MicroscaleandMacroscale

Techniques in the OrganicLab oratory

DonaldL.Pavia

GaryM.Lampman

George S. Kriz

Western Washington University

Bellingham, Washington

RandallG.Engel

North Seattle Community College

Seattle, Washington

THOMSON

*BROOKS/COLEAustralia. Canada. Mexico. Singapore. Spain

United Kingdom. United States

CHAPTER4HowtoFindDataforCompounds:

Handbooks and Catalogs

The best way to find information quickly on organic compounds is to consult a hand-book.Inthischapter,wewilldiscusstheuseoftheCRCHandbookofChemistryandPhysics,Lange'sHandbookofChemistry,theMerckIndex,andtheAldrichHandbookofFine Chemicals. Complete citations to these handbooks are provided in Chapter 30.Depending on the type of handbook consulted, the following information may befound:

Nameandcommonsynonyms

Formula

Molecular weight

Boiling point for a liquid or melting point for a solidBeilstein reference

Solubility data

DensityRefractive index

Flash point

ChemicalAbstractService(CAS)registrynumber

Toxicity data

Uses and synthesis

CRCHANDBOOKOFCHEMISTRYANDPHYSICS

This is the handbook that is most often consulted for data on organic compounds. Al-

though a new edition of the handbook is published each year, the changes that aremadeareoftenminor.Anoldercopyofthehandbookwilloftensufficeformostpur-poses.Inadditiontotheextensivetablesofpropertiesoforganiccompounds,theCRC

Handbook includes sections on nomenclature and ring structures, an index of syn-

onyms, and an index of molecular formulas.The nomenclature used in this book most closely follows the Chemical Abstracts

system of naming organic compounds. This system differs, but only slightly, from

42

44 Microscale and Macroscale Techniques in the Organic Chemistry Laboratory

CASRN

Den!gcm-3Chemical Abstract Service Registty Number. This number

is very useful for locating additional information on the

compound in the primary chemical literature (see Chapter30, Section 30.11).

Melting point of the compound in degrees Celsius.

BoilingpointofthecompoundindegreesCelsius.Anumber

without a superscript indicates that the recorded boiling pointwasobtainedat760mmHgpressure(atmosphericpressure).Anumberwithasuperscriptindicatesthattheboilingpointwasobtainedatreducedpressure.Forexample,anenttyof

234; 12216 would indicate that the compound boils at 234°C

at760mmHgand122°Cat16mmHgpressure.Densityofaliquid.AsuperscriptindicatesthetemperatureindegreesCelsiusatwhichthedensitywasobtained.

Refractive index determined at a wavelength of 589 urn, the

yellowlineinasodiumlamp(Dline).Asuperscriptindi-

cates the temperature at which the refractive index was ob-tained (see Chapter 24).

Solubility classification Solvent abbreviations1 = insoluble ace = acetone

2 =slightly soluble bz =benzene3 =soluble chI =chloroform4 =verysolubleEtOH=ethanol5 = miscible eth = ether6 = decomposes hx = hexane

Beilsteinreference.Anenttyof4-02-00-00157wouldindi-

cate that the compound is found in the 4th supplement in

Volume 2, with no subvolume, on page 157 (see Chapter 30,Section 30.10 for details on the use of Beilstein).

MerckIndexnumberinthe11theditionofthehandbook.

These numbers change each time a new edition of the MerckIndex is issued.

mp/OC

bp/oC

nD

Solubility

Beil. ref.

Merck No.

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

LANGE'SHANDBOOKOFCHEMISTRYThishandbooktendsnottobeasavailableastheeReHandbook,butithassomein-

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

'"Chapter4HowtoFindDataforCompounds:HandbooksandCatalogs45Table4.2PropertiesofisopentylalcoholandisopentylacetateaslistedintheCRC

Handbook

noticeable difference is in how compounds are named. For many compounds, the sys-

tem 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 oftenusescommonnamesthatarebecomingobsolete.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

Name

Formula

This is an identification number for the compound.

See examples in Table 4.3.

Structures are drawn out. If they are complicated, then thestructures are shown at the bottom of the page.

Molecular weight of the compound.Formula weightTable4.3ExamplesofNamesofCompoundsinLange~HandbookNameofOrganicCompoundl-Chloropentane

1,4- Dichlorobenzene4-ChlorotolueneEthanoic acid

tert-Butyl acetate (ethanoate)

Ethyl propanoateIsopentyl alcoholIsopentyl acetate (banana oil)Salicylic acidAcetylsalicyclic acid (aspirin)

Location in Lange's Handbook

l-Chloropentane1,4-Dichlorobenzene4-ChlorotolueneAcetic acid

tert-Butyl acetate

Ethyl propionate3-Methyl-l-butanol

Isopentyl acetate2-Hydroxybenzoic acidAcetylsalicylic acid

3627 I-Butanol, C5H120 123-51-3 5081 4-01-00-01677 ace 4; eth 4;

3-methyl EtOH4

Isopentyl alcohol 88.15 -117.2 131.1 0.810420 1.4053203631 I-Butanol, C7H1402 123-92-2 4993 4-02-00-00157Hp2;EtOH5;

3-methyl,acetate eth 5; ace 3Isopentyl acetate 130.19 -78.5 142.5 0.87615 1.400020

46 Microscale and Macroscale Techniques in the Organic Chemistry Laboratory

Beilstein reference

Density

Refractive index

Melting point

Boiling point

Flash point

Solubility in 100parts solvent

Anentryof2,132wouldindicatethatthecompoundisfoundinVolume2oftheMainWorkonpage132.Anentryof32,

188 would indicate that the compound is found in Volume 3of the second supplement on page 188 (see Chapter 30, Sec-tion 30.10 for details on the use of Beilstein).

Densityisusuallyexpressedinunitsofg/mLorg/cm3.Asu-perscriptindicatesthetemperatureatwhichthedensitywas

measured. If the density is also subscripted, usually 4°, it indi-cates that the density was measured at a certain temperaturerelative to water at its maximum density, 4°c. Most of thetime you can simply ignore the subscripts and superscripts.

Asuperscriptindicatesthetemperatureatwhichtherefrac-tiveindexwasdetermined(seeChapter24).

Melting point of the compound in degrees Celsius. When a

"d" or "dec" appears with the melting point, it indicates thatthe compound decomposes at the melting point. When de-composition occurs, you will often observe a change in colorof the solid.

BoilingpointofthecompoundindegreesCelsius.Anumber

without a superscript indicates that the recorded boilingpointwasobtainedat760mmHgpressure(atmosphericpressure).Anumberwithasuperscriptindicatesthattheboil-ingpointwasobtainedatreducedpressure.Forexample,an

entry of 10211 nun would indicate that the compound boils at

102°Cat11mmHgpressure.

This number is the temperature in degrees Celsius at which

the compound will ignite when heated in air and a spark is in-troduced into the vapor. There are a number of differentmethods that are used to measure this value, so this numbervaries considerably. It gives a crude indication of flammabil-

ity.Youmayneedthisinformationwhenheatingasubstance

with a hot plate. Hot plates can be a serious source of troublebecause of the sparking action that can occur with switchesand thermostats used in hot plates.

Parts by weight of a compound that can be dissolved in 100partsbyweightofsolventatroomtemperature.Insomecases,thevaluesgivenareexpressedastheweightingramsthatcanbedissolvedin100mLofsolvent.Thishandbookisnotcon-sistentindescribingsolubility.Sometimesgramamountsare

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

Chapter4HowtoFindDataforCompounds:HandbooksandCatalogs47

SoNentabbre~acionsacet=acetonebz = benzenechI = chloroformaq = wateralc =ethanoleth = ether

HOAc= acecic acid

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

Solubility characteriscicsi = insolubles = soluble

sls = slighrly solublevs = very solublemisc = miscible

THEMERCKINDEX

The Merck Index is a very useful book because it has addicional informacion not foundintheothertwohandbooks.Thishandbook,however,tendstoemphasizemedicinally

related compounds, such as drugs and biological compounds, although it also listsmanyothercommonorganiccompounds.Itisnotre~sedeachyear;newedicionsare

published in 5 or 6 year cycles. It does not contain all of the compounds listed inLange'sHandbookortheeReHandbook.However,forthecompoundslisted,itpro-~desawealthofusefulinformacion.Thehandbookwillpro~deyouwithsomeorall

of the following data for each entry.

Merck number; this changes each rime a new edicion is issued

Name, including synonyms and stereochemical designacion

Molecular formula and structure

Molecular weight

Percentages of each of the elements in the compound

Uses

Source and synthesis, including references to the primary literature

Opcical rotacion for chiral molecules

Density, boiling point, and melcing point

Solubility characteriscics, including crystalline form

Pharmacology informacion

Toxicity data

One of the problems with looking up a compound in this handbook is trying todecidethenameunderwhichthecompoundwillbelisted.Forexample,isopentylal-

cohol can also be named as 3-methyl-l-butanol or isoamyl alcohol. In the 12th edi-

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

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

Table4APropertiesof3-Methyl-l-butanolandIsopentylAcetateasListedinLange'sHandbookmISS 3-methyl- (CH3)2CHCH2CH2OH 88.15

I-butanol

i80 Isopentyl CH3COOCH2CH2CH(CH3)2 130.19acetate

1,392 -117.2 2 aq; mise ale, bz,chi,eth,HOAe0.25 aq; mise ale,

eth

0.81291\ 1.408515 132.0 45

2,132 0.876154 1.400720 -78.5 142.0 80

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IChapter4HowtoFindDataforCompounds:HandbooksandCatalogs49ThehandbookhassomeusefulappendicesthatincludetheCASregistrynum-bers,abiologicalactivityindex,aformulaindex,andanameindexthatalsoincludes

synonyms. When looking up a compound in one of the indexes, you need to remem-

ber that the numbers provided are compound numbers, rather than page numbers.Thereisalsoaveryusefulsectiononorganicnamereactionsthatincludesreferences

to the primary literature.ALDRICHHANDBOOKOFFINECHEMICALSThe Aldrich Handbook is actually a catalog of chemicals sold by the Aldrich ChemicalCompany. They include in their catalog a large body of useful data on each compoundthat they selL Because the catalog is reissued each year at no cost to the user, youshouldbeabletofindanoldcopywhenthenewoneisissued.Asyouaremainlyin-

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

listedasisoamylacetateintheAldrichcatalog.Thefollowingincludessomeofthe

properties and information they list for individual compounds.

Aldrich Catalog number

Name:AldrichusesamixtureofcommonandIUPACnames.Ittakesabitoftime

to master their names. Fortunately, they do a good job of cross-referencingcompounds. 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 references to the primary literature on the uses of the compound

Toxicity

Safety data and precautions

Flash pointPrices of chemicals

50 Microscale and Macroscale Techniques in the Organic Chemistry LaboratorySTRATEGYFORFINDINGINFORMATION:SUMMARYMost students and professors find the Merck Index and Lange's Handbook easier and

more"intuitive"tousethantheeReHandbook.Youcangodirecdytoacompound

without rearranging the name according to the parent or base name followed' by its

substituents. Another great source of information is the Aldrich Handbook, which con-tainsthosecompoundsthatareeasilyavailablefromacommercialsource.Manycom-

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

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

saws. nsf/ AldProducts?OpenPramesetPROBLEMS1. Using the Merck Index, find and draw structures for the following compounds:

(a) atropine(b) quinine(c) saccharin(d) benzo[a]pyrene (benzpyrene)(e) itaconic acid(f) adrenosterone(g) chrysanthemic acid (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 for the enantiomers ofcamphor.

6.ReadthesectiononcarbontetrachlorideintheMerckIndexandlistsomeofthe

health hazards for this compound.