Experimental Organic Chemistry: A Miniscale and Microscale Approach

966 Pages·2010·22.314 MB·English

by  John C. Gilbert, Stephen F. Martin

Equipment Commonly Used in the
Organic Chemistry Laboratory
Filter flask Büchner Hirsch Separatory funnel
funnel funnel with ground-glass
joints
Conical vial Claisen adapter Air condenser Reflux condenser Hickman stillhead Drying tube Pa steur
with port pipet
We st condenser Hempel column
Rubber
Round-bottom Claisen adapter Stillhead Thermometer Va cuum adapter
septum
f lask adapter with with ground-glass
Neoprene fi tting joints
First Aid in Case of an Accident
The occurrence of an accident of any kind in the laboratory should be reported
promptly to your instructor, even if it seems relatively minor.
F I R E
Your first consideration is to remove yourself from any danger, notto extinguish the
fire. If it is possible to do so without endangering yourself, turn off any burners and
remove containers of flammable solvents from the immediate area to prevent the
fire from spreading. For the most effective use of a fire extinguisher, direct its noz-
zle toward the baseof the flames. Burning oil may be put out with an extinguisher
classified for use on “ABC” type fires.
If your clothing is on fire, DO NOT RUN; rapid movement will only fan the
flames. Roll on the floor to smother the fire and to help keep the flames away from
your head. Your neighbors can help to extinguish the flames by using fire blankets,
laboratory coats, or other items that are immediately available. Do not hestitate to aid
your neighbor if he or she is involved in such an emergency; a few seconds delay may
result in serious injury. Alaboratory shower, if close by, can be used to extinguish burn-
ing clothing, as can a carbon dioxide extinguisher, which must be used with care until
the flames are extinguished and only if the flames are not near the head.
If burns are minor, apply a burn ointment. In the case of serious burns, do not
apply any ointment; seek professional medical treatment at once.
C H E M I C A L B U R N S
Areas of the skin with which corrosive chemicals have come in contact should be
immediately and thoroughly washed with soap and warm water. If the burns are
minor, apply burn ointment; for treatment of more serious burns, see a physician.
Bromine burns can be particularly serious. These burns should first be washed
with soap and warm water and then thoroughly soaked with 0.6 Msodium thiosulfate
solution for three hours. Apply cod liver oil ointment and a dressing; see a physician.
If chemicals, in particular corrosive or hot reagents, come in contact with the
eyes, immediately flood the eyes with water from the nearest outlet. A specially
designed eyewash fountain is useful if available in the laboratory. Do not touch the
eye. The eyelid as well as the eyeball should be washed with water for several
minutes. In all instances where sensitive eye tissue is involved in such an acci-
dent, consult an ophthalmologist as soon as possible.
C U T S
Minor cuts may be treated by ordinary first-aid procedures; seek professional med-
ical attention for serious cuts. If severe bleeding indicates that an artery has been
severed, attempt to stop the bleeding with compresses and pressure; a tourniquet
should be applied only by those who have received first-aid training. Arrange for
emergency room treatment at once.
Aperson who is injured severely enough to require a physician’s treatment
should be accompaniedto the doctor’s office, or infirmary, even if he or she claims to
be all right. Persons in shock, particularly after suffering burns, are often more seri-
ously injured than they appear to be.
Discovery Experiments
Chapter 3 NEWFormation of Polymorphs, p.109
Melting-Point Depression, p.119
Chapter 4 Comparative Fractional Distillations, p.142
Fractionation of Alternative Binary Mixtures, p.142
NEWFractional Distillation of Unknowns, p.142
Chapter 5 Separation of Unknown Mixture by Extraction, p.167
Isolation of Ibuprofen, p.167
Chapter 6 Effect of Solvent Polarity on Efficiency of Separation, p.186
Analysis of Plant Pigments from Various Sources, p.186
Analysis of Analgesics by TLC, p.187
Column Chromatographic Separation of Benzyl Alcohol and Methyl Benzoate, p.194
Analysis of Factors Affecting Retention Times, p.207
Effect of Stationary Phase on Separation of a Mixture, p.207
Molar Response Factors of Isomers, p.208
Molar Response Factors of Non-Isomeric Compounds, p.208
Chapter 7 NEWSolvent Effects on R -Values, p.218
f
NEWIodine as a Catalyst for Isomerization, p.222
Assessing Purities of Dimethyl Maleate and Fumarate, p.222
Chapter 9 Chlorination of Heptane, p.319
NEWChlorination of 2,3-Dimethylbutane, p.320
Chapter 10 Elimination of Alternate Non-Terminal Alkyl Halides, p.343
Elimination of Stereoisomeric Alcohols, p.355
NEWAnalysis of Bromohexanes, p.370
NEWBromination of (Z)-Stilbene, p.380
NEWSolvent Effects on the Stereochemistry of Bromination, p.380
NEWSubstituent Effects on the Stereochemistry of Bromination, p.380,
NEWRegiochemistry of Hydroboration/Oxidation of an Acyclic Alkene, p.394
Regio- and Stereochemistry of Hydroboration/Oxidation of a Cyclopentene, p.394
Chapter 11 Preparation of 3-Methyl-3-hydroxy-2-butanone, p.412
Chapter 12 Hydrolysis of Anhydrides, p.432
Chapter 13 NEWEffect of pH on Kinetic vs.Thermodynamic Control, p.453
Chapter 14 Analysis of S Reactions as a Function of Substrate, p.469
N
Effect of Temperature on Rates of Solvolysis, p.487
Effect of Leaving Group on Rates of Solvolysis, p.487
Chapter 17 Hydrogenation of 4-Cyclohexene-cis-1,2-dicarboxylic Acid, p.567
Formation and Reduction of N-Cinnamylidene-m-nitroaniline, p.573
Reduction of 4-tert-Butylcyclohexanone, p.583
Reduction of Benzoin, p.584
Chapter 18 Preparation of (Z)- and (E)-Stilbenes by a Wittig Reaction, p.606
Wittig Reaction of 9-Anthraldehyde, p.609
Preparation of a Stilbene by the Horner-Wadsworth-Emmons Reaction, p.620
Preparation of trans,trans-Dibenzylideneacetone, p.621
Chapter 19 NEWExploring the Influence of Mode of Addition, p.656
NEWPreparation and Characterization of a 3°Alcohol, p.659
Chapter 22 Preparation of Polystyrene, p.770
Stability of Polystyrene toward Organic Solvents, p.772
Polymers and Water, p.772
Cross-Linking of Polymers, p.773
t.
Periodic Table of the Elements
1 2
1 .0 1 4 .0 0
H He
H yd ro ge n He l i u m
3 4 5 6 7 8 9 10
6 .9 4 9 .0 1 1 0. 81 1 2. 01 1 4. 01 1 6. 00 1 9. 00 2 0. 18
Li Be B C N O F Ne
Li t h i u m Be r yl l i u m Bo ro n Ca r b o n N i t ro ge n Ox yg en Fl uo r i n e Ne o n
11 12 13 14 15 16 17 18
2 2. 99 2 4. 31 2 6. 98 2 8. 09 3 0. 97 3 2. 07 3 5. 45 3 9. 95
Na Mg Al Si P S Cl A r
S o d i u m M ag n es i u m A lu m i n u m S i l i co n P h o sp h o ru s S u lf u r C h lo ri n e Ar go n
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
3 9. 10 4 0. 08 4 4. 96 4 7. 87 5 0. 94 5 2. 00 5 4. 94 5 5. 85 5 8. 93 5 8. 69 6 3. 55 6 5. 39 6 9. 72 7 2. 61 7 4. 92 7 8. 96 7 9. 90 8 3. 80
K Ca Sc Ti V Cr M n Fe Co Ni Cu Zn Ga Ge A s Se Br K r
P ot a s s i u m C al ci u m Sc a nd i um T i t a n i u m Va n a di u m C h ro m i u m Ma n g a n e s e Ir on C o b a l t Ni ck e l Co p p e r Zi nc G al l i u m G er m an iu m Ar s e n i c S e le n iu m Br o m i n e K r yp to n
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
8 5. 47 8 7. 62 8 8. 91 9 7. 22 9 2. 91 9 5. 94 ( 98 ) 1 01 .0 7 1 02 .9 1 1 06 .4 2 1 07 .8 7 1 12 .4 1 1 14 .8 2 1 18 .7 1 1 21 .7 6 1 27 .6 0 1 26 .9 0 1 31 .2 9
Rb S r Y Zr N b Mo Tc R u Rh Pd Ag Cd In Sn Sb Te I Xe
R u b i d i u m S t ro n t i u m Y t t ri u m Zi r co n i u m N i o b i u m Mo l yb d e nu m Te c hn i c i u m R u t h en i u m R h o d i u m P a l l a d i u m S i l v er C ad m i u m In d i u m T in A n t i m o n y T el l u ri u m Io d in e Xe n o n
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
1 32 .9 1 1 37 .3 3 1 38 .9 1 1 78 .4 9 1 80 .9 5 1 83 .8 4 1 86 .2 1 1 90 .2 3 1 92 .2 2 1 95 .0 8 1 96 .9 7 2 00 .5 9 2 04 .3 8 2 07 .2 2 08 .9 8 (208.98) (209.99) (222.02)
Cs Ba La H f Ta W Re O s Ir Pt A u H g Tl Pb Bi Po At Rn
*
C e s i um Ba r i u m La n t h an u m H af n i u m T a nt a l um T un g s t en R h en i u m O s m i u m Ir i d i u m P l a t i n u m G o ld Me r c u r y T h al l i u m Le ad Bi s m u t h P o l o n i u m A s t at i n e Ra do n
87 88 89 10 4 10 5 10 6 10 7 10 8 10 9 110 111 11 2 113 11 4 115 11 6 117 11 8
(223.02) (226.03) ( 22 7 ) (263.11) ( 26 2 ) (266.12) (264.12) (269.13) (268.14) (272.15) (272.15) ( 27 7) (284) ( 28 9 ) (288) ( 29 2) (?) ( 29 4)
Fr Ra A c Rf Db Sg Bh H s Mt Ds Rg Uu b Uut Uuq Uup Uu h Uus U u o
**
Fr a n ci um R a d i u m A ct i n i u m Ru t he r fo r d iu m D u br i u m Se a bo r gi um B o hr iu m H a s si um M ei t n er i u m Darmstadtium Roentgenium U n u n b iu m Ununtrium Un u nq u a di u m Ununpentium Un u n h e x i um Ununseptium Un u n o c ti u m
58 59 60 61 62 63 64 65 66 67 68 69 70 71
*
L a n th an id e 1 40 .1 2 1 40 .9 1 1 44 .2 4 ( 14 5 ) 1 50 .3 6 1 51 .9 6 1 57 .2 5 1 58 .9 3 1 62 .5 0 1 64 .9 3 1 67 .2 6 1 68 .9 3 1 73 .0 4 1 74 .9 7
Se r i e s Ce Pr N d Pm S m Eu G d Tb D y H o Er Tm Y b Lu
C e r i um P ra s eo d ym i u m N eo d ym i u m P ro m e t h i um Sa m a ri um E u ro p iu m G ad o l i n i u m T er b i u m D ys p r o s i u m H o l m i u m E rb iu m T h u l i u m Y t t er b i u m Lu t et i u m
90 91 92 93 94 95 96 97 98 99 10 0 10 1 10 2 10 3
**
Ac t i n id e 2 32 .0 4 2 31 .0 4 2 38 .0 3 2 37 .0 5 ( 24 4 ) ( 24 3 ) ( 24 7 ) ( 24 7 ) ( 25 1 ) ( 25 2 ) ( 25 7 ) ( 25 8 ) ( 25 9 ) ( 26 0 )
Se r i e s Th Pa U N p Pu A m Cm Bk Cf Es Fm Md N o Lr
Th o ri u m P ro t ac t i n i u m U ra n i um Ne pt un i um P l u t o n i u m A m er i ci u m C u ri u m Be r k el i u m C a li f o rn iu m E i n s t ei n i u m Fe r m i u m M en d e l e v i u m N o b e li u m La wr e n ci u m
http://en.wikipedia.org/wiki/Periodic_table
Approximate 1H and 13C NMR Shifts
δ (ppm)
δ (ppm)
0 CH Si
0 CH Si 3
3
RCH 20 CH 3C (1° acyclic)
1 3 C H2R2 (2° acyclic)
RCH
2 2 C HR (2° acyclic)
2 2
R3CH CH C C 40 C HR3 (3° acyclic)
CH C C 3
3
C Cl (alkyl chloride)
H C C
2 CH C(=O)OR and R CH C C
3 2
CH C(=O)R
3
R CH NR 60
2 2
C OH (alcohol) and C OR (ether)
R CH CH
2 6 5
C CR
3
80
R CH X(X = Hal) and R CH OR*
2 2
4
100
R CH OC(=O)R
2
C CR
120 2
5
C
Y
140
H
6
C C
160
7
RC (=O)OH and RC (=O)OR
180
H
8
200
RC (=O)R1 (R1 = H or alkyl)
9
220
H C(=O)R
10
* CH groups typically resonate 0.3–0.4 ppm upfield of the corresponding
3
CH groups; CH groups are typically 0.3–0.4 ppm further downfield of the
2
CH group.
2
Experimental
Organic
Chemistry
A Miniscale and Microscale Approach
FIFTH EDITION
John C. Gilbert
Santa Clara University
Stephen F. Martin
University of Texas at Austin
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Experimental Organic Chemistry, © 2011Cengage Learning
Fifth Edition
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1 2 3 4 5 6 7 13 12 11 10 09
Contents in Brief
1 Introduction, Record Keeping, and Laboratory Safety 1
2 Techniques and Apparatus 27
3 Solids:Recrystallization and Melting Points 93
4 Liquids:Distillation and Boiling Points 127
5 Extraction 153
6 Chromatography 179
7 Stereoisomers 213
8 Spectral Methods 237
9 Alkanes 313
10 Alkenes 337
11 Alkynes 403
12 Dienes:The Diels-Alder Reaction 421
13 Kinetic and Thermodynamic Control of a Reaction 445
14 Nucleophilic Aliphatic Substitution:Preparation of
Alkyl Halides 461
15 Electrophilic Aromatic Substitution 491
16 Oxidation of Alcohols and Carbonyl Compounds 537
17 Reduction Reactions of Double Bonds:Alkenes, Carbonyl
Compounds, and lmines 563
18 Reactions of Carbonyl Compounds 601
19 Organometallic Chemistry 639
20 Carboxylic Acids and Their Derivatives 669
21 Multistep Organic Synthesis 703
22 Polymers 765
23 Carbohydrates 787
24 (cid:2)-Amino Acids and Peptides 803
25 Identifying Organic Compounds 833
26 The Literature of Organic Chemistry 905
iii
t.
Table of Contents
Chapter 1 Introduction, Record Keeping, and Laboratory Safety 1
1.1 Introduction 1
1.2 Preparing for the Laboratory 2
1.3 Working in the Laboratory 3
1.4 The Laboratory Notebook 4
1.5 General Protocol for the Laboratory Notebook 4
1.6 Types of Organic Experiments and Notebook Formats 5
1.7 Sample Calculations for Notebook Records 14
1.8 Safe Laboratory Practice:Overview 16
1.9 Safety:General Discussion 17
1.10 Safety:Material Safety Data Sheets 19
1.11 Safety:Disposal of Chemicals 21
Historical Highlight: The Importance of Record Keeping24
Chapter 2 Techniques and Apparatus 27
2.1 Glassware:Precautions and Cleaning 27
2.2 Standard-Taper Glassware for Miniscale Procedures 28
2.3 Standard-Taper Glassware for Microscale Procedures 29
2.4 Assembling Apparatus 31
2.5 Measuring and Transferring Liquids 32
2.6 Weighing Methods 37
2.7 Melting-Point Methods and Apparatus 38
2.8 Boiling-Point Methods and Apparatus 41
2.9 Heating Methods 43
2.10 Cooling Techniques 51
2.11 Stirring Methods 52
2.12 Centrifugation 54
2.13 Simple Distillation 55
2.14 Fractional Distillation 58
2.15 Vacuum Distillation 60
2.16 Steam Distillation 64
2.17 Filtration Apparatus and Techniques 66
2.18 Decolorizing Carbon 72
2.19 Decanting Solutions 73
2.20 Sublimation 73
2.21 Extraction 75
iv