sod. oxalate

alcohol (1° alcohol to 2° alcohol)

a n-Propyl alcohol to isopropyl OH
I
HI AgOH -CH-CH,
Conc. H,SO4, A CH,-CH-CH,
CH,CH,CH,OH " (-H,0) ’ CH;CH=CH, (Mark. -Agl
Isopropyl alcohol
Propylene
addition Isopropyl iodide
Propylalcohol (2° Alcohol)
(1° Alcohol)
alcohol)
totert-butyl alcohol (2° alcohol to 3°
10. Lsopropyl alcohol 2-methylpropan-2-ol
(CBSE 2015)
or Propan-2-ol to
-OMgBr
Cu/573 K
CH, CH,MgBr [CH,
CH or PCC/CH,Ch CC=0
CHOH
Dry ether
CH, CH,
CH
or K,Cr,0,H,SO,
(Oxidation)
CH Addition product
Acetone
Isopropyl alcohol or Propan-2-ol
OH
(2° Alcohol)
H*H,0 CH,
-Mg(OH)Br CH, CH,
tert-Butyl alcohol or 2-Methylpropan-2-ol
(3° Alcohol)

alcohol (2° alcohol to 1° alcohol)

: lsopropyl alcohol to n-propyl
B,H, Dry ether
CH Conc. H,SO4, 4 CH CH=CH, (CH,CH,CH,),B
CCHOH (Hydroboration)
-H,0
CH Propylene
Isopropyl alcohol H,0,/NaOH
(2° Alcohol)
(Oxidation)
’ CH,CH,CH, OH
n-Propyl alcohol (7° Alcohol)

(1° alcohol to 3° alcohol)

sobutylalcohol to tert-butyl alcohol
CH, CH,
CH, Conc. H,S04,A CH,-C =CH,
Dil. H,SO4
CH,- CH,
’
CH,Lsobutyl
HCH,OH alcohol
-H,0 Isobutylene
(Mark. addition of water)
OH
tert-Butyl alcohol
(1° Alcohol)
(3° Alcohol)
 A/64 PRADEEP'S NEW COURSE CHEMISTRY(XII) VOL
13. Ethanoic acid to 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol)

CH,COOH
Ca(OH), Dry distil CH, Dil. NaOH
-H,0
(CH,C00),Ca C= 0
(Aldol condensation)
Ethanoic acid Cal. acetate -CaCO, CH,
Acetone
OH

CH, "C-CH,-C-CH,
3
CH,
14. Acetic acid to tert-butyl alcohol 4Hydroxy-4-methyl-2-pentanone (Diacetone alcohol)

CH,-C-OH
C,HOH 2CH,MgBr CH3
Acetic acid
+Conc. H,SO4 CH,-C0C,H, -ChH,OMgBr CH,C-OMgBr
(few drops) Ethy lacetate
CH,
Addition product
CH,
H*H,0
-Mg(OH)Br CH, -OH

CH,
tert-Butyl alcohol
15. Acetone to acetamide
()HNaOH(-CHI,) SOClh NH¡ (excess)
CH,COCH, Iodoform reaction ’ CH,COOH
-So,,-HCI CH,COCI ’ CH,CONH,
Acetone (iü) Dil.HCI Aceticacid Acetyl chloride
-NH,CI
Acetamide
16. Propanoic acid to ethylamine
(HP Board 2009)
sOCI, NH, (excess) Br,KOH
CH;CH,COOH CH,CH,COC1 CH,CH,CONH,
Propanoic acid
-SO,, -HCI
Propanoyl chloride -NH,CI (Hofmann CH,CH,NH,
Propionamide bromamide Ethylamine
reaction
17. Acetic acid to ethylamine
(J&KBoard 2011)
SOC, NH, (excess) LiAlH Jether
CH,COOH -SO,,-HC CH;COCI ’ CH,CONH, CH,CH,NH,
Acetic acid Acetyl chloride
-NH,CI Acetamide Ethylamine
18. Acetone to acetaldehyde
L,/NaOH PCl, H, + Pd/BaSO, +S
CH,COCH, -CHi,
’ CH,CO,Na CH,COCI CH,CHO
Acetone (lodoform reaction) Sod. acetate -NagPO Acetyl chloride
(Rosenmund reduction)
Acetaldehyde
19. Acetic acid to 2-butanol

SOCl, (CH,CH, ),Cd’ CH,C0CH,CH, LiAlH4

CH,COOH -SO,.-HCI
CH;COCI CH,CHOHCH,CH3
in dry ether in dry ether
Acetic acid Acetyl chloride 2-Butanol
Butanone
 A/65
NPCAL
ALIPHATIC AND AROMATIC CONVERSIONS
1-Dichloroethane to 1, 2-dichloroethane
20., 1, Cl,/CHCIH
H,, Pd
Alc. KOH
HC = CH H,C= CH, ’ CICH, CH,Cl
CH,CHCI, Supported over BaSO, 1,2-Dichloroethane
Ethene (Lindlar's catalyst) Ethene
1.1-Dichloroethane

|Acetoacetic ester from acetaldehyde

21. C,H,OH/Conc. H,S0, (few drops)
K,Cr,0,H,S04 CH,CO0C,Hs
CH,CHO
CH,COOH (Esterification) Ethyl acetate
(Oxidation)
Acetic acid
Acetaldehyde
C,H,ONa/CzHOH CH,COCH,CO0C,Hs
(Claisen condensation) Acetoacetic ester
Ethyl acetoacetate or

3-dihydroxypropanal or glyceraldehyde
22. Acrolein to 2, Dil. alk. KMnO4
C,H;OH + Dry HCl gas
CH,= CHCHO ’ CH, =CH-CH(OC,Hs), (Hydroxylation)
(Protecion of-CHO group) Acrolein diethyl acetal
Acrolein
H*H,0 CH,-CH-CHO
CH,-CH-CH(OC,H), -2C,H,OH
OH OH
(Hydrolysis)
OH 2, 3-Dihydroxypropanal
3-Dihydroxypropanal diethyl acetal (Glyceraldehyde)
2,

TYPE III-MULTISTEP CONVERSIONS

1.Benzene from lime Red hot copper tube

H,0 CH= CH 773 K
CaO
3C, 2273 K, CaC2 Ca(OH)2 Acetylene Benzene
Cal. carbide
Lime

2. Acetone from acetylene K,Cr,07

Ca(OH),
(CH,CO0);Ca
H,0, Dil. H,SO4 CH;COOH -H,0
CH,CHO H,SO4 Cal. acetate
CH = CH HgSO,333 K
Acetic acid
Acetaldehyde
Dry distil
Acetylene CH,COCH,
-CaCO, Acetone

3. Ethyl alcohol to vinyl acetate Br

Na/Liquid NH,, 196 K

Conc. H,SO4 CH, = CH, BrCH, CH,Br -2HBr

Ccl, (Dehydrobromination)
CH,CH,OH 433-443K 1, 2-Dibromoethane
Ethylene
Ethyl alcohol (Dehydration) CH,COOH
HC =CH CH, = CH OCOCH,
HgSO4 Vinyl acetate
Acetylene
 A/66 PRADEEP'S NEW COURSECHEMISTRY (XI) VOL.I
4. Propanoic acid to n-butylamine
LiAlH, PBr Alk. KCN
CH,CH, COOH in ether
CH,CH,CH, OH CH,CH,CH, -Br
Propanoic acid n-Propyl alcohol n-Propyl bromide

LiAlH,
CH,CH,CH, CN in ether CH,CH,CH,CH, -NH,
n-Butyronitrile n-Butylamine

5. Formaldehyde to n-butane
H
CH,MgBr H*H,O PBr,
H-C-H H-C-OMgBr -Mg(OH)Br
CH,CH,OH CH,CH,Br
H Ethyl alcohol Ethyl bromide
Formaldehyde Addition product
Na/ether

(Wurtz reaction) CH,CH, CH,CH,

n-Butane

Methylmagnesium bromide needed for the reaction can itself be prepared from formaldehyde as
follows:

NaBH4 PBr, Mg
HCHO CH,OH CH,Br in ether
’ CH,MgBr
6. Ethylene to 2-propanol
Conc. H,SO4 H*/H,0 CçH,NH* Cro,CI, CH,Cl,
CH, =CH, CH,CH,OSO,H Boil CH,CH,OH
Ethylene Ethyl hydrogen sulphate Ethyl alcohol

OH
CH-MgBr
OMgBr
H*H,0
CH,CHO |CH, -CH-CH, (Hydrolysis)
CH,-CH-CH,
Acetaldehyde Addition product 2-Propanol

7. Ethanal to 2-hydroxy-3-butenoic acid

HCHODil. NaOH Ht,4
CH,CHO (Cross aldol condensation) HOCH, CH,CHO (-H,0) CH, = CH CHO
Ethanal 3-Hydroxypropanal 2-Propenal
(Acrolein)

HCN Ht /H,0 CH, =CH-CH-COOH

(1,2-Addition) CH, =CH-CH-CN (Hydrolysis)
OH OH

2-Hydroxy-3-butenenitrile 2-Hydroxy-3-butenoic acid

 ALIPHATIC AND AROMATIC CONVERSIONS A/67
PCAL
Acetone to 3-methylbut-2-en-1-oic acid (P, B-Dimethylacrylic acid)
ÇH, CH,
Ba(OH), H*H,0,4 CH,-C = CH--COCH,
(Aldol condensation)
’ CH,C-CH,COCH, (Dehydration) Mesityl oxide
OH
Acetone
Diacetone alcohol

CH, CH,
I,NaOH H*H,0 CH, C= CHCOOH
CH,-C = CH-COONa
(Acidification)
-CHI, 3-Methylbut-2-en-1-oic acid
(lodoform reaction) Sod. 3-methylbut-2-en-1-oate

diethyl ether
9. Dimethyl ether to Cl, ,hv Dry Ag,0
Na/ether (CH,CH,),0
CH0CH,
HI,373 K
2 CH,I (Wurtz
CH;CH, -HCI’ CH,CH,Ci -AgCl
Diethylether
-H,0 Ethyl chloride
reaction) Ethane
Dimethyl ether
alcohol
10. Propionic acid to isopropyl Conc. H,S04
Conc.H,SO4
LiAlH4
CH,CH,CH,OH ’ CH,CH =CH, (Mark.addn.)
CH-CH,COOH Dry ether
433-443K
Propylene
Propionic acid
n-Propyl alcohol (-H,0)
Boiling H,0 CH,-CH CH,
CH, -CH--CH, -H,SO4
OH
OsO,H Isopropyl
Isopropyl alcohol
hydrogen sulphates
2017)
(CBSE (OD) 2017, CBSE (Foreign)
11. Ethanoic acid to 2-hydroxyethanoic acid
Aq. KOH
Br,Red P Br-CH, -COOH HOCH, -COOK
(Hydrolysis) Pot. 2-hydroxyethanoate
CH,-COOH (H.V.Z. reaction) 2-Bromoethanoic acid
Ethanoic acid
H*H,0 HOCH,-CCOH
(Acidification) 2-Hydroxyethanoic acid
(CBSE (Foreign) 2017)
2-hydroxypropanoic acid
12. Propanoic acid to Aq. KOH
Br,/red P -CH-COOH CH, -CH-COOK
CH,CH,COOH (H.V.Z. reaction)
CH3 (Hydrolysis)
OH
Propanoic acid Br Pot. 2-hydroxypropanoate
2-Bromopropanoic acid

H*H,0 CH, -CH-COOH

(Acidification)
OH
2-Hydroxypropanoic acid
 A/68 PRADEEP SNEW COURSE CHEMISTRY (XII) VOL n

13. Ethylene to propylene

Br, NaNH,/Liq. NH,,196K NaNH, in liq. NH,
HC = CH
CH, =CH, CCI,
’ BrCH,-CH,Br (Dehydrobromination) 196 K
Ethylene Ethylene Acetylene
dibromide

CH,I H, -Pd/BaSO,
HC =CNat ’
(-Nal)
HC =C CH, +Sor quinoline
H,C = CH CH,
Sod. acetylide Propyne (Lindlar's catalyst) Propylene
14. Isopropylchloride to n-propyl chloride
C1 Alc. KOH, A B, H,/THF
CH,-CH-CH, (-HCI)
CH CH=CH, (Hydroboration) (CH,CH,CHJ),B
Isopropyl chloride Propene Tri-n-propylborane
H,0,-NaOH soCl,
(Oxidation)
CH,CH,CH,OH (-SO,,-HCI) CH,CH,CH,Ci
n-Propyl alcohol n-Propyl chloride
15. Iodoform to propyne
Agpower, A NaNH,, liquidNH3 CH,I
2CHl, CH = CH
196 K
CH=CNat
-Nal
CH-C= CH
-6Agl
lodoform Acetylene Sod. acetylide Propyne
16. Acetic acid to glycine
Cl, ,red P
Alc.NH3 CH,COOH/H,0
(excess)
CH,COOH -HCI CICH,COOH - NH,CI NH,-CH,COONH, NH,CH,COOH
-CH,COONHÊ
Acetic acid Chloroacetic acid Glycine
17. Ethanol to 2-hydroxybutanoic acid
Conc.H, SO4 ()CH,Mgl
433-443K CH, 0,Ag CH,CH,CH,OH
CH, OH (Dehydration) CH, S73 K CH, ()H*H,0 1-Propanol
Ethanol Ethene Epoxyethane
OH
c,H, NHCO,a,CH,C, CH,CHHCHO HCN H*H,0
CHCH,-CH-CN (Hydrolysis)
Propanal
OH
CH,CH, -CH--C0OH.
2-Hydroxybutanoic acid
18. Propanoyl chloride to dipropylamine
NH, (excess) LiAlH Jether CH,CH,COCI
CH,CH,COCI
-NH,CI
’ CH,CH,CONH, (Reduction)
CH,CH,CH,NH, -HCI
Propanoyl chloride n-Propylamine
LiAIH,/ether
CH;CH,CH,NH COCH,CH, (Reduction)
CH,CH,CH -NH CH,CH,CH,
Dipropylamine
VPCAL ALIPHATIC AND AROMATIC CONVERSIONS
A/69
OH
(CH,C-Ph -Phln
9. CH,CHOto
K,Cr,0,+H,SO4 CaCO, Dry distillation
CH,CHO CH,COOH (CH,CO0),Ca -CaCO,
(Oxidation)
Acetic acid
-cO,-H,0
Acetaldehyde Cal. acetate
OH
(i) PhMgBrlether
(CHs),C =0 (CH,),C-Ph
Acetone
(i)H*H,0 Dimethylphenylcarbinol

(CBSE 2010)
A/55)
D0. Ethyl cyanide to ethanoic acid (cf. with conversion 7, page
Conc.HCI Br,-NaOH
CH,CH,C-NH, (Hofmannbromamide reaction)
CH,CH,NH,
CH,CH,CN (Partial hydrolysis) Propionamide
Ethanamine
Bhyl cyanide
K,CH0,H,s04
HNO, CH,COOH
CH,CH,OH (Oxidation) Ethanoic acid
-Ng,-H,o Ethanol

AROMATIC CONVERSIONS
CONVERSIONS
TYPE I-TWO STEP

1. Benzene to aniline NH,

NO2
Sn + HCI
H,SO4, 333 K
Conc. HNO, + Conc. (Reduction)
(Nitration) Aniline
Nitrobenzene
(Bihar Board 2011 ; CBSE 2015)

2. Aniline to phenol
OH
N= NCI
NH2 NaNO,+ Dil. HCI, Boiling dil. HzSO4
273-278K
(Diazotization) Phenol
Benzenediazonium
chloride
Aniline

3. Aniline to benzene +
G=NCI
NH, H,PO,/Cu*
NaNO, + Dil. HCI,
273-278K
(Dlazotizatlon) Benzenediazonium
Benzene
chloride
Aniline
A/70 PRADEEP SNEW COURSE CHEMISTRY (XII) Vo m
4. Aniline to chlorobenzene
NH, N= NCI CI
NaNO, + Dil. HCI,
273-278K CuCVHCI

(Diazotization) (Sandmeyer reaction)

Aniline Benzenediazonium
chloride Chlorobenzene
5. Aniline to bromobenzene
NH2 N=NCI Br
NaNO, + Dil. HCI,
273-278 K CuBr/HBr
(Diazotization) (Sandmeyer reaction)
Aniline Benzenediazonium Bromobenzene
chloride
6. Aniline to iodobenzene (CBSE 2011)
+

NH, GN=NCI
NaNO,, Dil. HCI,
273-278 K KI, A
(Diazotization) -Ng, - KCI
Aniline Benzenediazonium Iodobenzene
chloride
7. Aniline to benzonitrile or cyanobenzene (CBSE 2007)

NH, N=NCT CN
NaNO, Dil. HCI
273-278K KCN/CuCN
(Diazotization)
Aniline Benzenediazonium Benzonitrile
chloride

8. Aniline to p-hydroxyazobenzene
+
NH GENCI
NaNO, Dil. HCI
273-278K Coupling with phenol
-N=N -OH
(Diazotization) pH 9-10
Aniline Benzenediazonium p-Hydroxyazobenzene
chloride

9. Aniline to fluorobenzene

NH, N=NBF F

NaNO2, HBF4
273-278 K A

(Diazotization) -BF3, -N2

Aniline Benzenediazoniunm Fluorobenzene
tetrafluoroborate
MPCAL ALIPHATIC AND AROMATIC CONVERSIONS
A71
10Aniline to nitrobenzene
4+

NH,
NaNO2, HBF4
N=NBF4 NO2
273-278 K
NaNO)
(Diazotization) + Cu powder, A
Aniline Benzenediazonium Nitrobenzene
tetrafluoroborate
11. Benzenesulphonic acid to aniline
SO,H SO,Na NH,
NaOH NaNH,, fuse
-Na,SO3
Benzenesulphonic acid Aniline
Sod. benzenesulphonate
(NCERT)
12. Benzene to m-nitroacetophenone
COCH3 COCH3
Conc. HNO3
(CH,C0))0, Anhyd. AICl3 + Conc. H,S04
(Nitration)
(FC. acylation) NO,
Acetophenone m-Nitroacetophenone
Benzene
(Hr. Board2011)
13. Benzene to benzoic acid
COOH
CH,
() KMnO/OH ,A
CHCl, Anhyd. AICl3 (Oxidatipn)
(EC. alkylation) (i) H*H,0
Benzoic acid
Toluene
Benzene
|14. Benzene to Benzyl alcohol
CHO CH,0H
() LiAlHy/ether
CO, HCI
(i) H*H,O
AICl/CuCl Benzyl alcohol
(Gattermann Koch reaction) Benzaldehyde
Benzene (Bihar Board 2011)
15. Phenol to acetophenone COCH3
OH
CH,C0Cl + Anhyd. AICl;
Zn dust, A
(FC. acylation)
-ZnO Acetophenone
Benzene
Phenol
16. Phenol to toluene
CH,
OH
CH,C1, Anhyd. AlCI3
Zn dust distil
(EC. alkylation)
-ZnO Toluene
Benzene
Phenol
A/72 PRADEEP'S NEw coURSE CHEMISTRY (XI) vOL)
17. Toluene to m-nitrobenzoic acid
CH, COOH COOH

K,Cr;0, +H,S04 Conc. HNO, + Conc. HzSO4, A

(Oxidation) (Nitration)
Toluene Benzoic acid NO,
m-Nitrobenzoic acid
18. Benzaldehyde to cyanobenzene or benzonitrile
CHO CH=NOH CN

NH,OH (CH,CO),0, A
-H,0 (-H,0)
Benzaldehyde Benzaldoxime Cyanobenzene
19. Salicylic acid to benzene
COOH COOH
OH Soda-lime, A
Zn dust, A (CaO + NaOH)
-ZnO -NazCO3
Salicylic acid Benzoic acid
(Decarboxylation) Benzene

20. Benzaldehyde tobenzene

CHO COOH
Soda-lime, A
KCr0,/ H,SO4 (CaO + NaOH)
(Oxidation) -Na,CO3
(Decarboxylation)
Toluene Benzoic acid Benzene
21. Benzoic acid to benzyl chloride
COOH CH,OH CH,CI
LiAlHJdry ether SOClh
(Reduction) -SO, -HCI
Benzoic acid Benzyl alcohol Benzyl chloride
22. Benzamide to benzene
CONH, COOH
Soda-lime, A
HONO (CaO + NaOH)
-N2, -H,0 -Na,CO3
Benzamide Benzoic acid
(Decarboxylation)
Benzene

23. Benzoie acid to benzamide (CBSE 2007)

COOH COCI CONH,

SOClh 2NH3 (excess)
-SO2, -HCI -NHCI
Benzoic acid Benzoyl chloride Benzamide
 ALPHATIC AND AROMATIC CONVERSIONS A/73
nECAL
Benzoic acid to benzaldehyde (NCERT;CBSE 2008, 2010 :CBSE (D) 2017 ;CBSE (OD) 2017)
24.
COOH COCI CHO

H,/Pd + BaSO4
SOCl, +S or quinoline
-SO,, -HCI Boiling xylene
(Rosenmund reduction)
Benzoic acid Benzoyl chloride Benzaldehyde

25. Benzaldehyde to acetophenone

CHOHCH3 COCH3
CHO
CsHsNH" CO,CI (PCC)
(i) CH;MgBr
(ii) H*H,0 CH,Cl,
Acetophenone
Benzaldehyde 1-Phenylethanol
(CBSE 2009)
26. Benzaldehyde to benzophenone
CHO CHOHCGHs COCGHs
CçHsNH" CrO CI (PCC)
() CçH_MgBr
CH,Cl,
(i) H*H,O Benzophenene
Diphenylcarbinol
Benzaldehyde
(NCERT)
27. Benzaldehyde to 3-phenylpropan-1-ol
CHOHCH,CHO
CHO
Dil. NaOH
-H,0
+ CH;CHO (Cross aldol
condensation)
3-Hydroxy
Benzaldehyde 3-phenylpropanal

CH=CHCHO CH,CH,CH,OH
H,/Ni
(Catalytic hydrogenation)
3-Phenylpropan-1-ol
3-Phenylprop-2-enal
(Cinnamaldehyde)

28. Benzoyl chloride to benzonitrile

CN
CONH)
COCI
P;O_, A or SOClh, A
NH3 (excess)
(-H,0)
NH CI
Benzamide Benzonitrile
Benzoyl chloride
A74 PRADEEP SNEW COURSE CHEMISTRY (XII) vOL)
29. Benzoic acid to m-nitrobenzyl alcohol
COOH COOH
CH,OH
Conc. HNO3
+ Conc. H,S04 () B,Hlether
(Nitration) or NaBH4/CH,OH
Benzoic acid
m-Nitrobenzoic acid
NO2 NO2
m-Nitrobenzyl alcohol
30. Benzaldehyde to a-hydroxyphenylacetic acid (NCERT)
OH
OH
CoH,CHO
NaCN/HCI
CçH, -CH-CN
HH,0
pH 9-10 (Hydrolysis) CH, -CH-COOH
Benzaldehyde Benzaldehyde a-Hydroxyphenylacetic acid
cyanohydrin (Mandelic acid)
31. Benzyl alcohol to phenylacetic acid
HBr, A KCN, A
HtH,0
CH,CH,0H or P+ Br CoHCH,Br CoH,CH,CN CoH;CH,COOH
(Hydrolysis )
Benzyl alcohol Benzylbromide Benzyl cyanide Phenylacetic acid
32. Bromobenzene to benzoic acid (CBSE 2010)
Mg CO, (s) H,0+
CçH,Br Dry ether CçHMgBr (Dry ice)
[CGH,COOMgBr]
(Hydrolysis)
CGHCOOH
Bromobenzene Phenylmag. bromide Benzoic acid

33. Bromobenzene to 1-phenylethanol (NCERT)

Mg/dry ether (i) CH, CHO

CGH_Br (Grignard reaction) CGH,MgBr CH,-CHCH,
(iü) H,o+ 1-Phenylethanol
Bromobenzene Phenylmag. bromide
34. Nitrobenzene to acetanilide
NO, NH, NHCOCH;
Sn + HCI (CH,C0),o
(Reduction) + CH,COOH
(Acetylation) Acetanilide
Nitrobenzene Aniline

35. Phenylhydroxylamine from benzene

NHOH
NO,
Conc. HNO, + Conc. H,SO4
333 K Zn dust/aq. NHCl
(Nitration) (Reduction under
neutral conditions)
Benzene Nitrobenzene Phenylhydroxylamine

36. Nitrobenzene to m-nitroaniline

NH,
NO2 NO2
Fuming HNO3 + Conc. H,SO4,
393 K (NH4),S
(Nitration) (Selective reduction)
NO, NO,
Nitrobenzene m-Nitroaniline
m-Dinitrobenzene
 A/75
AL ALIPHATIC AND AROMATIC CONVERSIONS
Chlorobenzene to benzene
37.
CI MgCl

Mg/THE, A H*H,O
(Grignard reaction) -Mg(OH)CI
Benzene
Chlorobenzene Phenylmag. chloride
(CBSE 2017)

38. Ethylbenzene to benzene

COOH
CH,CH3
Soda-lime (CaO + NaOH)
(i) KMnOJOH", A
(in) H*H,0 630 K
(Decarboxylation) Benzene
(Oxidation) Benzoic acid
Ethylbenzene (CBSE (OD) 2017)
39. Acetophenone to benzoic acid

-ONa OH
,C-CH3 I;/NaOH, A H*/OH
(Acidification)
(lodoform reaction)
Benzoic acid

Acetophenone
TYPE II THREE-STEP CONVERSIONS

1. Benzene to Deuterated benzene D

Br MgBr

Mglether D,0
Brz Mg (OD) Br
Anhyd. AIBr3 Deuterated
Bromobenzene Phenylmag. benzene
Benzene bromide

2. Phenylhydrazine from aniline

G=NCI NHNH,.HCI NHNH,
NH, NaNO, + Dil, HCi SnCl,/HCI NaOH (aq)
273-278 K -NaCl, - H,0
or Na,SO3
(Diazotization) Phenylhydrazine
Benzenediazonium hydrochloride Phenylhydrazine
Aniline chloride
(NCERT)
3. Benzaldehyde to benzophenone CaCO Dry distil.
(CH,CO0,0 Cotls CCoHs
CGH-CHO K,Cr,0,/HSO
(Oxidation) cHCOOH Benzoic acid
Cal. benzoate
-CaCO, Benzophenone
Benzaldehyde
Alternatively, SOCL, CçH /Anh. AlCl,
CçHs COCoH,
K,CHo,/H,S04 CGH,COOH ’ CoH;COCI (F.C.acylation)
CçHCHO (Oxidation) Benzoic acid Benzoyl chloride Benzophenone
Benzaldehyde