Karabinos, Joseph V

Lamberti, Joseph M

English

NASA Technical Reports Server

. . . ..-
-. .. ... . . . .. .. .
*
.
.:
.
-.*
.
.-
--
.“,
c) . MAR5 1946.
~NATIONALADVISORY
THE
-r ----
.
.,., ,- =.+.
COMMI~EE
.... . . -.. ----- —.
FORAERONAUTICS
.
..
TECHNICALNOTE - ““ “: ---
NC), 10U3
,.
SYNIWESISAD PURIFIC&j?IONOF~IC
I
- ml?YLBEIia
.-
.’.
By Jose~hV.KambtnosandJosephM.J2u&efii.
AircLaftlihgineResmr& Labcm&&ry
——
—
Cleveu, Ohio_
.- .
. .
=qpJrj7’
. .
.—..- . ..=- .
Wash!n@an
January1946 .
J-=-b F=.!,+: ,,q —.
,
.
.-
——. ..- .
*
https://ntrs.nasa.gov/search.jsp?R=19930081833 2020-06-17T22:48:26+00:00Z
1IlllrllllmmTflBllllllll‘
311760143388017 ,.-.. — ..
.,. ,
.. . . .-
.-
.— -—
NATIONALADVISORYCCMMITTEE
TECHNICALNOTENO.
FORKERONA~ICS
1019
TEESYNTHESISAND~lJ?ICATIONOFAROMATICHYDROC~Ol@
I- BUTYLBENZENE
,By Joseph.V I&rabinosand
.,. .
.
,., .
. .
:’,, SUMMARY
JosephM. Lamberti
,,
A 13-gallon..guantityof‘butylb~nzenewassynthesizedandpuri-
fiedby large-scaleprep~ationof4-phenyl-l-butenefromhenzyl-
mag~esiumchlmideandallylchloridewithsubsequenthydroge~tion
of theolefin.Thephysicalc&tants ~orpuresempl~@ 4-phenyl-
l-buteneandbutylbenzenew red6term!~ed.andthepositionofthe
T doublebondinthe
.,m
* ,-
,..
Thesynthesis
olefinwa8established.b ,
‘“INI&DUCTION
andpurificationofaromatichydrocarbonsi
partofa ~eneralinvestigationbein~conductedat theNACACleveland
laboratory’ontheevaluationof suchcompoundsasantiknockblending
agentsformrrentaviationf~els.Theinvestigationi cludesthe
aromaticsfrombenzenethroughallofthepossiblestructures-with
9 car%onatomsandsomewith10 carbmatqms,.Severalofthearomatic
.@drocarb’:ns:wereobtainedfromcommercials.ourcesandwarepurifid
,]~fractionaldistillation,fraction&1crystallization,rbychemi-
cal means.”me compoundsthatcouldnotbe coumerciall~obtained
weresynthesizedby theOrganicSynthesisS,ectiotif theFuelsand
LubricantsDivision. -
..
The,presentreport,whichisthef,irstof,a sqries,dealhgwith
thep~gyara$,ionofhydrocarbonsfor.uae’tn”enginetestsat the
Cl&el~’labor.story,describesthesyhthesis.andpurificationfa
13-gallonqtiantiityofpurebutylbenzeneandpresentsphysicalprop-
ertiesofbutylbenzeneand4-phenyl-l-btitenb.-Becausethereis
considerablediscrqanoyin theliteratureas-tothecorrectphysical
propertiesforthe‘olefinjthe:positi~~.p~,thedoublebondwasdeter-
minedby ozonolysis.Thes~thesisdescribedherqininvolvesthe
-----
. ---- .-
.—
-=, -.
2 ... NACATN tiO.1019
preparationf4-phenyl-l-3uteneandsubsequenthydrogenationf
theo~.efintobutylbenzene.A number~fmeth~daofsj’;.??~ceisi.:lg
thesohydrocarbonsaregivenintheliterature,hutoi-fi~tharela-
tivelyreoentpaperswillbeolted.
~!heolefin4-phenyl-l-butencwaspreparedby cgndermstlonf
benzyhhagnesiumchloride-withallyl-chlorideinrefe~hnce1 and
fromthesameGrignardreagentwithallyl-g-tcluenobuWoln~%i
reference2. Theolefinhasalsobeenpreparviby thecorxleneatton
~fbenzylmagneslumbromidewithallylchloride(ref~rence3),by
thec:ndeimatlonfallylmaghesiumchloridewithbenzylchlmidu
(reference4),andby treatmentof4-phenyl-l-bromtioutanewith
alkali(reference5). A Wurtz-Fittigsynthesiswithbromobenzene
andbutylbr:nideisreportedinreferance6 forthepreparationf
butylbenzenoinexcellentyiald.TlmI&iedel-Craftsreaotionof
butyrylchloridewithbenzeneandsubsequentreductioqof thoroac-
t-iunproductby th6Wolfl?-Kishnermethodwereutilized~inrefer-
mce 7. Theocmdoneationf phenylmagnesiumbromide+ butyr-
aldehyleisrapcwtcziby A.P.I;hydrocarbonsfw earohp~oJect45,to
givel-phenyl.l-butanol,whiohwasdehydratwitotheolefiand
hydrogenatedtoyieldbutylbenzene, -
Thepraparatimdebcribodheroin,~hichwasbeguninApril1944,
ispre[;entedintwomainaoctions:(a)a generaldiscussionofthe
methodandpresentationftheyields.andtheQhysioaloonstantsof
thehyclrocarb’~nsand(b)theoxper~mentaldetails.
DISCUSSIONOFSYNTEIISIS
Thomethod.used.atitheClevelandlaboratoryfor’thesynthesisof
butylbcnzeneconsistsinthecondensationfbenzylmagnesiumchloride
withallyl.chloridotogive4-phmyl-l-butenafollowedby hydrog-ona-
tionofthisolefin.Theplwpmxitionftheolefinwasaccomp~~ied
by a largeyiuldofdibenzylanda smallamountofitolueno.Libenzyl
isappsrmtlyFormedby thecondensationfbenzyl..magnesiumchloride
withhenzylohloridejandtolueneisformedby hydrolysisofthe
Grignarireagent.Bothimpuritiesareeasilyseparatedfromthe
desiredolefin.Th6yieldsofthethreeproductsobtainedfroma
typical&tin”05-395moles’ofbenzy”lchlorid”ew reasfollows: <+
Product Yield(kg)~(perc?nt)
—.
Taluene 0,7 1.9
Dibenzyl 17.0 47*3
&~&yl-lzb utene,18,8 36.0
.——
Total“.,...-”-..i.. . 85.2
*.
s:..
.
l
I?ACA~Nc).1019 3
Thepositionofthed~ublebondin 4.pheqy~.~~.bl~te~ ms determined
by ozontzationfollowedby oxidation,.Thei.~olatlonP@henyl-
proylonicacidconfil~~dthestructurof,thiso,lefin.The,~&O-
genationofthedoublebondin4.yh~l-l-~u”teneW&S-ctirf6d out
withextremeaseandgavea quantitativeyjeldofbutyl.benzene.
Whenthohydrogenationwasconductedat elel~atedtcmperaturos,the
result- productwasbutylcyclohexarw.Th,>reacttonswe illus-
tratedas follows:
..
.
.-:.
%~o ““ ““” . .—.—L
7
c#5cE3
(Td.uene)1
..-
C6H50H2C1 M& > /d~ner C6H5CE#&~l.,
(Benzylc~orlde) (Bar!!ylmagne8ik’\- ‘-”.:::””””’””.‘“ “:.-... ..:
c.fimxio)
i ‘\,~#cH2c1
I > c#5m#H##5I (Dibenzyl)..
J “’
.
.CH2=C&CE2C1 . . -
H2+Ni -’$ H2+Ni
C6H5~#H2~2w~” < c6H5c15#H2cH=cE2 > c#~~oH2cH2CH2cH3
(Butylbenz::jne) 60°C (4-Phe~l-l-buten~) 1760:c (Bu.tylqyclohexane)
J
C6H5CH2CH2COOU
(~-Phmylproplon~c-
mild)
,- .-- T-..._ _ .-
,.
. . .. .
. .
4 “- “’ ““”: “’
-...&~; ~;, ,izigi..r..,..
.+ ... ..... .. ..:.:> -.,.
8-~ .- . . .
res;l~tanoe~hermometey.Physicalgonstantsofbutylbenzeneand
4-pl~a-@-2-l-%~t~ne-d6temine at theCleveland@boratoryare
recoriied,.intableI aswellasvalue~<rm”a,,nmber.~f..x?femnoqe.. ,.
..----- ...... ...l-,-.. ,. ----- ,. :.,.;
..”. . ...-.!...:-. , .-.-:%“+.f., ‘“:”=$.,.; .-.:-..-. t. -..:.: : -: .-.. r..= ..... : ....:”..:;., -.=.”---z
-, ...!,
,...,:”-:.’...:,,...”i,;.....:~...
c“ -“: :~- ,.~,.,, ‘“,“.l..’w”~-~ D~M:. .<.+~ ..=,.. ?.:-.! ..”...:,”=~:~:~--- - -:, 2.
., .:.* ..”
&e@ration& ~-~henyl-l-butenw.- A glase-linedreactorwith
a 100-gal.loncapacitywasusedforthesynthesis.Thereactorwas
~acl;$ted,.forste~and hotorcoldwaterandwasequippedwitha
powe~”.~tirrer,an efficientrefluxconienser,anda coppertankfor
the:=fiiixrufliquids,bthe reactor9.6kilograms(395moles)
ofmagn6sluiiturning~wascoveredwith10gallonsof ether,which
was~~reviouslydriedby passingitthrougha 2-inchby 10-feat
columnofFlorite.An ethersolutioncontaining2 molesofbenzyl-
mag~,q~$!,~:chl:?rid.eand1.8.kilogrsmsofbenzylchloridewasadded
tothemixture.$ftertheinit$~l..reactionhadsubsided,reflux
was~ai.ltalnedby thooontiquoueqfidition of 48,1kitigramsof
...—...*.-S-..1.-- ---benz~ic.h?.ovidddfssulved.in10gallonsofether~Thepr~paratfon
ofthc:@gnard r&gehtrequlre~2 day~. Titrationof a.sample
with”~G&5“j.ndicatecthe.presencafapproximately350molesof
Grigni@irsagunt.
solutionco”ntatn~.ng13.2gra?gsof
.—=.
. .
.<-.!:..’. . .
.. = -.
,.-’
4-phenyl-l-buteno
.,
,
.- . ..——
.-
NACATN No.1019
absoluteth~la~tatewas.saturatedwithozone.
5
The solvent vae
evaporated@-aiatresmofairatroomtemDeratum
-.
d.wasreplaced,..-
by 50ccof’glaclalaceticacid.Thissolutbn-wasDlacedina
three-necked-flaskanda mixtureconsistingof 50cc-d water,
1 cc ofconcentratedsulfuricacid,end35 gramsofhylrogenper-
oxide(30-percentsolution)waeaddeddropwise. , ....-~
Theresultingmixkt&ewas.refluxedfor2 hours,,. cooledinan
icebath,endextractedwithether.Theetherlayerwasdriedand
thesolventremovedleavinga yellowoilthatcrystallizedfrcma
largevolumeofwater.Q-Phenylpropionicacid(8.0grs.nsofneedles)
46°to4’?,5°C;.wasobtainedononerecrystallization:meltingpoint,
neutralequivalent,150;~-brcxaophonacylester:.meltingpoint,103°
to 104°c. Theseconstantsagreewellwiththefollowingvalues
giveninreference8
-~-phenylpropionicapid: meltingpoint,48°C;
neutralequivalent,150;~-br,cmop@nacylestqr:meltingpoint,104°C. .
Preparationfbutylbenzene.
-Butylbenzenewaspreparedfrcsn
7.5kilograms(55.8moles)of4-phenyl-l-butenei whichwassuspended
2 parcentofU.O.E’.Hy&ogenation.Catalyst(nickelonkioselguhr).
Thereactioriwascarriedoutiria st~elaatoole,veof 20-litercapacity,
fittedwitha rockar-Q@e‘shaker.H@rogengasW?Saddedandheat
applied.At 60°C anda pressureof 1000poundspersquareinch,the
reactionprcceededeasilyand.thetheoreticalquantity&’hydrogen
wasconsumed.ThereactionwasQult:e+exothetic,Aftercooling,the
contentswereremovedandfilt,eped,~ t~ecolorlessbutylbenzene
wassubjectedtofractionaldistillatfqn“h a 10.6-theoretical-plat.e
columnof20-galloncapacity,Theyieldofbutylbenzm.ewasquanti-
tativeandabout13galloqswasproducedby thismethod.Thephysical
constentsarelistedintah-l~~,l”.““’”-
. ,..
Butylclyclohexamwasobtainedwhentheolofinwashydrogenated
athighGrkempOrat~eB.A 60-pprcen~yieldwasobtainedat 170°C
,,,
,,,
.: :,. L
. . . . .
. . .
-.
.,
. - :. .k ‘..,..:, ‘.
.’ ,..’ -t..
,, !.:. . .. ...’ ... . . 1 . . . .’%’
—
6anda pressureof1000poundsperscjuareinch.
stanw of theImtylcyclohexanegreedfavorably
refe]3ence12.
-.
..
T$.hCATN No.1019
Thephysicalcon-
withthovaluesin
—
AircraftEngineR#aearchLaboratory,
NationalAdvisoryCommitteeforAeronautics,
Cleveland,Ohio,August23,1,945.
REFERENCES
1,,Lovina,I& Ya.,andPetrov,D.A.: Oatalytl.cIsom6’rizationof
UnsaturatedHydrocarbonswitha DoubleBondInthe~,&-Position.
Chore.Abs.,vol.31,no.16;Aug.20,1937,p. 5772. (Original
articleinJour.Gen.Chem,(U.S.S.R.),vol.7,1937,
“pp.747-749.)
.-
2.Gilman,Henry,andBoabwr,NathanielJ.: !TheReparationof
‘-Hydrocarbonsy theReactionbetweenAlkylSulf’ofitesand
OrganomagnesiumHalides.Jour.Am.Chem.Sot.,~ol.4-7, ‘“
no.2,17eb,1925,pi,.51f3-525.
3.Kc,zacik,A.I?,,andRo3d,E. EhmetrLengtheni~-CarbonChains
by ThreoUnits:Aesayof P@imary BromidesfromtheAdditionof
HydrogunBromide.Jour.Am.Chem.Sot.,vol.60,no.10,
oct:1938,”pp.2436-2438.
“ 4:.Gilman,Henry,andMc Glumphy,J.H.: La PreparationIZXie5endan@
duBromured’Allylmagn~sium.Bull.Sot.Chim.France,M&oires}
t. XLIII,sdr.4, art.136,1928,pp.1322-1328* .-
,..
5,Lagerev,S ‘P.:TheEffectofRadicalsontheDirectionofthe
AdditionoftheComponentsofHydrogenIWideAcids.Chem.
Abs.,VO1.35,no.7,April10,1941,p. 21i9, (Originalarticle
inTrudyUzbekskogoGosudarstUniv.,vol.6,1936,pp.71-88,)
6.Read,R.R.,andFoster,L. S.: NormalButylbenzone.Jour.Am.
3hem.SOC.,vol.48,no.6,June1926,pp.1606-1607.
7.Schmidt,AlbertWolfgang,Eopp,Gerhamd,undSchoeLler,Viktor:
:DarstellungsweiseundPhysikalischeDatenvonM>noalkylbenzolon.
J3erichted. D.Chem.Gesellschaft,Abteilung13(Abh,),
,Ja~g, 72)-Nr. 11, Art. 319,Nov.8, 1939>PP.1893-1897. ,
,:
—
I
.-
NACATN No.1019 7 .—
8.
9.
Shrinor}RalphL.,ad Fuson,ReynoldC.: TheSystsmatioIdenti-
ficationofOrganicCompaunds.JohnWiley& Sons,Ino.,2d cd.,
1940,p. 98;
Hurd,CharlesD.,andBellman,HarryT.: TheP.mrolYsisofAlpha
Un~aturatedHy&ocarbons.jour.~. Chem.So~.,~ol.55,n:.2,
Feb.1933,pp.699-702.
10.1%.ns,E.B.: TheViscositiesofHydrocarbons.‘PartsVIIand
VIII. Jour.Inst.PetroleunTechnologists,vol.24,1938,
pp.537-555.
11.Parks,G.S.,andHuffman,H.M.: Same Fusion.andTransition
DataforHydrocarbons.Ind.and~. C%em.,vol.23,no,10,
Oct.1,1931,pp.1138-1139.
12.Doss,M. P.: PhysicalCkmstantsofthePrincipal3ydrooarbons.
. TheTexasCo.(NewYork),4thcd.,1943,p.100.
.
w
I’?ACATNNo. 1019
TABLEI - PHYSICALCONSTANTSOFBUTYLBENZXNEAND4-PHENYL-1-BUTENE
BoilinRPoint Refrac-DensityFreez-
Compound Sourceof tiveTem~g~ture:&&- at 29°C ing
constants index (gys/ p:;:;
(~) n:
%-Phenyl-l-NACACleveland 181.5 760 1.5074 0.8822-69.95
butene laboratory
Reference1 62.5 13 1.5064 .8915------
Reference2 175-177 ------------ .906 ---.--
Reference3 181-182 -.---------- --------------
Reference5 75.0 15 1.520 .890 ------
Reference8 175.0 -----1.5090----.--------
Reference9 177-178 754 1.5059 .8831------
ButylbenzeneNACACleveland 183.3 760 1.4899 0.8601-87.97
laborator~
NACACleveland 183.2 760 1.4898 .8601-88.19
laboratory
Reference6 181-184 -------------------- -----
Reference7 ----------“ ----1.4899 .8613------
Reference10 182.1-183.1760 1.4880 .’8668------
Reference11 ----------------------- ---------88.5
a“Best”sample.
bEnglnesample.
NationalAdvisoryCommittee
forAeronautics
f
“4
..+ 9
l“. . . . . . . .
. .
“..“.“”.
““” : l..”
G
0
x-
-1
z
z
0
.
0
w
la.
M.
;
il,g.
~
.,
d
la.
w
m
-1
r-b t *
. . . . . . . . . . ~ l
. “ “.. ”
-“.:::”: “..
Iiiiiiiiiil
I
+
z ,
z
o
0
to!
I .-
{* ,“ b
. . . . . . . . . .
. . . .
“. :“ :“”.
.,
., . ..”
I
1
,
I


The synthesis and purification of aromatic hydrocarbons I : butylbenzene

Abstract

Similar works

Full text

Available Versions

NASA Technical Reports Server