Chapter 9: Alkynes

Hello
Chapter 9: Alkynes

You might want to add this to your reaction notebook before the section on alkynes (kinda like a table of contents)
Chapter 9: Alkynes
Topics:
I. Introduction to Alkynes
II. Nomenclature of Alkynes
III. Acidity of Acetylene and Terminal Alkynes
Hello
IV. Preparation of Alkynes
V. Reduction of Alkynes
VI. Hydrohalogenation of Alkynes
VII. Hydration of Alkynes
VIII. Halogenation of Alkynes
IX. Ozonolysis of Alkynes
X. Alkylation of Terminal Alkynes
XI. Synthesis Strategies
3
I. Introduction to Alkynes

• Alkynes  are  molecules  that  possess  a  C≡C  triple  bond

Hello
I. Introduction to Alkynes

• Given  the  presence  of  pi  bonds,  alkynes  are  similar  to  alkenes  in  
their  ability  to  act  as  a  nucleophile  
• high  electron  density  around  the  triple  bond  

Hello

• Many  of  the  addition  reactions  of  alkenes  also  work  on  alkynes
I. Introduction to Alkynes

• Acetylene  is  the  simplest  alkyne  (H-­‐C≡C-­‐H)  

• It  is  used  in  blow  torches  and  as  a  precursor  for  the  synthesis  
of  more  complex  alkynes  
• More  than  1000  different  alkyne  natural  products  have  been  
isolated Hello
I. Introduction to Alkynes

• An  example  of  a  synthetic  alkyne  is  ethynylestradiol  

• Ethynylestradiol  is  the  active  ingredient  in  many  birth  control  pills  

Hello

 
II. Nomenclature of Alkynes

• Alkynes  are  named  using  the  same  procedure  we  used  in  Chapter  
4  to  name  alkanes  with  minor  modifications  
1. Identify  the  parent  chain,  which  should  include  the  C≡C  triple  
bond  
2. Identify  and  NHelloame  the  substituents  
3. Assign  a  locant  (and  prefix  if  necessary)  to  each  substituent  
giving  the  C≡C  triple  bond  the  lowest  number  possible  
4. List  the  numbered  substituents  before  the  parent  name  in  
alphabetical  order.  Ignore  prefixes  (except  iso)  when  ordering  
alphabetically  
5. The  C≡C  triple  bond  locant  is  placed  either  just  before  the  
parent  name  or  just  before  the  -­‐yne  suffix
II. Nomenclature of Alkynes

• Alkynes  are  named  using  the  same  procedure  we  used  in  Chapter  
4  to  name  alkanes  with  minor  modifications  
1. Identify  the  parent  chain,  which  should  include  the  C≡C  triple  
bond  
Hello

2. Identify  and  name  the  substituents.

II. Nomenclature of Alkynes

• Alkynes  are  named  using  the  same  procedure  we  used  in  Chapter  
4  to  name  alkanes  with  minor  modifications  
3. Assign  a  locant  (and  prefix  if  necessary)  to  each  substituent  
giving  the  C≡C  triple  bond  the  lowest  number  possible  
Hello

– The  locant  is  ONE  number,  NOT  two.  Although  the  triple  bond  
bridges  carbons  2  and  3,  the  locant  is  the  lower  of  those  two  
numbers
II. Nomenclature of Alkynes

• Alkynes  are  named  using  the  same  procedure  we  used  in  Chapter  
4  to  name  alkanes  with  minor  modifications  
4. List  the  numbered  substituents  before  the  parent  name  in  
alphabetical  order.  Ignore  prefixes  (except  iso)  when  ordering  
alphabetically  Hello
5. The  C≡C  triple  bond  locant  is  placed  either  just  before  the  
parent  name  or  just  before  the  -­‐yne  suffix
II. Nomenclature of Alkynes

• common  names  derived  from  acetylene  are  often  used  as  well  

Hello

• Alkynes  are  also  classified  as  terminal  or  internal

II. Nomenclature of Alkynes
Provide  a  systematic  name  for  each  of  the  following  compounds:

a.  

Hello

b.  

c.
II. Nomenclature of Alkynes
Answers: Both  are  okay.    First  uses  the  new  rules,  
second  one  uses  the  old  rules.
1
4-­‐Ethyl-­‐5-­‐methyl-­‐3-­‐propylhept-­‐1-­‐yne
2
a.   4 6
4-­‐Ethyl-­‐5-­‐methyl-­‐3-­‐propyl-­‐1-­‐heptyne
3 5 7

Hello Sometimes   y ou   s ee   this   a s   well:

4-­‐Ethyl-­‐5-­‐methyl-­‐3-­‐propylheptyne

b.   4
5 6
2-­‐methyl-­‐3-­‐hexyne
1 2
3
2-­‐methylhex-­‐3-­‐yne

2
(R)-­‐3,7-­‐dimethyl-­‐1-­‐octyne
c. 1 3 4 5 6 7 8
(R)-­‐3,7-­‐dimethyloct-­‐1-­‐yne
III. Acidity of Terminal Alkynes

• Recall  that  terminal  alkynes  have  a  lower  pKa  (i.e.  more  acidic)  
than  other  hydrocarbons  

Hello

• Acetylene  is  19  pKa  units  more  acidic  than  ethylene,  which  is  1019  
times  stronger
III. Acidity of Terminal Alkynes

• Acetylene  can  be  deprotonated  by  a  strong  based  to  form  the  
conjugate  base  (acetylide  ion).  

Hello

• Recall  ARIO  to  explain  why  acetylene  is  a  stronger  acid  than  
ethylene  which  is  stronger  than  ethane
III. Acidity of Terminal Alkynes

• Recall  that  terminal  alkynes  have  a  lower  pKa  than  other  

hydrocarbons  

Hello

Less  stable

• The  acetylide  ion  is  more  stable  because  the  lone  pair  occupies  a  
sp  orbital
III. Acidity of Terminal Alkynes

• A  bases  conjugate  acid  pKa  must  be  greater  than  25  for  it  to  be  able  
to  deprotonate  a  terminal  alkyne

Hello
III. Acidity of Terminal Alkynes

• Any  terminal  alkyne  can  be  deprotonated  by  a  suitable  base  

Hello

• NaNH2  is  often  used  as  the  base,  but  others  can  be  used  as  well
III. Acidity of Terminal Alkynes

Hello
II. Acidity of Acetylene and Terminal Alkynes
In  each  of  the  following  cases,  determine  if  the  base  is  sufficiently  
strong  to  deprotonate  the  alkyne:

a.   + NaNH2

H
Hello

H
+
b.  
NaH

+ t-BuOK
c. H
 II. Acidity of Acetylene and Terminal Alkynes
Answers:    Use  your  pKa’s  as  your  guide.    The  larger  the  pKa  of  the  conjugate  acid,  
the  stronger  the  base.    Since  the  pKa  of  the  protonated  alkyne  is    approximately  
25,  any  base,  whose  conjugate  acid  is  greater  than  25  will  deprotonate  the  alkyne.

a.   + NaNH2

H
pKa  =  25 Hello pKa  of  conjugate  acid  =  38
Yes,  it  will  deprotonate  the  alkyne.
H

b.  
+ NaH

pKa  of  conjugate  acid  =  35

pKa  =  25
Yes,  it  will  deprotonate  the  alkyne.

+ t-BuOK
c. H pKa  of  conjugate  acid  =  18
pKa  =  25
No,  it  will  not  deprotonate  the  alkyne.
IV. Preparation of Alkynes

• Like  alkenes,  alkynes  can  also  be  prepared  by  elimination  

• Need  a  dihalide  to  make  an  alkyne

Hello
IV. Preparation of Alkynes

• Such  eliminations  usually  occur  via  an  E2  mechanism    

• Geminal  or  vicinal  dihalides  can  be  used

Hello
geminal
dihalide

vicinal
dihalide
IV. Preparation of Alkynes

• excess  equivalents  of  NaNH2  are  used  to  shift  the  equilibrium  
toward  the  elimination  products  

Hello

• Aqueous  workup  is  then  needed  to  produce  the  neutral  alkyne:
IV. Preparation of Alkynes

• Overall,  a  terminal  alkyne  is  prepared  by  treating  the  dihalide  with  
excess  (xs)  sodium  amide,  followed  by  water:

Hello
IV. Preparation of Alkynes

For  the  following  transformation,  predict  the  major  product  and  

draw  a  mechanism  for  its  formation:

1. xs NaNH2/NH3
Br 2. H2OHello
Br
IV. Preparation of Alkynes
Answer:    Basically  two  E2  elimination  steps  will  provide  you  with  the  
terminal  alkyne.    Make  sure  each  elimination  step  occurs  anti  to  the  
leaving  group! H
N

H H

Hello
1. xs NaNH2/NH3
Br 2. H2O
Br

NH3
H
NH3 N
Br
Br H
H
H

Br
V. Reduction of Alkynes

• Catalytic  hydrogenation  –  alkyne  is  concerted  to  an  alkane  by  

addition  of  two  equivalents  of  H2  

Hello

• The  first  addition  produces  a  cis  alkene  (via  syn  addition)  which  
then  undergoes  addition  to  yield  the  alkane
V. Reduction of Alkynes

• A  deactivated  or  poisoned  catalyst  can  be  used  to  stop  the  
reaction  at  the  cis  alkene,  without  further  reduction:  

Hello

• Lindlar’s  catalyst  and  P-­‐2  (Ni2B  complex)  are  common  examples  

of  a  poisoned  catalysts
V. Reduction of Alkynes

• The  poisoned  catalyst  catalyzes  the  first  addition  of  H2,  but  not  
the  second.

Hello
V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  

Hello

• This  reaction  is  stereoselective  for  anti  addition  of  H  and  H

V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  
• The  proposed  mechanism  is  shown  below  (Mechanism  9.1)

Hello
V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  
Mechanism  –  Step  1  

Na  atom  transfer  an  eHello

lectron  
to  the  alkyne,  forming  a  
radical  cation  intermediate  

• Note  the  use  of  fishhook  arrows  to  show  single  electron  movement
V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  
Mechanism  –  Step  1  

the  paired  electrons  aHello

nd  the  
single  electron  adopt  an  anti  
geometry
V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  
Mechanism  –  Steps  2  and  3

Hello
V. Reduction of Alkynes

• Dissolving  metal  reduction  –  reduces  an  alkyne  to  a  trans  alkene  

using  sodium  metal  and  ammonia  
Mechanism  –  Step  4

Hello
V. Reduction of Alkynes

• Know  the  reagents  needed  to  reduce  an  alkyne  to  an  alkane,  a  cis  
alkene,  or  a  trans  alkene.

Hello
V. Reduction of Alkynes
Draw  the  major  product  expected  from  each  of  the  following  
reactions

H2
Lindlar’s catalyst

Hello
H2
Pt

H2
Ni2B

H2
Ni

Na
NH3(l)
V. Reduction of Alkynes
Answers:    Familiarize  yourself  with  these  different  reagents
H2
“Poisoned”  catalyst.  
Lindlar’s catalyst Stops  at  the  cis  alkene.

H2 Complete  reduction.
HelloPt

H2 “Poisoned”  catalyst.  
Ni2B Stops  at  the  cis  alkene

H2 Complete  reduction.
Ni

Radical  Mechanism.  
Na The  intermediate  requires  the  
NH3(l) free  radial  and  the  lone  pair  of  
electrons  to  be  trans.
V. Reduction of Alkynes
Identify  reagents  that  you  could  use  to  achieve  each  of  the  
following  transformations:

Hello
V. Reduction of Alkynes
Answers:

Hello
Na/NH3(l) H2/Lindalr’s Catalyst
or

H2/NiB
VI. Hydrohalogenation of Alkynes

• Hydrohalogenation  affords  Markovnikov  addition  of  H  and  X  to  an  

alkyne,  same  as  with  an  alkene.  

addition  to  an  alkene

Hello

addition  to  an  alkyne

• Excess  HX  affords  a  geminal  dihalide

geminal  dihalide
VI. Hydrohalogenation of Alkynes

• If  the  mechanism  was  analogous  to  HX  addition  to  an  alkene,  it  would  require  
the  formation  of  a  vinyl  carbocation:  

Hello

• Vinayl  carbocations  are  extremely  unstable,  so  this  mechanism  is  unlikely  
• Kinetic  data  also  suggests  a  different  mechanism  is  in  play
VI. Hydrohalogenation of Alkynes

• Kinetic  studies  suggest  the  rate  law  is  1st  order  with  respect  to  the  
alkyne  and  2nd  order  with  respect  to  HX  

Hello

• The  mechanism  must  be  consistent  with  a  termolecular  process

VI. Hydrohalogenation of Alkynes

• Proposed  mechanism  

Hello

• Its  possible  several  competing  mechanisms  are  occurring.

VI. Hydrohalogenation of Alkynes

• HBr  with  peroxides  promotes  anti-­‐Markovnikov  addition,  just  like  

with  alkenes  

Hello

• This  only  works  with  HBr  (not  with  HCl  or  HI)  
• This  radical  mechanism  is  covered  in  chapter  10
VI. Hydrohalogenation of Alkynes

• Hydrohalogenation  of  alkynes,  and  elimination  of  dihalides  

represent  complimentary  reactions:

Hello
V. Reduction of Alkynes
Predict  the  major  product(s)  expected  for  each  of  the  following  
reactions:

xs HCl

Hello
Cl
Cl 1. xs NaNH2/NH3
2. H2O

Suggest  reagents  that  would  achieve  the  following  transformation:

Cl Cl Cl

Cl
V. Reduction of Alkynes
Answers:

xs HCl
Cl Cl

Hello
Cl
Cl 1. xs NaNH2/NH3
2. H2O

Cl Cl Cl
1. xs NaNH2/NH3 xs HCl
2. H2O
Cl
VII. Hydration of Alkynes

• Alkynes  can  also  undergo  acid  catalyzed  Markovnikov  hydration  

• The  process  is  generally  catalyzed  with  HgSO4  to  compensate  for  
the  slow  reaction  rate  that  results  from  the  formation  of  vinylic  
carbocation
Hello
VII. Hydration of Alkynes

• The  alkyne  attacks  the  mercury  cation  to  form  the  mercurinium  ion  
intermediate,  which  is  attacked  by  water,  followed  by  
deprotonation

Hello
VII. Hydration of Alkynes

• The  alkyne  attacks  the  mercury  cation  to  form  the  mercurinium  ion  
intermediate,  which  is  attacked  by  water,  followed  by  
deprotonation  

Hello

• A  proton  then  replaces  the  Hg2+  to  form  an  enol  intermediate
VII. Hydration of Alkynes

• The  enol  then  tautomerizes  to  the  ketone.  

• Process  is  called  keto-­‐enol  tautomerization  

Hello

• The  enol  and  the  ketone  are  tautomers  of  one  another  
• Equilibrium  generally  favors  the  ketone
VII. Hydration of Alkynes
Draw  the  major  product  for  each  of  the  following  reactions:

H2SO4, H2O
HgSO4

Hello
H2SO4, H2O
HgSO4

Identify  the  alkyne  you  would  use  to  prepare  each  of  the  following  
compounds  via  acid  catalyzed  hydration:

O
H2SO4, H2O
HgSO4
VII. Hydration of Alkynes
Answers:

H2SO4, H2O
HgSO4
O

Hello O
H2SO4, H2O
HgSO4

There  are  two  internal  positions  so  

you  will  get  a  mixture  of  isomers
O

O
H2SO4, H2O
HgSO4

This  alkyne  is  symmetrical  so  forming  the  ketone  

on  either  side  will  give  the  same  product.
VII. Hydration of Alkynes

• Hydroboration-­‐oxidation  of  alkynes  is  the  same  as  for  alkenes  

• Regioselective    for  anti-­‐Markovnikov  addition  
• It  also  produces  an  enol  that  tautomerizes  to  aldehyde    

Hello

• In  this  case,  tautomerization  is  base-­‐catalyzed  (OH-­‐)

VII. Hydration of Alkynes

• Base-­‐catalyzed  tautomerization  mechanism:  

Hello

• Enol  is  deprotonated  to  form  an  enolate,  which  is  protonated  at  
the  carbon  to  produce  the  aldehyde.
VII. Hydration of Alkynes

• If  BH3  is  used,  then  the  alkyne  can  undergo  two  successive  add’ns.  
H
H
H B
H B H
H
R Hello Undesired product
R H BH2

• To  prevent  the  second  addition,  a  dialkyl  borane  is  used  (instead  of  
BH3)
The  bulky  alkyl  groups
provide  steric  hindrance
to  prevent  a  second
addition
VII. Hydration of Alkynes

• The  modified  borane  reagents  allow  for  conversion  of  a  terminal  

alkyne  to  the  corresponding  aldehyde:

Hello
VII. Hydration of Alkynes
Draw  the  major  product  for  each  of  the  following  reactions:

1. 9-BBN
2. H2O2, NaOH

Hello
Identify  the  alkyne  you  would  use  to  prepare  each  of  the  following  
compounds  via  hydroboration-­‐oxidation
O
1. 9-BBN
2. H2O2, NaOH
H
VII. Hydration of Alkynes
Answer:
O

1. 9-BBN
H
2. H2O2, NaOH

Hello
Answer:

O
1. 9-BBN
2. H2O2, NaOH
H
VII. Hydration of Alkynes
Proteases  are  enzymes  that  break  covalent  bonds  in  proteins  and  therefore  
play  an  important  regulatory  role  in  our  biological  processes.    Compound  3  
is  a  potential  therapeutic  agent  since  it  is  a  protease  inhibitor.  
Draw  the  structure  for  alkyne  2  and  predict  the  reagents  required  to  go  
from  1  to  3.    
Hello

Br Ph O O Ph O
2
Br
OH OH
1 3
VII. Hydration of Alkynes
Answers:    Once  you  start  having  more  than  one  step,  you  have  the  
option  of  either  working  backwards  or  working  forwards.    It  is  up  to  
you!

Br Ph O Ph O O Ph O
Hello
1. xs NaNH2 H2SO4 (aq)
Br 2. H2O HgSO4
OH OH OH
1 3
2
VII. Hydration of Alkynes

• For  a  terminal  alkyne:  

– Markovnikov  hydration  yields  a  ketone  
– Anti  Markovnikov  hydration  yields  an  aldehyde

Hello
VIII. Halogenation of Alkynes

• Halogenation  of  alkynes  yields  a  tetrahalide  

• Two  equivalents  of  halogen  are  added  with  excess  X2

Hello
VIII. Halogenation of Alkynes

• When  one  equivalent  of  halogen  is  added  to  an  alkyne,  both  anti  
and  syn  addition  is  observed  

Hello

• The  mechanism  for  alkyne  halogenation  is  not  fully  understood.    If  
it  was  like  halogenation  of  an  alkene,  only  the  anti  product  would  
be  obtained.
VIII. Halogenation of Alkynes

• Ozonolysis  of  an  internal  alkyne  produces  two  carboxylic  acids  

Hello

• Ozonolysis  of  a  terminal  alkyne  yields  a  carboxylic  acid  and  carbon  

dioxide.
IX. Ozonolysis of Alkynes

• Predict  the  product(s)  for  the  following  reaction

Hello
IX. Ozonolysis of Alkynes

• Predict  the  product(s)  for  the  following  reaction  

Hello

• Ozonolysis  of  symmetrical  alkynes  is  particularly  useful  to  prepare  

carboxylic  acids:  only  one  product  is  formed….  two  equivalents  of  it
IX. Ozonolysis of Alkynes
Draw  the  expected  products  for  the  following  chemical  reactions:

1. O3
Hello
2. H O2

1. O3
2. H2O
IX. Ozonolysis of Alkynes
Answers:

OH
1. O3 HO
2. H2O
Hello O
O

O
HO
1. O3
C
2. H2O
O
O
X. Alkylation of Terminal Alkynes

• Recall  that  terminal  alkynes  are  completely  converted  to  an  

alkynide  ion  with  NaNH2  

Hello

New  C-­‐C  bond

• Alkynide  ions  are  good  nucleophiles  

• SN2  reaction  with  alkyl  halides
 X. Alkylation of Terminal Alkynes

• Alkylation  of  an  alkynide  ion  is  SN2  substitution,  and  so  it  works  best  
with  methyl  and  1˚  halides  
  (E2  elimination  dominates  with  2˚/3˚  halides)  
New  C-­‐C  bond

Hello

• Acetylene  can  undergo  two  successive  alkylations

X. Alkylation of Terminal Alkynes

• Note  that  that  double  alkylation  of  acetylene  must  be  stepwise:  

Hello

• Complex  target  molecules  can  be  made  by  building  a  carbon  

skeleton  and  converting  functional  groups  
X. Alkylation of Terminal Alkynes
Identify  reagents  that  can  be  used  to  convert  acetylene  into  
8-­‐methyl-­‐4-­‐octyne

Hello
X. Alkylation of Terminal Alkynes
Answer:    The  first  part  of  this  problem  is  writing  down  the  correct  
structures.  
steps?

Now,  you  will  need  to  Hello

determine  what  steps  are  required  in  order  to  go  
from  your  reactants  to  your  products.    In  this  case  there  are  four  steps  
and  it  doesn’t  matter  which  of  the  two  alkylations  you  do  first.
1. NaNH2 (1 equiv.) 1. NaNH2
2. Ethyl iodide (EtI) 2. I

1. NaNH2 (1 equiv.) 1. NaNH2 (1 equiv.)

2. I 2. Ethyl iodide (EtI)
X. Alkylation of Terminal Alkynes
(−)-­‐Lepadiformine  A,  which  is  isolated  from  a  marine  
organism,  is  toxic  to  several  tumor  cell  lines.    Compound  3  is  a  
synthetic  precursor  to  (−)-­‐Lepadiformine  A.  
Identify  reagents  that  can  be  used  to  synthesize  compound  3  
from  compounds  1  and  2.    
Hello

OR OR
OR OR

OH +

3 2 1
X. Alkylation of Terminal Alkynes
Answers:    First,  make  the  OH  into  a  good  leaving  group  by  
using  something  like  TsCl.    Then  the  terminal  alkyne  (1)  can  be  
alkylated.    
OR
OR

OHHelloTsCl, pyr. OTs

2 4

OR
OR OR

1. NaNH2
2. compound 4

1
3
XI. Synthesis Strategies

• Recall  the  methods  for  converting  triple  bonds  to  double  or  single  
bonds  

Hello

• But,  what  if  you  want  to  reverse  the  process  or  decrease  saturation?  
XI. Synthesis Strategies

• Halogenation  of  an  alkene  followed  by  elimination  yields  an  alkyne  

Hello
• These  reactions  give  us  a  handle  on  interconverting  single,  double  
and  triple  bonds
 9.11  Reactions  of  Alkynes  -­‐  Summary
• Review  of  Reactions

Copyright  ©  2017  John  Wiley  &  Sons,  Inc.  All  rights  reserved. 82 Klein, Organic Chemistry 3e
 9.11  Reactions  of  Alkynes  -­‐  Summary

Copyright  ©  2017  John  Wiley  &  Sons,  Inc.  All  rights  reserved. 83 Klein, Organic Chemistry 3e
XI. Synthesis Strategies
Propose  an  efficient  synthesis  for  the  following  transformation:

Hello
XI. Synthesis Strategies
Answer:    In  order  to  figure  out  all  of  the  intermediates  in  this  
synthesis,  you  can  always  start  with  the  product  and  work  backwards,  
or  you  could  work  forwards.    I  often  find  working  backwards  to  be  the  
easiest  especially  as  things  get  more  complicated.

Hello

Br

Br

1. Br2, CCl4 1. NaN2 Na(s)

2. xs NaN2 2. MeI NH3(l)
3. H2O
XI. Synthesis Strategies
Propose  an  efficient  synthesis  for  the  following  transformation:
Br Br
+ Enantiomer

Hello
XI. Synthesis Strategies
Answer:    I  definitely  think  working  backwards  is  key  here!

Br Br

Hello

Br Br
1. NaN2 H2 Br2, CCH4
2. EtI Lindlar
II. Nomenclature of Alkynes
Provide  a  systematic  name  for  each  of  the  following  compounds:

i.   v.  

Hello

ii.   vi.  

iii.  
vii.

iv.
CCl3
II. Nomenclature of Alkynes
Answers:

5 6
i.   1
2 4 v.   7 8 9
3 6

3 4 5
3-­‐hexyne 2
1
Hello 7-­‐methyl-­‐5-­‐propyl-­‐1-­‐nonyne
2 1
5 3
ii.   4
vi.   7 8 9 10
6 6
7
5-­‐methyl-­‐3-­‐heptyne 5
2 1 4 2
3 1
7 6 5 3
8 4
iii.   5-­‐ethyl-­‐7,7-­‐dimethyl-­‐3-­‐decyne

3-­‐octyne vii.
10 9 8 7 6 5 4
iv. 3 4 3
2
2 CCl3
1 1
3,3-­‐dimethyl-­‐1-­‐butyne 1,1,1-­‐tricholoro-­‐8-­‐ethyl-­‐4,4-­‐dimethyl-­‐2-­‐decyne
II. Nomenclature of Alkynes
Draw  a  bond-­‐line  structure  for  each  of  the  following:

viii.    4,4-­‐Dimethyl-­‐2-­‐pentyne  

Hello

ix.    5-­‐Ethyl-­‐2,5-­‐dimethyl-­‐3-­‐heptyne
II. Nomenclature of Alkynes
Answers:

4
viii.    4,4-­‐Dimethyl-­‐2-­‐pentyne   3 5
2
1

Hello

3
ix.    5-­‐Ethyl-­‐2,5-­‐dimethyl-­‐3-­‐heptyne 1
2
4

5
6
7
IV. Preparation of Alkynes

For  the  following  transformation,  predict  the  major  product  and  

draw  a  mechanism  for  its  formation:

Hello
Cl
1. xs NaNH2/NH3
x. 2. H2O
Cl
IV. Preparation of Alkynes

Answer:    Basically  two  E2  elimination  steps  will  provide  you  with  the  
terminal  alkyne.    Make  sure  each  elimination  step  occurs  anti  to  the  
leaving  group!
H
N

H Hello
H

Cl
1. xs NaNH2/NH3
2. H2O
Cl

Cl
H

H
H
N

H
IV. Preparation of Alkynes

The  Alkyne  “Zipper  Reaction”  isomerizes  an  internal  alkyne  to  a  

terminal  alkyne  through  successive  protonation-­‐deprotonation  
steps.    Propose  a  mechanism  for  the  following  transformation

Hello
NaNH2
xi.
 IV. Preparation
Answers:    The  key  to  this  rof Alkynes
eaction   is  that  the  sp3  carbon  adjacent  to  the  alkyne  can  be  
deprotonated  since  the  anion  is  resonance  stabilized.    However,  the  reaction  ends  as  soon  
as  the  terminal  alkyne  is  formed  since  the  pKa  of  the  terminal  alkyne  is  much  lower  (the  
alkynide  ion  has  the  lowest  potential  energy  and  the  equilibrium  favors  this  intermediate).  
Don't  worry  if  your  arrows  aren’t  exactly  the  same  as  mine  but  you  still  pushed  electrons  
to  get  to  the  product.    In  reality,  its  believed  that  the  first  two  steps  of  this  process  occur  
at  the  same  time  so  there  isn’t  really  aren’t  any  sp2  anions  floating  around  in  this  reaction

Hello H
H
H
N
NaNH2 N H
H
· H

H
H
H
N
H
H N
H H H reaction gets “stuck” here H
N
N H
H H H
H N

H
· ·
H
H N
·
H
H
H
H
N

H
V. Reduction of Alkynes
Identify  reagents  that  you  could  use  to  achieve  each  of  the  
following  transformations:

xii.
Hello
V. Reduction of Alkynes
Answers

xii.
Hello

H2/Pt
Na/NH3(l)
or
H2/Pd
V. Reduction of Alkynes

xiv.    An  alkyne  with  the  molecular  formula  C5H8  was  treated  with  
sodium  in  liquid  ammonia  to  give  a  disubstituted  alkene.    Draw  the  
structure  of  the  alkene

Hello
V. Reduction of Alkynes
xiv.  Answer:    

Na
Hello NH3(l)
Disubstituted  alkene.

or

Na
NH3(l)
Monosubstitued  alkene.
V. Reduction of Alkynes
Predict  the  major  product(s)  expected  for  each  of  the  following  
reactions:
xs Brl
xv.  

Br Br
Hello
1. xs NaNH2/NH3

xvi.   2. H2O

Cl Cl

1. xs NaNH2/NH3

xvii.   2. H2O
3. HBr ROOR

Cl Cl

1. xs NaNH2/NH3

xviii. 2. H2O
3. xs HBr
V. Reduction of Alkynes
Answers:
xs Brl

xv.   Br Br

Br Br

1. xs NaNH2/NH3
Hello
xvi.  
2. H2O

Cl Cl
Br
1. xs NaNH2/NH3

xvii.   2. H2O
3. HBr ROOR
Br

Cl Cl Br Br

1. xs NaNH2/NH3
xviii. 2. H2O
3. xs HBr
V. Reduction of Alkynes
xix.  An  alkyne  with  the  molecular  formula  C5H8  is  treated  with  
excess  HBr,  and  two  different  products  are  obtained,  each  of  which  
has  the  molecular  formula  C5H10Br2.  

a.  Identify  the  starting  alkyne.  

Hello

b.  Identify  the  two  products.

V. Reduction of Alkynes
xix.  Answer:  

Br Br
Hello
xs Brl

Br Br

Since  we  have  an  internal  alkyne,  the  first  Br  and  add  to  
either  carbon.    The  second  Br  will  always  add  to  the  
same  carbon  as  the  first  Br.
VII. Hydration of Alkynes
Draw  the  major  product  for  each  of  the  following  reactions:

xx.   H2SO4, H2O

HgSO4

Hello H2SO4, H2O

HgSO4
xxi.  
Identify  the  alkyne  you  would  use  to  prepare  each  of  the  following  
compounds  via  acid  catalyzed  hydration

xxii.  
O
H2SO4, H2O
HgSO4

O
H2SO4, H2O
HgSO4
xxiii.
VII. Hydration of Alkynes
Answers:

O
xx.   H2SO4, H2O
HgSO4

O
Hello H2SO4, H2O

xxi.   HgSO4

Symmetrical  alkyne  so  only  one  product  is  formed.

Answers:

O
xxii.   H2SO4, H2O
HgSO4

O
H2SO4, H2O

xxiii.
HgSO4
VII. Hydration of Alkynes
Draw  the  major  product  for  each  of  the  following  reactions:

xxiv.   1. Disiamylborane
2. H2O, NaOH

Hello 1. R2BH
xxv.   2. H2O, NaOH

Identify  the  alkyne  you  would  use  to  prepare  each  of  the  following  
compounds  via  hydroboration-­‐oxidation

xxvi.   O

1. R2BH
2. H2O, NaOH

H
1. R2BH
xxvii. 2. H2O, NaOH O
VII. Hydration of Alkynes
Answers:
1. Disiamylborane
xxiv.   2. H2O, NaOH
H

1. R2BH
Hello 2. H2O, NaOH
xxv.  
O
Answers:
O

xxvi.   1. R2BH
2. H2O, NaOH

H
1. R2BH
2. H2O, NaOH
xxvii. O
VII. Hydration of Alkynes
Identify  the  reagents  that  you  could  use  to  achieve  each  of  the  
following  transformations:  

Hello O
xxviii.  

xxix. H
VII. Hydration of Alkynes

Answers:

H2SO4(aq)
xxviii.   Hello HgSO4
O

O
xxix. 9-BBN
H2O2, NaOH H

Other  boranes  like  R2BH  or  

disiamylborane  would  also  work
IX. Ozonolysis of Alkynes
Draw  the  expected  products  for  the  following  chemical  reactions:

1. O3
xxx.   Hello 2. H2O

xxxi. 1. O3
2. H2O
IX. Ozonolysis of Alkynes
Answers:

OH
xxx.   Hello
1. O3
2. H2O
HO

O
O

1. O3
xxxi. 2. H2O O O
OH HO
IX. Ozonolysis of Alkynes

xxxii.  An  alkyne  with  the  molecular  formula  C6H10  was  treated  with  
ozone  followed  by  water  to  produce  only  one  type  of  carboxylic  acid.    
Draw  the  structure  of  the  starting  alkyne  and  the  product  of  ozonolysis.  

Hello

xxxiii.  An  alkyne  with  the  molecular  formula  C4H6  was  treated  with  ozone
followed  by  water  to  produce  a  carboxylic  acid  and  carbon  dioxide.    Draw
the  expected  product  when  the  alkyne  is  treated  with  aqueous  acid  in  
the  presence  of  mercuric  sulfate.
IX. Ozonolysis of Alkynes
xxxii.  Answer:  

O
1. O3
2. H2O OH
(2 equiv.)

Hello
The  alkyne  must  be  symmetrical  to  form  only  one  product.

xxxiii.  Answer:

O
H2SO4 (aq) 1. O3
CO2
HgSO4 2. H2O HO
O OH

The  alkyne  must  be  a  terminal  alkyne  to  form  CO2  as  a  product.
X. Alkylation of Terminal Alkynes
xxxiv.  Starting  with  acetylene,  show  which  reagents  you  
would  use  to  prepare  each  of  the  following  compounds:

a.  1-­‐Butyne  
b.  2-­‐Butyne   j.  
Hello
c.  3-­‐Hexyne  
d.  2-­‐Hexyne  
e.  1-­‐Hexyne  
f.  2-­‐Heptyne   k.
g.  3-­‐Heptyne  
h.  2-­‐Octyne  
i.  2-­‐Pentyne
X. Alkylation of Terminal Alkynes
xxxiv.  Answers:  

1. NaNH2 (1 equiv.)
a.   2. Ethyl iodide (EtI)

Hello
1. NaNH2 (1 equiv.)

b.   2. Methyl iodide (MeI)

3. NaNH2 (1 equiv.)
4. Methyl iodide (MeI)

1. NaNH2 (1 equiv.)
c.     2. Ethyl iodide (EtI)
3. NaNH2 (1 equiv.)
4. Ethyl iodide (EtI)

1. NaNH2 (1 equiv.)
d. 2. MeI
3. NaNH2 (1 equiv.)
4. (1-iodopropane)
I
X. Alkylation of Terminal Alkynes
xxxiv.  Answers:  

e.   1. NaNH2 (1 equiv.)
2. 1-iodobutane

Hello
1. NaNH2 (1 equiv.)
f.   2. MeI
3. NaNH2 (1 equiv.)
4. 1-iodobutane

1. NaNH2 (1 equiv.)

g.     2. EtI
3. NaNH2 (1 equiv.)
4. 1-iodopropane

1. NaNH2 (1 equiv.)
h. 2. MeI
3. NaNH2 (1 equiv.)
4. 1-iodopentane
X. Alkylation of Terminal Alkynes
xxxiv.  Answers:  
1. NaNH2 (1 equiv.)
i.   2. MeI
3. NaNH2 (1 equiv.)
4. Ethyl iodide (EtI)

Hello
1. NaNH2 (1 equiv.)
2. EtI
j.   3. NaNH2 (1 equiv.)
4. Benzyl iodide

1. NaNH2 (1 equiv.)
k.     2. Benzyl iodide
3. NaNH2 (1 equiv.)
4. Benzyl iodide
XI. Synthesis Strategies
xxxv.  Propose  an  efficient  synthesis  for  the  following  transformations:

a.  

H
b.   Hello O

OH
c.    

d.   HO

Br Br

e.
XI. Synthesis Strategies
xxxv.  Answers:    I  am  going  to  split  up  the  retrosynthetic  analysis  
(backward  approach)  with  the  final  answer  so  you  have  a  chance  to  
figure  out  what  reagents  are  necessary  to  go  from  step  to  step.

a.                  Retrosynthetic  Hello
Analysis:
XI. Synthesis Strategies
xxxv.  Answers:  

a.

Hello
1. Br2, CCH4 1. NaNH2 H2
2. xs NaNH2 2. EtI Lindlar
3. H2O
XI. Synthesis Strategies
xxxv.  Answers:  

b.    Retrosynthetic  Analysis

Hello
Br H

Br
O
XI. Synthesis Strategies
xxxv.  Answers:  

b.

Hello
Br H
Br2, CCH4 1. xs NaNH2 9-BBN
Br 2. H2O H2O2, NaOH
O

Any  R2BH  would  work  

here  instead  of  9-­‐BBN
XI. Synthesis Strategies
xxxv.  Answers:  

c.    Retrosynthetic  Analysis

Hello OH
XI. Synthesis Strategies
xxxv.  Answers:  

c.  
OH
H2 dilute H2SO4
Lindlar
Hello
XI. Synthesis Strategies
xxxv.  Answers:  

d.    Retrosynthetic  Analysis

Hello

HO
XI. Synthesis Strategies
xxxv.  Answers:  

d.  

Hello
H2 1. BH3·THF HO
Lindlar 2. H2O2, NaOH
XI. Synthesis Strategies
xxxv.  Answers:  

e.    Retrosynthetic  Analysis

Hello Br Br Br
=
Br

These are the same meso compound.

XI. Synthesis Strategies
xxxv.  Answers:  

e.

Br
1. NaNH2 Hello Na(s) Br2, CCl4
Br Br
=
2. EtI NH3(l)
Br

These are the same meso compound.