Chapter 8

8.1 Name the following compounds: (a)

CH3 CH3CHC CH3 CCHCH3

2,5-dimethyl-3-hexyne (b)
CH3 HC CCCH3 CH3

3,3-dimethyl-1-butyne (c)
H3CHC CHCH CHC CCH3

2,4-octadiene-6-yne (d)
H 3C H3CH2CCC H 3C CCH2CH2CH3

3,3-dimethyl-4-octyne (e)
H3C H3CH2CCC H3C CH3 CCHCH3

2,5,5-trimethyl-3-heptyne (f)

6-isopropyl-cyclodecyne 8.2 There are seven isomeric alkynes with the formula C6H10. Draw and name them. Solution:

1-Hexyne

2-Hexyne

3-Hexyne

3-methyl-1-pentyne

4-methyl-1-pentyne

4-methyl-2-pentyne

3,3-dimethyl-1-butyne

8.3 What products would you expect from the following reactions? (a)
H2 C H3 C C H2

C CH

H2 C

Cl
C H2 C CH

Cl

2Cl 2

H 3C

Cl
(b)

Cl

CH

+
C C

HBr

CH2

Br

(c)
H2 C H 3C C H2 H2 C

CH3

C 4H 9

HBr Br

H C

CH3

8.4 What product would you obtain by hydration of the following alkynes?

(a)

hydration C 3H 7 C C C3H 7 C3H 7 C O

(b)

H2 C

C3H 7

3HC
H3 C CH H2 C

hydration C C C 3H 7
H3 C

3HC
CH H2 C

C O

C C 3H 7 H2

8.5 What alkynes would you start with to prepare the following ketones?
O

(a)

CH3CH2CH2CCH3

(b)

CH3CH2CCH2CH3

Solution: (a)

CH3CH2CH2C

CH (b)

CH3CH2C

CCH3

8.6 What alkyne would you start to prepare each of the following compounds by a hydroboration / oxidation reaction?

O CH2 CH

CH3

CH3CHCH2CCHCH3
(a) Solution:
CH C

(b)

CH3

CH3

CH3CHC
(a) (b)

CCHCH3 CH3

8.7 How would you prepare the following carbonyl compounds starting from an alkyne?

Br

O
solution:
Br Br

HgSO4, H3O
O

1.BH3 2.H2O2 / NaOH

8.8 Using any alkyne needed, how would you prepare the following alkenes? (a) trans-2-Octene (b) cis-3-Heptene (c) 3-Methyl-1-pentene solution: (a)

Li,NH3
(b)

H2 Lindlar catalyst
(c)

H2 Lindlar catalyst

8.9 Propose structures for alkynes that give the following products on oxidative cleavage by KMnO4: (a)
CO2H

CO2

(b) 2CH3(CH2)7CO2H + HO2C(CH2)7CO2H Solution: The structure is: (a)

(b) CH3(CH2)7CC(CH2)7CC(CH2)7CH3

8.10 The pKa of acetone, CH3COCH3, is 19.3. Which of the following bases is strong enough to deprotonate acetone? (a) KOH (pKa of H2O = 15.7) (c) NaHCO3 (pKa of H2CO3 = 6.4) Solution: (b) Because pKa (C2H2) > pKa (CH3COCH3) 8.11 Show the terminal alkyne and alkyl halide from which the following products can be obtained. If two routes look feasible, list both. Answer: (a)
H3CH2 CH2CC H3CH2CH2C CH CH Br

(b) Na+ -CCH (pKa of C2H2 = 25) (d) NaOCH3 (pKa of CH3OH = 15.6)

CH3
CH2CH2CH3

CH3

3HCC

Br

(b)

H3C H3CHC C C CH2CH3

CCH3 C

H3C H3CHC C CH

Br

CH2CH3

CH C

BrCH3
(c) 8.12 How would you prepare cis-2-butene starting from propyne, an alkyl halide, and any other reagents needed? This problem cant be worked in a single step. Youll have to carry out more than one

reaction. Answer:
H3CC CH

NaNH2 NH3 H2

BrCH3 THF HC
H3C

H3CC

CCH3

CH CH3

H3CC

CCH3

Lindar catalyst

8.13 Beginning with 4-octyne as your only source of carbon and using any inorganic reagents necessary, how would you synthesize the following compounds? (a) Butanoic acid Solution: (a)
O

(b) cis-4-Octene

(c) 4-Bromooctane

(d) 4-Octanol (4-hydroxyoctane)

(e) 4,5-Dichlorooctane

KMnO4 H3O
(b)
H2 Lindler catalyst

OH

(c)
H2 Lindler catalyst

HBr, ether

Br

(d)

H2 Lindler catalyst

1.BF3 , THF 2.H2 O2 , OHOH

(e)
H2 Lindler catalyst

X2 CH2Cl2
Cl

Cl

8.14 Beginning with acetylene and any alkyl halides needed, how would you synthesize the following

compounds? (a) Decane (c) Hexanal Solution: (a) (b) 2,2-Dimethylhexane (d) 2-Heptanone

NaNH2

Na C

CH

CH3 CH2 CH2CH2CH2CH2CH2CH2Br

2H2 Pd/C

(b)

NaNH2

Na C

CH

(CH3)3CCH2CH2Br

2H2 Pd/C

(c)
NaNH2 Na C
CH

CH3CH2CH2CH2Br 1.BH3 2.H2O2

(d)

NaNH2

Na C

CH

CH3CH2CH2CH2CH2Br

H2 SO4, H2O HgSO4

8.15 Name the following alkynes, and predict the products of their reaction with (i) H2 in the presence

of a Lindlar catalyst and (ii) H3O+ in the presence of HgSO4:

(a)
HC C C H2 H3C C H2C CH3 CH3 H3C

(b)

CH3

HC C H2 C C CH2 CH H3C CH3

Solution:

/L in dl ar

Ca

8.16 From what alkyne might each of the following substances have been made?

(a)
CH3 CH H3C C H2 H2 C C H O H2 C

(b)
H2 C CH3 H C C H2 Cl C Cl CH3

SO Hg
H
2

i /L

rC la nd

/H
3

O
at

H2 C C H

O gS
4

/H
3

Solution: (a) is from

CH3 CH H3C H2C C CH
H2 C H2 C CH3 H C C H2

H2 C C H

CH

4-Methyl-pentyne

and (b) is from 1-Ethynyl-2-methyl-cyclohexane

8.17 How would you prepare the following substances, starting from any compounds having four

carbons or fewer?
HO CH2 C H2

CH

HC C H2

(a)

H3 C

HO H C C H2
O H2 C C C H2 H CH3

OH

CH

CH2

Zn(Cu) Ether H 3C

CH C H2

HC

CH2 C H2

Solution:

H3C

H2C

(b)

O H2 C C C H2 H CH

H2SO4, H2O HgSO4 H2C

C

H2 C C H2 H

C CH3

H2C

Solution:

8.18 The following cycloalkyne is too unstable to exist. Explain.

H2C C H2

CH2

Solution: Its not possible to form a small ring containing a triple bond because the angle strain that would result from bending the bonds of an SP-hybridized carbon to form a small ring is too great.
8.19 Give IUPAC names for the following compounds. CH3

CH3 CH2C
a. b.

CCCH3 CH3

CH3C

CCH2C
CH3

CCH2CH3
CH3

c. CH3CH

CC

CCHCH3

CH3

HC
d. e. H2 C

CCCH2C CH3
CHCH

CH

CHC

CH

CH2CH3

CH3CH2 CHC
f. Solution:
CH2CH3

CCHCHCH3 CH3

a. 2,2-Dimethyl-3-hexyne b. 2,5-Octadiyne c. 3,6-Dimethyl-2-heptene-4-yne d. 3,3-Dimethyl-1,5-hexadiyne e. 1,3-Hexadiene-5-yne f. 3,6-Diethyl-2-methyl-4-octyne

8.20 Draw structures corresponding to the following names:

a. 3,3-Dimethyl-4-octyne b. 3-Ethyl-5-methyl-1,6,8-decatriyne c. 2,2,5,5-Tetramethyl-3-hexyne d. 3,4-Dimethylcyclodecyne e. 3,5-Heptadien-1-yne f. 3-Chloro-4,4-dimethyl-1-nonen-6-yne g. 3-sec-Butyl-1-heptyne h. 5-tert-Butyl-2-methyl-3-octyne

Solution:

a.

3,3-Dimethyl-4-octyne

b.

3-Ethyl-5-methyl-1,6,8-decatriyne

c. 3,6-Dimethyl-2-heptene-4-yne

d. 3,4-Dimethylcyclodecyne

e.

3,5-Heptadien-1-yne

Cl

f.

3-Chloro-4,4-dimethyl-1-nonen-6-yne

g.

3-sec-Butyl-1-heptyne

h. 5-tert-Butyl-2-methyl-3-octyne
8.21 The following two hydrocarbons have been isolated from various plants in the sunflower family.

Name them according to IUPAC rules. (a)

H3C C H C H C C C C C H C H C H C H C H CH2

(b)
H3C C C C C C C C C C C C H CH2

SOLUTION: (a) (b) (3E, 5E, 11E)-1,3,5,11-Tridecatetraen-7, 9-diyne. 1-Tridecene-3, 5, 7, 9, 11-pentayne

8.22. Predict the products of the following reactions.

H

H2, Pd/C

H2/Lindlar
SOLUTION: A:
H2 C C H2 H2 C CH3

B:

H C C H

H C CH2

8.23 A hydrocarbon of unknown structure has the formula C8H10. On catalytic hydrogenation over the

Lindlar catalyst, 1 equivalent of H2 is absorbed. On hydrogenation over a palladium catalyst, 3 equivalents of H2 are absorbed. a) How many degrees of unsaturation are present in the unknown? b) How many triple bonds are present? c) How many double bonds are present? d) How many rings are present? e) Draw a structure that fits the data. Solution: a) c) e) 4 degrees of unsaturation are present. 1 double bond is present. The possible structure can be: b) 1 triple bond is present. d) 1 ring is present.

etc...
8.24 Predict the products from reaction of 1-hexyne with the following reagents:

a) 1 equiv HBr c) H2, Lindlare catalyst e) H2O, H2SO4, HgSO4 Solution:

b) 1 equiv Cl2 d) NaNH2, in NH3, the CH3Br f)2 equiv HCl

HCl

a)

1-hexyne
Cl2

Cl
Cl

b)

1-hexyne
H2 Lindlar Catalyst

Cl

c)

1-hexyne

NaNH2

CNa

CH3Br

d)

1-hexyne

NH3

H2SO4,H2O HgSO4

e)

1-hexyne
Cl

2HCl

f)

1-hexyne

Cl

8.25 Predict the products from reaction of 5-decyne with the following reagents:

(a) H2, Lindlar catalyst. (b) Li in NH3. (c) 1 equiv Br2. (d) BH3 in THF, then H2O2, OH-. (e) H2O, H2SO4, HgSO4. (f) Excess H2, Pd/C catalyst. Solution:
H H H C4H9 Br C4H9

(a)

C4H9 C4H9

C4H9. O

(b)

C4H9

. (c)

C4H9

Br

. (d)

C4H9

C4H9.

C4H9

(e)

C4H9.

(f)

C4H9

8.26 Predict the products from reaction of 2-hexyne with following reagents:

(a) 2 equiv Br2. (b) 1 equiv HBr. (c) Excess HBr. (d) Li in NH3. (e) H2O, H2SO4, HgSO4 Solution:
Br H3C Br
H3C H H3C C3H7

C3H7 Br H Br Br C3H7 H Br
H

+
Br C3H7 Br H

(a)

. (b)

etc.. .

Br H3C

H C3H7

H3C

(c)
H3C

and
H3C O

Br

H
H3C

(d)

C3H7.

(e)

C3H7

and

C3H7

8.27 Predict the products of the following reactions:

CH3CH2CH2CH2 CH2C CH 1.BH3,THF 2.H2O2 O CH3CH2CH2 CH2CH2CH2 CH

(a)

Br CH2 C NaNH2,NH3 CH

(b)

Br

Br CH3 NaNH2,NH3 C CH

(c)
8.28 Hydrocarbon A has the formula C9H12 and absorbs 3 equivalents of to yield B,C9H18 ,when hydrogenated over a Pd/C catalyst. On treatment of A with aqueous H2SO4 in the presence of mercury(II), two isomeric ketones, C and D, are produced. Oxidation of A with KMnO4 gives a

mixture of acetic acid (CH3CO2H) and the tricarboxylic acid E. Propose structure for compounds A-D, and write the reactions. Solution:
H2 C C C CH3 H2 H2 O C C C

H2 H2 H2 C C C CH3 H2 O H2 C C C CH3

CH3

H HOOCH2C C CH2COOH CH2COOH H2 C C C CH3 H2 Pd/C H2 H2 H2 C C C CH3 H2 H2 O C C C H2 O H2 C C C CH3

(1)

(2)

H2 C C C CH3

mercury(II) H2SO4

CH3

(3)

H2 C C C CH3

KMnO4

H HOOCH2C C CH2COOH CH2COOH

CH3COOH

8.29 How would you carry out the following reactions?

(a)

H3CH2CC

CH

H2SO4, H2O HgSO4 1, BH3 2, H2O2

CH H3CH2C CCH3

(b)

H3CH2 CC

CH

CH3CH2CH2CHO

(c)

CH3

NaNH2 CH3Br
H C CCH3

(d)

H2 Lindlar catalyst
CH3

(e)

H3CH2CC

CH

KMnO4

CH3CH2CO2H

(f)

CH3CH2 CH2 CH2CH

CH2

1. Br2 2. KOH, ethanol

CH3 CH2 CH2CH2C

CH

8.30 Occasionally, chemists need to invert the stereochemistry of an alkene, that is, to convert a cis

alkene to trans alkene, or vice versa. There is no one-step method for doing an alkene inversion, but the transformation can be carried out by combining several reactions in the proper sequence. How would you carry out the following reactions?

(a)

trans-5-Decene

1. Br2 2. KOH, ethanol 3. H2 , Lindlar catalyst 1. Br2 2. KOH, ethanol 3. Li, NH3

cis-5-Decene

(b)

cis-5-Decene

trans-5-Decene

8.31 Propose structures for hydrocarbons that give the following products on oxidative

cleavage by KmnO4 or O3 (a) CO2 + CH3(CH2)5CO2H

CO 2 H

CH3CO 2H
(b)

(c) HO2(CH2)8CO2H (d) CH3CHO + CH3COCH2CH2CO2H + CO2 (e) OHCCH2CH2CH2CH2COCO2H + CO2 Solution:

(a)

(b)

(c)

(d)

(e)

8.32 Each of the following syntheses requires more than one step. How would you carry them out?

(a)
CH3CH2 CH2C
CH

CH3 CH2CH2CHO

(B)
H CH2CH3

(CH3)2CHCH2C

CH (H3C)2 HCH2C H

Solution: (a)

H2 Lindlar catalyst

1. O3 2. Zn/H3 O
O

(b)
(CH3 )2CHCH2C
CH

NaNH2

(CH3)2CHCH2 C Li NH3

CNa H

CH3CH2 Br
CH2CH3

(CH3)2 CHCH2C

CCH2CH3

(H3C) 2HCH2C

8.33 How would you carry out the following transformation? More than one step is needed.
H C H

H2C H3C CH2

H C H2

H CH3

H2

C CH3

H C

H2C H3C CH2

H C H2

H CH3

8.34 How could you carry out the follow conversion? More than one step is needed.

CHO

Solution:
OH BH3 H2O2/OHPCC CH2Cl2 CHO

8.35 How would you carry out the following transformation? More than one step is needed.

Br Br

Br2 CH2Cl2

KOH Ethenal

C CH

KNH2

CH3Br

Li NH3

8.36 Synthesize the following compounds using 1-butyne as the only source of carbon, along with any

inorganic reagents you need. More than one step may be needed. (a) 1, 1, 2, 2-Tetrachlorobutane Solution:
Cl HC C CH2 CH3 CH2CH3 C H C Cl Cl Cl C Cl CH2 CH3

Cl2 CH2Cl2

Cl2 CH2Cl2

C Cl

(b) 1, 1-Dichloro-2-ethylcyclopropane Solution:

H HC C H2 C CH3 H C H C CH2CH3 Cl Cl C H2C CH CH2 CH3

H2 Lindlar catalyst

CHCl3 KOH

(c) Butanal Solution

H HC C CH2 CH3

H C C CH2CH3

H2 Lindlar catalyst
H

1. BH3, THF 2. H2 O2, OH-

OH H C H

H C H CH2 CH3

8.37 How would you synthesize the following compounds from Acetylene and any alkyl halides with

four or fewer carbons? More than one step may be required. (a) CH3CH2CH2C CH (b) CH3CH2C CCH2CH3 (c) (CH3)2CHCH2CH CH2 (e) CH3CH2CH2CH2CH2CHO
O (d) CH3CH2CH2CCH2CH2CH2CH3

HC CH
Solution: (a) (b)
HC CH NaNH2 NH3

NaNH2 NH3

HC C Na

CH3CH2CH2Br THF

CH3CH2CH2C CH

HC C Na

CH3CH2Br THF

CH3CH2 C CH

CH3CH2Br NaNH2 CH3CH2C CCH2 CH3 CH3CH2C C Na NH3 THF

(c)
HC CH NaNH2 NH3 HC C Na (CH3 )2CHCH2Br (CH3)2CHCH2C CH H2 (CH3)2CHCH2CH CH2 Lindlar catalyst

(d)
NaNH2 NaNH2 CH2CH2CH2Br CH3CH2CH2Br HC C Na CH3CH2 CH2C C Na CH3CH2CH2C CH NH3 NH3 THF THF O H2 SO4,H2O CH3CH2 CH2CCH2CH2CH2CH3 CH3CH2CH2 C CCH2CH2CH3 HgSO4 HC CH

(e)
HC CH NaNH2 CH3CH2CH2CH2Br 1.BH3 HC C Na CH3CH2 CH2CH2C CH NH3 2.H2O 2 THF CH3CH2CH2 CH2CH2CHO

8.38 How would you carry out the following reactions to introduce deuterium into organic molecules?

(a)
D H3CH2CC CCH2CH3 ? C C2H5 C C2H5 D

(b)
? H3CH2CC CCH2CH3 D C C2 H5 C D C2H5

(c)
? H3CH2CH2CC CH H3CH2CH2CC CD

(d)

CH ?

DC

CD2

Solution:

D CH3CH2C CCH2CH3

D2 Lindlar catalyst
C2H5 C2H5

CH3CH2C

CCH2CH3

Li,ND3

C2H5

C2H5

Na+NH2H3CH2CH2CC CH H3CH2CH2CC C

Na+

D2O

H3CH2CH2CC

CD

NH3
CD C CD

CH C

C
+ -

CD2

Na NH2 NH3

D2O

D2 Lindlar catalyst

8.39 How would you prepare cyclodecyne starting from acetylene and any alkyl halide needed?

Solution:
H H

+ 2 NaNH2

NH3

Na

Na THF

8.40 The sex attractant given off by the common housefly is an alkene named muscalure. Propose a

synthesis of muscalure starting from acetylene and any alkyl halides needed. What is the IUPAC name for muscalure?

cis- H3C(H2C)7HC

CH(CH2)12CH3

Solution: The IUPAC name for muscalure is cis-9-tricosene.

NaNH2
H C C H H3 C(H2C)7 Br H3C(H2C)7 C C H

NaNH2

H3C(H2C)12

Br

H3C(H2C)7 C H C

(CH2) 12CH3

H2 Lindlar

H3C(H2C)7

(CH2) 12CH3

8.41 Compound A (C9H12) absorbed 3 equivalents of H on catalytic reduction over a palladium catalyst

to give B (C9H18). On ozonolysis , compound A gave, among other things, a ketone that was identified as cyclohexanone. On treatment with, gave C (C10H14) .Give the structure of A, B, C. Solution:

A:

B:

C:
8.42 Hydrocarbon A has the formula C12H8. It absorbs 8 equivalents of H2 on catalytic reduction over

a palladium catalyst. On ozonolysis, only two products are formed: oxalic acid (HO2CCO2H) and succinic acid (HO2CCH2CH2CO2H). Write the reactions, and propose a structure for A. Slution:

8H2

Pd/C
cyclododecane

O O3

O C OH + 2 HO

O C CH2CH2

O C

2 HO

8.43 Identify the reagents a-c in the following scheme:

a

Solution:
1. NaNH2, NH3 2. CH3CH2Br H2 / Lindlar Cat

CH2I2 / Zn(Cu)

8.44 Organometallic reagents such as sodium acetylide undergo an addition reaction with ketones, give OH alcohols: O
1. Na+ C
CH
+

C R R C CH

C R R

2. H3O

How might you use this reaction to prepare 2-methyl-1,3-butadiene, the starting material used in the manufacture of synthetic rubber Solution

1. Na+ C 2. H3 O
+

CH

OH

H2 SO4, H2O THF

H2 Lindlar catalyst

8.45 Erythrogenic acid, C18H26O2, is an acetylenic fatty acid that turns a vivid red on exposure to

light. On catalytic hydrogenation over a palladium catalyst, 5 equivalents of H2 are absorbed, and stearic acid, CH3(CH2)16CO2H, is produced. Ozonolysis of erythrogenic acid gives four products: formaldehyde, CH2O; oxalic acid, HO2CCO2H; azelaic acid , HO2C (CH2)7CO2H; and the aldehyde acid OHC(CH2)4CO2H. Draw two possible structures for erythrogenic acid, and suggest a way to tell them apart by carrying out some simple reactions. Solution The problem can be described as following illustration:

O H O 5H2 O3 Zn H3+O O
16

C C O HO O HO

OH OH O H2 C OH O H2 C
4

C18H26O2

C18H36O2 H2 C

H3C

C O

OH

OH

And first we can predict the unsaturated degree of starting material by the fact that it can absorb 5 H2 and form a carboxylic acid. So The molecular has 5 double bonds or 1 triple bond and 3 double bonds or 2 triple bonds and 1 double bond besides a C=O bond, and there is no rings in the molecular. Second we can think about the products after it is treated with problem.
O3

,and we can get the solultion t the

H O HO C C C H2 C C C H2 C C H C
7

H O HO C H2 C C C C C H2 C CH C
7

You can see two possible starting materials according to the problem exactly. However, we can tell them apart from each other by following method. STEP1 Treat the SM with Lindlar catalyst, and then we can get the product only contains double bond but no triple bond. STEP2 Treat the product get from the step with O3 ,H3O+ and Zn and then we can get the products following. STEP3 Analyze the products and you can find the differences written following between the different SMs . At last we can tell them apart easily.

HCHO H O HO C C H C H H2 C C 7 H C H H2 C C O3 H HC C O H Zn H3O HC O H2 C O HO C H2 C O CH O CH

O CH

HCHO H O HO C H2 C C 7H C H C H C H H2 C CH C H Zn H O 3 O3 HO O HC H2 C O C O HO C H2 C O C OH O CH O CH

8.46 Terminal alkynes react with Br2 and water to yield bromo ketones. For example:
O

Br2 , H2O

CH2Br

Propose a mechanism for the reaction. To what reaction of alkenes is the process analogous? Solution:
H O H

H Br Br O Br

H H

Br

H O

H H

O Br

rearrangement

Br

The mechanism here is just like the halohydrin of alkene.

8.47 A cumulene is a compound with three adjacent double bonds. Draw an orbital picture of

cumulene. What kind of hydridization do the two central carbon atoms have? What is the geometric relationship of the substituents on one end to the substituents on the other end? What kind of isomerism

is possible?

R 2C
Solution:

CR 2

(a) They are sp hybridized.

R R C C C C R R

(b) The geometric relationship of the substituents on one end to the substituents on the other end is cis and trans. (c) Stereoisomers.
8.48 Reaction of acetone with D3O+ yields hexadeuterioacetone. This is, all the hydrogens in acetone

are exchanged for deuterium. Review the mechanism of alkyne hydration, and then propose a mechanism for this deuterium incorporation.
O H3C C CH3 D3O+ D3C O C CD3 Hexadeuterioacetone

Acetone

Solution:
O C H3C CH2 H H3C O H C CH2 D3O+ H3C

OH C CH2 D

D3C

O C CD3