Final Flashcards
Same side of double bond
Z
Opposite side of double bond
E
RCOOR
Ester
ROR
Ether
OCNH2
Amide
Formal charge
(# of valence e-) - (lone pairs + 1/2 bonds)
Aromaticity
4n + 2
Conjugated
+ and - count
What is the hybridization of the orbital containing the unshared e- on the nitrogen atom in pyridine?
sp2
Benzene hybridization
sp2
R-CH2
Carbon hybridization
sp3
Ketone carbon (dbl bonded to the O) hybridization
sp2
R-OH
O hybridization
sp3
Most stable heat of combustion
Highest kJ/CH2
Most stable carbocations
R-CH
+ on the carbon closest to the benzene ring
Near pH 7
NH3+ and O-
Strongest base
R–CH2NH2
Carboxylate strongest base
CH2CH2CH2COO-
Strongest to weakest acid
OH+>NH3+>OH>NH2
Most acidic to least acidic
1 ketone and 1 COOCH > ketone> COOCH > CH3CH3
Greater acidity of p-nitro phenol
- on both NO2 O’s and + on N
Most acidic proton
OH
Smallest pKa
Least acidic H
Strongest to weakest acid
SOOH >SOOH > COOH
R-CH2CH3 –H2O/H+–>
Add OH to the same carbon CH2CH3 is on
R–CH3 –1.B2H6/2.H2O2, NaOH–>
CH3 up and OH is added one carbon down from CH3 pointing down
Hg(OAc)2, H2O followed by NaBH4
Adds an OH where a double bond was
HCl
Adds Cl to most substituted carbon
Nucleophile that adds an OH to a double bond
H2O
H2O, H2SO4/HgSO4
Creates a ketone on the carbon that had double bonds closest to the ring
Propene to Propanol
B2H6, followed by H2O2, NaOH
Adding Br2 to (E)-3-hexene
One meso compound
R-CH3 –1.Hg(OAC)2, H2O/2. NaBH4–>
OH added to same carbon as CH3
Furan —Br2/CH3OH–>
Adds OCH3 next to O and Br next to OCH3
- R-BH/2. H2O2, NaOH
Adds aldehyde at the very end of the double bond
R-C (triple bonded)CH –> R-Ketone
H20,H2SO4/ HgSO4
A compound with two double bonds + HCl + CL2
Cl on each of the double bonds
R-CH3 –HCl–>
Cl adds to the same carbon as CH3
Double bond in a ring —> Epoxide
RCO3H
Butene —CHCl3/(CH3)3COK–>
Dimethyl cyclopropane with the CH3’s pointing it two different directions and 2 Cl’s at the top
R-CH3 —Br2/H2O–>
CH3 and OH on one carbon (CH3 up OH down) and Br (up) one carbon down
Different compounds with the same molecular formula
Isomers
Isomers that have a different atom connectivity
Constitutional Isomers
Isomers that have the same connectivity but differ in the arrangement of their atoms in space
Stereoisomers
Stereoisomers that are nonsuperimposible mirror reflections of each other
Enatiomers
Stereoisomers that are not mirror images of each other
Diastereomers (two molecules switched)
A mixture of two enantiomers in equal concetrations
Racemic
Optically inactive
compound is “superposable” on its mirror image (not to be confused with superimposable, as any two objects can be superimposed over one another regardless of whether they are the same.
Meso
Nucleophile attacks carbon bound to electronegative atom
Substitution Reactions
Nucleophile can be a base and react with acidic protons of alkyl substrates
Elimination
! step
Bimolecular
Rate is 1st order
Inversion occrus
Sn2
2 steps
Ionization of alkyl substrate then reacts with nucleophile
Unimolecular
sp2 tetrahedral
Sn1
NuH + X-
E2
compound + NuH or compound + X-
E1
Primary
Strong (like OH-) or Weak base (like Cl-)
Good Nucleophile
Sn2
Primary
Strong Base (like OH-)
Non-nucleophilic bases
E2
Secondary
Strong (like OH-) or Weak Base (like Cl-)
Sn2
Secondary Poor Nucleophile (like H2O or HOR)
Sn1/E1 (slow), in polar, protic solvents
Tertiary Strong base (like OH-)
E2
Tertiary Weak base (like Cl-)
Sn1/E1 in polar, protic solvents
Tertiary Poor Nucleophile (like H2O or ROH)
Sn1/E1 in polar, protic solvents
O-H and N-H Frequency
3400
C-H (sp3)
3000-2850
C-H (sp2)
3000-3100
C-H (sp)
3300
C (triple bond) C and C (triple bond) N
2100
C=O
1700
C=C, aromatic C-C
1600
Aromatic C-C
1500
atom with 4 bonds
sp3
atom with 3 bonds
sp2
atom with 2 bonds
sp
atom with 1 bond
s
Carbocation stability
Tertiary > Secondary > Primary > Vinyl
Ranking acids
EN > Distance from EN molecule> No EN molecule
pH of 12
Deprotonates
Acidity
HI>HBR, HCl, HF
Larger atom
More nucleophilic
Allylic and Benzylic halides undergo
Sn2 faster
If catalyzed by acid, and nuc = primary amine
C-N imine
If catalyzed by acid and nuc = secondary amine
C=C enamine
Strong basic nuc like grignard or metal halides
1,2 addition
Weak basic nut like R2CuLi
1,4 addition
Stability of organic radicals
Allylic/Benzylic > tertiary alkyl > secondary alkyl > primary alkyl > methyl > vinylic/aryl
Initiation
Generates radicals
Step 1
Propagation
Radical reacts with stable molecule to produce a new radical
Step 2
Termination
Destroys radicals and stops the reaction
Step 3
Hydrogen atom count decreased
Oxidation
Hydrogen atom count increased
Reduction
Oxidizing agents
CrO3, K2Cr2O7, K2CrO4, KMnO4
Chromium used under acidic conditions
Potassium Permanganate used under basic conditions
Oxidize only to aldehyde state
CrO3-2 pyridine, PCC, PDC
Cleavage
HIO4 by ozone
CH3MgBr
Oxidizes C=O and turns OCH3 into OH
Hg(OAc)2, NaBH4/NaOH
Combines two molecules removing the double bond and the H from the OH
NH3/H2,Pt
Oxidizes C=O and adds NH2
KOH, CH2=CHCH2Br, H20 NaOH/heat
breaks apart two fused rings leaving only one c=c behind and adds NH2
SoCl2/heat, NH3, Br2/NaOH
reduces ketone and replaces OH with NH2
R-C(OH)HCH3
yellow precipitate
NO2
meta directing
Most to least reactive with NH3
Cl > anhydride > ester >amide
SoCl2
Turns carboxylic acid to anhydride
-OD/D2O
replaces only the alpha hydrogens
NaCN
1,4 Addition
