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Flash vacuum pyrolysis of 3-mercaptopyridine-2-carboxylic acid(74), gave 3-mercaptopyridine(83) and di-(3-pyridyl)disulfide(84). FVP of 3-hydroxy-pyridine-2-carboxylic acid(75), gave dipyrrolo[1,2-a;1',2'-d]pyrazine-5,10-dione(91). FVP of 2-hydroxypyridine-3-carboxylic acid(76), gave di-[2]-pyridylether(101) and trimer(102).

A cyclic ketene acetal is an olefin that is substituted at one end by two electrondonating hetero atoms, like O, N, S, where these heteroatoms are connected together by a chain. Delocalization of the lone pair electrons of the two hetero atoms to the double bond makes the β-carbon (the exocyclic methylene carbon) electron rich and nucleophilic. A major goal of cyclic ketene acetal chemistry is to provide functionalized cyclic ketene acetal monomers as precursors to polymers of desired properties. The cyclic ketene-N,O-acetal 3-methyl-2-methylene-oxazolidine, generated in situ from 2-methyl-2-oxazolinium iodide and triethylamine, reacted with aryl isocyanates in refluxing THF to give α,α-bis(N-arylamido) lactams via the iodide-catalyzed rearrangement of β,β–bis(N-arylamido) cyclic ketene-N,O-acetal intermediates. However, similar β,β–bis(N-arylamido) cyclic ketene-N,O-acetals having two methyl substituents at C-4, did not rearrange due to hindrance of the iodide attack on C-5. 3,4,4-Trimethyl-2-methylene-oxazolidine reacted with aryl chloroformates to form both mono- and di-aryloxycarbonylation adducts. The two methyl groups at C-4 Template Created By: Damen Peterson 2009 hindered the alternative polymerization route. 3-Methyl-2-methylene-oxazolidine, which does not have two methyl groups at C-4, underwent cationic polymerization under identical conditions. Benzoylation of 2-methyl-2-oxazoline with benzoyl chloride gave a ring-opened N,C,O-trisbenzoylation product via O-benzoylation of the N,C-bisbenzoylated intermediate, followed by chloride attack on C-5. The N,C,O-trisbenzoylated product underwent N,O-double debenzoylation by KOH to give the cyclic ketene-N,O-acetal, 2- oxazolidin-2-ylidene-1-phenylethanone. This compound (an ambident nucleophile), upon deprotonation, reacted with benzoyl chloride to give the β,β-bisbenzoylated cyclic ketene-N,O-acetal, and reacted with phenyl chloroformate to give a novel heterocycle, [1,3]oxazine-2,4-dione. The benzoylation of 2-methyl-2-oxazine gave a similar ringopened N,C,O-trisbenzoylation product. Reactions of 2-methyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline and 2-methyl-2- thiazoline with trifluoroacetyl anhydride gave C-trifluoroacetylated cyclic ketene-N,O(S)- acetals. However, trifluoroacetylation of 2-methyl-2-oxazine gave the β,β- bistrifluoroacetylated cyclic ketene-N,O-acetal. In summary, a novel iodide-catalyzed rearrangement of β,β–bis(N- arylamido)- cyclic ketene-N,O-acetals was found. The [1,3]oxazine-2,4-dione heterocycle synthesized during this research also demonstrates the synthetic potential of cyclic ketene acetal chemistry in pharmaceutical industry. Functionalization of cyclic ketene acetals based on the chemistry developed in this work will find applications in polymer industry.

Ketene dimethyl thioacetal monosulfoxide was prepared in 68% overall yield in two steps starting from methylmagnesium chloride. The yield of dithioacetic acid was improved significantly by employing tetrahydrofuran as solvent and using elevated temperatures. A one-pot synthesis of ketene thioacetals from alkyl halides was developed and several ketene thioacetals were prepared by this method. Direct oxidation of ketene thioacetals using m-chloroperoxybenzoic acid provided a general route to ketene thioacetal monosulfoxides. In cases where E and Z isomeric ketene thioacetal monosulfoxides were possible, the E/Z isomeric ratio increased as the substituents on the ketene double bond was increased in size.

(1)Flash vaccum pyrolysis of furo[3,2-c]pyran-4-one gave starting material, but in photolytic system we gave a isomer: furo[2,3-c]pyran-5-one. (2)Flash vaccum pyrolysis of benzoic 1,2-dimethyl-3-indoly anhydride,via a ketene intermediate,gave a dimmer.

This thesis describes the synthesis of the C1'-C10' portion 72 of the pamamycin-621A using a cuprate conjugate addition to join enone fragment 52 and organostannane fragment 64a. Fragments 52 and 64a were both synthesized from (S)-methylketene dimer 51. / Master of Science

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