Amino acids are metabolized by a transamination reaction in which the amino group of the amino acid changes places with the keto group of an a-keto acid; the amino acid and a new a-keto acid. Draw the products of the transamination reaction between threonine and 2-oxopentanedioate. • You do not have to consider stereochemistry. • Use the charge tools to adjust the charges of the amine and carboxyl groups to the form in which they would be found at physiological pH. • Draw one structure per sketcher. Add additional sketchers using the drop-down menu in the bottom right corner. • Separate multiple products using the + sign from the drop-down menu. ? √n [ Ⓡ ChemDoodle

3. When aspirin is made from acetic acid, the by product is H₂O; when acetic anhydride is used, the by-product is acetic acid. When acetyl chloride is used (see above), the by product is HCl. Which route should you use if you were working for Leica, a company that mass produces aspirin on a daily basis? Why?

Write an equation for the reaction of chloroacetic acid (Ka=1.5103) with trimethylamine (Kb=5.9105) . Calculate the equilibrium constant for the reaction. If 0.10 M solutions of these two species are mixed, what will be their concentrations at equilibrium?

The deuterium kinetic isotope effect (kH2O/kD2O) for the hydrolysis of aspirin is 2.2. What does this tell you about the kind of catalysis exerted by the ortho-carboxyl substituent? (Hint: It is easier to break an O¬H bond than an O¬D bond.)

Figure 3 shows a substitution reaction between triphenylmethyl chloride and an excess of the base methanamine. What is the minimum mass of this amine required to produce 5.000 grams of the organic product N-methyltriphenylmethanamine? Molar masses are given in Figure 3. [Round the answer to three decimal places. Do not type in the unit. Use a decimal point.] * Do you need to add imidazole to the reaction mixture used in this question to absorb the hydrogen chloride gas produced during the reaction?

Specialized reagents and their acronyms: MCPBA= meta-chloroperbenzoic acid; HOAC = acetic acid, NaOAc = Sodium Acetate; Ph= phenyl = C6H5-; P(Ph)3 = triphenyl phosphine; NBS = N- bromosuccinimide, PBr3, SOCI2, AICI3, FeBr3, H2SO4, Li, Na, Mg, Br2, CrO3, LDA = lithium diisopropylamide, PCC = pyridinium chlorochromate, KO-C(CH3)3, LAH = LIAIH4, (sia)2BH = disecondary isobutyl borane, KMNO4, HIO4 = periodic acid %3D %3D %3D %3D %3D write the missing reagents and solvents over the arrows. Some transformation require multiple steps. In some cases there will be multiple arrows. Ph CH CH o 0om ilubongo CEC-Ph In questions 14-24, write the products of the following transformations. If there is no reaction write NR. Indicate R or S or racemic or indicate cis or trans where appropriate OH + LDA THF solvent (S) Ph

Estrogens are female sex hormones, the most potent of which is B-estradiol. OH AYA Но B-Estradiol In recent years, chemists have focused on designing and synthesizing molecules that bind to estrogen receptors. One target of this research has been nonsteroidal estrogen antagonists, compounds that interact with estrogen receptors and block the effects of both endogenous and exogenous estrogens. A feature common to one type of nonste- roidal estrogen antagonist is the presence of a 1,2-diphenylethylene with one of the benzene rings bearing a dialkylaminoethoxyl substituent. The first nonsteroidal estrogen antagonist of this type to achieve clinical importance was tamoxifen, now an important drug in the treatment of breast cancer. Tamoxifen has the Z configuration shown here. NMeg A B NMeg ? ОН Tamoxifen Propose reagents for the conversion of A to tamoxifen. Note: The final step in this synthesis gives a mixture of E and Z isomers.

Why do you wash the dichloromethane solution of your reductive amination product with sodium bicarbonate, rather than dilute aqueous HCl? a) Sodium bicarbonate is a good method of removing aldehydes from organic solvent.b) The amine product will be protonated by acid and remain in the aqueous layer as a salt.c) Sodium bicarbonate transfers the amine starting material into the aqueous layer.d) Sodium bicarbonate reacts with leftover NaBH(OAc)3 and removes it from the mixture.

Provide an explanation without using the pka values : Why is phenol stronger acid than butanoic acid?

Draw structural formulas for the two compounds you could use to prepare the amine shown by reductive amination. H₂C You do not have to consider stereochemistry. Do not include the reducing agent in your answer. • If there is more than one combination, draw only one. • Draw one structure per sketcher. Add additional sketchers using the drop-down menu in the bottom right corner. ⚫ Separate multiple reactants using the + sign from the drop-down menu. ? √n [ ChemDoodle > 16