MicroscaleandMacroscale

Techniques in the Organic

Lab oratory
Donald Pavia L.

Western Washington
Bellingham, Washington

GaryM.Lampman

George S. Kriz University

North

RandallG.Engel

Seattle

Community

College

Seattle, Washington

Australia.

Canada.

United

BR
*

THOMSON

Mexico.

Singapore.
States

Spain

Kingdom.

United

The best way to find information

book.Inthischapter,wewilldiscusstheuseoftheCRCHandbookofChemistryand

Phys Lang Han ofth Che the Me Ind an A H o

CHAPTER4HowtoFindDataforCompounds:

Handbooks

and

Catalogs

quickly on organic compounds

is to consult a hand-

Fine Chemicals. Complete citations to these handbooks are provided in Chapter 30. Depending on the type of handbook consulted, the following information may be found:
Nameandcommonsynonyms

Formula

Molecular

weight

Boiling point for a liquid or melting point for a solid Beilstein reference Solubility data Density Refractive index Flash point
ChemicalAbstractService(CAS)registrynumber

Toxicity

data

Uses and synthesis

This is the handbook though

madeareoftenminor.Anoldercopyofthehandbookwilloftensufficeformostpur-poses.Inadditiontotheextensivetablesofpropertiesoforganiccompounds,theCRC

CRCHANDBOOKOFCHEMISTRYANDPHYSICS

that is most often consulted of the handbook

for data on organic each year,

compounds. that

Alare

a new edition

is published

the changes

Handbook

includes

sections

on nomenclature

and ring

structures,

an index

of synAbstracts from

onyms, and an index of molecular formulas. The nomenclature used in this book most closely system of naming organic compounds. This system

follows differs,

the Chemical but

only slightly,

42

44

Microscale and Macroscale Techniques in the Organic Chemistry Laboratory

mp/OC

bp/oC

Den! gm-3 c
is very useful for locating additional information on the compound in the primary chemical literature (see Chapter

Chemical

Abstract

Service

Registty

Number.

This

number

CASRN

30, Section 30.11).

Melting point of the compound in degrees Celsius.

BoilingpointofthecompoundindegreesCelsius.Anumber

without
wasobtainedat760mmHgpressure(atmosphericpressure).Anumberwithasuperscriptindicatesthattheboilingpointwasobtainedatreducedpressure.Forexample,anenttyof

a superscript

indicates

that the recorded

boiling

point

234;
at760mmHgand122Cat16mmHgpressure.Densityofaliquid.AsuperscriptindicatesthetemperatureindegreesCelsiusatwhichthedensitywasobtained.

12216 would

indicate

that

the compound

boils

at 234C

Refractive

index determined

at a wavelength

of 589 urn, the

nD

Solubility

Solubility classification 1 = insoluble 2 = slightly soluble

yellowlineinasodiumlamp(Dline).Asuperscriptindi-

cates the temperature at which the refractive index was obtained (see Chapter 24). Solvent abbreviations ace = acetone bz = benzene

3 = soluble

chI =

5 = miscible 6 = decomposes
Beil. ref.
Beilsteinreference.Anenttyof4-02-00-00157wouldindi-

verysolubleEtOH=ethanol

eth = ether hx = hexane

in 30,

cate that the compound is found in the 4th supplement Volume 2, with no subvolume, on page 157 (see Chapter

Section 30.10 for details on the use of Beilstein).

Merck No.
MerckIndexnumberinthe11theditionofthehandbook.

These

numbers

change

each

time

a new

chloroform

edition

of the Merck

Index is issued.
Examples and isopentyl of sample handbook entries for isopentyl alcohol (I-butanol, 3-methyl) acetate (I-butanol, 3-methyl, acetate) are shown in Table 4.2.

teresting differences and advantages. Lange's Handbook has synonyms listed at the bottom of each page, along with structures of more complicated molecules. The most

LANGE'SHANDBOOKOFCHEMISTRYThishandbooktendsnottobeasavailableastheeReHandbook,butithassomein-

Cha 4for Han toow Fin Da Co H C 4 H 2 E 5 Tabl 4.3 a Exam ofH Nam of Com in La ~ Nam of Orga Com
'"
Table4.2PropertiesofisopentylalcoholandisopentylacetateaslistedintheCRC

Handbook

3627

I-Butanol,

C5H120

123-51-3

5081

4-01-00-01677

ace 4; eth 4;
EtOH4

3-methyl

Isopentyl

alcohol

88.15

-117.2

3631

I-Butanol,

C7H1402

123-92-2

131.1 4993
142.5

0.810420 1.405320 4-02-00-00157

0.87615

3-methyl,acetate

Isopentyl acetate

130.19

-78.5

eth 5; ace 3 1.400020

noticeable difference is in how compounds are named. For many compounds, the system lists names as they would appear in a dictionary. Table 4.3 lists examples of how some commonly encountered compounds are named in this handbook. Most often, you do not need to identify the parent name. Unfortunately, Lange's Handbook often
usescommonnamesthatarebecomingobsolete.Forexample,propionateisused

rather than propanoate. Nevertheless, this handbook often names compounds as a practicing organic chemist would tend to name them. Notice how easy it is to find the

entries for isopentyl acetate and acetylsalicylic acid (aspirin) in this handbook.
Once you locate the compound by its name, you will find the following

useful

information: Lange's

number

This is an identification

number for the compound.

See examples in Table 4.3.

Name

Formula

Structures are drawn out. If they are complicated, structures are shown at the bottom of the page. weight of the compound.

then the

Formula

weight

Molecular

Location

in Lange's Handbook

l-Chloropentane

1,4- Dichlorobenzene 4-Chlorotoluene Ethanoic acid

l-Chloropentane 1,4-Dichlorobenzene 4-Chlorotoluene Acetic acid

tert-Butyl acetate (ethanoate) Ethyl propanoate Isopentyl alcohol Isopentyl acetate (banana oil) Salicylic acid Acetylsalicyclic acid (aspirin)

tert-Butyl acetate Ethyl propionate 3-Methyl-l-butanol Isopentyl acetate 2-Hydroxybenzoic acid Acetylsalicylic acid

46

Microscale

and Macroscale

Techniques

in the Organic

Chemistry

Laboratory

Beilstein

reference
Anentryof2,132wouldindicatethatthecompoundisfoundinVolume2oftheMainWorkonpage132.Anentryof32,

188 would indicate that the compound is found in Volume 3 of the second supplement on page 188 (see Chapter 30, Section 30.10 for details on the use of Beilstein).
Density
Densityisusuallyexpressedinunitsofg/mLorg/cm3.Asu-perscriptindicatesthetemperatureatwhichthedensitywas

measured. If the density is also subscripted, usually 4, it indicates that the density was measured at a certain temperature relative to water at its maximum density, 4c. Most of the time you can simply ignore the subscripts and superscripts. Refractive index
Asuperscriptindicatesthetemperatureatwhichtherefrac-tiveindexwasdetermined(seeChapter24).

Melting point

Melting

point

of the compound

in degrees

Celsius.

When

"d" or "dec" appears with the melting point, it indicates that

the compound decomposes at the melting point. When decomposition occurs, you will often observe a change in color of the solid. Boiling point
BoilingpointofthecompoundindegreesCelsius.Anumber

without
pointwasobtainedat760mmHgpressure(atmosphericpressure).Anumberwithasuperscriptindicatesthattheboil-ingpointwasobtainedatreducedpressure.Forexample,an

a superscript

indicates

that the recorded

boiling

entry
102Cat11mmHgpressure.

of 10211 nun would

indicate

that

the compound

boils at

Flash point

This

number

is the

temperature

in degrees

Celsius

at which

the compound will ignite when heated in air and a spark is introduced into the vapor. There are a number of different methods that are used to measure this value, so this number varies considerably. It gives a crude indication of flammabilwith a hot plate. Hot plates can be a serious source of trouble because of the sparking action that can occur with switches and thermostats used in hot plates.
ity.Youmayneedthisinformationwhenheatingasubstance

Solubility in 100 parts solvent

Parts by weight of a compound

partsbyweightofsolventatroomtemperature.Insomecases,thevaluesgivenareexpressedastheweightingramsthatcanbedissolvedin100mLofsolvent.Thishandbookisnotcon-sistentindescribingsolubility.Sometimesgramamountsare

that can be dissolved in 100

provided, but in other cases the description will be more vague, using terms such as soluble, insoluble, or slightly soluble.

SoNentabbre~acions acet =acetone bz = benzene

Cha 4for Han toow Fin Da Co H C

47
=
water

chI =
aq

alc = ethanol
eth = ether acecic acid
HOAc=

Solubility characteriscics i = insoluble s = soluble sls = slighrly soluble vs = very soluble misc = miscible

Examples of sample handbook entries for isopentyl alcohol (3-methyl-l-butanol) and isopentyl acetate are shown in Table 4.4.
THEMERCKINDEX

The Merck Index is a very useful book because it has addicional informacion
intheothertwohandbooks.Thishandbook,however,tendstoemphasizemedicinally

chloroform

not found it also lists listed in

related compounds,
manyothercommonorganiccompounds.Itisnotre~sedeachyear;newedicionsare

such as drugs and biological

compounds,

although

published
Lange'sHandbookortheeReHandbook.However,forthecompoundslisted,itpro-~desawealthofusefulinformacion.Thehandbookwillpro~deyouwithsomeorall

in 5 or 6 year cycles. It does not contain all of the compounds

of the following Merck

Name,

data for each entry. this changes

synonyms

number;
including

each rime a new edicion

and stereochemical

is issued

designacion

Molecular Molecular Percentages

Uses

formula weight

and structure

of each of the elements

in the compound

Source and synthesis, including references Opcical rotacion for chiral molecules Density, boiling point, and melcing point
Solubility
Pharmacology

to the primary literature

characteriscics,
informacion

including

crystalline

form

Toxicity data One of the problems with looking up a compound

decidethenameunderwhichthecompoundwillbelisted.Forexample,isopentylal-

in this handbook
alcohol.

is trying to

cohol
cionofthehandbookitislistedunderthenameisopentylalcohol(#5212)onpage886.Findingisopentylacetateisevenamorechallengingtask.Itislocatedinthehandbookunderthenameisoamylacetate(#5125)onpage876.Often,itiseasierto

can also be named

as 3-methyl-l-butanol

or isoamyl

In the 12th edi-

look up the name in the name index or to find it in the formula

index.

i80

Table 4Aasch Proper ofAce 3-Me andet Isop List inH Lan Ha
.j:Oo

co

mISS

3-methyl-

(CH3)2CHCH2CH2OH

88.15

1,392

0.81291\
0.876154

1.408515
1.400720

-117.2

132.0

45

2 aq; mise ale, bz,

I-butanol

'" (t '" ;:I 0.'"

Q E} ~

0 '" (')

Isopentyl acetate

CH3COOCH2CH2CH(CH3)2 130.19

2,132

-78.5

142.0

80

0.25 aq; mise ale, eth

'" (') '" (t

i>1 (')

..0 = (1)
'" S'
(1)

0 .... oq

'" 2. (')

n ::r
(1)

8. vo
~

'" c::r 0 .... '" 8 -<

t""

(') ....

synonyms. When looking up a compound in one of the indexes, ber that the numbers provided are compound numbers, rather
Thereisalsoaveryusefulsectiononorganicnamereactionsthatincludesreferences

to

the

The Aldrich Handbook is actually a catalog of chemicals sold by the Aldrich Chemical Company. They include in their catalog a large body of useful data on each compound that they selL Because the catalog is reissued each year at no cost to the user, you
shouldbeabletofindanoldcopywhenthenewoneisissued.Asyouaremainlyin-

Cha 4for Han toow Fin Da Co Ha C 4 ALD HAN OF FIN CH

I

ThehandbookhassomeusefulappendicesthatincludetheCASregistrynum-bers,abiologicalactivityindex,aformulaindex,andanameindexthatalsoincludes

you need to rememthan page numbers.

primary

literature.

terested in the data on a particular compound and not the price, an old volume is perfectly fine. Isopentyl alcohol is listed as 3-methyl-l-butanol and isopentyl acetate is
listedasisoamylacetateintheAldrichcatalog.Thefollowingincludessomeofthe

properties Aldrich
Name:AldrichusesamixtureofcommonandIUPACnames.Ittakesabitoftime

and information Catalog number

they list for individual

compounds.

to master their names. Fortunately, they do a good job of cross-referencing compounds. They have a very good molecular formula index.
CASregistrynumber

Structure

Synonym

Formula

weight

Boiling

point/melting

point

Index of refraction Density Beilstein reference Merck reference

InfraredspectrumreferencetotheAldrichLibraryofFT-IRspectraNMRspectrumreferencetotheAldrichLibraryofBCandIHFT-NMRspectra

Literature Toxicity

references to the primary literature

on the uses of the compound

Safety data and precautions Flash point Prices of chemicals

50

Most students
more"intuitive"tousethantheeReHandbook.Youcangodirecdytoacompound

without

substituents.
tainsthosecompoundsthatareeasilyavailablefromacommercialsource.Manycom-

handbooks.
mula,catalognumber,andCASregistrynumber:http://www.sig;ma-aldrich.com/

saws.

STR FOR FIN INF SU PRO

Microscale and Macroscale Techniques in the Organic Chemistry Laboratory

and professors
the

find the Merck Index and Lange's Handbook easier and

according to the parent or base name followed' by its

rearranging

name

Another great source of information

is the Aldrich Handbook, which con-

pounds are found in the Aldrich Handbook that you may never find in any of the other
The Sigma-Aldrich web site allows you to search by name, synonym, for-

nsf/

AldProducts?OpenPrameset

1. Using the Merck Index, find and draw structures

for the following compounds:

(a) (b) (c) (d) (e) (f)

(g)

atropine quinine saccharin benzo[a]pyrene (benzpyrene) itaconic acid adrenosterone

acid

chrysanthemic

(chrysanthemumic

acid)

(h) cholesterol
(i)vitaminC(ascorbicacid)2.FindthemeltingpointsforthefollowingcompoundsintheeReHandbook,Lange's

Handbook, or the Aldrich Handbook: (a) biphenyl (b) 4-bromobenzoic acid (c) 3-nitrophenol 3. Find the boiling point for each compound in the references listed in Problem 2: (a) octanoic acid at reduced pressure (b) 4-chloroacetophenone at atmosphere and reduced pressure (c) 2-methyl-2-heptanol
4.FindtheindexofrefractionnDanddensityfortheliquidslistedinProblem3.

5. Using the Aldrich Handbook, report the specific rotations camphor.

6.ReadthesectiononcarbontetrachlorideintheMerckIndexandlistsomeofthe

for the enantiomers

of

health

hazards

for this compound.