Aceto acetic ester synthesis

Winch, if any, of the following compounds can be prepared by an aceto-acetic ester synthesis Explain. 

Anhydrides—Continued reduction to alcohols, 155 reduction to lactones, 535 Arenes, see Hydrocarbons, aromatic Amdt-Eistert reaction, 433, 487, 573 Aryl esters. Fries rearrangement, 344 hydrolysis, 169 preparation, 169 Aryl halides, see Halides Atyloxy acids, preparation, by aceto-acetic ester synthesis, 430 by malonic ester synthesis, 429 from atyloxy alcohols, 419 from atyloxy cyanides, 414 preparations listed in table 48, 460 Aryloxy acyl halides, preparation, 547 preparations listed in table 61, 553 Aryloxy esters, preparations listed in table 55, 516... 

How would you prepare the following compounds using either an aceto-acetic ester synthesis or a malonic ester synthesis ... 

From Aceto-acetic Ester.—Glutaric acid may also be made by either the aceto-acetic ester synthesis or by the malonic ester synthesis as follows,... 

For retrosynthetic analysis, a methyl ketone is a characteristic product of the aceto-acetic ester synthesis starting with ethyl acetoacetate, and other complex ketones can be derived from other j8-ketoester starting materials. 

Synthesis from Glycerol.--Citric acid is related to the two preceding acids and its constitution has been established by two syntheses, one from glycerol and the other from aceto-acetic ester. 

From Aceto-Acetic Ester.— The synthesis from aceto-acetic ester takes place according to the following scheme ... 

The constitution of the iso-dialuric acid was established by its synthesis from aceto-acetic ester and urea. 

S3mthesis of Collidine.—The most important synthesis of pyridine homologues is that of collidine from which pyridine may be obtained by elimination of the methyl groups by oxidation and loss of carbon dioxide. When aldehyde ammonia is heated with aceto-acetic ester a derivative of a di-hydrogenated collidine is obtained, as follows ... 

Acetoacetic ester synthesis (Section 22.7) The synthesis of a methyl ketone by alkylation of an alkyl halide with ethyl aceto-acetate, followed by hydrolysis and decarboxylation. 

From Acetic and Formic Acids.—A fourth method of synthesis from acetic and formic acid esters will be explained in detail in connection with the next acid. All of these syntheses prove the constitution of pyro-racemic acid as an a//>/fa-ketone acid as given. It may be considered as aceto formic acid which is in accord with the fourth method of synthesis. As an acid it forms all acid derivatives and as a ketone it undergoes the characteristic ketone reactions, e.g.y with phenyl hydrazine and hydroxyl amine. On heating to 150° with dilute sulphuric acid in a sealed tube it loses carbon dioxide and yields acet aldehyde. 

Paterson et al. [98] in their attempt used a similar disconnection for rhizopodin as described by Menche (fragments 144 and 149) (Scheme 2.151). However, unlike, Menche, they used silyl ketene acetal 16 in an asynunetric VMAR for the addition to ( )-iodoacrolein (142) to obtain dioxinone 143 in 94% ee. Methanolysis removed the aceto-nide, and the subsequent Narasaka reduction [99] provided the syn-diol 144 in 80% yield and a 10 1 selectivity for the desired isomer. The synthesis of segment 149 started with aldehyde 145, which was ultimately derived from Roche ester. Carbon chain extension was achieved through a chelation-controlled Mukaiyama aldol reaction with silyl ketene acetal 146, which installed the new chiral center with excellent stereocontrol (20 1 dr). For the installation of the third secondary alcohol, six-membered lactone 148 was obtained by treatment with K COj in methanol. Subsequent borane reduction provided stereospecifically the desired alcohol, which was then further transformed to the desired acid (149). 

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