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SINHA IIT CHEMISTRY 1

BOND ENERGY Bond type &Length D


BOND Kcal/mol kJ/mol
Bond type Length D
O-H 110-111 460-464
C-H 96-99 400-415 C-CSp3-sp3 1.53
N-H 93 390 Sp3-sp2 1.51
S-H 82 340 Sp3-sp 1.47
C-F 2 2
Sp -sp 1.48
C-H 96-99 400-415 2
Sp -sp 1.43
C-O 85-91 355-380 Sp-sp 1.38
C-C 83-85 345-355 2
C=CSp -sp
2
1.32
C-Cl 79 330 2
Sp -sp 1.31
C-N85 69-75 290-315 Sp-sp
63
1.28
C-Br 66 275 C ≡CSp-sp
Inductive effect of groups relative to hydrogen 1.18
+I -I C-HSp3-H 1.09
Sp2-H 1.08
O- NR3+ COOH OR Sp-H66 1.08
COO- SR2+ F COR C-OSp3-O 1.43
CR3 NH3+ Cl SH Sp2-O 1.34
CHR2 NO2 Br SR C=OSp2-O 1.21
CH3 SO2R I OH Sp-O57 1.16
D CN OAr C ≡Cr C-NSp3-N 1.47
SO2Ar COOR Ar 2
Sp -N 1.38
CH=CR2 C=NSp2-N
1.28
C ≡N Sp-N
31 EM IT A
1.14
C-Ssp3-S
0 9 H I NH

1.82

50 Y
2
sp -S 1.75

55
-0 TR sp-S
C=Ssp-S
1.68
1.67
SI

49 IS
C

Carbanion stability
Vinyl > phenyl > Cyclopropyl > ethyl > n-propyl > isobutyl > neopentyl >cyclobutyl > cyclopentyl
Reducing Agent
Reagent Preferred Solvents Functions Reduced
Sodium Borohydride ethanol; aqueous ethanol aldehydes to 1°-alcohols
NaBH4 15% NaOH; diglyme ketones to 2°-alcohols
avoid strong acids 1,2-reduction of enones is favored by
CeCl3inert to most other functions
Lithium Aluminum ether; THF aldehydes to 1°-alcohols,ketones to 2°-
Hydride (LAH) avoid alcohols and amines alcohols.carboxylic acids to 1°-alcohols
LiAlH4 avoid halogenated esters to alcohols,epoxides to alcohols
compounds nitriles & amides to amines
avoid strong acids halides & tosylates to alkanes
most functions react
Lithium tri t- ether; THF fast:-acid chlorides to aldehydes
Butoxyaluminohydride avoid alcohols and (at -78° C),3°-amides to aldehydes (at -78°
LiAlH(Ot-C4H9)3 amines,avoid halogenated C),nitriles to aldehydes (at -78° C)

1-D-10 Talwandi & B-7 JAWAHAR NAGAR,KOTA. 93149-05055


SINHA IIT CHEMISTRY 2
compounds slower:,aldehydes to 1°-alcohols
avoid strong acids ketones to 2°-alcohols
Diisobutylaluminum THF; toluene fast:-acid chlorides to aldehydes
Hydride avoid alcohols and amines (at -78° C),3°-amides to aldehydes (at -78°
AlH[CH2CH(CH3)2]2 avoid halogenated C),nitriles to aldehydes (at -78° C)
compounds slower:,aldehydes to 1°-alcohols
avoid strong acids ketones to 2°-alcohols
Diborane ether; THF carboxylic acids to 1°-alcohols, aldehydes
B2H6 = 2 BH3 sulfide complex in to 1°-alcohols,ketones to 2°-
CH2Cl2,complexes with alcohols,nitriles to amines,esters &
amines,avoid alkenes & epoxides slowly reduced
alkynes
Hydrogen & Catalyst alcohols, ethers, alkenes & alkynes to alkanes (fast)
H2 & Pt, or Pd, or Ru, or hydrocarbons nitro groups to amines (fast)
Ni or carboxylic acids imines to amines (fast)
aldehydes & ketones to alcohols (slow)
nitriles to amines (slow)
Modified (poisoned) may remove benzylic groups
Catalyst alkynes to alkenes
acyl chlorides to aldehydes
Reactive Metals liq. ammonia & ether ketones to 2°-alcohols
Na, or Li, or K cosolvents alkynes to alkenes
or alcohols or amines conjugated π-systems
(e.g. aromatic rings, dienes & enones)
31 EM IT A
cleaves C-X and benzylic groups
0 9 H I NH

50 Y
Mg or Al or Zn or Fe cleaves activated substituents
water, alcohols, acetic acid nitro groups to amines

55
-0 TR
or aqueous mineral acid C=O (aldehyde/ketone) to CH2
SI

Oxidising Agent
49 IS
Reagent Preferred Solvents Functions Oxidized
Jones Reagent aqueous sulfuric acid & acetone 1°-alcohols to carboxylic acids
H2CrO4 (avoid acid sensitive systems) aldehydes to carboxylic acids
2°-alcohols to ketones
avoid amines and sufides
Collins Reagent methylene chloride 1°-alcohols to aldehydes
CrO3 • 2 C5H5N (CH2Cl2) 2°-alcohols to ketones
C

Pyridinium Chlorochromate methylene chloride 1°-alcohols to aldehydes


ClCrO3 • C5H5NH (CH2Cl2) 2°-alcohols to ketones
Dimethyl Sulfoxide CH2Cl2 or ethers or DMSO A Mild Procedure
(CH3)2S=O & 1°-alcohols to aldehydes
DCC or Ac2O or (CF3CO)2O 2°-alcohols to ketones
or SO3 or (COCl)2
Potassium Permanganate water and aldehydes to carboxylic acids
KMnO4 aqueous solvent mixtures 2°-alcohols to ketones
pyridine alkenes to vicinal-diols (vic.-glycols)
often used catalytically alkynes to carboxylic acids
Osmium Tetroxide avoid amines and sufides
OsO4 alkenes to vicinal-diols (vic.-glycols)
Periodic Acid water or aqueous mixtures vic.-glycols to carbonyl compounds
HIO4
Lead Tetraacetate vic.-glycols to carbonyl compounds
Pb(OCOCH3)4 benzene or acetic acid
Peracids CH3CO3H CH2Cl2 or ethers alkenes to epoxides,ketones to esters
C6H5CO3H, etc. avoid amines and sufides
Ozone CH2Cl2 or CHCl3 cleaves alkenes & alkynes
O3 (sometimes alcohol) avoid benzene derivatives
amines and sufides

1-D-10 Talwandi & B-7 JAWAHAR NAGAR,KOTA. 93149-05055