Chemistry 262 Homework 2 Part II Winter 2018

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1 Chemistry 262 Homework 2 Part II Winter 2018 The following homework covers Chapter 10 in Loudon & Parise s Organic Chemistry, 6 th ed. and contains 24 questions, valued at point each, as well as 3 bonus questions valued at point each Name: ALCOL AND THIOL ACID BASE CONSIDERATIONS 1. Which of the following has the highest pk a value in aqueous solution? a. Phenol b. Isopropanol c. Cyclohexanone d. Ammonium chloride e. para-toluene sulfonic acid ALCOL AND THIOL ACID BASE CONSIDERATIONS 2. Which of the following has the lowest pk a value in aqueous solution? a. Phenol b. Isopropanol c. Cyclohexanone d. Ammonium chloride e. para-toluene sulfonic acid ALCOL AND THIOL ACID BASE CONSIDERATIONS 3. Which of the following would be substantially (> 10 %) deprotonated by sodium phenoxide (PhONa) a. Benzyl alcohol b. Ammonium chloride c. para-toluene sulfonic acid d. 2 of the above e. All of the above

2 DEHYDRATION OF ALCOLS 4. What is the expected outcome when 3-methyl-1-cyclohexanol is heated in conc. H 3 PO 4? a. 3-methyl-1-cyclohexene b. 1-methyl-1-cyclohexene c. Cyclohexanone d. Adipic acid (1,6-hexanedioic acid) e. A 1:1 mixture of (a) and (b) BONUS I: AN ALTERNATIVE PATHWAY TO DIRECT REARRANGEMENT IS REPETITIVE ELIMINATION AND ADDITION. SHOW HOW THIS COULD EXPLAIN THE FORMATION OF 2-METHYL-2-PENTENE FROM 4-METHYL-2-PENTANOL IN AQUEOUS H 2 SO 4 : DEHYDRATION OF ALCOLS 5. What is the expected outcome when 3-methyl-1-cyclohexanol is heated in conc. HBr? a. 3-methyl-1-cyclohexene b. 1-methyl-1-cyclohexene c. 3-methyl-1-bromocyclohexane d. 1-methyl-1-bromocyclohexane e. All of the above REACTION OF ALCOLS WITH HYDROGEN HALIDES 6. What is the expected product when 2-methyl-2-propanol reacts with conc. hydrochloric acid? a. Isobutene b. Isobutane c. tert-butyl chloride d. Isobutyl chloride e. sec-butyl chloride

3 BASE COMPATABLE ALCOL-DERIVED LEAVING GROUPS 7. What is the expected product if n-butanol is treated with tosyl chloride in pyridine, followed by tbuok in tbu? a. 1-butene b. 2-butene c. Butyl tert-butyl ether d. (a) and (b) in equal amounts e. (a) and (c) in equal amounts BASE COMPATABLE ALCOL-DERIVED LEAVING GROUPS 8. What would be the expected outcome of the following transformation? H SO 2 Cl CO - 2 Product? base C 2 H 5 H 3 CCO 2 H H O 2 C H 3 CCO 2 OSO 2 C 2 H 5 C 2 H 5 C 2 H 5 I II III a. I b. II c. III d. Equal amounts of I & II e. None of the above

4 BASE COMPATABLE ALCOL-DERIVED LEAVING GROUPS 9. Which of the following will not convert an alcohol into a good leaving group? a. Tosyl chloride b. Mesyl chloride c. Triflic anhydride d. Dimethyl sulfate e. N/A; all of the above will convert an alcohol into a good leaving group MODERN METHODS FOR CONVERSION OF ALCOLS TO ALKYL HALIDES 10. Which of the following will not convert an alcohol into an alkyl bromide? a. SOBr 2 + pyridine b. PBr 3 + pyridine c. Ph 3 PBr 2 + pyridine d. Conc HBr + heat e. N/A; all of the above will convert an alcohol to an alkyl bromide MODERN METHODS FOR CONVERSION OF ALCOLS TO ALKYL HALIDES 11. Please show the mechanism by which benzyl alcohol is converted to benzyl chloride by thionyl chloride (SOCl 2 ) in the presence of pyridine (C 5 H 5 N) ORGANIC REDOX REACTIONS 12. Which of the following compounds is most oxidized? a. CH 4 b. CH 2 Cl 2 c. d. CH 2 O e. CCl 4

5 ORGANIC REDOX REACTIONS 13. Considering only the anisole (phenyl methyl ether), the following is a CH3 a. 2 electron reduction b. 4 electron reduction c. 2 electron oxidation d. 4 electron oxidation e. None of the above OXIDATION OF ALCOLS 14. Which of the formal oxidation number on manganese in KMnO 4? a. +4 b. +5 c. +6 d. +7 e. +8 OXIDATION OF ALCOLS 15. What is the final formal oxidation number at C1 after 1-hexanol has been heated with a concentrated alkaline solution of KMnO 4? a. 0 b. +1 c. +2 d. +3 e. +4 CHEMICAL AND STEREOCHEMICAL GROUP RELATIONSHIPS 16. How many chemically nonequivalent sets of hydrogens are found in trans-3-hexene? a. 2 b. 3 c. 4 d. 5 e. 6

6 CHEMICAL AND STEREOCHEMICAL GROUP RELATIONSHIPS 17. How many chemically nonequivalent sets of hydrogens are found in 1-bromo-1-chloro-2- methoxyethane? a. 1 b. 2 c. 3 d. 4 e. 5 CHEMICAL AND STEREOCHEMICAL GROUP RELATIONSHIPS 18. What is the term best describing the methylene hydrogens at C3 in (S)-2-butanol? a. Homotopic b. Enantiotopic c. Diastereotopic d. Prochiral e. (c) and (d) OCTET EXPANSION AND OXIDATION OF THIOLS 19. Which of the following is most oxidized? a. CH 2 SH b. CH 2 SCH 2 c. CH 2 SSCH 2 d. SO 2 Cl e. ( ) 2 SO OCTET EXPANSION AND OXIDATION OF THIOLS 20. Which of the following will oxidize butanethiol to the corresponding disulfide? a. Conc. HNO 3 b. I 2 in aqueous Na c. KMnO 4 /Na/ d. K 2 Cr 2 O 7 /H 2 SO 4 e. All of the above

7 SYNTHESIS OF ALCOLS 21. What principal product would you expect from the following reaction? H 3 O +? I II III a. I b. II c. III d. IV e. V IV IV SYNTHESIS OF ALCOLS 22. What principal product(s) would you expect from the following reaction sequence? i) BH 3, THF ii) H 2 O 2,Na? + enantiomer + enantiomer I II III IV a. I b. II c. III d. IV e. III & IV in equal amounts

8 RETROSYNTHETIC ANALYSIS 23. Please synthesize butyl methyl ether from n-butanol RETROSYNTHETIC ANALYSIS 24. Please synthesize di-tert-butyl ether from 2-methyl-2-propanol BONUS II: PLEASE SYNTHESIZE ETHYL BENZOATE FROM BENZYL ALCOL AND ETHYLENE BONUS III A. What is the principal drawback to the gasification of coal for energy? C + 2H 2 CH 4 Answer: B. What do you get when you mix tosyl chloride with iceberg lettuce? Answer:

c. Cyclohexanone Chemistry 262 Homework 2 Part II Winter 2018

c. Cyclohexanone Chemistry 262 Homework 2 Part II Winter 2018 Chemistry 262 Homework 2 Part II Winter 2018 The following homework covers Chapter 10 in Loudon & Parise s Organic Chemistry, 6 th ed. and contains 24 questions, valued at 0.3333 point each, as well as