Organic Chemistry - Reactions & Synthesis

Base for Enolisation of Standard Carbonyls

NaNH2 (NH2-), LDA

Base for Enolisation of β-Dicarbonyls

Matching Alkoxide

Epimerisation Reaction

H+/H2O attacks from either above or below of the enol form, forming epimers - stereoisomers that only differ in the orientation of one carbon

Deuterium Incorporation

D+/D2O attacks the enol form.

Halogenation of General Carbonyl Compounds

Formation of α-HaloKetones, requires CH3CO2H catalyst and X-X halogen reactants.

Haloform Reaction

Reactants: Enolisable Carbonyl with excess X2, OH- and H3O+
Products: Carboxylic Acid, Haloform (CHX3)

Hell-Volhard Zelinsky

Reactants: Carboxylic Acid, PBr3, Br2 (1 eq), H2O.
Products: α-Bromo Carboxylic Acid

α-Alkylation of Enolates

Reactants: Enolisable Carbonyl, LDA and R-X.
Products: α-Alkylated Carbonyl

Aldol Reaction

Reactants: Enolisable Carbonyl, Keto Carbonyl (can be same), OH-/RO-, H+/H2O.
Product: β-Hydroxy Carbonyl

Aldol Condensation

Reactants: β-Hydroxy Carbonyl, H3O+/Heat.

Product: α,β-Unsaturated Compound

Claisen Condensation

Reactants: Enolisable Ester, Keto form of Ester, Matching Alkoxide (1 eq), H+/H2O.
Product: β-Keto Ester

Malonate Reactions

Reactants: Malonate, R-X, NaOH (excess), Conc. HCl and Heat

Products: Carboxylic Acid, CO2

Ethyl Acetoacetate Reactions

Reactants: Ethyl Acetoacetate, R-X, NaOH (excess), Conc. HCl and Heat
Products: Methyl Ketone, CO2

Michael Reaction

Reactants: Enolisable Carbonyl, , LDA/Matching Alkoxide (if Dicarbonyl), α,β-Unsaturated Compound, H+

Product: 1,5-Dicarbonyl Compound

Mannich Reaction

Reactants: Formaldehyde, Enolisable Ketone, Secondary Amine

Product: Mannich Base (R1COCH2CH2NR2R3)

Betti Reaction

Reactants: Formaldehyde, Phenol, Secondary Amine

Product: Betti Base R1R2NCH2(Phenol)

Lobry de Bruyn-Alberda van Ekenstein Reaction

Interconversion from Aldose to Ketose

Reduction of Sugars to Alditols

Reagents: H2/Pd, H2/Pt, NaBH4, Na(Hg)

Oxidation of Sugars to Aldonic Acids

Reagents: Br2(aq), Fehling’s Solution (Cu2+, Basic Sodium Tartrate), Tollens’ Reagent (Ammoniacal AgNO3)

Oxidation of Aldose to Aldaric Acid

HNO3

Kiliani Fischer Ascent

Reactants: Aldose, NaCN, pH 8.5, H2SO4 and Heat, Reducing Agent (Na(Hg) or similar)

Hydrate Formation/Hemiacetal/Acetal Formation

H2O/ROH and H+

Glycoside Formation

ROH/H+

Fischer Proof

1) Glucose has the molecular formula C6H12O6; assume the bottom hydroxyl is on the RHS.

2) Arabinose forms both D-Glucose and D-Mannose through Kiliani-Fischer Ascent. Hence these compounds only differ by the Carbon in the 2nd Position

3) Upon oxidation with HNO3, Arabinose forms an optically active compound → C2 in Arabinose on LHS, C3 in D-Mannose/D-Glucose on the LHS

4) Oxidation of both D-Mannose and D-Glucose form optically active acids → C4 on RHS

5) (+) Glucaric Acid can be made from both (+) gulose and (+) glucose → D-Glucose must have C2 on the RHS.

Basic Oxides

Group 1 and 2 Metal Oxides

Acidic Oxides

Main Group Oxides

Amphoteric Oxides

BeO, Al2O3, Ga2O3, MoO3, V2O5, SnO2, Sb2O5

Hard Acids

Small and High Charge Density → Group 1 and 2, Fe3+, Co3+

Soft Acids

Large, Low Charge Density, Polarisable, Au+, Pt2+

Intermediate Acids

Pb2+, Fe2+, Ni2+, Cu2+

Hard Bases

Small and Electronegative, F-, Cl-, O-bound

Soft Bases

Large, Less Electronegative, I-, C-bound, S-bound

Intermediate Bases

Br-, N-Bound

Lability Trends

1) High Lability = Large Radius, Low Charge.
2) d10 Compounds generally Labile

3) Very Small metals less labile due to stronger M-L bond strength.
4) M(III) less labile that M(II) due to stronger M(III) ligand bonds.
5) 4d, 5d less labile due to CFSE
6) d3, d6 inert due to CFSE

Cisplatin Formation

1) Start with [PtCl4]2-
2) React with NH3 once, and twice according to the trans effect to yield cis -[Pt(NH3)2Cl2]

Cisplatin Action

1) Cisplatin reacts with H2O once and twice to form [Pt(NH3)2(H2O)2]2+, which is trapped within the cell.
2) Attaches to N7 guanine to form coordination complex.
3) Leads to kink in DNA
4) Programs Apoptosis

Trend in Nucleophile for Interchange Associative Pathway

CN >PR3 = SCN- >I- > N3 - = NO2 - > py = NH3 = Br- > Cl- > OH- > H2O

Template Effect - Cyclam

1) Start with NH2 - (CH2)3 - NH - (CH2)2 - NH - (CH2)3 - NH2
2) React with [Ni(H2O)6] 2+ to form a coordinated compound with denticity 4, featuring two NH and two NH2 bonded to the Ni, with separation of 3 and top and bottom and side on separation of 2.
3) React with Glyoxal (O=CHCH=O) to form a double imine on the RHS of nickel centre.

4) Reduce with NaBH4 to form a coordinated compound with all NH, separation of 3 at top and bottom, separation of 2 on sides.
5) React with excess NaCN to isolate the charge neutral macrocycle.

Here, the metal directs the steric course of the reaction.

Heat Engine Efficiency

1 - Tc/Th

Enthalpy Definition

delta H = delta U + P delta V,
at constant pressure

Entropy Definition

dS = dq(rev)/T

Work Function Definition

Minimum energy to remove e- from the fermi level to the vacuum level

Electron Affinity Definition

Minimum energy released when introducing e- from vacuum level to material (difference between vacuum level and bottom of conduction band in semiconductor)

Ionisation Potential

Energy required to move highest energy e- from material to vacuum level.

n-p Junction

Doped electrons from the n side from the the holes on the LHS p side.
Creates a buildup of - charge on LHS and + on RHS, which forms an electric field at the depletion region.
Energy levels recalibrate to form slope from left to right.
When light is absorbed in the depletion region, an electric current forms.