lecture62012nonotes

lecture62012nonotes - 1 2 3 Oxidation of Phenols - Quinones...

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Unformatted text preview: 1 2 3 Oxidation of Phenols - Quinones 4 Vitamin Vitamin K Coenzyme Q - ubiquinone Doxorubicin 5 HETEROCYCLES Molecules in which one or more rings contain at least one other atom than carbon. Common heteroatoms are O, N, S, P, etc. O Piperidine Pyrrolidine H N Tetrahydrofuran O O O Piperazine Morpholine 1,41,4-Dioxane 6 Nicotine Coniine (Socrates) Cocaine O O Sex pheromone of the Grey Duiker antelope 7 Saturated Heterocycles As nucleophiles: Acylation 8 Alkylation 9 Enamine Formation 10 11 12 13 14 Basicity of heterocyclic amines H N N pKb 3.0 pKaH 11 N H H 2.8 H N H N O 4.2 8.4 9.8 11.2 5.6 H N N H H N N H H H O N H H H 15 Nucleophilicity of acyclic vs. cyclic amines k R R N + R CH 3-I rate constant R R N CH3 I R N N Tr iethylamine N Q uinuclidine N DA BC O pKb 3.3 4.0 5.2 krel 1 63 40 16 17 BaylisBaylis-Hillman Reaction 1. Aldol Condensation 18 BaylisBaylis-Hillman Reaction 2. Elimination and formation of -carbonyl product 19 BaylisBaylis-Hillman Reaction 3. Conjugate Addition 20 BaylisBaylis-Hillman Reaction 21 BaylisBaylis-Hillman Reaction 22 BaylisBaylis-Hillman Reaction 23 24 Aromatic Heterocycles N N S O H Pyridine Furan Pyrrole N N N N Pyridazine Pyrimidine Thiophene N N Pyrazine (DNA/RNA) N N N N H H N Pyrazole Imidazole (DNA/RNA) Quinoline 25 Antipyrine One of the oldest synthetic drugs (1887) Quinine 16th century (antimalarial) Sulfapyridine First effective Antibiotic (1938) Chloroquine (antimalarial) Tagamet Ulcer treatment (1970) Viagra (1997) 26 Huckel’s Aromaticity Rules: If a molecule is: Aromatic molecules have full outer shell: stable, inert inert 1. Cyclic 2. Planar, fully conjugated Each member of the cycle has a p orbital parallel to all the others 3. Total number of electrons in p orbitals: 4n+2, n= integer= 0, 1, 2, 3, n= 0, 4n+2= 2 n= 3, 4n+2=14 4n+2 n= 1, 4n+2= 6 n= 2, 4n+2= 10 27 Nucleophilicity of acyclic vs. cyclic amines 28 29 BaylisBaylis-Hillman Reaction 30 31 32 33 ...
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