Answer 18. In his
article entitled "A Sobering Experience with lsopropyl Ether Peroxide", Irwin B. Douglass writes:
"In sorting through some bottles of chemicals in a basement storeroom recently we found two 2½-L glass-stoppered bottles labeled
Isopropyl Ether – Student Preparation. Although no date was on the labels, we knew that the bottles had been there for more than twenty years.
"Both bottles were nearly a third full of camphor-like crystalline solid beneath the liquid upper layer. Having heard of the tendency for isopropyl ether to form a peroxide, we suspected that the solid might be dangerous although it looked harmless enough. The bottles were taken to the dispensing stockroom, and the supernatant liquid poured down the drain. Water was added but the solid proved to be insoluble. The bottles with their contained water and solid were allowed to stand around several weeks awaiting disposal.
"As part of a general stockroom cleanup the bottles were finally loaded into a box along with sundry containers of sodium scraps and unlabeled chemicals and taken by the writer and the stockroom keeper to the dump, located in a marshy area, at the edge of town. Still aware that the white solid might be dangerous we tossed one bottle as far as possible out into the bog and the second after it in the hope that both would be broken. Failing in this attempt, we threw stones at the bottles to break them. When the first stone struck, there was s. violent explosion which blasted mud and debris over the surrounding landscape. Fortunately, neither the writer nor his assistant were hit by flying glass."
What would you do and NOT do if you were in Dr. Douglass's shoes?
Answer 19. Describe in your own words the criteria used in organic chemistry to determine if an organic compound has been oxidized or reduced in a chemical reaction. [Answer: See 4.7.2]
20. Acetic acid is (a) more acidic than phenol, methanol, and ethanol; (b) more acidic than carbonic acid but less acidic than phosphoric and nitric acids; (c) more acidic than methanol but less acidic than phenol; (d) more acidic than phenol but less acidic than carbonic acid.
Answer 21. Would you expect phenol to react with metallic sodium?
Answer 22. The correct order of acidity is (a) H
2SO
4 > H
3PO
4 > H
2CO
3 > CH
3COOH > C
6H
5OH (phenol) > CH
3OH; (b) H
2SO
4 > H
3PO
4 > CH
3COOH > H
2CO
3 > H
2O > C
6H
5OH (phenol) > CH
3OH; (c) H
2SO
4 > CH
3COOH > H
3PO
4 > H
2CO
3 > H
2O ≈ CH
3OH > C
6H
5OH (phenol); (d) H
2SO
4 > H
3PO
4 > CH
3COOH > H
2CO
3 > C
6H
5OH (phenol) > CH
3OH ≈ H
2O.
Answer 23. Write equations/schemes for the following reactions: (a) Cu-catalyzed oxidation of 1-propanol to propanal with O
2; (b) oxidation of benzaldehyde with Cu(OH)
2; (c) oxidation of 3-methylbutanal with Ag
+; (d) oxidation of formic acid with Ag
+; (e) the Clemmensen reduction of methyl ethyl ketone; (f) esterification of benzoic acid with methanol; (g) esterification of acetic acid with 1-butanol; (h) hydrolysis of ethyl benzoate with aqueous NaOH; (i) hydrolysis of ethylene glycol diacetate with aqueous KOH.
24. Esterfication is a reversible reaction. What is the standard method to shift the esterification equilibrium toward the ester product?
Answer 25. Write a chemical equation for the Williamson reaction between iodomethane and potassium ethoxide.
Answer