May, 1947

.·. Jf NEW DERIVATIVE METHOD FOR THE

.. IDEN'rIFICATION OF OLEFINS

by

Hugh B. Donahoe B.s., Rockhurst College, 1943

submitted to the Department of Chemistry and the Faculty ot the Graduate School of.the University of Kansas ·in partial fulfillment of the requirements for the degree of Master ot :Arts.

ti·,:

.~OKNOWLEDGMENT

The author wishes to thank

Dr. Oalvin A. Vanderwerf and

Dr. Jacob Kleinberg for their

indispensable guidance and

assistance during the course or this .work.

·TABLE OF qoNTBNTS

I

~AGE

m storice.l ••. •' • • ' '. , .. .. ' .. . . . • • • • • • •

·Discussi-on of :the Fr'oblem •••••••••• 10

Discussion ot Results • • • • • • • • • •. • · 20

Experime~tal . • ; • , • · ·• '. • • · • • • • ' ' •· '. .. .. . 24

131b11ograp~y • • • . • • • • • .• • .• • • • • • 37

1.

HISTORICAL

At present there is no satisfactory method tor

the identification of individual olefins as they occur

in the pure state or in mixtures. The development ot a

practical procedure for identifying members of this

homologous series would m~ke a significant contribution

to the·science of organic qualitative analysis.

The identification of individual ethylenic

hydrocarbons has always been difficult because all have

the same general formula CnH2n and_ thus all contain

85.'7 per cent of· carbon and 14.3 per cent of hydrogen.,

Molecular weight determinations will give the molecular

formula through the usual physical or p~yeico•chem;oal

methods· (determination of vapor density, cryoecopio or . ,. . ' ' '

ebulliosoopio·methods), but even this will not differ-

entiate between possible isomers.

Particular interest centers about the.identi-

fication of the lower members of the alkene aeries

because the unsaturated hydrocarbons of commercial

importance usually contain from two to eight .. carbon atoms.

They·are gases or low boiling liquids at ordinary ·

temperatures and pressures.

There ere two phases under which one may study

the determination of .olefins. In industry many oases

arise where it is of prime importance to know the per

cent of olefinic unsaturation present in a hydrocarbon

mixture lying in the gasoline boiling range. Here the

first consideration 1s complete reaction and removal of

all double bonded compounds without regard to the

structure of any individual one. bn the other hand, it

is often necessary to determine the identity or one

purified olefin. In this case the criterion of a good

identification method lies in the formulation of sharp

meltin~ derivatives that can be simply prepared and easilJ

purified rather than 1n a complete reaction with the ' .

reagent.

In most cases single olefins are recognized by

a study of such physical properties as density, index of

retraction, specific rotation, specific dispersion and

simple chemical tests ( 41, 28).

The obvious addition products, suoh as those

resultirg from the reaction of bromine and the hydrogen

halides with oletins, are very· seldom satisfactory

because the resulting co~pounds are usually liquid.

Nitrosyl chloride addition compounds have been used to

identify some ethylenic hydrocarbons in the Oa to C11

range ( 39). '!'he reagent has found more use in the study

of terpene ohem1stry·(33) and in the last several years . .

the reaction of NOCl with olefins has become the first

step in a generai method to prepare surface active

sulfonates to act as de-tergents, wetting and dispersion

agents (2). ···

3.

Oxidation of a symmetrically substituted olefin

or a l•alkene will produce an acid which in some oases

ma.,r serve as a derivative. The oxidation 1 s usually

accomplished by permanganate.

RCH=CHR· - 0-..,.--..., ~ RCooH

RCH==CH.i • RC oo H -+ C0-1

If the acid is a liquid, it is usually necessary to

characterize it by means of a suitable derivative •. An

untrymmetr1cally substituted olefin will give a mixture or two acids and this will greatly increase the difficulty

of identification.

Mercaptans (22) and thiophenols (21) have been

found to condense with olefins to give the corresponding

sulfides.

)

CH3' o' R.-C.H ... Sn

These sulfides, although usually liquids, can be oxidized

to sulfones which are solids and easily purified or

converted to the solid PdCl2 complexes. A tew cases are

known where the sulfone has been nitrated to raise the

melting point of the derivative.

4.• ,

~he addition or thiophenol to olefins proceeds

contrary to Markownikotf' s rule in the absence of acid

catalysts to gives

I

RCH=CH.a + R SH--..RCH~CH~SR'

This reaction is always carried out in a steel bomb at

high pressures (20 tq 30 atmospheres of nitrogen) and

te~per~tures (to 10000). Reaction at room temperature

was found to take approximately one month.

Hydrocarbons containing conjugated double

bonds readily condense with maleio. anhydride (13) or

o<..-napthoquinone (14) to give solid derivatives.

0 0

+ 00.~

0 0

The use ot this reaction 1~ the determination or per cent

unsaturation will be discussed later.

Dermer and Dysinger (15) found that thio-

oyanogen (S0N) 2 reacted with olefins to give dithio•

cyanates. Boting that thiocyanoge~ had been used to

s.

identify 1soprene and 2.,3-dimethylbutadiene-l,3 (8 ),

these workers were able to prepare a ser1os of dithio-

oyanates. All but four of the olefins tried yielded

oily products and two ot those four had been reported

before (23). All of the derivatives have disagreeable

odors and an irritant action on the skin. It has been

suggested (15) that (leON)2 would pr~bably give

derivatives ot higher melting points, but the difficult7

~n obtaining metallic eelenocyanates and the unpleasant

characteristics of this reagent make its usefulness

doubtful.

Osmium tetroxide (12) he.a been suggested as a

possible reagent because it adds to olefina with the

formation of esters of osmic acid

-CH u

-CH )

Very little work has been done on this reaction.

llcyl halides will. undergo addition reactions

with ethylenio aliphatic hydrocarbons under the influence

of etanni c chloride (ll). The products are /3 -chloro

ketones which by the loss ot HOl give -<-ethylenic ketones

(or sometimes a mixture of o(- e.nd (' -ethylenio

ketones).

6.

''O?H~ ot the few, attempts ·to prepare the· solid . .

derivatives of a series ot unsaturated hydrocarbons ,• "~' ' • - ~~ ' , , •• • • • I

has· been reported. by Lester, Rodgers. and ae1d ( 26 ) •

Us1ng·4·mercaptob1phenyl as thei~ reagent they prepared

solid· der1vat1 ves · of the· 1-olefins .from hexene~l to ·

pentadecena-1. · The close proxim1 ty ot melting . points ot the.members rendered these solids of little value ·tor

ident1f1oat1on or olefins.

-1.sindloated earlier in the discussion, the

second ·.. type ot ~d~n~1f1ca.t1on of unsaturated compounds

deals with .dete:rmina.tion of the per cent. of ole1'1n1o un-

sa'.t;uration. '. This type of reaction results in the addition ~ ' ·, .

of: some reagent to the olefin, ·but the stress is placed on

~uantitative reaction and ease of removal or the addition

compound •.

the synthetic.rubber 1ndustry.-gave ad.ded impetus

·to. the search tor a simple chemical method for routine

,determination of . conjugated diene·s in crude products from

.cracking experiments. ; .Reagents tried were bromine· (27), ' ..... · .· . ' - . ' ' '.

s~lfttr dioxide (38), aromatic d1azo~1um compounds (34),

me.leio anhydride (1. 38), and ohloroma.J.e1c anhydride (31).

All but the last two.proved nonspecific tor conjugated

dienes or did not react quantitatively.

~he use of chloromaleic anhydride 1s of special

interest since excess reagent will not affect the

determination because of the difference in reactivity

betwee~ the. highly active tertiary chlorine of t~e adduct

and the unreactive vinyl chlorine of the reagent. Thia

permits_ refluxing· w1 th --~eous AgNo3 . to remove chlorine

oompletel7 f~om the addition product, leaving the chlorine

of the anhydride untouched.: The reaction with isoprene is

· given b7 the equation:

It is also possible to obtain reagents which will

remove all olefina. Two examples are nitrogen tetroxide

( 6) and· cuprous chloride (17). The cuprous chloride

complex combined with condensation anal~sis (low tempera-

ture fractionation) gives a p~ecise method for the complete

analysis of gaseous hydrocarbons accurate to within 0.2

per cent.,

Nitrogen tetro:d.de will react rapidly and com-

pletely with all commonly available olef1n1c materials in

a.

a 't~perat~re range of 400 to 21000. · converting them ,· ' ; .', ._., • . ,, .',' J

into heavy. oily addition products. the majority of ~

which ere ot ver:r iow volatility and from v1hich any

unreacted compon~nts of thEr;·m1:xture can be separated by

a simple steam distillation._ Little is known about the

nature of the products formed by the interaction· of

nitrogen tertoxide and olet1ns. According to S1dgwick

(36) such .reaction pro9-ucts ere known as nitrosates or

. "Dinitrt!re," possessing the structure ·:.. ,

>C - C.( I I , respectively.

Nool N~

The d1ff1oulties of this method are 1) the

vapors of n1 trogen · tetro:x!de are ·toxi·o, . so all operations . ' ' '

must be carried out under an efficient hoods 2) some

organic compounds :react to form products which are

violentl,- explosive.·

' . ~ '{~ : ; ' ~

eati~te.'otory method to prepare solid derivatives of o~etin~,

especially. those with lower molecular weight. The ideal.

solution to the problem would be a reagent that is safe to

handle,· requiring no special apparatus and having a high

enough molecular weight to raise the melting point of the

der11rat1ve 1 \flell above r·oom temperature,· If the .·reaction were;a on:e step ·process leaving only isolation end purification after ~dd~t;1on, that reaction would .be a

· .• , . • •' ·, , . · .. • '.: I,, .. •. • . .. . . .

valu·e.ble addition to the field of organic qualitative ·, ,'.•.-,.', , . . ..

analysis • . ·' -,. . .' ' :

, DISCUSSION OF THE PROBLEM

According to the electronic theory, organic

molecules are activated by the development, either

permanently. or tranaiently,·ot positive and negat'ive

centers, within the molecule. A large number of organic

reactions are initiated bj- the attack of a positive or .... ~ '• ... • 1 •

' ' ·: ' .

10.

n,egative center of o.ne molecule at the oppositely charged

center of the second molecule.

If one were to consider the olefin, this

activation 1s a.result of the tautomerio shift of one of

the ~wo ·pairs of electrons as·sooiated with the. double . ·

bond. This, shift, inv~lves a change in .th.e octet. af1'1l1-

;at,i<>1:1S o~· thi~ electron pair without de:oomposit1on -ot the

molecule .•. This tautomerio effect may be represented ass

H HR:E::E:H

H R: c:

+

H•• C:H ••

The theory ot reaction ot olefins_ was first

recognized by Lapworth (25) in his concept of an1ono1d

(nucleoph111c) and ostio~iod (electroph111o) centers.

He considered organic molecules as either fundamentally

nucl~ophilic or electr~philic. As a result these . .

molecules tend' to re·s.ct only with molecules of the

opposite.nature.

11 •

. Olefina are nuoleophilic substances. This ie

not something that could be predicted !. priori because,

the act1,ated form of the molecule contains both electron•

rich and electron-poor oarbon atoms and either of these

could be Pl'!idicted to have a strong tendency to form

covalent bonds.. · The proof lies' in the fact that olefins I • •

.. add electrophilic substances such as ozone, halogens.and

strong acids. 'l'he add1t1on ot the h~logens to olefins

'(19} may be oon~i~ered. to take place through attack ot an

· electron-poor (positive) halogen ion on the nucleophilio

center...ot the olefin followed b7 reaction with the

additi_on of the negative ion. The brominat1on of benzene

with iron as a catalyst has been explained by the tor-·

m9:tion of the complex Ill'+ fjelll'J- in which the positive

bromine attacks the activated form ot the be.nzene

structure.

The discovery in recent years (9) that iodine

and bromine may form coordination compounds with organic

ba.ses in which they act as positive univalent 1ona

together with the accepted theory of the reaction ot the

h·alogens_ with double bonds suggests a means of preparing

solid. derivatives of olefins.

·aofman (10 l suggested that hypoiodous acid

might have the properties of a., labile base, IOH. This

was proved by the investigations of Ca.rlsohn (9).

9ol!e91ng that lOH could be stabilised by coordination

with tbe baste organ1o molecule p,r1d1ne (py), he ,·,

pttepared a .".er~es o~ , bases ~ {pr )OB. and l (py )2oa. In

these compotlnda tbe iodine 1s present in a positive

uni volen-t; state.

· These salts are usually prepnred by trontlng

. the ·ellYeJ- Or· mercurottS: salt Of Q given &C1c!i with the

calculated amount of ·:iodine and a small excess ot

12.

pyridine in an 1nert solvent· such as chloroform. Immediate • ' ;.I

reaction takes plllCG in accords.nae with the equation:

0•• H1-o-c-cH3 + n + Iol.

0

:t(fd)·O·~·Clfa + Aa l

A few ·or the ooord1nat1on complexes that were

prepatted in dof1n1te crystnll1ne compounds ares

0:i:cn,o-c-o :C.(f1) 0- ~-

0

0

"O:C(~)-O-C NO~0. . ,,re,~)- o-c-f'43

0

::C(M)-o-C!Q

13.,

At approximately. the. so.me time B1rckenback and

his coworke~e .were studying the r~actions.ot a ~ro~p of

compounds given the general name ot pseudohalogens·.

Typical compounds that. fa11·1n this group are iodine

isocyanate,. iodine nitrite, ,nd iodine thiocyanate.

Birokenback (3) .round that INCO and cyolohexene when

cooled to -aao in absolute ether solution gave the

addition compound 2•1odooyolohexyl1sooyanate.

0 + INCO )

Ethrlene, ~hen treated with INCO for two days at approxi-

1:ttat~ly -150 • gav~ the addition p~od~ct which.with ammonia

gave an 82 per cent 71eld or 2-iodoethylurea.

It is ·of interest to note that Birckenaok . . .

suggested (4) that. these o( ,/3 •1odo1socyanates, which

give crystalline ureas and corresponding o~azolines,

might_ give a method to isolat~ and characterize o1ef1ns.

In a later work (5) Birckenback found that the

silver salt of aoetio .. acid would react with iodine and

cyclohexene to form the acetate of 2•1odooyolohexanol.

14~

The same x-·eactibn' was· performed' using· silver.·benzo~te·~

'·J.3otb''··este:re ·w~re:, liquids bo111ni(at 120~ ·~t ·12 mm. and-185°,,at,,-10; :mm.· respectively~· ,, ·

Usohakov; Ohestov and Zelil}sk11. (,40) pr~pared • '; 1 / ' / !,. i : ' > ' ~ '\ f -' > l ', ' ~ ' • ; I \ ' I ' ; ; ; •

a series ot bromine esters. (see ,Te.l?le #1). in which '' • . 1 _ r_, ' J: ,: .· ,' . ' : '

chloroform was used ·as the solvent at a temperature ot . .:Ss0 •

TABLE I

POSITIVE HALOOEM ADDITION COMPOUNDS OF ~CLO~.JE

Salt ··Halogen

... AgCNO·. :12 ., (3)

AgNO. 2 (S)

AgC;L 108~' at 8 mm.•. o~ CS)

120°·at 12 nm. O.::c.o,:tc (S)

- ($)

. 189' at 10 mm. CS)

Salt Halogen Jlelting or Bolling Point .Product Reference·

0 .. c6~ (7) AgOOCC3H7 Bi-a lJ.6 }l.t 14 .Jm4 )01-~,tl, ·. () '

AgOOC/J Bra: 6Mh.So o~.-~ (40)." . 0oo· o~ NO~ AgOOO Br2 ·.·flLS° -o-'i;O . (bo)

. . 0

o~AgOOCOH3 Br 108-JllO at '12 mtn.·-o-o-CH3

(ho) a If

. 0 .

AgOOCC#s ~2 126-128° at 11 mm. o:re3 H~(40)

AgOOCC3H7 Br2 J.45° at lS nm. 0: Q ..('~ 11.,(40).

~

.AgOOC,:{ C12 S().5-51.S0 O~-r1 (~)

· 16.

·.The na.tux-.~. ~f' the,_ so~ vent .employed ·and th~ .

. conoentration of re.actants ai-e cf· prime importance • ., ~ > ' •• ' ·.' ' • ' ; • ' ' ' • ' f,

These factors determirie .. whethc,n't the final· product· will

be a mono~. or .d-1- aster. , .Benzene seems to favor· the pro•

d~~tlo~ ot the 1.,2\Mdibenzoate while chloroform, carbon

tetrachloride and·ethe:r favor mono-ester formation.

(,, ·'', Tl,.~ ~&action between equivalent· quant~ties of

the si.lver. salt .. and .the .halogen results in the ·formation , '

o~. a complex, which will. rea~t .with: the olefin to_ give . . .

the. diester •. · According to·. Prevo at ·( 30) the· hal~ ens

01, Br and I react with ROOOAg in indifferent and

. anhydrous solutions according to the equation;

in which X,~:lways ,plays; the .part ot· the ·positive ion.

Thia complex reacts in ,benzene solution with ethylene -. J ,· i ' - , I •

compounds in two phases according to the equations:

Aa (Rcootx + R1

CH-:CH R" - R'CH(oocR.) CHXR''

+ RCOOF1i-- RiX T ·· R' CH(ooct?) CH(oocR) Rn

17.

~~ 0014 1s used as solvent the halogen, esters. can be

, i.solated as the second phase takes pl~oe very slowly 1n

this, sol.vent •

. 'J!he reaction between equ1molar quantities (5)

results.in the formation of the positive halogen

· derivative or the organic acid which will add across the ·. double bond of the olefin to form the monoester.

These early experiments which show the halogen-

ation of an olefin in organic media' in the presence of a

silver salt resulting in the addition of an atom of

·halogen. and ,t,he anion of the salt seem to indicate a

method of preparing solid derivatives of double bonded

cpmpounds. The preparation of these so-called haloalkyl

~sters, using a nitrated or other appropriately substi-

tuted aromatic acid should raise the molecular weight ot

the addition products to a point where solid derivatives

would be probable.

· Table :tI· shows the melting points (20, 32) ot

. the alkyl esters or several well known nitro substituted

,benzo1o·acids. Since·the derivatives to be made by the·

. process outlined above would be e.pproxima'ted closely. by

these alkyl derivatives in which one ot the hydrogen .

atoms alpha to the oarbon·conta1n1ng the ester group is

replaced bya halogen atom, the melting points ot the

· 18,

··;derivatives should .be in, the same gener~ range,

• ,, i ; ,:

. The· p:roblemj 'therefore, consists of determining

whether the r~iaction or', the positive halogen. salt of a

· substituted benzoio acid w1ll react with a. series of i,,. ~···· ~· . . ; ~ . ., .. , ::. ... · ~; .· ;~' i .· .. '. ,· ' : ! ' : ' • ' ' • • ' \ ' ~ .• !:· ' ,.

oief'1ns to,nroduce. solid derivatives. The use ·or this ' ... ' ' . ; ' • ! ; >! f ;·:' , ' ' r' 1

, , ,ire~~en:t 1n. organ.ic qual~t~~ive. 11.nalysis would depend• •.•• • ,. • • : , ' . ~ ' • '. ' ' ' • ' • ' · . , • • • : • < • , • ;, 1 • ~ • ' ' , • I '. ',. • '

:)1pon the spread .of melting points of the various

derivatives and their ease of preparation, isolation and

purification.

19 •

. TABLE ·II

·ALK~· ESTERS OF .NITRO SUBSTITUTED BENZOIG'·JJ\CIDS

m-nitro Est:er· ., Benzoic

acid

Methyl '78

··Ethyl''; 47(41)

n-pr. -.......

l•pr. .---n~bu. ---'1-btt. ---·n•amyl ---1-emyl ---ter•bu. .........

n•he~l ---n-heptyl ---n•octyl :...... n-nonyl ----eyclo- ---hex,rl

p-nitro 31 6•d1n1tro :Berizo1o' Benzo1c··

acid acid

96 107

-57 93

35 74

lOB-10· 122

·---- 64

--- '75

···- 46

:-•- 61

--- 142

--- 59

·-- 47

--- 61

--- 52

--- 112

2,4,6-trinitro · · Benzo1o

acid

160-+

156-7

146•6

154-6

125-6

127-B

124-5

134-5

------------------

DISCUSSION ·op' 'RESULTS

The silver salt of m•n1trobenzoic acidreo.cted

with bromine 1n a. cooled ohlqrotorm solution to form. the . ' , . . : ' ' . ,~

positive bromine :salt of the organic acid. and ~he pre•

c1p1tat1on of eilyer bromide., To. this salt was add:ed an

olefin and _the result_1ng product was a halogen substi•

tuted.ester in which the halogen.was alpha to the ester

_group and a p1:1r~ of the alkyl .radical.

This procedure, while it did give good y1elds

·of the condensation product, was not suited for 1dent1-

fication Pll?posea 't>eca.u.se not many of th~ products were

solid at ro_om temperature.

1n· an. attempt ·to raise the molecular weight ot · the addition compounds, both the halogen and acid were

changed to iodine and 3,5-dinitrobenzoio acid, respectively.

Because of the tendency of the din1tro acid to form com-

. plexes in the presence of sodium hydroxide,· the procedure

for preparation of the silver .. ~alt ·was mod1t1ed to in-

clude ammonium hydro~de -as the base.

:The' same series or reactions were run aga~n using

·the new 'reagents. The melting points of corresponding . ' ;

ol'ef in . addt tion comp'ounds . were ra1 sed from forty to fifty ' . .

degrees. The ditferences··between melting points were such

as to indicate that the method would serve as a general

21.

· identification method •.

''!here are many fact~~s that favor this reaction

and the reagents used .•. Absolute ether 1s used as the , ·'." :. . . .. : " , i . . ' '. ; , ! • <.... ' ' ' ' ' \ : . . . ,' ', t ·:, ' • ' : ' • , ' I • ,' " ;

solvent because or the greater solubility of iodine in

it than in chloroform. : todine, being a solid, is much,

safer and easier to, .~andl.e,. It can be added to the ,; !··.,,

reaction mixture in the solid state and manual shaking·

of the. slu~ry, will induce almost immediate reaction .

. with the discharge of:the iodine color ·and the precipi-

tation ot silver iodide. In ever7 case, aftE!r addition

was ,complete,· the excess halogen was :r:emoved and tho

.. so.lution was washed. wit~ sodium carbonate and· dried.

, ., .. · A· s~udy of the, melting points indicates th~t

s,mDle~ryin ~he mol~otile tends to increase.the melting . . " - '

. point. Whereas the iodine-dinitro acid addition compound ., .., '. ' . .. . ' ~ ..

iwith penten~-1 meltir a.t '17°, the same addition to /. '•. • -1 , o· ' ,. •~· r ·, · '

()y~iopentene places·themelt1ng ·point at 111°. On the

'average the'melt:tng point~ ;of the esters with an even

.nUlltbE!~ of. o~rbon at~m~ in .the .alkyl group tend to be

lower than the corresponding odd molecules, The branch-

, ing of the chain also raises the melting point.

While· no special· precautions were taken to

determine the mode of addition to the double bond. it

: is assumed that normal addition ocoured and compounds of

22.

the genePal stru~tur$ shown below were obtained.

o . H . L.J .' .. •• ' . ~ R-C-~I .. + R--C: c~H

0 R f-f' • II • I ___ _.,, R-t-o-c-~-I •• . H ·H

Since an alkyl ·radical h~s a ·greater· tendency to release

electrons, thr{ normal addition product would place the

1cid1ne on· the .terminal carbon (tor 1-olefins).. The

absence. of any evidence ot :more than one compound :, )

coupled with the :fact that· the reaction seems almost

ionic in character,· seems to indicate the type of

add1t1onp<>stulated. above. Purther study to determine

the effect of peroxide's on the direction of addition .

suggests itself as an interesting continuation ot the.

present work.

ln this preliminary research no attempt was made

to;determine opt1mwn.cond1t1ons.to~ maximum Jields. The

main purpose was to.devel9p a simple laboratory method

or ident.ifioation ot oletins •.

23 • .

TABLE'III. · sot1n ·DERIVATi:vEs· op 's1MPLE oLEFINs

:I..· De~1vatives.'o·t ·3,5•d1nitrobenz~1·c· acid

Halo'gen. %Yield Melting Point

Eth,-iene· I2 4?.2 91•2~92°

Prcpjlen• I2 44.4 e2.·2-a3° ·

Blltene•l. Ia 55.0 '73.1

2•74°

. tsot'.,utylene Ig 42.·2 108 ,'4-109, 20

Pentene•l 12 58.0 76.2•'77°

liexene-1 12 65,0 49,4•60,4° '1 ... ;

octylene•l. ·1.2 --~· Liquid

O:vc;opentene Xs 61,0 · lll•lll,80

O,..clohexene :~2' 66,0 158,4-159~

Bal·ogen ~ Yield Melting Point.

: .·.. ': ' 0o,-olopentene Bl-2 43.0 so.a-01.2

o,-olohexen, · . ;J3r2,- 40.0 '74,8-75.1°

24.

EXPERIMENTAL

A.· PREPARA~ION OF THE O~EFINS.

Whenever·possible the olefins·used were

obtainep.,_,tro~ commercial sources._ Those not available

were prepared in the laboratory by dehydration of the

corresponding alcohols over activated alumina or sulfuric

acid.

Dehydration With Alumina ·, '. >

A pyrex glass dehydrator was made by sealing

two 29/42 ground glass joints _to a long tube. The over-

all length was· ·3.1/2 feet and internal diameter was

. 28 mm. The hQ$.t1ng element was prepared by v1ind1ng a

iar•ger pyrex glass tube with .·nichrome wire and covering

it with magnesia pipe insulation. The inner column was

supported by winding one-hal.f inch asbestos tape to just

fit into the external jacket at both ends of the tube.

The asbestos supports were then built up to the level

jacket. -· ,.

or the oute:ri The tape was held fast by SO!J-king

in water g·lass be:t'o-re winding •.

The column was pack~d with Harshaw Grade A

aot1yated alumina. (Pu.ralox) supported by a glass wool

plug. Tpe catalyst was preceded by a layer of glass beada

25.

to act as a, preheat er. . A vari tran' (Model. v-2 ). was used

to heat, ; the column~;

~emperatures were read on ·a Type HA port~ble

Hoskins "High.Resistance" Pyrome·t~r ·using an alumel

th~rmocouple.:. '?he' the'rmo:couple was taped to the inner

reaction tube 1n: .the ·spe..~e between' th~ two tubes~

The .furnace and reaction tube were suspended ' . ,,

.vertically and titt.ed with a gr·aduated dropping funnel •

. A two-necked' flask was ,used as 'a receiver •. It was

piaoed· in An ice-salt bath with the' outlet connected to .

a dry ice trap.

··Dehydration.With SU1~ur,1c ,Acid

To prepare gaseous olefins a mixture of the

acid.catalyst and.the appropriate alcohol were heated.in :.; . ' . '; ;' ' ' ' ' ' . '

a ·two-necked one litel" flask fitted with a·dropping ; '

tunnel and a ref~ux condenser. From the top of the

conden·ser. a tube v,as +ed through. a washing 1'bottle con-

· taining. a .concentrated. solution of.sodium hy~oxide.and

:a .drying, tower to the, reaction .. .,easel •.

Liquid olefins were prepare4 by heating a

mixture of the acid catalyst end appropriate alcohol.

· The ol.efirt was distilled through an efficient condenser

into a flask cooled inan·1ce bath. To remove traces of

26.

, i,ulturou.s ,acid ,from ,the product, the distillate was • ' .;, ; :, < • ' , • '

: ~raneterred to a separatory,· funnel and washed w1 th a

19 per cent sodium hy~oxide solution. - The hydrocarbon

layer was dPied over calcium chloride and distilled

through an efficient fractionating column ( 35) •

.. . Those gaseou~ olefins that. could be purchased

~ere pass.ed .':through a drying tower directl-y · into the

reaction -mixture. .' .. :

,Ethylene was purchased from the Ptlritan Compressed Gas .

~~rpor1:1t~~n an.d ·was of· sufficient purity to be used

a.a an anesthetic~

Propylene (18) was prepared from isopropyl alcohol

~sing th~ "l t 1 acid" made by mixing equal volumes

· ot water and concentrated sulfuric acid. The re-

action mixture was ·heated to 1400 in an oil bath.

Butene•l was purchased fl'om the Phillips Petroleum

Company. '!'he minimum purity was 99 mol per-cent.

Isobutylene (18) was prepared from tertiary butyl

alcohol using the 01: 2 acid" made by mixing two

volumes of water wi.th one volume of concentrated

sulfuric acid. The l'eaction mixture was heated on

a steam bath.

Penetene-1 was purchased from Phillips Petroleum Company.

27.·.

'?he minimum pttr1~f was 95 mol. per cent. Thie olefin

was ~1st111ed through an etfio1en~_fraot1o~at1on

column and. a cut boiling from 39-40° was used· in the

preparation of the'der1vat1ve.

He,cene•l (24) wa_s prepared from h~xanol-~. by dehydration

o~er activated alumina at 360°0. The alcohol.was run

into the reaction chamber at a rate from 35 to 60 ml.

·per hour. At the end of the run the water layer was

removed and the olefin layer distilled. A traction

boiling from 61.5 to s20. was used.

Ootyleti~-1 was puroha_sed from Eastman Kodak Company

and .rep~i.1'.~ed: by distillation. A fraction ~oiling

at 125~128° w~s ~sed.

0,-olohexene ·was ·pu:rche.sed·from,Eastman Kodak Company

and r,purified by d1st1llatio~. A fraction boiling

at a2.s-s30 was used.

0,,clopenten~ was prepared through the following series

of reaotionss O,,~lohexanol was oxidized to ad1p1c ~ 1 ' • ' ' ' ' l •

' '

acid with nitric acid (16); the adipic acid was

converted to orolopentanone thr_ough the barium salt '·

( 37) J oyolopents.none was hydrogenated to oyclo-

pentanol using Raney nickel at 120° and a pressure

· ot .1500 pounds per square inch;. the oyolopentanol ' .

was dehydrated. over alumina at 3'75°.

B.~ TB~. REACTION ·OF: OLEFINS WITH ~HE POSITIVE BROMINE

DERIVATIVE OF M-NITROBENZOIO AOID.

Preparation O.f Silver m~Ni trobenzoate

28.

Exactly 11 g. of sodium hydroxide was dissolved

1n 200 ml.· of water.and m•nitrobanzoio acid was added

until the sol~tion became slightly acid to litmus. The

last halt of the acid was added while the solution was

heated on a steam bat~. Approximately 44 g. ot acid was

_reqttitt:ed. '?he .solution was then cooled to about . 450 and .

filtered.

A. solution ot 45 g •. of silver nitrate in 100 ml.

'ot, water was added, slowly and with s.tirring to the cooled

mixture.· After the addition of the silver nitrate the

solution was d1lluted to about 1500 ml. and the.white

precipitate of silver m•n1trobenzoate waa washed several

times·, ~nd filtered by suction. The salt may be dried in

an oven at a temperature·not to exceed 45°. The yield

ot silver salt was 65 g., 89 per cent ot theoretical.

29.

,. ·Preparation, · Of · The Ester

. . (j ,JO·..... ··o· a.. r~o ... _c .· .·

;(4\. typical ru.n .consisted of preparing a suspension . .

of 15 g, or silver m•nitrol)enzoate in lOQ ml. of dried

".chlorotorm, cooling .. to .below -10° and ·adding dropw1se to

the sti)!red··mbt~r:e .lo, g.: .. of· bronifne dissolved in 35 ml.r .,;

of. CHOl3. A I cooling bath ot 96 per· cent alcohol or a . . ,. ·'"'""·

50..;50:per ·oent·m1xture of.OH013•C014 was used and dry 1oe

wa.sadded when needed·to keep the·temperature within the

p:r~per range. ·Silver bromide was preo1pite.ted during·

the addition-but this did not interfere with the reaction.

An excess of the olefin was then added slowly . .

'(because of· the· slight ·excess· ot ·bromine used) and the.·

mixture stirred until· all color was remove.d. The. solution

was stirred·e.nd cooled.for at least 15 minutes after the

-addition was complete. The ·reaction mixture-was·t1ltered

b:-t suction_·. and the precipitate we.a• extract.ed twice with

0~013 ._ All extracts were combined, washed w~th 10 per

cent sodium carbon~te s~lution and water ~nd dried, and

the so~vent was then r~oved by- di~t1llat1on on a steam

bath or evaporatio~ ~ver_night 1n an open dish.

~e-~esidueobtained was pur1~1ed, by washing

tw:toe with 10 ml. por_tions of 96 per cent alcohol and ,

t.hen d~ssolVing the residu·e in hot ·95 .Per cent· ·alcohol

(l.O ml.· pei- .sr~ .ot cru~~ .product). and cooling ·slowly •

. The. derivatl ve, it solid~ usu'e.lly sepnrate·d eas11,-·· on

. cooling.·. It was seldom necessary to recrystallime the s ~ • I ' ' . ' ' " • ' '

de~ivat1ve.more than twice to get a constant melting

range.

30 •.

31.

Derivatives With m-Nitrobenzoic -Acid ' '

Oyolopentene.derivat1ve -- Added 4.5 g. ot cyclopentene

~n 25 ml! of : OHOl3 to . the .. standard .. br~~ne salt solution. .Obtained 6.8 g. ot. cl'ude solid •.. The

yield was ~O .p~r.cent.

M.W. -. 314.14 M.P.= 74.8•75.lo

.. Calculated . Br -- 26,44% Found: Br -~. 25,7, 26.0

I •• • ) ~ < .' ; • • • ' '

Oyclohexene derivative -- Added 5 g. ot cyclohexene in

25. ml •. of OH013• .Qbtained ·,7,.'75 ·g. of crude solid.· ·

'fhe ylsld was.. 43 . per . ce.nt •.

· ·M·.W•. • · ·328 .17

Pentene-1 derivativei_;_ Added 5,5 g. ~r pentene-1 in

25 mi~ . ot. ~oi3• Upon evaporation Qf the sol vent the residue was. a ;viscous· liquid •. It was 1not possible

to obtain a , sol~d by reor:;sta;11zation·. A second run

gave exactly the .. same results.· The ·Use ot .0.014 ·in a

third :r-un resulted in no reaction as t.he·, evaporation

of:the solvent left no residue.·

Octylene-1 der:lvativ~r'-- ~dded 7 g·~ of ootylene-1 in

25 ml.· ot , OH013 • · Upon evaporation ot. the sol vent a

very poor yield of a brownish liquid was obtained.

· !his liquid .could not be sol1·d1f1ed.

32.·

< < •

. O. THE REACTION OF OLEFINS WITH THE POSITIVE XODINB

DERIVA~IVE_OF 3,5-DINITROB~NZOiq ACID ,, • • < I ,. :·_: - , 1'> •

···Preparation· Of Silver 3.5•Din1trobenzoate ..

.Ho-~(?fJOa

.' ooft/"a NH-o-c _., <

, < • • • "''l <

~aatly 53.03 g. (0.25 mole) _or 3,6-dinitro-• ' <

I ,,

_benzoic acid. was added portionwise to a hot solution of • < '

16.7 ml. ot conaentl'~ted ~40H (15 H) in 400 _ml. of

wateruntil all ~he.solid had dissolved and the solution

tested acid to litmus. An excess of NH40H had to be

added because ·of evaporation. The solution containing

tho ammonium salt was filtered hot and then allowed to

cool to soo. · To this ~as ·ad,ded 42.47 g. (0.26 mole) ot

silver nitrate in 250 ml. ot water and the entire . ; . ' : : ,', \ '.

·solut_ion was .diluted to approximately two liters.· The

precipitated salt was. filtered• washed several times, and

dried at 450. To taoili tate drying the salt can be

washed with 95 per cent. alcohol but .when used the dry

salt seems to take on a darker color.

The average yield was V4 grams. This was 92.6

per .. cent of the theoretical.

33 •

. Preparation Of ·The ·Ester·

)

0"ONOa,RaI + I-o-c .· . NO.a,

. 0 '' . 0 ,, O·"'Oa. .I-o-c ·. H R ,, aOa,

+ RCH=CH.1 --..) r-c-c-o- (! tf t-f , , 1\-0a. NC)a

Irt a 500.ml-. er~enmeye~ flask _12.'76_.S• (0.04

mole) of s~l!e: . ~,.6:dini tr~ben,oate w~s shak~n with 125

ml. 9t· ~b-~olt1t! ether~ .. · Th?. ol~~in (~.04 ~ol!~ was mixed

w'ith ·th~. slurry, and lQ.15. g. (0.04. mole) ot solid iodine ~ ' . ~ ...., ...... ,' ... .\ ) -/' •' ... ·,, . \• ', " .'

wart added in small. amounts. · After, .ea9h addition. the . r, . .... ,.. .•.• . .,.. .

mixture was she.ken until the color of the iodine was

discharged a.nd the addi.tions were ·continued until the ~ . ' .

color remained after several minutes.of 'shaking~

The r·eaotion · mixture was filtered from the ' . . '• ~ ~

preci~itat~d~I and the salt w!ls extracted· several times

with ether. The combined ethereal solution was washed

· with 10 per cent ·wa2003 solution to which had been added . .

a small amount ot Wa2S203 to r~move any tree iodine

present. . The ; solution. was then washed::Wi th water and

·dried.

'fhe ether w_e.s removed by distillation or evapo-

ration ,nd a brovmis~ residue was obtained. The residue . . '

. ..

was recrystallized trom high bc:>iling skelly. "' ' ' - ' ~

Two or three

recrystallizations wer'e usually enough to obtain a sharp . . . '

melting white solid.

Liquid ole:f'ins w~re weighed d~rectly• dis- , ·

. ttblved 1n 25 ml.· of absolute ethe:r and edded to ·the

· slttrry.-· Gaseous alkenes ·Were washed· and. dried. ·e.s : ,:. 'I l •'

d&s.crlbed un.der preparation of olefins and passed

· di~eotly int~: the slurry with a· de~i very. t~be .: : TJ;le" ~ • ' ~ ! .. ' ' . • '.. • . '

34.

tdd.1t1on of olefin was c~ntinuous while the ·iodine was , ) '. ,., ·. ·.·: ,1,1,,

introduced po~t.ionw1:se •. . ~

I

35.

Derivatives With 3,5~Dinitrobenzoio Acid

Ethylene derivative -- Ethylene gas was passed directly '·. ' - ' ' , : ' . • ' : ' • • 1 • : ·~. ~ : ' ! ' : . - . . . ' . . ' • .. . t,

into the. ether s.olution of the reagents. A crude .•, : '· 'i' ~ •• : ' ' .- •~ • ; '. t ; ' ' ~ : 1 ', •: I '"'

y1eid of 6.9 g. was obtained •.. 'l'he. yield was: 147 .2 per

~·: ...... . ', ,. ' . . . : . ~. . .·." ' ' ' .

cent ot theoretical· •.

. M.W. - 366.09 M.P.: 9l.2-92Q.

Propylene derivative ·- Propylene gas was prepared

fr~m .. isopropyl_ .al~C>hol. , 4\ cr~~e. yie.ld ot 6.6 g.

was obtained. ·The. yield was 44.4 per cent ot theoretical.

. •·.w. - 300.14

,, ;

Su:tene-1 derivative-~ A orttde 7ield of 8.6 g. was

obtained.·· 'Phis was 65 per: cent of theoretical.

: M.W• .;. 394.14· ,•,: ·,up •'

Isobutylene deri'V'ative -- Isobutylene gas was prepared·

tro~ ter~ifl.l'y butyl alcohol. A crude yield of 6.3 g.

was,ob~ained g~ving a percentage yield of 42.2 per oent. ·

Pentene-1 derivative•• Added 2.8 g. of pentene-11n

25 ml. ot ether. Exactly 9.6 g. of· crude solid was

obtained. The percentage yie~d was 68 per cent.

M.W. • 408.16

36.

Hexene-1 derivative-~ Exactly 3.8 g.-of hexene•l in

25~:111;r of .ether was added to .the reaction mixture,;

· ~he crude product. weighed ll· g. The percentage .

,-i~ld was 65 per cent •.

M.W. --422.19

·ootylene-l derivative --·Added. 4.5 g •. of octylene-1 in

of ether., Upon evaporati'on of· the solvent a

. br'ownish viscous iiquid was obtained, This liquid

could ,not be :·solidified •. Cooling in a dryfee bath ' . ' ' .

·. -~au·sed '.the ,p;oduc~ to .set to ,a glass ·which remelted

. ' upon. warming ,to ,room temperature •...

' ' ' :· /'•.

9tclohexe1:1e der1 vati ve. --<Added 3 .·3 g. of cyclohexene in ':·;,·,' : \'

as m1.· of ether4 . obtained 10.1 g. ·ot crude .pr_~duot 'I.

' !';

which .·was ·66 per cent ot theoretical.,

Oyclopentehe derivativ~ --Added.2.7 g. _ot oyclopentene • ; . ,• . '. ,• , ; / ; , • \ ! ~ I ( ' ! f : :' / : ' _' ~ ,_ ; ' ' '. : : '. •• '- ; ;• ' • ' • _. i' •!{I,• : ' I ' ._.' : : I ',' ' .' '

. 1n 25 mli. qt.ether.. .'J.'hec~uije y1eld was 9.9 g. Thia . · ~ ~ 61' ~er),ent. o~ .ih~~l'~~ib.a1°i . . . · · ·

Y 012Hno~N2~' : · 111·:~,' ..... ·4oa~:i.s:·,;..,,m.p.: 111-111.0° ' '' ,; . ' ' . ' ; ! : ' ; ' ~ ' ' \. ' ,.. .', , '

l ' '· . ~ ~ : ·•

The samples of the various derivatives have \ ,:;I·_! i <· , ' '

','

be'en sent "awe:yfol" analysis and -the results are e·xpected ~ . ., ', •.

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.. . ' . ' '

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