Homework 1 2302271 Organic Chemistry I

Assigned: August 19, 2013 Due: Wednesday August 28, 2013

1.

For each molecular formula, draw all the isomeric alkynes and give their IUPAC names. Circle the acetylenic hydrogen of each terminal alkyne. (a) C4H6 (2 isomers) (b) C5H8 (3 isomers) Show the reagents and intermediates involved in the synthesis of 3-decyne from acetylene and any necessary alkyl halides. Show how you might synthesize the following compounds, using acetylene and any suitable alkyl halides as your starting materials. (a) 1-hexyne (b) 4-methyl-2-hexyne Show how you would synthesize 2-heptyn-4-ol beginning with acetylene and any necessary additional reagents. Show which of the following compounds could be synthesized in good yield by a double dehydrohalogenation from a dihalide. In each case: (1) show which base you would use (KOH or NaNH2). (2) show how your starting material might be synthesized from an alkene. (a) 2-butyne (b) 1-octyne (c) 2-octyne Show how you would convert (a) 2-pentyne to cis-2-pentene Show how 1-hexyne may be converted to (a) 1,2-dichlorohexene (b) 1-bromohexene (c) 2-bromohexene (b) 2-pentyne to trans-2-pentene (d) 1,1,2,2-tetrabromohexane (e) 2-bromohexane (f) 2,2-dibromohexane

2.

3.

4.

5.

6. 7.

8.

For each compound, give the product(s) expected from (1) HgSO4/H2SO4-catalyzed hydrolysis (2) hydroboration-oxidation (a) 1-hexyne (c) 3-hexyne (b) 2-hexyne (d) Cyclodecyne Predict the product(s) you would expect from treatment of each compound with (1) dilute, neutral KMnO4 (2) hot, basic KMnO4, then dilute acid (a) 1-hexyne (d) 2-methyl-3-hexyne (b) 2-hexyne (e) Cyclodecyne (c) 3-hexyne Write structural formulas for the following compounds. (a) methyl-n-pentylacetylene (e) (b) ethynylbenzene (f) (c) cyclohexylacetylene (g) (d) 5-methyl-3-octyne (h) trans-3,5-dibromocyclodecyne 3-octyn-2-ol cis-6-ethyl-2-octen-4-yne 1,4-heptadiyne
1

9.

10.

11.

Predict the product(s) of reaction of 1-pentyne with the following reagents. (a) 1 equivalent of HCl (g) Cold, dilute KMnO4 (h) Warm, conc. KMnO4, NaOH (b) 2 equivalents of HCl (c) Excess H2, Ni (i) Na, liquid ammonia (d) H2, Pd/HaSO4, quinoline (j) NaNH2 (e) 1 equivalent of Br2 (k) H2SO4/HgSO4, H2O (f) 2 equivalents of Br2 (l) Sia2BH, then H2O2, -OH Show how you would transform the following compounds to the specified compounds. Show all intermediates. (a) 2,2-dibromobutane to 1-butyne (b) 2,2-dibromobutane to 2-butyne (c) 1-butyne to 3-octyne (d) trans-2-hexene to 2-hexyne (e) cis-2-hexene to 1-hexyne (f) 1-hexyne to 2-hexanone and CH3COCH2CH2CH2CH3 (g) 1-hexyne to hexanal and CH3(CH2)4CHO (h) trans-2-hexene to cis-2-hexene Potassium hydroxide is mixed with 2,3-dibromohexane, and the mixture is heated at 200oC in a sealed tube for 1 hour. The product mixture (A) is mixed with a copper(I)-ammonia complex, and a precipitate forms. The precipitate (B) and the liquid phase (C) are separated. The precipitate is acidified, and the product (D) is distilled (bp. 71oC). Product D is treated with sodium amide, followed by acetone, and then by dilute acid to five alcohol (F). The liquid phase (C) is distilled, and the products are collected over a boiling range of 80 to 85oC. This distillate is treated with sodium amide at 150oC for 1 hour, and the product mixture is distilled to give a pure alkyne (E) of boiling point 71oC. Give the structures of the alkynes present in product A through E, and give the structure of alcohol F.

12.

13.