A guide for the perplexed organic experimentalist
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A Guide for the
Perplexed
Organic Experimentalist
Second Edition
JOHN WILEY & SONS
Chich~st e,
New YO<~
Bri1bane
SALLE + SAUERLANOER
AHa u Fr1nkfun a m Maln Salzburg
SingaPOre
Vi,,i
Vnla1 .S.01>ô11n<!ttAG,A>" ã
NQ,..,1ofthi1bool<n>a1 bcr
L<><~Ã,n,hal, H.J . E
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J.
Typ,:1« ln\Oonll
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Contents*
I
On Surohln1 lhf Lllfrl.!Ut. Th• lmpoMIRI
SourttJ. U1ln1 You Hn d
? On SHrchin1 th• Uttrlture-U,fn1 th• Compu1u
(and VourHnd)to RttritvoSU\lctur<1,
Rdorenon, Ruot101111nd UoH Onlln•
3 B,skSofot)' RulH
4 Runnln1Sm1.ll-Kal, Rea
L•bo ro tory
•.-i1 ,t.aptn ,.
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8 On S"'ãIIÃã<ã~ rn, m1 ot100
9 g:.:;~~r<>&rulloo-Tltt CindrôU. of lhr 0<1nk
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Preface to First Edition
The perplexed o•aanic cxpcrjmcntalill i,in mynpcriencethc
be1innina;,tt<:arCh$tudcnt and(frcquemly)1hepo11-doct0Hl
rc,earch worker. Hci s !heoncwhocarlyon discovcntha! he
hasro11andonhiso•1 n tl'o'Ofttt,in1hcta1kof1urchin1for
informaiiononhis subjec1andi n a!lthc prac1ical asJ)«lsof his
,..o,k-andthat meansnmonlyhowtor11n a rcactionb111 al,o
howtochooscandacq11ircthc tooblndma1erial1ofhist radc
Alltoooftcnit isnotbychoiccrhat hefindshim!
researcher. But in the majority of ca.« he has Ions since
abandoncdthclaboratorybenchandis nov.·busywithadminil·
1ra1ion,withwricin1andrdcroein11rcscar-hgran11pplication,
and ocicmiftc papcu, and with tcachin& and 1hinki11i, In the
proceuhewillhavefor1101tenmostor1hcprac1icalknowled&•
whichhehadtoacquirepainfollyinhisowndayandwillhavc
~omeunawareoflaterde,·elopmcnn
Thea,erqe&raduateSludentisill-preparedfor >
him to think for him>
wi1h,cn, itivcrcqenn1ndundcrd ryand anacrobiccondition,.
Nonc,1nfar as ! know,doanythi11ito auiitliim(orhiiiupcr•iror)101rapple wi1h indi tferon< Jupplieu, manuflcturer, and
admi niftratou.
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This,malll>ookanemp1s1ofillsomeo f1heaap;1,onthebll,i,
1hal orpnic chemistry i• an experimental science ~m and
foremos1, and 1ha1 in the &nal ana!ysis-wi!h aU of modern
insm,mentHion and computedsil!ion-it ii 1he organic
chemist' s bnin andown1wohand,1hat are and ,..iJ!,emain
indispensable . Hence there is linlc on inst rumental
s~trosco pkand a nal)'1ical1 echnique,andotherspecialfiel d,,
whichare qui1e adcquatelydea.ltwith elJCwhcre. Thcimpor1am
matterof,afetyis, with r
Workersincertain areassuchucarbohydratesorpeptidesmay
~nd comparati"
book. J shall be happy if their mis1ivings willinducc 1hem a ll
to write asimilarl>ook oftheiro,.·n
l a m indebtedtomanyfriends andcollea1uesforconmucti,e
advkeandcri1ici1m, andabo,·calltoProfessorR.A. Raphael,
F. R.S. (Unisersity of Cambridge), forhi1enroura1cmen1 a nd
11«athelp,and10 Professor O.J e1er (SwissFederallnS1itu!eof
Zu,ich) whoMe hospit ali!~ enabled me to CC! started
~:~h~t!!~i:
Haifa,
Januaryl978
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Preface to Second Edition
This«lition was writt en forthrttiood,e ..onl . The fim v.·a,
thatthech.allenaeexpr<sscdin11>cla
lamentable fact !hat in the 11 years sin« the apl)<'arance of
the ~rst edition there has b«n little if any pros.re" in traini!IJ
the synthctk orpnk chemist in two essentials, findin1 the info,.
mationhe reallynccd1,andu1in1hi1owntwohandsindoi111
what distinaui,hcs chemimy from 1he 01hcr 1drncts, viz
crcatinathcobj«tsofilio"·nstudy. Thethirdreasonwasthc
succcs,or1hefimedition.a ndthcpublishc,'1sugaestion10
v,riteanotheroM
Much of 1hc added material, and al,o some omissions,
based on commcnu on the first edition, moH or whkh were
favounb!e . A few quaint excep!ions: the chemi1t, actina u
watchdog(orshouldoncsaywatchbitch7)forafcminil(organi.. tion, who succeedo
dispensin& wi1h a condenser in small-s.tale distilla1ion and
in1teadcoolin5with analcohol-soa kedswabofcottonwoolled
toinebtiation anddemoralisa1ion in the laboratory.
h i, a 1reat pleasure 10 thank Dr E. Zall (Laboratory or
Or&anic Chemistry, ETH, Zurkh) for the en1husium and , r... t
1bilitywi1hwhichhe1ackled1he sisyphuntukofwri1ingabout
use of the Compute, in Information Retri<'Val. l am a!ro
indebted lo Dr J. Schrcibu (ETH, Zurich) for a numbtr of
=
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expercly drawn mum11ion,. Finally. I wish to up,us my
sincere 1hanh to Prof. A. E
hospit11i1y,andoneeapint0Prof.R. A.Raphae!(Univm i1y
of Cambridge. UK) ro, fruitfuldiscun ions.
Ha;J<1.
OctaMrl989
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On Searching the Literature.
The Important Sources .
Using Your Head
Thisctiap1ercomesfostb«ause1huiswhe,eitou5htlobe.l'llo
seriousprogrammeof...,,earch, chemicaloro1herwioc, i,cver
embarkedup0nbefo,ea1horoughiovcsti&a1ionofthecurrent
st1teofknow!ed1eofthe,ubjecthasbeenundenaken.l nshon,
looki11Jforinforma1ioni, 1he,·ery fimthin11,you,1hebqinnini
researcher, will be called upon 10 do in 1he val\ majority o f
cucs, whe!htT In an academic institution or in induscry; and
moreoften,hannotyouwillbecomplotel)·unpreparedforthal
lllk.
Thedecade1h.athaspa.s sedsinccthefimedi1ionof1hi, book
appearedha,see n a nunprecedenttduplosionoftheamountof
informat ionpubli1hedin0111;inicchemistry and adjacen1field,.
l'onunately, ai the same time there has been an impressive
dcvelopmentofcomputer-aidedmeansformriovingthat infor·
m11ion. Unfonunately.ontheother hand. itit jutlthiswhich
may dtludeyou intolhinkin11ha1 from now on the com puter
1: ~.~~ur v,·ork ..archinJ the literature. There you would
:1~;
Chapi
muns all. imp0nan1 rourcu. and aoin1 back only for a limi1cd
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l
AO\!IDEFORTHEPERPLEXEDOIIOAr
ixriodorcimea1thin11,11andatprescn1. Ho,.,e,1er, yourmosc
impor1an1computerbyf1Ui1 11>eoneatthetopofyourspine,
andagaim1cha!, as you should constantly keepinmind,the
entire ftamev.·ork or modem information retrieval is no more
thanawillingbutl\upidhorsethatwiUdothedonkey"·ork-if
you will pardon the expr,.,ion. And that hor
a,ve,yexpensive.
The fo!lowini; sections are meant 10 aive you a purpos•oriemed brief overview of a numher of the imponant currently
available 1ource1 of inform ation, irrnpcctiveofwhether the}·
happen tohe 'online' at thetimeofwritina;ornot, and then,
by a series o f concrete exampltt, how to achieve the goal of
gettin111hefullestinformationbyanime11ra1ed effonin,·olvin1
their combined use
SOME GENERAL RULES FOR SEARCHING THE
LITERATURE
A numher of ex~llent books on Lhe chemical li1era1ure have
apixarcdinrecentyears, 1-ã andifyouwanttospecialiseinthis
fieldoratln,tfcelthe urgeforsomereasonorothertoacquire
adetailô1and sys1ematicuperti,einit,}Ãou areindcedadvised
to bôome well acquainted with one or 1wo of th<'Se. Ho,.·eve,,
foryoua1 ancxpcrimcntalin,thati,n011olikelytobe1hccas,;
Herewe,hou ldl)(rhaps1tartwith 1 few&ene,a!ruleswhich
will help you in tl,e ,careh for information. The ~ner points
which are detcribed in 11,reatcr decail in the book, mentioned
above you will most likclypickupa,you 11oalo!lll
Th e fim i• the ru~ of Rttrosf)«tivity, or in other word,, ltffl
from the p,=nt and work backward, in time. Of cours,;, this
may mean ac1in11 a11ain11 in11r1ined habits and commonly
acqui,cdbehaviouralpaltern1(infactjus1 as inlc1rni!lllhow10
ski for the first time!), but ii ha1asolid lo11ical basis hcrc. ln
o•cr9S ~ ofallcasnyouarcn01thc~mtolookforthatspecific item of information . Someone was lhett before you, and
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he in 1urn will have discovered othcrs who wero there before
him. So why not bend\ from the labour, of your most immcdiate predecei,or, to be1in wi1h? lnconcrctctcrm,this meant
lookina &rn at th< lo1cs1 availablc 1bmac1, indeJr. the molt
rec<:ntlyavail able cditionofacollectivewo,k,uchu!kil,1rin's
Handbucl, drr Organi.J<:hcn Chemie (usually «fcrred to simply
u Btilsuin) {with which you wiU soon become acquainted) and
the most rcccntlypublishcdre•icwormono1raph
Thcs=ndrulc is:Kttpyour eyc,oprn,brow,e. ondno/t
down. You will soo n discover thl! in formation which in the
lon1runwill1urnou1tobemuchmorcuscfulwillturn upby
1hewayside1ather1ha.n 1ttheori1inalde,;tination. Many(pe1h.i)"mrut)import1ntlineiofrescarchande,·enimpo11an1discoverieihave1lanedinthi1 way.Butltwill allbeprettyuscln•
without your having a pen or pencil and some pie<:cofpapcr
(cvcnabustkkttorsalcsslipwilldo),to...,,i,ri1do"'nimmtdiou/y.Thc1ystcmaticfilin11nd110rageof1hcincidcn1alinformalion you have thus picktd up can and ,hould come
aflc,wards. and more on that point later.
Thcthirdroleis10Kno-.,ond0Uowsptt1.Nc,·errcstassured
that, havi ng arri,·cd at the desired information. your work i,
done. Keep in mind the followin1 ponibi\ities: (1) it may be
inaccurH<,\b)it m1ybeincomplcteal>d(<)i1 maybe slanted.
no1tosaymi1lc1ding.Pos1 ibili1y(a)is~Jdomdcliberate. More
likely it is the re,ult of sloppine,s or the lack of mean, , or
bolhoftheH. Forobsiou, reason,,thcfonhcryou11obackin
time the more likely you wil! encoumcr it. All the ,!,a.me, it i,
remark able how reproducible work lasl done in 1he non inmumemation aae can !urn out to be (1hhough it round,
ridkulom, one
bility (bl is Mmctim« dclibuate but more frequently due to
ne1le<:1.e.1,i nno11oing farenouahin1ryi111ou1difrerem
reaction conditions. Muchofyou,ownsoo:esswilldcpcndon
making up for that. Possibilicy (c) is deliberate by de~nition
S
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truth, One example mi1h1 be the selective citation or non·
cimion of the work ofothe,s. ano1her 'for1enin1' to ,t ate
whether the yieldquotcdi,ofi1ola1cdmaterialor 'byGLC'
SEARCHING FOR A COMPOUND, ITS SYNTHES IS ANO
PROPERTIES
The mo,t frequent object of a litera1urc search is to find out
whetheracertaincompo und i,known , how it is belt prepared
and what i11propertiu areorappeartobe. Here in particular
you will end up at a point that will indicate where your own
work should start off.
Instead of &ivin1 sy1temaiic survey1, tables, i cheme, , etc ..
which •nalyse the most imponam rourc,:, and which you will
find in most ofthc cxcxllcnt booksdtcd abo,·c, lhc fol1owin1
will bridy describe thne rourcu and the mos1 important prob·
lem , andadvamagcs u soei~,cdwilh them, lllld lea,·cthere,1 to
1heExamplC$ at theendofthechapter
Thisisand remainstheuniguelyindi,pen,able ,ourcoofreccnt
informationforthisda5'ofscarch objcct.perhapsles,,ofor
others. 'Recem'hercmeans',incctheappearanceofthc!alClt
relcvantvolumc ofHri/Jrcin' (.«below)-assumingyourinsti·
tutiono,placeofworkcan,tillalford to,ub,cribetolhelauer.
Ili,tobehopedthatyou r libraryha, a ,cction .. ta,ide rolely
re,en·cd for CMmical A b,m1c1S and i1 1 perusal, which generally
involvo,comultin&andmovin& around,...·oralhoavyvolumcs
,imultanoou,Jy. lllld that under no circumsta ncei will any
,0Jumo o•er loa,othat area cxcoptfor bindin1-no1ovcn for
photoeopyin1.1owhich1hcrci1 not much point anyway
The mo5t important pan, are the lndexe1: the Colltt:tiãr
fnde:ôsinsofarutheyha,eappearcd andth o ,omiÃannual one,
ifno1.Bcforo l9i11herowa,onlyono!xnr,al/ndrr.,inco thon
1hi1 hasb«nsubdividcdintoth0Chemica/Sulman~/ndrx and
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cho Gtrtt "1/Subjtt1/ndu. Tho 1woo!herimpor1ant oncsa,e
1heFormwlalndtx andtheAw1horlndrx. Wi1h1he apl)<'a ranco
andbindinaofoach newCol/«1ivr /ndtxallthoprecodingttmi·
annualone1c11ns.afelybeconsigned1ooblivione,.,.,ptl)<'rhaps
tho Author Inda-there may alway, be cho time when you will
belooki111for,om<1hingpubli,hodby,o.and-1oin1heycarX.
Thero are four main problems encountered by tho \>eainnin11
reiearcher, thosoofnomondature. ofovoluatin11thoen1ry,of
ovaluatinathe abs1rac1i1i
sou rctrtferrodto.
Herecho aoldon rule is ~o,rguordal/1ht 1imt.1fyouthink
tha1 JUPAC nomenclature is now universally accepcod. you are
mi1takon; Chtmica/ Abs1racu form a link uni,·eri< of thdr
own. Of oouri<. the tver-incmuinc UK of computer ttarching
andprintingprovidesagoodrea,on(no11 0,ayexcui<),but
Chemical Abstracrs do has·e 1omc quirks whkh do not fit even
that kind or rationale. And what complicates matters most is
thowaytheyhavei nthe pastchanaodt hoirmind,evorycouplo
ofyoan.lfthercisoneindisl)<'l\1ableadvicetoaivo,;1 i1thi,:
use the lnd~x Guide~on$tantly. It i, tho one inst rumen! that will
1uidc you throu11h the many confusion,, incon,iotende, and
in,ongruitiosyou ..·moncoumer
The'oasy'wayou1of1he nomencl atu reprodieamontu,ually
chos,nbybeginncrsis1olook upth0Formula/ndtx.Tfyonarc
lucky youwillhavcsomethinali ko20-)0i,omenwiththcaame
empirical formula 10 ,hoott from and d«ide on one whott
name loob reasonably like that of the ,ompound you uo
lookin1for. lfnot,youwillbavoov,:r IOOtomu!lov«. Probably you will soon come 10 the tondu$ion that one might u ,,,o11
faccthonomenclatu,ep,oblcmhead-ontol!artwith.
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Ev1/u11ingrh11Enr,y
Thi> b wh«e you can save a lot of time by u, 101 your power,
ofdeductlon andocca,ionallyinmicion.Here oneface,thefact
that hundrtd> of people are involved in pr~parina Chtmlc,,I
Absm,cr, and that human na1ure and 1ubjectivi11· play thei r
part. However, 1here have Men con,iderable improve,nents in
recent)'Url . For example. 'preparation of ... · now does refer
to where a compound wa, indtcd prepared, quoci111 e,pcrimental delails; previously in many CI J
Entries such as 'caI<.inogcnk acti•ity of .. . .". or 'in l["apc
frui10tt
not likely to turn upin Clltrie, referrin1to ' Raman 1p('ctrum
of...',buttheymightbcJi venor atlcasttherelevantliterature
cited. in entries referrin1 to 'magnetic susceptibility o f .. .'
Entries suc h as "oxidationof ... ', 'rcactionwithtribu1yltin
hydride' or 'N·prot ectionofpcptide end 1roup,with .. .' were
once au fet>etthatthcrourceinqucstionwoulddescribcorat
lea,tcite thecompound'ssynthesis: nowadays inalllikrlihood
you will find 11 but that tM compound w11 obtained from !he
Y.Z . Company and used as rô
lndex i, not lil:clytobe informati•c.
~;: ~a
ting tha Abstra~r and rha Journal /or othfr soorca)
lnthi1sec1ion,jcurnalsare m0$tlyrefcrredtoby thcircommon
Cf>emia,/Absrracrsabbreviai;ons asthi1 is the form in which
aiuwcr51os,arche,ue obtained. lnthcJoodoldday,,an
abmact , callywasanab1t ra1;1 and pve enou1hde1ailto J
shu ntin1 poin1enrou1e1otheori1inalpublica1ion.Evaluation
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;, 1hu1 rcduccd 1odeddinJ which journal to look at ~m and
which1olook Hat all. Jfithappenstobc inyourownlibrary
the,ei, no problem . lf l>OI , a, bappen,mort and morc1heff'
day,,1hequestion ari
Cdlt rosikl. S
know1helangua1e: and knowi nssomronewhod~sand!hen
orde,in11copyi,no1 1lway1a,olu1ion . Therearefewuperienctsasfrumatin1.ur rying1ot ransla!t anarticlein Yakugah
ZalSlriwith 1he help of• Japanese Ucture, in Social
Economics. WiihRnuianjournals, howe,·er,animponambul
, til!notwidelyknown fact is that a numbcrare now avlilable
in EIIJ,lish translation, such as J. C.,n . Clrtm. USSR (Zh
0/Jshch . Khim.) and J. Orr. Chem. USSR (Zlr. Ort . Khim .)
An imponam poi nt to ascertain iswhotherthojonrnal i,in
the formofacommunicaiion, andif,o, in which journal. In
Angrw. Chtm. (includinJ the International Edition in Entlislr),
Cht m. Commun . or Chimja yon are not likel y 10 find much
upetimental det ail. There i1 more chance of that if ii ii in
Tt tralrtdron Lm .• J. Ort. Chem. or J. Am. Chem. Soc. As far
u tholatteri1conce,ncd,yonwillsoon~nd1hatcenain aut hors
pubhshnothin1butcommunication1andonlyecryrare!y1full
paper. Here 1he prospect of ever ge!t inJ fuller information is
not bri1h1 unless the Senior Author is wilting to se nd ii to you
aflcr writing to him penona!ly (and when )'OU wrile, do no!
for1tt lo chtckwher hertherth11 b«n ac hangeofad dre11from
that Jiven in 1he paper, !est you commil the unpardoMble
offence of not knowin1that he/ shehas moecdtoamorepres·
ti1io us in!l itution or posi1ion). And now even "'ith full papers
theô are more and more aunãa1in1 instances where expe,.
imenta! detail will b< sc,nt 10 you "' '1 npplememary material'
on!yaf1eryouhave ff'ntachô1uãfor a trininJ •um, forwhkh
the bank maychar1e you morttoproc
i, not mktly in the or1anic chomimy field need not deter yon
Someofthebcstandmostdetailedinformationcanturnup in
Journal1 such a1 Agrk. Biol. CMm .. Plry1ochtmi11ry J nd J
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Or1a~omn Chem. , which cover adj1cen1 field• in which 1he
m1.jorityof au1hor1 sta rted off as oraanic chemisll, ind it is
onlyna1uralforthem to1ry anddemonStra,etha11heyhavenot
los,:.~:• i~;:u: h r:~d : : : ~ : , oo v.·l>ere 1he abstract i1 of a
patent. This is a real problem when you are nowhere near a
Pa ten! Library and where the abstract ai,·es no worthwh ile
detail. By and Jara• it is dc~nitcly advisable to order a copy by
airmail or ifpessible Tele, or Fa.. assuming you have made
sure1ha11heinformationinqu..1ionh u notb«npublishedin
a rca u!ar form, which do.. happen. T urnina up one' , no,c
a utomatica llya1 a patenti1 notjust i6ed;tbis authorcanr«:all
anumberofcue,inhis experience"·herein1hepreparationof
atrickykindofcomp0und,followina a pa1em a ndno1apaper
ina',eputable'journalledtosuccess.Moreovcr,inmanyfield,
of commerdal importance only patcnU ue published and you
then have no alt ernative . Ho,.·ever, remember the bottom Line
inconnectionwithpatents: thcy arewrinenby people whohrst
and forcmo5t arc lawye,.and not scicmim and who,c prime
objecth'eisnot publicationofknow!cdae fo, itsown sa ke(or
even 1hc sake of their own ?C•sonal advancement), but pur
away more information than is absolutely neetSHty for 1hat
S.lht.it,':, H• ndbuch "-' 0,y.nl~ch.,, Ch;,mit,
There i, probably no1hin1 to comp.are with 1his work in any
01hcrbra nchofscience andweoraanicchemim u cuniquein
benefain1 from a compendium of its kind . While there arc
incrcasinJ doubt, for many of u1 on how much lon1cr we can
a!Tordi1,wc shou ldmakethe full.,.tp0ssible useofwha11here
is. Thc factthati1iswritteninGerman(up101he founh supple,
mem)is noexcuseat allfornotdoinj;so. There is plenty of
material' written in En11!ilh, includini a alossary of German
words used andtheir<"quivalentinEn,lishllildFrench,to &uide
youinu,in1Bd/sreln, andmos1oti1i,availablefreeonapp!i·
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ON SEARCHING THE LITERATURE. THE l~IPORTANT SO\i~CES
9
To summarise, Btils1dn is organised in,o a<,yt lic (Volume,
l-4), isocydic (carbocydic) {Volumes $-16) and hemocyclic
pans (Volume, 17-27). There once were additional but now
unimportant oolume,. In each oolume !he ori11inal ,·onion
(Hauptwerk, H) ha, l>een complimented by 1ddi1ional series
(Er11intun11,bllndt, El, El!, Em, EIV; from Volume 17
onward, the lauer iwo ore combined); and those fou, Complementary Seri•• arc now comple!e 1oi:e1her v,Ãith ã Formula
/,rdexandS11bjô1/ndex.Theu,o,Ãe,allorsanicoompound1on
whichinformationhadbeenpublished11p1oandindudinglltt
year J9j9 , That year is thu1 1hecu1-ajJdattbetweenBtilstt in
andChemica/Abslr<Klsa,thing1Handa1pre>em,andhen<0on
the wholt ,here is no nttd 10 look for a compound in !he
Cltt mica/Abstracr, Indexes before che Col/tt:/joe fndt xts for
the period 19,7-196!. Thi, is assuming, of course. that the
Hburyrnwhichyouhaoeacces,isfonunateinl>einaup-to-date
inthi stesp«1.Aoewcomp1ehensiveGtneral/ndexforall1he>e
series including the original His presently comin11 out . h ii
probably vory adoisablc to acquire this, even bylib,aries who
have recently gioen up on Brils1ein for &nancial rtuons,
becaustapartfromaivin1 atot1lpicturcofal1thati,knownto
date it wm indicat ewht1heritis v,·orththetroubletosttkout
morefortunatelibrarieswhi
ioformatioohadbtenpublishcduptoandindudini 1919, and
chis i, now in English: however, ,o far this applies only 10
Volumes )7~19 and thu! to hetrrocydes with one or two oxygen
The rule of retro,pectivity applie, aJ,o to Btil.stt jn, Each
,cries refer> back. with every compound, lo the appropriate
page in previous ,cries. An impor1an1 aw,iliary ii the Systtm
Numbfr allotted 10 each compound and iu homologous and
func!ionalmodificuion,. Thi1,:on1jnut1unchOnftdtltrou11tou1
al/serit1 a ndhelpsinloc11ing1l>eappropria1ebook(panicularly in later series whe,euch 'Volume' is spread out over a
numl>erofseparatebookJ).
The areal advantage of compound ,earchina in Btilsttin
ratherthanChtmica/A/Jslro,·/sliesnotonlyinthefac!thacyou
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11n full details-far more c,en than in an old Cht mlrol
Abs1racrsabstract-butthatyouabobenefitfromacri1ical ani·
tudc: not everything reponed is taken for 1ran1ed and later
~:~~!~;~~;~~~:!:~c11~:
~~:::•:::e·~~:t~~:::;::a:;;:sf~~
tu,e. Abo,·eall,&ilsrclni,idealforbrowsing.toanextent
un1hin kable ofin thecascofChemic,,/Abslru~1sand probably
neve rtobeanainableinthefores~ablefutureinanonlinerom
puter search (see Chapter2). Whu is meant hereisexptoitina
the fact that near the compound ,earchedforonewill find in
deri,·ative,a ndhomoloaue,and. ofcour1e, 1heirprop,ertiesand
methods of preparation.
However. to get the most ou1 of Beilsrein. yo~ must know ,he
:;.s:::; e~~ :er::~~
~~~e~h·:~~::;:!~c::::~; ;~d:~:::
add.ortoavoidthefrunrationeausedbythefaelthat a com·
poundsuehu1ucc:inicanhydridei.snowl>erenear,ucc:inicacid
hut will be found in the ,olume marked 'Heie,oeycles, JO,
Mono· and ?olyoxo Compounds'. How ...·cr. the main poinl is
that there is a system and lhal it has remained practically
uncha~ed during then yearsofthework',eJtinencein in
present buk form.
0 1he•. Mino r. Sou,cea of Valu e for Compound Searching
This work, published forthelast lOO)'UUbytheMerekCo .,
limsubsta nces(bothdefinedchemica!comp0und1andothers)
of mainl)· me
substancesarra!IJ«l throuahout by,erial numbtr. lfthecompoundyouhappentobelookingfori, amon11ho,e lOOOOyou
arc in luck bf\,ausc the information i, pre,enled vuy
thorou1hly. What you will see are 1tructure, lUPAC and
alternative name,, 1enerk and commercial brand names,
physicalpropertie>.therapeuticefftct and/or generalu1e,arel·
evan1rtccntliteratureci1ationort"·o.crol5·indexe>also 1ivin1
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the Chomka/ A bstNKts name. a Formula htdu and one of
Organic Namt Rtoclions, vuiou, tables , and incidenially also
with uch rompound its Chtmko/ Afutnuts Registry Numl>cr (a
very important it em for Chaptn 2). All in all. for a one-•olume
workthisi, arulbar,:ain.
Dictionary of Organic Compounds lEd. J. Buckinghtml '
Thi s ,ucce!l
willrefer!Othistooas'l/eilbron',forconvenicnceonly).!tha.,
,o far appeared in ~ve main and four suppkmemary volumes.
Compoundsarc1tilllinedonapurelyalphabeticalba,i1,wi1h
stmcturC$,phy$ical propertie,(indudin1thoseof1impled0
indudctrivial namC$andcompound,ofHill unknov,·n con,ti·
1u1ion)1tenowgivcn a running serial num\>erwhichmal:esit
ca1irrtousrtwoadditionallnduvolumcs:one acrost-inde,of
al1emati,·e name!, the 01her with a molecul ar formula index, a
'hettroa1om'indn(uM'fulwhen,earchin11fora11oupofcom·
poundscontainin11, e.1 .. 1ulphur,goldorarsenic),andal,oa
Ch~mical Abstracts Regimy Number Index (see Chapier 2)
Howe,·er , the basic wukness is and remains the alphabetical
arran11ement(i.e.compound,arenotgroupedundorsomeba,k
mucture), and thus it can by no means take the place of
Chemic,,/ Abslracts or Btilstt in for a thorough comp0und
..arch. Abo, i1 wi111ake 1he experienced user Jes, than five
minutes to find, or rather not find, at lea.i hal f-a-doun
perfectlyordinaryandcommoncomp0und1,hat areno11i1ted
• tall
SEARCHING FOR A METHOD, REACTION. CONCEPT.
PROCESS
Thisi,muohmoredifticultbecau,ethesearchobjec1isbynatutt
lest well defined. If it is • name reaction (e.1. Reformats ki,
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Hell - Volhard- Zelinski), • standard ind well documented
procedure(sil)faiion, hydroacna1ion)ora.cop1edconccp!
(noi11hbo\lringgrouppar1icipation,1ran..,nnularroac1ion),thc
task is rolui,dy simple. !twill become more and more diflicuh
aJ its designation becomes more daboraieand complex (e.1
Michael.typointramolecular addition - cycli,..1ion, au chroma·
toaraphy ofsilylated amino acids, dfc.,t of solvent, on enoli·
,..tion) .
There are two pouible approaches 10 this problem. One is 10
take imo account !ha! most such genonl search obi~• can
beexprened inanum"oetofway1 and tha11he ab1tractor'sor
indexcr'sidu,onthi,willfrequentl)·"oedilferemfromyours.
Much will depend on yourability!opu! your1c!finhi1placc;
anditi1 inanycasca .. Ju1aryandoducationalnerci~fimto
sitdownandwrittanumbcrofvari1tio11$hywhichyourprob·
lem an "oe formulated. But 1his means employin11 your Intellectual p0wer, for more than merely changini the order of
keywords-anyoldcompu1crcando1hat.
The second approach lies in examinina how your problem can
be ,plit into component parts, euminingeach soparaicly and
!hen ,..,ina how !he rosulu can be imograted. For example,
when11udyina thcpoHibilityofgcninaproductBfrom,taning
material A. po"ibly u,i111 • reaction ,uch u Rand a reagent
such as X, one can proceed u follows:
(a) look up ,very knm,·n review on Rand ,co if the Tabular
Suf'·cy show, anythina likeA u ,1artingpoint andlikeB11
result;
(b) look up A in, for example, Btilst~i~ and look up wheiher it
or homologue,orderi,·ati,·tshaveoverbeen subjc.,tedtoa
similarroac1ion(ane,,ampkof'Beils1tin·brow,ing');
(c) look up ll in !he ,ame ,.·ay and ,.., whtther it or ,;milar
oompoundãhavebot-nobtainodinalikcmanner;
(d) look upX in roferenô books de,ottdtorcagcnn and>eo
whtther iu use ha, over been usodued with compound,
such as Aor B
Natu rally, whichever approach you embark on you will be
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cn1aied in much toing and froin11, 1,ying1ouscmblc, tic up
and djsc,nt ang.lc bill of informuion from diffc.-ent sour«cs. A
sc,ucheren11a11edonthiskindof1askeanusuallybcsponedby
1hcglazcdand ye1de1erminedlook inhiseye1andby1hc:"·ay
he foraeu appoin1men11 and rails to , eco11niK even e!Ol'e
friends . Wha1isprac1icallycertaini1 thalin1hi,kindorKarch
in particular he will come acro,s a lo1orunexp,cctcd ond )'Ct
potentially useful information by the wayside, bu11heul1i matc
benefit from lhi,,just asfrom thesea«hfortheinitlalobject
itsc,lf.willde))t'nde nti relyon thcwayinwhich theinformation
is noted down and ul1imately ~led a,.·ay for rmurc rducncc.
He,e 1he rule or mrospeC1ivi1y is p.;mkularly importanc A
workerwhohasin1hepa.s1uK
application ofa p,u ticular concep1, 1hc,e he cannot &
!herefc rceswil!sec lo that.
Wcucdeali11£hcrc with a1y))t'Oflitera1Ure1tarc hwhcre1hc
numbuofpotentialsource,-ofinformationis•erylarac. Wha1
thcbtai nncr needs issomeguidctuthe most gcncrallyu1tfol
une1.andlo!heproblcm1ofscopcandlimita1ions1hatmustbc
1akcnintoaccount.
Thellhelme r'• Syr,th• tlc M• tll(H# of Org• n/c Ch• m ls try ' '
Here is ano1her unique compcndium which, afcer 1enin1 used
1oworkin1withit,1hcor11anicc•J)t'•im<'Tltalistwillsoondecide
hccan no1dowithout. Whatcomô 1heni, tha1hewillhearhow
much it com, andhewillbt!dtwondcrinaand"Ãorryina how
muchlon1crthclibraryheuscscanafford1ocon1inue101ub.
scribe co it. forty-lhrecãolumc, ha•csofar appcared, almOl't
onecachycar,ande,·ery6fthvolumchasaeollectfrcindc,.Th,
literature coverage and choice of~amples leave no room for
complaint,cvcn1hou1hoocasio nally1howin1 asubjccti>·eslan1.
E,eryeu.mpleJive,-fullmu..iures (apparent!y1hcmos1'rostin1ensivc'i1eminthis"·ork)of,1anin1moted als,in1crmediates
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andproduc11,andbriefMtail,with1efrrcn,,esn01onlyforthc
uample in qua tion but also for oiher do,cly 1imilar work. The
moll important part ;, _the de1ailed and carefully cros,.
referencedindcx.Jtise"1"yrarctolindoneins!lncc-,for
eumple, whe re a reference for 'A. ,1anin1 material for B' wa,
not matched by a corrcspondi nsoneunder 'B, from A'. The
indexrcfcntot he Example1'umber1mdnot101hc pa1e.h al,o
list• rea1en11 (inorga nic and mctal-or11anic alwa)'' under the
metal or non.carbon element). name reaction, and ,ca,tion
types. A speci al Guide for usin,g this work hai appeared.'"
There;, a distin<."tive system and symbolism for dieision in10
reaction cl asses which looks rather in1imidatin11 and tend , to
fri11htenofT1he be11inner , butm a.stcringitisnotrcallyc1scn1ial
11 isesumial, howC"Vcr,tosctacquaintedwithit if you intend
to exploit Th t ilhtimt r like Bri/.slt in for browsins a nd 1c1ti n1
information by a1sodation, , in-e it 1roup, reactions of the
generaltypcto11c1hcr. Thi1,incidentallyi1anothercxample(as
wi1hfuj/sltin)whcrcthefae11hatthi,workisnow available for
online compu ter rescarchi n& is of no sonscqucnee regardi ns
'browsabi lity'
Al the end of each ,·olu me1he reis a ,·cryimpor!a n! Table
which lim later supplementary reroren-es for eumples 1iven
in presious volumes. This must be used with some cart. For
examplt, 'Vol. l. . . 23, VoL 28 . .. JO' mtans that pagt 10 in
Volume 28 contains an example or other information which
com p!emt nts t xampl~ 23 in Volume I. Each volume i, also
prefaced by an in1roduction which , um l up special dcvelopmems1i nce1he a ppnranceofthepreviousone
Thebindin1 ofthiswor kused tobe1erri blc (fnrits pric•)- in
practicall yeveryl ibrary the aut horhasbetnco. Volume 10hai
gonethrou1has1a11cofcompl<1c disin1e1ra!ion. but since then
there has becnconsiderab!eimprovemen! inthis,eprd ,
Since1headventofthedivisionof 1heorisinat Subjec1 /ndt x
into the Cht m ical Substance Index and the Ot ntral Sub)«t
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lndtx, the lattu should by ri1h 11 serve 11 an important means
for,earchingforreac!iom, me1hods andconcept,. Veryof,en
it dMs indee
ands1amina. a lotofcarcfuljudgmuthas tobeut1ciscd,1hc
••=n bein1, as mcn!ione
The1earchcrmaybelookinaforamc1hod "''hich speci ficall)'
effects mera-bromina1ion of phenols. In Thtilhtimtr, lndu
of Coll,:,;1ivc Vol. 40, he will find: "mna-bromination'-!his
refcr,toVol.J.6.examplc474.Thisref«11oapapcrby J .C
Jaqucsy ti al., Clrem. Commun. 110 (1980). which show,
that 4-alk yl and 2.6-dialk)'lphenols are brominated ,pcci&calty in !he meta position when di.,ol,·e
747(1981)',meaninachatthereoncwil!findadditionalinfo,.
malion. !n Chemical Abstracts, on,heolhcr hand(Genen,/
Su/Jjrc:1 lndtx, CoUtt:tivc Vol. 1977-81) th< followina si1ua1ionis cncountcre
one w/11 find 'bromin ation of. in super-add, mecha ni,m or
(93. 94918a), "'·hich i, found 10 refer ,o the at>ove Chem.
Comm~n. p;ipcr-however. lhett is no mention of 'mt ra' or
of the Tt l!ahedron pal)fr. On 1he other hand, unMr
'bromination"onc willfind'mt/Q', but now!his i,qualified:
'of dimcthylphcnol and -aniw!c, in super adds', and !his
rdcrsonlyto9S,80l47t,whichistheabmac1ofthe TetrQhtdronp;1pcr .
Thi, isthew,tofthinathatha pl)fnsallthetimeinasu,ch
of this kind in Chemical A/Jsiram, but that 5hould not
nc«uarilypu1youoffcon1ultingi1alto11.e1her.Ther
~~i;~ is mi,.ing from. e.g ., Tht ilheimt r. to make ii
:;,~; . .
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Fleur a nd Fleur'• RH g , nts fot Organic S rntlN,sis'
Thi, work, !4 volumeã of "Ã hich have apP<"arôl so far, delivers
far more than its title would1uue<1, 1ince it i,1he work in
which to bnd imponam and uwto-daie information by
browsin1andassociation,but !henonlyifi1i , readandn01
mcre!yu1ô1asawor k ofrtfôtnce.Thisiãwhy,in1hiãauthor'1
opinio n, it is probably the best 1inglc investment an
CXP<"riment alorgankchemis1canacquire a11hepre1enttlme. h
deals alphabetically with reaaents u,«l in or1ank chemimy,
their use wi1h differmt subs11ates, how they are prepar«l or
wherethoycanbebouaht, ondineachvolume referenceismade
to the rea&em·, treatment in previous volumes. There i• a
1eneral index and . more imponant, an 'Index of Rt<18tntr
A<:<:ordinz toTyfHs',"·hiohineffccti,1nindextoreac1ion1and
methods. The only snag lies in 0tta1ional and unexpcct«l
chan1csinnomendaturefromone,·olumetothenextandeven
in the ume volume betwten the index and the tul to whic h il
refero. Bu1wi1ha,.·ork likethisitmayevcnbe a blessi111indis·
1;uisc, since puttin1 thismai1h1 m•ywcll put you on to more
unexpected1crn1orinformat ion bythe ....·ay,idc
M athoden dlr Organ/sch.,, Chemif (Houben-Weyo •
Thercis a loltha1need,tobeHidaboutthi1elephan1inework
(82pam uptolastcountin1!)whkhdeal,withclasscsofor&anic
compounds,1heirpreparationand,eac1io11$. Forth•beainnin1
lit era1ure1u rcheritcould P<'rhapsben be,ummarisedaifol,
lows: m11Ch of it i, not easy to use, to put it mildly; 1o mc of it
i
1hefine1oldleucri111on1hchackorwhat wulcr1ofi1, 1u...
which of ri,·e or ,ix ~o!umcs (all mar ked. for exampk 'oxy1cn
comp0unds') mi11h1possiblybe1heri11htonc,admire aru11-pa1e
phoro1nph of a Vuy Jmponant Peuoo, skip throu1h 2-4
pa,:es of mi ,cellaneous forewords and prefaces and wade
throuah 14 pages or more of journal abbreviation, before
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geuingto1heniny.griuyofalistofactualoomenu.Reccnt
,olumesha vc donc awaywithmostofthat nonso,nse, but now
one hu co cope wi1h fiendish new-ny~ indc~cs that mention
ac1ual oompounds ;roupcd under rather arbitrarily selected
basic mucturcs but 1ha1 arc woefu lly short of listing more
aencral topicsandconccpt1. Asforthe ac1ualcontents. wmeof
the newer volumes a rc supcrh (c.1. thoso on orsanometallic
oompounds and the new supplememary volume on a ldchydcs),
01heuarejuttplainawfulasfaraslcvelandco,era5euecon.
ccrned.Al!ogotheronegeutheimpre.. iooofaladof a11uiding
handandof11eneralprinciplesofcons1ruction-inthi1re,pcct
Hou~n- Wql. althoua h also a German work, is the anti!h«is
of Bt ils1ti11, No wonder this work is almost ignored outside
German-,pcakin1 coumrie,, which in some ways is un fortunate.
The Ex
O'fll!nlcRucrlons
This old-cs11bli1hed ,cries C()llcetin1 review, on 'na me"
reactions1nd01hcu ofaweildefinedcharac1cri1pcrhapsthe
best kn\>wn of int)'])t. Each suchroviewhassection,diocu.,in1
mochanism,soopcandLimitationsoftheruct iondiscussed,buc
the mostimportantparUarcthcTabul arSurveys. Only astudy
ofthel'ewill1n,,.·erthecard inal quc11ionincverycasc: how a
speci fic reaction will work within a particular molecular
environment and/orinthcprucncc\>fo1hcrfunctional groupi
Mo,1 of the Tables have had aloe of,.·orkpulint\>thcm and
this occas ionally borders on the incredible, such as the 11<·0
author re,iew on the Aldo! Reaction (Volume 16). which lim a
totalof 23S9 rdcrenc....
The !\>Ill number of volumes has now reached 36. but itis
unlikolyrhatyou canoonsidor any o f,hc ch apton publishedin
(he &,st 20vol umel'ascon.citulinJ any1uidc a1 1lltoprcsent
kno1<·ledaeof1hesubj«1. For any subjoctdeah within 1h""'
youaremon1Lyadviscdrnlookforaii1orcreccntrevicw(stt
below, ' On Reviews in General' ) which in all likelihood you will
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