HYDROCARBON

REPORT 1112

AND NONHYDROCARBON DERIVATIVES OF CYCLOPROPA.NE

By VDENONA. SLABEY,PA6L H. WISE, and LouIs C. GIBBONS

SUMMARY

The md.hod%wed to prepare and putijy 19 hydrocarbonderimiitw of cyclopropane are di+wu.med. Of thae hydro-carbon, 13 we synth.aiwd for the first time. In add&ion tothe hydrocarbons, six q@qwopyl.c.arbino18, fine alkyl cyclo-pro~l ketmw, three qiclqropyl chloride+ and one cyclo-propandicurboxylute were prepared as syn$he.sis intermedti.

The nutting ptiti, boili~, point8, refrti”ve indice8, densi-ti.e8, and, in some in&?ance8, hem% of combu.dion of both thehydrocarbon and nonhydrocurbon derioatiux of qclopropamwere determined. Thae data and b injrared qoectrum ofeach of the 84 eyclopropa~ compound8 are presented herein.

The infrared absorption bad chara.ct.m”dti of the cycl.Q-prop@ ring are discu#8ed, and 8ome ob8erdun$ are made onthe contribtitin of tlw cyclopropyl ring i%the mole&r rejfrac-tionq of cycl.opropam compound8.

INTRODUCTION

The synthesis and purification of cyclopropane hydro-cmbons was begun at the NACA Lewis laboratory in 1944 inorder to provide high-purity samples of substitukd cyclo-propancs for ru+ investigation of the effect of molecularstructure on combustion characteristics and other propertiespertinent to research on fuels for aircraft propulsion systems.The present report summarizes the research pertaining tothe synthesis of 19 hydrocarbon and 15 nonhydrocarbonderivatives of cyclopropane.

Few general methods for preparing hydrocarbons whichcontain the cyclopropyl ring are Imown. The method ofG%tavson, which involves the reaction of a,y-dibromideswith zinc dust in a protonic solvent, has frequently been used(refs. 1 to 6):

ZnCHrCHrCHi _ CHFCH,

$r ‘c’i,

CH2Br C“H2 CD,

AZn

O H7\c/

—CH3 _

h H,Br L<, \cH3

A modiikation of the Gustavson reaction, in which mag-nesium reacted in tetrahydrofumn with an a,-j-dichloride,was recently used tu prepare methylenecyclopropane (ref. 7):

The pyrolysis of pyrazolinek haa ako found limited use for thepreparation of certain cyolopropanes (refs. 8 to 11):

CH, CH3 CHS CHS\n/ . \n/

A method reported by Whitmore and co-workers (refs. 12

to 15) involves the removal of hydrogen halide from alkylhalides in which the halogen atom is one carbon removedfrom a quaternary carbon atom:

CH, CH, CHI

ANa

‘CHr , —CH,C1 _\c/

/\

In each of these methods the cyclopropane ring is formedduring the reaction.

Another approach to the synthesis of cyclopropane hydro-carbons is that which involves the conversion of nonhydro-ca.rbon derivatives of cyclopropane to the correspondinghydrocmbon derivatives. For example, some of the carbinolderivatives of cyclopmpane have been dehydrated with acidiccatalysts to the corresponding cyclopropylalkenesto 20):

c? CH, c? C H,

1

A— —CHS _

i’

CH— A=CH,

$CH A2 H d s

(refs. 16

Exhaustive methylation of cydopropylcarbInyltie9 alsoh~ been reported to yield cyclopmpylalkenes (ref. 21):

In an analogous manner, cyclopropene has been preparedfrom cyclopropylamine (ref. 22). For the preparation of

81

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(

82 RI?JJ?OETlll*NATIONAL ADVISORY

certain cyclopmpylalkanea, the WoliT-KiShner reduction ofcyclopmpyl ketones hss been used (refs. 23 to 25):

c?

1N2H4

fi:H-I-cHa —C? CHS CH*

1

hKOH

CH—

1

\EN—NH* _ CH—CH~CHJ

/Hj $ 2

The usefulness of all the reactions described is limited bythe availability of starting materials. With few- exceptions,the a,-y-dibromides for the Gustav~n reaction, the pyra-zolines, the halidea suitable for hydrogan halide eliminationreactions, and the nonhydrocarbon derivatives of cyclopm-pane are not commercially available. Consequently, cyclo-propane hydrocarbons generslly have been prepsred only inlimited research quantities. With the exception of cycJo-propane itself, which has been used m an anesthetic, none ofthe cyclopropane hydrocarbons are available commercially.

The announcement during World War II of the commercialavailability of methyl cyclopropyl ketone wincided with theinterest of the Lewis laborakmy in the preparation of cyclo-propane hydrocarbons. It was believed that this nonhydm-carbon derivative of ,cyclopropane wuld be used to preparea series of cyclopmpane hydrocarbons in the followingmanner: The ketone was known to react with Grignard re-agents to give methylallgdcyclopmpylcarbinols (refs. 26and 27):

~, hydrocarbon radical; X, halogen atom]By using @.fferent R—X compounds for the preparation ofR—Mg—X, the length and the degree of branching of thehydrocarbon chain could be varied. The methyla@lcyclo-propylcarbinols were bow-n to dehydrate in the presence ofacid catalysts to the cyclopropylslkenes (refs. 16 to 20), al-

though the practicability of the reaction as a synthesismethod had not been established:

The selective hydrogenation of the cyclopropyhdkenes to thecorresponding cyclopmpykdkanes had not been iuvestigatdd;but it was believed that by proper selection of catalyst, tem-perature, and pressure,”the desired hydrogenation could beaccomplished:

C? CH*

(!CH— —R

orCHi CH, c? CH,

i

\&

HtC H— =R(—H) _

L

L!CH— H—R

$ z $ ?.

Coammtmil FOR AERONAUTICS

(Concurrently with the present research, the authora of refs.28 and 29 attempted the, catalytic hydrogenation of 2-cyclo-propylpropene and vinylcyclopropane. The cotnlyst andthe reaction conditions employed by them yielded the cor-responding cyclopropyhdkanes but also gave considerable~OllIltS of pWdiI1.iC hydrocarbons.)

A toixil of 12 cyclopropylalkenea and 5 cyclopropyhdkaneawere prepared in this, manner from methyl, cyclopropylketone:

By dehytiation of alkyloyolopropylwrbinols,—Vinylcyclopropane2-Cyclopropylprop ene ,.

2-Cyclopropyl-l-butene2-Cyclopropyl-l-p entene%Cydopropyl-1-hexene2-Cyclopropyl-3-methyl-l-butene2-Cyclopropyl-2-butene (1.b.)2-Cyclopropyl-2-butene (h. b.)2-CycJopropyl-2-pentene (1.b.)2-C?yclopropyl-2-pentene (E b.)2-Cyclopropyl-2-hexene (1.b.)2-Cydopropyl-2-hexene (h. b.)

(The abbreviations 1.b. and h. b. denote the low-boiling and@e high-boiling geometrical isomers, r~pectively.)

By hydrogenation of cyclopropylalkenes,—,~clopropylpropsne2-Cyclopropylbutane2-Cycilopropylpentane2-C?yclopropylhexane2-@lopropyl-3-methylbutane

Of these 17 hydrocarbons, 12 mre prepared for the first time.In addition to the hydrocarbons, six cyclopropyhwrbinols

-were‘obtained as synthesis intwmediatea, ~and five oyclo-propyl ketones tiere obtained bm the ozonization of the2-cycJopropyl-l-alkanes: .

Cyclopropyloarbinols from Ch’ignardreaotions.—DimethylcyclopropylcarbinolMethylethylcycJopropylcarbinolMethylpropylcyclopropylcarbinolMethylisopropylcyclopropylcarbinolMethylbutylcyclopropylcarbinol

Cyclopropyl ketones from ozonization of 2-oyolopropyl-l-alkenes.— I

Methyl cyclopropyl ketoneEthyl cyclopropyl ketonePropyl cyclopropyl ketoneIsopropyl cyclopropyl ketoneButyl cyclopropyl ketone

Cyclopropylcarbinol from rednotion of cyolopropylketone.—Methylcyclopropylcarbinol

Two other cyclopmpane hydrocarbons, spiropentano andthe smallcat of the &cyclic hydrocarbons, dicyclopropyl,vmre prepared in the present investigation. Spiropentanewas obtained from the debrmnination of pentaerythrityltetrabromide, which was accomplished in a manner similarto that described by HW and co-workers for preparingcyclopropfme (ref. 30):

HYDROCARBON

BrCH2 CH,Br\c/ Zn

~rc<, \cH,Br NaI~cOa

AND NONHYDROCARBON DDRIVATTVIIH OF C!YCLOPROPAITEI 83

C H, C H,

ii

\c/

$b,a

The preparation of dicyclopropyl involved the photochemicdchlorination of cyclopropane (ref. 31) and the reaction of oneof the chlorination products, cyclopropyl chloride, withlithium in ether:

CH,

1

CH,\ hv

CHi + C1i _

1

\

/CH—C1 ‘

Hi $ 1

c? C Hj CH, “

1

I,iCH—C1 _

i!

\CH—C$

/ / \H,H, Hs

From the photochemicxd chlorination of cyclopropane,two other cyclopropyl chlorides were isolated, namely,1,1-dichlorocyc.loprcpane and tram-l,%dichlorocyclopropane.

Molting points, boiling points, refractive indices,’densities,and, in some instances, heats of combustion of the hydro-carbon and nonhydmcarbon derivatives of cyclopropanewhich were either prepared for the fit time or isolated in ahigher state of purity than heretofore were determined. Theinfrared spectra of the 34 cyclopmpane compounds were alsodetermined, and wch of the spectra is presented herein.Some observations on the molecular refraction of cyclopro-pane compounds are included in the report.

APPARATUS ~

The Grignard reactions were tied out in either a 10-or a 30-gallon glass-lined reactor which w’sa double-walledsc that the reaction temperatures could be controlled bypassing steam or cold or hot water between the inner andouter walls. The reactors were equipped with efficientmotor-driven stirrers, bigh+apscity reflux condensers, andstainlesssteel tanks from which liquid reactants -iverefed bygravity into the reactors.

The column used in dehydrating some of the cyclopropyl-”carbinols consisted of a 2.5- by 90-centimeter pyrex tubewhich was tilled with 8 to 14 mesh ahunina and heated byresistance-element tube furnaces. Temperatures of thefurnwes were controlled by manual adjw-trnent of variabletransformers between-the furnaces and the laboratory pomrsupply. Column temperatures were read from an indicatingpotentiometer connected to thermocouples which were heldin phme against the outer walls of the pyrex dehydrationtube by means of copper strips. A bellows-type pump wssused to force the liquid carbinols into the top of the culumn;the vaporized products issuingfrom the bottom of the columnwere condensed by a water-cooled spiral condenser andcollected in a flask at room temperature. The flask in turnwas comected to a trap chilled with solid carbon dioxideand acetone, so that products volatile at room temperature

could’ also be collected. A sketch of the assembly is shownin figure 1.

1Tube

furnaces-~,.‘.

,,--Alumina.> 1

..--,-- Thermocouples/

,’t’

.’

FIGWEEl.—Ap@%tasnssdindehydrating oyclopmpylcarblnols ovor almnha.

The hydrogenation reactions mre conducted in high-preasure steel autoclaves of 1-, 3.4-, and 4.41iter capacities.The autcclavw were equipped with rc@er-type shakingmechanisms, resistance heaters, thermocouples and potenti-ometers for determining reaction temperatures, and appro-priate valves, pressure gsges, and high-pressure lines forintroducing hydrogen into the vessels.

Fractional distillation columns were used in the pyrifkationof intermediates and fial products. For fractionation atreduced pressures, 2.5- by 180-centimeter pyrex columns,which were packed with fi~inch single-turn glass helices,were used. Columns 2.2 by 180 centimeters, packed with)&inch single-turn glass helices, were used for fractionationof those intermediates which could be distilled at atmosphericpressureand for the initial fractionation of the hydrocarbons.

84 REPORT lll%NATIONAL ADTTSORY COMlUTT13E FOR A13RONAlJTICS-

For final purification of the hydrocarbons, 2.5- by- 180centimeter Podbielniak columns, operated at ficiencies inexcess of 150 theoretical plates, were employed.

The ozonization apparatti, used in the identification of cy-clopropylalkenes, was similarto that described in reference 32.A 0.25 kilovoh%mperb transformer with an input of 120volts and an output of 25,000 volts was used to supplythe necessary potential to the electrodes of the ozonizwtube.

The app&atus for the photochemical chlorination ofcyclopropane was essentially the same as that demibed inreference 31 except that the recycling systam was eliminated.The ‘reactor was cmstructed of 0.7+mtimeter pyrex tubingwhich was bent to form a planar grid; total length of thetubing ma 470 centimeter. The reactor was illuminatedby two G. E. type-RS sun lamps placed directly in front ofthe grid and mounted so that their distance from the gridcould be varied. The scrubbing towers for removing thehydrogen chloride and the chlorige from. the reaction prod-u@s were constructed of 0.45~ by 122-centimeter pyrmtubing and were packed with %-inch Berl saddles to increasethe contact area. .The flowmetera in the system were usedprimarily to check the constancy of gas flows; quantities ofreactants were measuredby loss in weight of the gas cylinders.A sketch of the apparatus is shown in figure 2.

at “

[

ioOH

*XIde-. !!7

FIGURE2—Appamtm Ilswl for plmWbkxi3mtkm of Oydopmpana

The infrared spectrophotometm used in detwmining thetimed spectra of the hydrocarbon and nonhydrocarbonderivatiwa of cyclopropane was a Baird Associates double-beam recording spectiophotometar equipped with a sodiumchloride prism. Liquid sample cells of O.1-millimetw thick-ness were used, and the spectra of undiluted samples andalso of sampl~ diluted with either carbon tetrachloride orcarbon d.isulfidewere obtained. .

DISCUSSION OF SYNTHESES

Descriptions of the synth-es have been generalized in the -following discussion; for detailed descriptions of each syn-

thesis, the reader is referred to the synthesis reports pre-viously published (refs. 33 to 39).

ALKYLcYcLoPFtoPYLcARmoLa

Methylcyclopropyloarbinol,—Five-mole quantities ofmethyl cyclopropyl ketone were reduced by four methods:(1) with sodium metal in 75-percent ethyl alcohol,’ (2) withlithium aluminum hydride in ether, (3)-with hydrogen inthe presenw”of Raney nickel catalyst, and (4) with hydrogonin the presence of copper chromite catalyst. The reactionsand products are summarized in the following table (ref. 33):

Moles of R~;~ Moles of Yfeld of Ylold ofR&inaku agent y#i# - ketone oarblnol, Pm@lcn;z,

trim, “o mmvemdparent

mlmhol.+ +--.--l :$INaandaqnmmI I

LW4------------------- z.---l--- d: I None

I

41

I

o

Hi-RanoY Nf-_-_-_-l Theoretical .1 93-12SI&o 76

a4 2

I-Pti Ctidb------- ..-_do_... &

INone

I90Do-------------------. . . ..do ----- Nono 87 I :

Do-------------------- --do--- 1S0 Nono 70 m. 10

These data show that of the methods investigated, the hydro-genation of methyl cyclopropyl ketone in the presence ofcopper cbromite catalyst was the most satisfactory for prc+-P- metiyloyclopropylcmbinol. The reduction withlithium aluminum hydride was also acceptable for preparingsmall quantities of the carbinol, although the yields werenot so high as those obfmined catalytically with copperChromite. Neithen the reduction with sodium nor that withRaney nickel was satisfackmy because of the low yields ofcarbinol obtained and also, in the latter method, becauso ofthe formation of a close-boiling impurity, pentanol-2,

MethylaIkylcyclopropylcarbinols.-The methylalkylcyclo-propylcarbinols were prepared in ether by the re?ction ofmethyl cydopropyl ketone with the Grignard roagenta ofappropriate alkyl halides. In general, the Grignard rm.gentwas prepared (ii 2 to 5 percent excess) by adding tlm dkylhalide to a suspension of magnesium mqtal in ether, thcmadding the ketone to the Grignard reagent, and finallyhydrolyzing the products of the reaction with satumtcxlaqueous ammonium chloride solution. The quantitica ofreactants and the yields of the carbinols are summarized inthe following table:

AR+ halfde MhO&f CyolopropyluubInol ;~:t Roferonm

Meth 1ohlorfde------ 1K3 Dhnetbyl . . . . . . . . . . . . . . . 04 34Etby bromide-------Pmp 1hmndde- . . . . . . . Ii

;Bnty bmmfdo..-- . . . .kpmpyl bmmfdo. . . . . . 1%

wi%i:~~::::::

g ;

.- . . . . . . . . .Methylfwpropyl, . . . . . . . 51 36

Because no attempt w= made to determine the reactionconditions necessary for optimum yields of the carbinols,any relations existing between yields of tho carbinols andtheir structures could not be deduced.

Halogenated impuritiw vrere found in all the cmbinols.,“It has been su~ested (ref. 28) that the use of an excess ofammonium cfi&ide & the -product is responsible for

hydrolysis of the Grignarclthe haloganated impurities.

HYDROCARBON AND NONHYDROCARBON DDRI+ATIVE8 OF CYCLOPROPANE

Although ammonium chloride may affect the extent of theside reaction which yields the halogenated impurities, asimple metathesis of the carbinols and the ammoniumchloride does not appear to be the source of the impurities.For example, in the preparation of methylethylcyclopropyl-

g “2.-$’2

4 6 8 10 12 14 16

Wavelength, m&ons -

(a) MethyloycfepropyfmrbfnoL(b) DlmetbyI@fxbpylmrbInoL(o) bfetbyfethyloydopmpylmrbfnoL(d) bfetbylpmpyloycfopmpylmrbfnoL(e) bfetbyllwpmpyloyckpmpyIcarblnoL(0 bfethylbntyleyckmmpyhxblod

FIOLME %-In(mnM ~tm of ewfopmpylwbbml% Lfqnfd Pkmw$O.1-mflffmeter IALUPfMI h’am, dflukf MO with mrlxm tetmehlmfde; lower trace,undllotd.

85

carbiuol, the halogenated impurity was isolated and theelemental analysis of it corresponded not to a chloride, butto a bromide, C7HJ3r. The infrared spectrum of the im-purity indicated the basic structure to be that of a type IVolefln (R,R’C= CHR”) rather than a cyclopropane derivrt-tive. The impurity was prehuned to be l-bromo+l-methyl-3-hexene; a similar structure was obtained -whendimethyl-cyclopropylcarbinol was treated with hydrogen halide(ref. 40). The halogenated impurities were removed fromthe carbinols by refluxing them with alcoholic sodium hy-droxide, removing the precipitated sodium halide by extrac-tion with water, and fractionating the carbinol at reducedprcwure.~ The physical properties ‘of the cyclopropylcarbinols are

campared in the following table with those propertiespreviously reported:

MelmiyCyelepmpykarbfnol

“o

hfetbyl-..Lite@myDiI

. ...---.-1 -3LM!. -- . . . . . . . . . –3-,L1-

Jnethyl_________Llter8tlue______ --80Methylethyl --------Lltemtum__...__- J1.

Metbylpmpyl-_._...Literatnm _________ .-:I-

Methylbntyl-._.__.Literatnro ________ x!--

Metbyllmpmpyi----- (q

E!!%L 4316L 4316

H%L 4412L 44103

L44S3L44344

L 44%3L 44514

L4406

0.8s0

:%!.E$4!a.Em7.8?.555

. mm

.Sm!l

.6785

.87447

.s3s3

Refemnee

33!2034B3420

3420

3426

2s

● Prmsore 700mm Hgnnkss othemEwmted.bEqnflfbrkm meftlng mrwJ cmdd not be obtafneiLoFormd@esw.

The infrared spectra of the cy-clopropylcarbinols are shownin figure 3; characteristic abso~ti~n ~o~the hydroxyl groupis observed between 2.8 and 3.0 microns and for the cyclo-propyl group, between 9.75 and 9.80 microm..

cYci.oPEoPYLmKlmm

The cyclopropylalkenes vmreprepared by dehydrating theappropriate alkyl- or methylal&cyclopropylcarbinols. TWOmethods of dehydrating the carbinols were investigated:

Alumina,-The carbinol (in some cases, dissolved in tol-uene) was passed at a rate of 5 to 10 milliliter per minutethrough a 2.5- by 120-centimeter pyrex tube which -mapacked with 8 to 14 mwh alumina and heated to between200° and 300° C. A sketch of the apparatus is shown infigure 1.

The yields of products and the reaction conditions for thedehydration of methylcyclopropylcarbinol are summarizedin the following table (ref. 36):I I 1 I

_uCo%%?’r-‘g’Pmfmne

—

Ws+a)----------- 1023s+m----.___ 10 izw-3@3--_--J--- 5 6

Yfeld of pmdne@ p?rcmt

!2-Metbyl-tetrehy-dmfomn

J443

h each of th~e expedients the carbinol was disdved in anapproximately equal volume -of toluene, and the solutionma passed through the dehydration column.

86 RDPORT 11 12-NATION&L ADVISORY COMMTJ5’EE FOR AERONAUTICS

It can be seen from the data presented in the table thatalthough increasing the temperature from the range 265° to280° C to the range 285° ti 300° C increased the yields ofproducts to some extent, the change in rate of introducingthe solution of carbinol into the dehydration column had amuch greater effect on the yields of products. At the lo-iveIrate the yield of vinylcylopropane was si~cantly reduced,and the yields of other products except the tetrahydmfuranand isoprene were increased. The decomposition and isom-erization of vinylcyclopmpane in the presence of aluminahas not been invatigated; therefore, it is not known ~hethczthe increase in the yields of propene and 1,3-pentadienes atthe lomr rate is caused by decomposition and isomerizationof vinylcycloprepane or by isomerization of the methylcyclo-propylcarbinol” and subsequent dehydration of the resultantcarbinol.

Several methyla&-lcyclopmpylcarbinols were also de-hydrated by passing the pure carbinol or, in the case ofdimethylcyclopropylcarbinol, a toluene solution of the car-binol, over ahmi.na at a rate of 5.ndhliters per minute andat temperature%betwem 200° and 250° C. With the excep-tion of dimethylcyclopropylcmbinol, the dehydration of all

1.4(

1.4{

1.44

1.42

1:4:

1.44

~o L~~-c~.

% 1.42=

.$6’ 14:Ez

a 1.44

1.43

“ 1.42

1.44

1.43

1.42

1.4 I

I I IDehydrating agent

o Alumino❑ Sulfuric acid

Meihylbutylcyclopropy lcarb inol

l—wUO—~ - ~ ‘

J Methylpropylcyclo~opylcmrbinol

Methytethylcyclopra pyfcarbinalI

~

~-= -=

ioot +,

4 IDimethykycloprapy lcorbinol *

— I I I20

Distill%, percent ~~v~eight80 Irx)

FIGOEE4.-DMfffatfon of pmdnota from dehydmtfon of methylakyloyaloprapylcarbinols.

the methyl~loyclopropylcarbinols investigated gave mis-tures of 2-cyclopropyl-l- and 2-alkenea. Dimethylcyclo-propylcarbiuol gave in addition to 2-cyolopropylpropenesmall amounts of methylpentadienes and 2,2-dimethyltetra-hy@ofuran. The yields of 2-cyclopropylalkenea from mchof the carbinols are given in the following table:

r

Dfmsthyl---- 210-2f0 M&oIopmpyl- S7 . . . . . . . . . . . . . . . . . . . . . . . . . ~

Methybtb@-. 2M-2&l 2&m~$&yl- 82 2-07~p~pyl- 47 84

%!w- : :J.--.—..

Metbylpropyl - 225-2b0 %o#clOalJ

::;:;;:-- =m2%2-.ml-m X%IOIXOPY

DY]- >methyl-1

-.

l— I l-r-ma >bulfl- 89 %Oyol[

——-lfompyl- 41,.nnn ‘K!ti.” -1 64.r.

%&’@ 0 “I I bntens. - ‘-

I I I I I I I I

These data indicate that in general the, yiel& of the2-cyclopropyl-l-alkencs inorease as the length of the alkylchain increases, while the yielda of the 2-cyclopropyl-2-alkenes decrease. The presence of branching at the carbonadjacent to the hydroxgl group also increases the yield ofthe l-alkene and decreases the yield of the 2-alkene.

Sulfurio acid,—In the dehydrations of the methylalkyl-cyclopropylcarbinols with concentrated sulfuric acid, 6 to10 moles of the carbinol with 0.4 to 0.8 dlilitera of wi~was heated to reflux in a flask attached to a 2.2- by 160-centimeter fractionating column w%ich w-m packed withj&nch glass helices. The dehydration produots were re-moved through a distilling head at the top of the columnas they formed. The only products obtained by thismethod -were the 2-cyclopropyl-l- and 2-alkenes. Thequantitiw of reactants and the yields of products are sum-marized in the following table (ref. 34):

c14.8.4.8 H

2-oyofo-~:$

.,

. . . . . . . . . . . .-bntone.-.

%%::

Ylold,wcont

--...-bo:

From these data the length of the alkyl chain does not~ppear ta have a significant effect on the yields of thekycdopropyl-1- and 2-alkenes.

A dependence of the yields of products on the method ofdehydrating the methyhdlgdcyclopropylcarbinols is iUus-irated by the distiU@%on data presented in figura 4. Inihe case of dimethylcyclopropylcarbinol, the dohydmtionwith sulfurio acid welded only the 2-cycloprop ylprop eno,rhereas the dehydration with alumina also gave smallpantities of a product of higher refractive index (probablynethylpentadien~) and a product of lower refractive index:2,2-dimethyltetrahydrofuran). In the case of the otherxwbinols, the dehydration with sulfuric acid did not give soarge a proportion of the 2-oyclopmpyl-l-alkene as did thedehydration with alumina.

HYDROCARBON AND NONHYDROCARBON D3MWVATIVDS OF C!YC!LOPROPU@ 87

Distillation data are also presented for the products from‘tho dehydration of methylcyclopropylcarbinol (fig. 5) andfor the dehydration of methylisopropylcyclopropylcarbiuol(fig, 6) with alumina. From methylcyclopropylcarbinol,propene and isoprene were obtained at the beginning ofthe fractionation and 1,3-pentadienea and. 2-methyltetra-hydrofuran at the end of the fractionation. From methyiso-propylcyclopropylcarbinol, only thq l-alkene (2-cyclopropyl-3-methyl-l-butene) and a high-boiling residue were obtained.

With the exception of 2-cyclopropylpropene and 2-cyclo-propyl-3-methyl-l-butene, the cyclopropylalkenes mmrepuri-fied by azeotropic fiactionations with appropriate entmine.min the Podbielniak columns after prdimimuy fractionationat efficiencies of 50 to 60 theoretical plates. Azeotropicfractionation w-asfound to be necessary in order to separategeometrical isomers and close-boiling imptities from thecyc10propylrdkene9$ In the follmvi.ngtable pertinent phys-ical properties of the hydrocarbons, the entrainers, and theazeotropea are given:

Oyclopmpylolfmne $%

L 4139L 4319L44Z3

L 4474

L4M2L4469

L4fQ2

L44113L44W

L 4629

Entroiner n%

TEthanol_ ._. L 3014.__do . . . . . . . L?$14.-..do ______ L 3814

..--do_ ._. L 3014

PmwnoL--- L W.--do-—--- L3864

.–..do—--- L3364

CfelkWIVO-_ L40TJ--do ------ L40iQ

.-..do---- L407B

Amotmpa

L 4106L 3976LWM

L59W

L40?5L4029

L=

L 42!16L4Z3

L4249

39

E76

06WI

m

131132

132

Dlstlllote, percent by weight

FlouaE 6.-DlstflIatlon of Prmiuotdfmm dehydration of methylcyelopmpylmrbfnol overahunfnaat2ii5’t02W0.

. .

FmuEE &—DfatfIlatlon of pmdnota fmm dohydmtlon of methylfwpropyl-wclopmpyk=bfnel ova alnmfna. DMfItate, WZI ~

The physical properties of the cyclopropylalkenes axegiven in the following table. In those instances-in whichthe compound has been previously reported, reference is--made to ‘tie properties obt&ed by other investigators.

Mmdh~Oycfopmpy*e

“o

TVlnyh3ydopmf.wm---- –Iw.glRef. 29___________ –m 6Ref. Al__________ -------

~~wpylwwe-- ~~~~-----------------

Ref. 2%.. _________ --.-.--

X3yolopmpyl.1-buk] b—11~ ~

–12L 94-------–97. 83

–74. 07

--.-----W3. 87

–n& M

–107. 61

–Iw 10Glare

–97. 40

–m. m

Rol&g

“o

40.19

a%% a(ms.y)

69% o(761&n)

lIW~& 8

107.46

105.&-lc13IZ394

mm

law.

14%69162w

lam

116,m

@D

L 4123L41ML 417Z$lw&

L42SL42624

L 4319

L 4SKIIL4M

L 4474

L44W3L4362

L44bS

L 4032

L44CQL44M

LW

L4337

a ~wl

.7?J(IWO)

.mm

.7614

.746W

. 75s20

:%

.78746

.7&14

.m

.ilwa

.&

.78447

.m

.i%306

.77W

retbeatdmmb!w

Jl&’ole

m—..—.-..-—-

876----—----.--

LOZ.6

.-.-.--Lfdu

------.

. .. ----~ W5

~ 106

--. -.—

Lszl----.--

Lms

i, ma

&?&”m%”%%%%!%=

88 REPORT 11l&NATIONMJ ADVISORY COMMXM’ED FOR AERONAUTICS

The estimated melting points for zero impurity, thedepressions in melting points per mole percent of addedimpurity, and the calculated purities of some of the cyclo-p~pyl~enes are given in the following table:

I

–m. 82 –ma a-10234 –102 n-m. 65 –lIQ. m–97. Sa –’m. 02–74. 07” –74. 03

—U3.m —113.8s–113 0s –m 66–w. ol –107.43-120.04 –125. %3–Km 10 -1oo. Oa

be.=. . 2s

.- —------- —---------------.—---.---------...---------.-------

ckdc&

Py&

pyalt

03.9w 9

—--—--------...-.—---------—-.------.-------

Although the purities of only the fit two cyclopropylalkeneswere crilculated, it is believed that the purities of the otherslisted in the table are better than 99 mole percent, because,the dMerences in the estimated melting points for zeroimpurity and the observed melting points are small. Thegeometrical isomti of 2-cyclopropyl-2-hexene are not in-cluded in the table, because the lower-boiling isomer couldnot be crystallized and the melting curve of the higher-boiling isomer was not of sticient duration to make areliable estimate of the melting point for zero impurity.

Tie infrared spectra of the cyclopropylalkenes from 2 to16 microns are shown in figure 7. It can be seen that forthose molecules having a terminal C= C, the absorption forthe double-bond stretching frequencies occurs at 6.1+0.02microns; whereas for those molecules having an internalC=C, the absorption occurs at a lower wavelength, 6.02+0.02 microns. The intensity of the absorption is muchgreater for the ‘terminal double bond than for the internaldouble bond. Characteristic absorption for the cycloyropylring occurs at 9.78 microns in those molecules having aterminal double bond; in those molecules having an internaldouble bond the absorption for the cyclopropyl ring occum ata slightly higher wavelength, 9.81 microns.

ALKYLCYCLOPROPYLKRTO~

The alkyl cyclopropyl ketones were obtained as fragmentat-ion products from the ozonolysis of the 2-cyclopropyl-l-alkenes. The methods of ozonolysis and hydrogenation ofthe ozonide have been described in reference 32. In general,the olefin was &solved in 100 to 150 milliliters of absolutealcohol and an osygen-ozone mixture containing from 5 to 10percent ozone was passed through the solution until all theolefi had been converted to ozonide. The ozonide solutionwas then transferred to a low-pressure hydrogenationapparatus, and the ozonide decomposed with hydrogen in thepresence of a palladium catalyst ta give the W@ cyclopropylketone and formaldehyde. The alkyl cyclopropyl ketoneswere identified by their physical properties and by analysis oftheir 2, +Minitrophenylhy+razone derivatives. The quanti-ties of olefin used, the yields of the alkyl cyclopropyl ketones,

and the melting points of the 2,4-dinitrophenylhydritzonederivatives are given in the following table:

Oldn ~#g- YW2-0ycb3pmpyl-ldkene * Www.t Refer.moles’ tone pxcmt phcnylhgdro. onm

zono, O

-pgp?&:-------- o:~ mthtzl. --. . . . . . . . . . . . . . . . . . . -p ,+ %’ %wg ~

-Jpene..... ------------- .4st

. . . -- 43 I& o-w, 6 :mm------------------ .5 Bnty . . . . . . ~ 114.6-IM”O

-Wnethyl+bntme.- ----- .3 Impropyl. . . 167.5-1s9.o 3s

OP. %%nesnrolbtedfwo.* The shnatnms of the propyl-~ra were also proved by omnolyak; only tbosc

%%%$i%%$!pm%nwlat the boflingtempxat. roofthekctone maklnglt dlrncult todetmmfne theyfel of theketone.

The infrared spectra of the al.kyl cyclopropyl ketonm meshown in figure 8. All show strong absorption ttt5.9 microns,which is ch~cteristic of the’ carbonyl group. With theexception of methyl cyclopropyl ketofie, all show chmacter-istic absorption for the cyclop.ropyl ring between 9.75 and9.80 microns; cyclopropyl ring absorption in methyl cyclo-prcpyl ketone occurs at a lower wavelength, 9.69 microns.

2-CYCLOPROPYLALKANR9

The 2-cycloprop@dkanes were prepared by hydrogenrttingthe 2-cycloprqpyl-l- and -2-alkenes in the presence of nbarium-promoted copper chromite cntalyst. The l-tdkenesand %&enes were hydrogenated separately, becttuso thoposition of the double bond was found to affect the eam ofhydrogenation and the yields of products. In genernl, tlmolefi, w equal volume of ethanol, and a quantity of thocatalyst equal to 10 percent of the weight of the oleiin wemput into the hydfogenator, and hydrogen was ndmittecl tobetween 1500 and 1800 pounds per square inch gage. Thehydrogenator rocking mechanism and the resistance honterswere turned on, 1and ;the vessel was heated to 1006 C, Tho2-cyclopropyl-l-alkenes hydrogenated readily at thistempera-ture, the heat of reaction generally raisiig the tempemlum tobetween 120° and 130° C. The 2-cyclopropyl-2-d.ken@hydrogenated sluggishly eiwn at 130° C, and, in somoinstances, the reaction temperature was increased to as highas 175° C in order to obtain more rapid hydrogenation. Thereaction conditions and the yields of products are summar-ized in the following table: -

ohRn I Fteadobnmmdf- 1 Ketlmotcdcoguwdtlon of Produota

I&ea-o o-

WPY

-prophz-.

-l-bntemo--

-!mdene—-1-fmntmlb

-Moxene-...3-1:b;t&$l-

Tem-g

“o

lIXI-130

1OO-1W

110-1301W11O

lm-130llxi-lzo

ll!&176lfm-140

1,w

1,W

1,m1,m

1,7MI1,m

1,am1,WI

w3yd0-fxopyl-dkne

-propme..

-bntrme.-.

..-.. do___-boxane... .

__-do._..&&l:f

i’elgtp2r-mnt

99

72w

$79w

WolghtMcthyMkrmo -

Xt

—

Rcfcr.mm

—

37

37

3737

3737

3736

—

Unhydrogawkadeloti wnsfonndInthe pmdnct fmm esohof tho 2do?nc&

T&e data and the distillation curves shown in figure 9indicate that the hydrogenation of the 2-cyclopropyl-l-alkenes yields the corresponding 2-cyclopropyMkanes in

HYDROCARBON AND NONHYDROCARJ30N DERIVAHS OF CYCLOPROPANE 89

100

80

60

40

20

02 4 6 8 10 12 14 16

100

80

60

40

20

02 4 6 8 [0 12 14 16

100

80

60

40z: 202c- 02 4 6 8 10 12 14 16‘:

10

8

6

4

2

10

8

6

4

2

100

80

60

40

20

02 4 6 8 10 12 !,4 16

10

8

6

4

2

100

80

60

40

20

02 6 8 10 12 14 16

100

80

60

40

20

02 4 6 8 10 12 14 16Wavelength, microns

(a) Vlnyloyclopropene. (g) 2-Oyclopropyl->b.tene, low MdlIng. ~(b) 2-OyclOpmpylpmpwm.(o) 2-Oyclopropyl-l-bnteno.

(h) 2@yolopropyl-2-brWne, bIgh LmIllng.(1) 2Wyd0pmpyl-2qw.nteme,low Lwtllrrg

(d) 2-Oyclopiupyl-l-pmtene.(e) 2:cYclopropY1-1-tWne.

(j) Xlyc10pmpyP2-pont8n~ I@ ixdlhg.(k) N3yclopmpyk>- low Mllng.”

(f) ,2tOyclopmpyl+met~yl-1-butene. (1) 2-oycJ0propyk2-Mxen%blgb Mung. .

FKWEE7.—Intrurcdspectraof oyclopropyldkencs Llqtdd Phww O.1-mOHmetercdl. UPLXXbaa?, dllutcd 1:10with mrkmntotmcbkn’idwlower tmwi nndllutml.

purities between 98 alicl ,99 percent, whereas the h@ro-~enation of thb.2-eycldpropyl-2~alkenes yields also sign&antquantities of parcdiin.ichydrocarbons. The pardinic hy@-cnrbons do not appear to result horn hydrogenolysis of thecyclopropyl ring, because if this were the case, larger amounts

321OOG-G*7 .,

of the p-c hydrocarbons would be obtained also frbmthe hydrogenations of the 2-cyclopropyl-l-alkenes. Thedata support the proposal made in reference 28 that ayatemsin which a cyclopropyl ring is conjugated with a double bondcan add hydrogen by either a 1,2- or a 1,4-mechanism.

90

Purification

RDPO13T 1112—NATIONAL ADVISORY

of the ~-cyclopropylalkanes was dif%cnlt inthose experiments in which methyhdkanes were formed,because the boiling points of the paraflinic hydrocarbons

Wavelength micmns

(8) Methyl cydoprapyl ketane.(b) Ethyl oyclapropyl keti(0) PrOpyl OsdOpropylketmm(d) 19JPMPY1CYCiOPMPYlkti

. (e) Bntyl O@OPMPYl hm

FIGUE=~—hfromd sratra of okyl O@OPTOPtiketanm Lfqaid phi=% O.1-mfIffmetacalLlJPSW ham dfhlkd MO with arbon tebmkdoride+lower IXIKZ3,tmdflntsd

were within 2° C of the corresponding cyclopropylal.lmnes.fkotropic hactionation8 with appropriate entrainara werefound to be effective for separating the close-boiling mixtures.Pertinent data for the azeotropic pixtures are giw+ in thefollowing table: . /

.

coMMTFI’ED FOR AERONAUTICS

Oycloprapykdkne ““”F-‘*”*L 4024 EtlmnoL .. . . L 3o14 1.WOl 701.4112 Pm noL_. 1.3364 1.am1.41i% C%&olve... 1.4079 L4117 ;~L 4173 Batanol_.. 1.S%Q2 L 40M1.4140 RowoL... 1.S8s4 L 3s99 m

Purifications of the 2-cyolopropylalkanca were considmedcomplete when (a) the melting curves of selected sampleswere, interpreted to be indicative of purities of bottcr than

Distillate o 2-Cyclopropyl - I -alkones

1.39(g) ❑ 2-CyclcproWl-2- alkenes

-c-o o- ~ ~ I 1.Y o-

549 2- Cycloprapylp+openeL3a

1.45

1.44 .

L43

L42

r

L4” I2- Cyclopropylbutenes

2° 2701-

;L40 + ~ ~ w -a- -a. 322g

“; L39>=

g 1.42c 2- Cyclopropylpentenes

44814 I ~ ~ ‘ ~ ~ & ~

A d d284

1.40

‘L45

L44.

1.43

L4’22- Cycla+uopylhexe nes

— -500 “ ~ mU-Q ~1618

L4 1*~ - ~. .20Distill~~, percent $%eight

80

Fmam 9.—DMfIWfon of prodtrob from hydragenotfonsof %aycloprapylrdkenm,

99 mole percent, or (b) repeated fractionation and azeo-tropic hactionations through columns rated at better. than150theoretical plates gave no rngn.ifhnt changes in refractiveindex and density of the hydrocarbons. ,

.

.

HYDROCARBON AND NONJ=DROCARBON DERIVATIVES OF 0YCLOPROPAN13

Wavfiength, microns –

(s) >Oyclopmpylpmpsne.(b) !2-OYoIompylbds.na.(a) 2-OmJmopylmK(d) 2-Oydopmpyllwmm.(e) !XWclopmpyl+methylbntsne.

FIGURE Io,-hfmred spsotm of %yolopmpylelkana Ll@d PJMM;O.1-~eteI ceU-Upp3r tm~ dllnted 1:10with cmtmntetmchloti% lower ba% nndffatd.

The physical properties of the 2-cyclopropylalkanes arepresented in the following table; previously reported prop-erties are also referenced.

Although thepuritiesof only two of the2-cyclopmpylalkanescould be calculated, it .isbelieved that the other three hydro-carbons are of similar purities.

The infrared spectra of the 2-cyclopropylaUmnea areshown in figure 10. All the spectra show characteristiccyclopropyl ring absorption at 9.82 microns.

T–lU 97 ~llzfc---8 –Ilh !24

--------

-3%! J7.wG!ass .----..-

bil% 9Q9 ~y.20 w

------ ------.. . . . . --..-- U?E

4 XI m7 ~.i g----- ------ .

l.wL3SS31.4024L 41111.417sL 4140

s%

C4as9

72ss0742ai

%%

91

- Dekrmfned by gmmetzfml method of mferenca4Lb.@@=lnsdbysddfn#hcmmmnonnts of%mtbylptano.* MoMng omwewes no of suffiebnt dnmtion to make cafmdetfonvsltd.d Detarmbwf by addhg known amountsof 4methyktane.

cYcLoPRoPrz CHLolur)m

Cyclopropyl chloride, 1,1-dichlorocyclopropane, and trans-1,2-dichlorocyclopropane were isola&d ‘fiorn the reactionproducts of the photochemical c~.orination of cyclopropane.A sketch of the photo&lorinaixon apparatus is shown infigure 2. In a typical reaction the source of illumination(tmo sun lamps) was placed 11.5 centimeters from thereaction chamber and the cyclopropane ivas passed throughthe reaction chamber at a rate of about 0.12 mole per minute.Chlorine was then added at a,rate of about 0.046 mole perminute. The gases were passed through ‘ the reactionchamber simultaneously for 6 hours, and at the end of thisperiod the amount of cyclopropane used was 44.4 moles(1866 g), and the amount of chlorine 16.2 moles (1148 g).The excess cyclopropane was distilled from the products,and the products “were then combined with the productsfrom eleven similar chlorination experiments. Distillationof the.combined ‘products gave the data plotted in figure 11.

m 180

+1.500 )140

o.-.~0

1.480 [00 :c~1’d .

~o SJ“c- 1.460 60

%uc b.p..- < ,?al.=

; [.440 — — — — — Oavn w 20~

.,

1.42 0-*lOD

— — — ~

1.40 0020 40 60 . 80 100

Dlstil~ote, perc~t by weight

FmuEE 11.—DfstJllatMnof pmdmb fmm Pkotoohlorlnatbn of oyafopmwTotd dWlfat% 815Ssmm$ msidu%015~

.

.

92 REPORT 11 l&NATIONAL ADVISORY COMWT1’RD FOR AERONAUTICS

l?rom these data and subsequent bctional distillation data,the following composition of the chlorination products wasestimated: 52 weight percant cyclopropyl chloride, 24 weightpercent 1,1-dichlorocyclopropane, 2 weight percent tran.+l,2-dichlorocyclopropane, 2 weight percent of a compoundbelieved from its physical properties to be l,l,3-trichloro-propane, and 20 weight percent of a complex mixture of poly-halides which could not be separated by fractional distilla-tion,

The cyclopropyl halides were purified by refractionationat efficiencies of 50 to 60 theoretical plates. The physicalproperties of the purified halides are compared in the follow-ing table with those values previously reported: ‘

Cyelo ropyl cbloride-----------4!

1

.—97.09 43.43 L 41fr3(ref. )------------------------------- -------- 22 ~.b14079 $&%l,l-DItiomydopm~e ------------- *–37. 47 1.21s3W. 4)------------------------------- -=iK7i ~~ bL4277 b1.2178trand-12-Dlrhlonxyclopmpno ------- L46Z3 L2439(ref. 4)... --.-.. ----... -:------------ –1Q5 s: 2 bL4Kt2 bL~

● Freczirm ooht. ‘C.b At 26° d.- ‘

The infrared spectra of the three cldorinated cyclopropanesme shown in figure 12; the absorption band characteristic of

10

8

6

4

2

Wavelength, microns -.-

, (n) O@oPrOPyf cldorid~(b) 1,1-Dlchform@epmrmna(o) irand-l$Dlchlomuydeprepane. .

the cyclopropyl ring is seen to shift from 9.7”3 microns. (cyclopropyl chloride) to 9.66 microns (l,l-dichlorocyclo-

propane) as the number of chlorine atoms is increased. Theabsorption shifts to even lower frequency when the tmo.

chlorine atoms are on different carbon atoms (9.58 micronsh tran8-1,2-dichlorocyclopropane).

DICYCLOPROPYL

The reaction ,of cyclopropyl chloride ‘ with lithium orsodium was used to prepare dicyclopropyl. The reactionwas tried with lithium both in methylcyclohexane and inether, and with sodium in ether. 1+ generil, the chloride,~as dissolved in the reaction solvent and added to a suspen-slog of the metal in the solvent contained in a flask equippedwith- a stirrer; a reflux condenser, and an addition funnel.All reactions were oarried out at 25° to 36° Cl. Otherrcwction conditions and yields of products are summarizedin the following table (ref. 38):1 , ( I

cu&-

mOf&

-’i4

Meb31Alkeu metal gmrn-

atollls

“ ++Ylolds&luot9,

I$T&.f?dvent time,

day8 Oyolm Dl&ol@pmfmno pmpyl

Ether. . ..-.. .-... -.-.-.do -- . . . . ..--.. 1;

40 10Methyloyclohemne. N%o N%o

These data indicate that the reaction with sodium or lithiumin ether gives approximately the same yields of the twoproducts listed in the table. The fact that no reaction wasobtained in methylcyclohexane solution clearly !mIicrttesthat the solvent in some reamer influences the course of thereaction.

Although cyclopropane and dicyclopropyl were tho prin-cipal reaction products, trace quantities of two other hydro-carbons were detected in the crude reaction product bymeans of infrared spectra. The infrared evidence indicatedthat one of these hydrocarbons was l-hexyne; the other wasnot identified.

Dicyclopropyl was pu+ied by extracting the hydrocarbonwith an ice-cold saturated solution of silver nitmite to removothe unsaturated impurities, passing the extracted hydro-cmb’on through silica gel, and, finally, azootropicdly frr.w-tiona~i the h@rooarbon with ethanol through a Poclbiel-niak column. The purified hydrocarbon had tho followingphysical properties:Meltingpcint, ‘C-------------------------------------- —82.02Boiling@nt at 760 mmHg, OC------------------------- 76.10Refractive index, ~mD----------------------------------- L 4220Density, g/fi-— ---------------------------------------- O.78070Net heat of combustion, kcwmole ----------------------- SS6

The infrared spectrum of dicyclopropyl, shown in figuro13, has a strong absorption band at 9.82 microns, which ischaracteristic of the cyclopropyl ring. . I

= 100

~ 80xC- 60.=.: 40E2 200I=o

6—Wovejength, microns “–

mum 13.-rnfmrd ~trmn O(dIoyeIeProPYL LiqnId Pm O.1-mUUmoti w1l.UPC@-co dilntiV1O*h mrlmntotroohleridwlowortmm,mdllutod.

HYDROCARBON AND NONHYDROCARBON DERIVATIVES OF CYCLOPROPAN13 93

SPIROPENTANE

Spiropentane was prepared by the debromination. ofpentaerytbrityl tetrabromide (ref. 44) with zinc dust in theprewmce of sodium carbonate and sodium iodide. The re-action was conducted by adding small portions of the pow-dored tetrabromide to a slurry of the zinc dust, sodium car-bonate, and sodium iodide either in molten acetamide or in76 percent ethanol (ref. 39). The hydrocarbon product wasdistilled from the reaction mixture as it formed, and wqs col-lected in receivers chilled with a mixture of solid carbondioxide and acetone. In addition to spiropentane, two otherhydrocarbons were obtained from the reaction, namely,methylenecyclobutane and 2-methyl-l-butenb. Some typi-ctd experiments are summarized in the following table(rOf.39):

< #

I I

SOMmmI Ethon:l . . . . . . . . . . . . 5 I mI 6Iam21 I 43I 12............. 6 !m .E3 22 44 12

Acetmn[de. . . . . . . . 1 6 L; .16 22 4 11 IThese data indicate that the reduction in either solvent givesnearly identical yields of spirepentane, but that the reductionin ethanol gives ten times the quantity of methylenecycl~butane as the reduction in acetamide. For preparations ofsufficient size so that precise fictional distillations can beemployed to separate the products, reduction in ethanol isthe preferable method, especially if methylenecyolobutaneas well as spiropentane is desired. For small preparations ofspiropentane, the reduction in acetamide may be more sukable. (ref. 45).

The physical properties of spiropentane are given in thefollowing table with those values previously obtained:

I

LIyd-ben F*8pJInL

7603$W 5 7Kl

1.41!22 0:;:11.4117

The infrared spectrum of spiropentane is shown in figure14. The absorpkon band ch-&a&ristic of the cyclopr~pylring is located at 9.54 microns, a shorter wavelength than in

.

Wav~length, mic;ons -

FIGURE14.—Infror0dspectrumof s@’opmhne. Llqald pbaa O.1-millimetercell.Upper truce,dtlutcd 1:10with carbon tetrachkx4de:low -% andllnted.

any of the other compounds prepared in the present in-vestigation. Such a shift in the absorption is not entirelyunexpected, because the force constants in the spiro structurewould be different from those in the other cyclopropanes.

DIETHYL CYCLOPROPANE-1,1-DICARBOXYLATZ

The diethyl cyclopropane-1,1-dicarboxylate was prepazedby the method of reference 46 in which a solution of sodiumethoxide, obtained by &solving 365 .~ (16.5 g-atoms)of sodium metal in 55OOmilliliters of absolute ethanol wasadded dropwise to a mixture of 1275 grams (8 moles) ofethyl malonate and 1550 grams (7.2 moles) of ethylene,bromide. The products of the reaction were.distilled at 10millimeters of mercury pressure, and the material boilingbetween 80° and 120° C was collected for subsequent frac-tionation at about 50 theoretical plate efficiency at atmos-pheric pressure. The yield of diethyl cyclopropane-l,l-dicarboxylate was 495 grams (33 percent). Several hac-tions of constant refractive indm were combined and passedthrough silica gel in order to obtain the ample used for thedetermination of physical properties and infrared spectmm.-The physical propertiw are compared in the following tablewith values previously reported:

Dlethyldlcar&%%?m~”l’l-

-47.@3 217.’4 i@J ,- ,W

ml. 47-.-..--------.-.-.-–. ------- 114 22 L4231O Lm15

The infrared spectrum of diethyl cyclopropane-l,l-dicarboqlate is shown in figure 15; strong ‘absorption is

observed at 5.8 microns, the region in which carbonyl groupsabsorb Stro-hgly,and also at 9.7o microns. The 9.70-micronbandisundoubtedly thatband characteristicof the cyclopropylti.

INFRAREDABSORPTIONCHARACI’ERISTICOFCYCLOPROPYLRING

The d.ifiiculty in establishing the presence of the cycle-propyl ring in organic molecules by chemical means haspromoted interest in identifying the p,resenceof the ring byinfrared techniques.. Infrared absorption bands in threeregions of the spectrum have been proposed to offer a means ~of identifying the cyclopropyl ring. In reference 4 bands at9.75 and 11.55 microns were employed. The authors ofreference 48 found that in the spectra of 14 eyclopropane

94 REPORT 1ll%NATIONAL ADVISORY COMMTIT’EE FOR AERONAUTICS

hydrocarbons a strong band was present between 9.8 and10.0 microns, but that strong absorption did not occur con-sistently at 11.6 microns. It was reported recently in refer-ence49 that a study of the 3- tb 4-n@ron region with a lithiumfluorido prism disclosed that all the cyclopmpane derivativesinvestigated had absorption bWds at 3.23 and 3.32 micronswhich were characteristic of the C–H titrations of the cyclo-propyl ring system.

The infrared spectra of the 34 cyclopropsne derivativereported harein have been examined in &ch of the threeregions proposed previously. Unfortunately, a c@-al

~ osamination of the 3- to 4-micron region could not be madein the present work, because-the sodium chloride prism, em-ployed in detwmining the specti, does not give sufficientresolution to saparate both the 3.23- and 3.32-micron cyclo-propyl ring C-H bands from other carbon-hydrogen bandsin this w.gion. An examination of the spectra of the dilutedsamples does d.imlosethat many of the cyclopropane deriv~tives have bands at 3.23+0.02 microns and at 3.33+0.02microns. In compounds such as vinylcyilopropane, dicyclo-propyl, cyclopropyl chloride, and .@ropentane, in whichthere is little interference from carbon-hydrogen bands otherthan those of the ring, the 3.23- and 3.32-micron bands showup clearly (table I).

Nearly all the cycloprepane derivatives show strongabsorption between 11 and 12 microns; however, the posi-tion of the absorption which might be characteristic of thecyclopropyl ring is dif6cult to determine because of thebroadneas of the absorption. Interfering absorption horncertain olefinic structure9 also occurs in this region.

The absorption which appears to be most promisiig fordetermining the presence of the cyclopropyl ring is that usedin reference 48. In the spectra of all the cyclopropanecompounds prepared in the present investigation, a strongband was pbserved at 9.7 to 9.8 microns (table II). Inonly a few instances was the band shifted appreciably fromthis region,. and in these instanw,. for example, in spiro-&entane and in tram-l+dichlorocyclopropane, the shiftjn absorption is not entirely unexpected. Ffot only is theabsorption strong in the undiluted spectra, but it is per-sistent also upon dilution.

MOLECULAR REFRACTION OF CYCLOPROPANEDERIVATIVES

The experimentally observed molecular refractions ofcycloproprme compounds -are generally higher than thosecalculated tim the atomic and group refractititiea. Thisdifference in observed and calculated values was interpretedby Tschugaeff (ref. 50) to result from a contribution to therefraction by the three-carbon ring structure. From acomparison of observed and calculated refractions of threecyclopropane derivatives and several bicyclic tapeneswhich had three-carbon rings in their structures, Tschugaeilestimated the ma&itude of the ring contribution to beabout 0.7. A more comprehensive investigation by dstling(ref. 51) yielded a value which agreed well with that ofreference 50. Subsequent’ investigations, however, showedthat the difference between observed and calculated molec-

ular refractions varied considerably among different classe~of cyclopropane derivative and even among members of thesame class (refs. 26, 27, and 62). Data obtained in thepresent work (table III) also showed this variation in AMR.

The lack of agreement among the AM~ valuea from variou.classesof cycloprepane derivatives and even among mombor.of an homologous series is not surprising. It must bcassumed in detwmining ring contribution by this procedurethat the atomic and group refractivities are truly constantand additive. Atomic and group refractivities, howmwrme constant and additive only within limitations (ref. 63).and as the character of the atoms or groups in the struoturcis varied, the atomic and group refractivities also varyConsequently, AME reflects not only ring contribution, butalso deviations horn constancy of the atomic and grouIrefractivities used to determine the calculated moloculalrefractions.

In a recent investigation, Jeffery and Vogel (ref. 47) em-ployed a procedure for determining ring contribution thatreduces the effect of inconstancy of atomic and groulrefractivities. The observed molecular refraction of rtstructurally similar acyclic compound is subtracted from thesum of the observed molecular refraction of the cyclo-propane compound and two hydrogen atomic refmctivitios:

CH, R’ CH, R

1

\c/

J

\c$+ 2H— = Ring .contrIbutlon

$, \R,, \Hs R

From data obtained principally with alkyl cyclopropmxmono- and dicarbo@ates, the ring contribution to themolecular refraction waa calculated to be 0.614 (ref. 47).

Vogel’s procedure has been used in the present work tcdetermine the ring cor@ibution in the cyclopropylallamos andin some of the cyclopropylalkenes (table IV). A nearly con-stant value for ring contribution among the cyclopropyl-alkanes is obtained by this procedure in contrast to theinconstant AM~ in table HI for the same compounds. Al-though Vogel’s procedure minimizes the effect of environmenton the atomic refractivities of carbon and hydrogon, tho dis-crepancy between the ring contribution obtainod with, thecyclopmpylalkanes and that obtained with the cyclopropanccarbo~latw, 0.44 and 0.614, respectively, indicates thatthe natnre of the-ring substituents also influences the ringcontribution. While it may be said that the compbund:used by Vogel are capable of conjugation between the cyclo-propyl ring and the carbonyl double bond, and that tlmvalue 0.614 in’dudes exaltation due to conjugation, novor-theless, environmental factors influence the combihecl offe~tsof ring contribution and conjugation as indicated by thedata in table IV’ for the cyclopropylalkenesj methyl cyclo-propyl ketone, and diethyl cyclopropane-1 ,1-dicarboxTlote.

Because -of the varyi& influence of the substituent group.on the cyclopropyl ring, it iE doubtful that any of the pro-posed values will, adequately express for all structures thecontribution of the cyclopropyl ring to the molqcular refrac-tion. The calculation df molecular refraction of cyclopro-pane derivatives can, therefore, at best give only m approxi-mation of the observed refraction.

.

HYDROCARBON AND NONHYDROCARBON DDRIVAti OF CYCLOPROPANE 95

CONCLUDING REMARKS

The methods of synthesizing and pwifying 34 hydrocarbonand nonhydrocarbon derivatives of cyclopropane were dis-cussed, and the physical properties and the infrared spectraof each of the compounds were presented.

It was found that a series of cyclopropylalkenes could beprepared by dehydrating appropriate al&l- or methyla~l-cyclopropylcmbinols, either with concentrated sulfuric acidor with alumina at temperatures between 200° and 300° C.Furthermore, in the presemm of a barium-promoted copperchrmhite catalyst, the cyclopropylalkenes were catalyticallyhydrogenated to the corresponding cyclopropyhdkanes.The position of the double bond was found to greatly influ-ence both the ease of hydrogenation and the yield of products.The cyclopropyl-1-alkenes hydrogenated readily at 100° Cto give the corresponding cyclopropylalkane and only 1 to 2percent of paraflinic product, whereas the cyclopropyl-2-alkeneahydrogenated sluggishly even at higher temperaturesto give 15 to 17 percent of paraihic product in addition tothe cyclopropylalkanes. In the hydrogenation experiments,additional evidence was found ta support the proposal thatconjugated cyclopropyhdkenes can add hydrogen by both a1,2- and a 1,4-mechanism.

Dicyclopropyl, the smallest of the dicyclic hydrocarbons,was prepared for the fit time. Spiropentane, the smalleatof the spiro hydrocarbons, was also prepared.

Infrared absorption bands characteristic of the cyclo-propyl ring were discussed, and some observations were madeon the contribution of the cyclopmpyl ring to the molecularrefractions of cyclopropane derivatives.

LEwrs l?LIGHT PROPULSION LABORATORY

NATIONAL ADVISORY ComrmxrEn FOR AERONAUTICS-CLEVELAND, Oreo, Augud 16, 1962

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1.

96 REPORT 11 l%NATIONAIJ ADTTSORY COMkH’ITEEl FOR AERONAUTICS

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32. Henne, Albert L., and Perilstein, Warren L.: The Prepar&on ofAldehydes and Ketones by Ozone Oxidation. Jour. Am. Chem.Sot., vol. 65, no. 11, Nov. 1943, pp. 2183-2185.

33. Slabey, Vernon A., and Wisq Paul H.: The Reduction of iMethylCyclopropyl Ketone ta MethyloyclopropylcmbinoL Jour. Am.Chem. .Soc., VOL71, no. 9, Sept. 1949, ‘pp. 3252-3253. “

34. Slabey, Vernon A-, and Wise, Paul H.: The Dehydration ofMethylal&lcyc.lopropylcarbinols. Isolation and Purification of’2-CyclopmpylaIkenea. Jour. Arm Chern. Sot., VOL 74, no. 6,March 20, 1952, PP. 1473-1476.

35. Slabey, Vernon A.: Synthwis and Purification of 2-Cycloprppyl-3-methyl-l-butene and 2-Cyolopropyl-3-methylbutane. Jour.Am. Chem. Soo., VOL7< no. 19, Oct. 5, 1952, pp. 4963-4964.

36. Sfabey, Vernon A.: Dehydration of hfethyloyclopropylcarbinolover Alumina. A Synthds of Vinylcyolopropane. Jour. Am.Chem. sec., VOL74, no. 19, Oct. 5, 1952, pp. 4930-4932.

37. Slabey, Vernon A., and Wise, Paul H.: Hydrogenation of 2-Cyolopropyl-1- and -2-Alkenes. Isoldion and Puritioation of2-Cyelopropylalkanw. Jour. Arm Chem. Soo., VOL 74, no. 15,+ug. 5, 1952, pp. 3887-3&39.

38. Slabey, Vernon A.: Reaction of Cyolopmpyl Chloride withLithium, Isolation of DioyolopropyL Jour. Arm Chem. Sot.,vol. 74, no. 19, Oot. 5,’1952, pp. 49284930.

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57.

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hfurray, M. J., and Stevenson, Eugene H.: The Debrominat.ionof Pentaerythrityl Bromide by Zino Isolation of Spfropentano.Jour. Am. Chem. Sot., vol. 66, no. 5, May 1044, pp. 812-816,

Do+ Arthur W., and Yoder, Later: Spiro-pyrindd.frw HI.Condensation of Cyclopropane-1,1-dicarbo~ylfo E&or with Ureas.Jour. .&n. Chem. Soo., VOL43, no. 9, Sept. 1921, pp. ,2097-2101.

Jeihry, George H., and Vogel, Arthur 1.: Physical Properties ondChemical Ckmstitutions. Part XVIII. Three-membered andFow-membered Carbon It&w Jour. Chem. Sot. (London),1948, Part II, pp. 1804-1809.

Derfer, John M., Pickett, Edward E., and Boord, Ceoil E.: InfrnrcklAbsorption Spectra of Some Cyolopropane Hydrocarbons, Jour.Am. Chem. sec., VOL71, no. 7, July 1949, pp. 2482-2485.

Wiberley, Step@n E., and Bunce, Stanley C.: Infrared Speotm inIdenti60ation of Derivativ& of Cyolopropane. Anal. .Chem,, vol.~- no. 4, April 1952, pp. 623-625.

Tschugaeff, L.: Ueber @ Thujen, ein neues byoyclisohee Terpen.Ber. D. Chem. GwelL, Bd. XXXIII, 1900, pp. 3118-3126.

&tf.ing, Gustav Jim: The Intluence of Three- and Four-memberedRings on the Refractive and Dispersive Power of OrgmdoCompounds. Jour. Chem. WC. Trans. (London), VOL 101 I,1912, pp. 457-476.

Bruylants, P.: Contribution h l’6tude dcs. compos6s oyolIqumtridthylhiqum. Bull. Soo. Chim. Belg., T. 36, No,ll,Nov. 1927,pp. 519-532.

WeL&erger, A., ed.: Physical hfethods of Orgmdo Chemistry.VOL I, pt. II., Interecience Publishers, Ino., (New York), 1949,

Voge~ Arthur 1.: Physioal Propertka and Chemical Constitution,Part XXIII. Miscellaneous Compounds. Investigation of thoSo-called Co-ordinate or Dative Link in Eatera of Oxy-aoldsand in Nitro-parafEns by Molecular Refractivity Determinations.Atomic, Structural, and Group Parachors and Refrnotivities,

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,-

1

HYDROCARBON AND NONHYDROCARBON DDRIVATlN13S OF CYCLOPROPAN13 97

TABLE I.—CARBON-HYDROGEN’ ABSORPTION BANDS IN INFRARED SPECTRA OF CYCLOPROPANE DERIVATIVES

OydOp,Om@ derivatives

b3.21-3.2d

Tvavdength, mlawne

73.43-3.&a 3.51-3J6

%4s ---------3.43 ---------X49 --------&49 ..iii---

--.------

3.2%3.30 8.31-33.5 3.33-3.43 3.41-3.46

!WYeleprepyl m~e..-...-.--.--. ------.—...E

3.242-Oyclopmpyl ntie ---------------------------- .3262-Oyclopropy~tane.- --------------- . . . . . . . . . . 3.2s‘xJyolopropy osane...- . . . . . . . . . . . . . . ------->Oydopmwl+methylbntie -------------------

-----..----------.

me------------------------------ 3.2‘Woo. . ---- -.--- . . . . . . . . . . . . .

le. . ..-.. ---— -------------- $:ne.--..----------.-—.-..- 3.2m.. -.-— ------------------ . . . . .yl-l-butene --------------- 3.2..- -

. b.)------------------- as1.b.)---------------- 3.2

~e(I. b.)----------------- 3.2

Xwd.------.--------------.----

----..-.---.-.-.--

---------3.4Z&ad3.42s3.43s

---------3.%%23 --..-----

1a32--.------

*W--.------

Zw$Xm

25n2.522. . . . .24

—-------3.33

. . . . . . . . .*3. m

3.27

---------3.3383.37%37

--..-..-----------

3.4233.463.44&48

--------- .... -—..x 4783.43a “:::::::

......... ---------

.........3.48 H----------

3.37-.-------3.343.3s3.Ma

3.3a

&43---------

&&

3.41

+

%49 ---------3.47 --i-E---

---------

3.49 ---------3.4s ..i.ti...

-—------

----------------— ------—-

3.39

---------3.373.40

--- —---

-~’2-O@opmpyl->bnW ~b.)------------------ 3.24

S Iropenhme . . ---------------------------------&wdopropyl ----------------------------------- 324

--.---------------

K27..--.--.-

........-&%

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

3.30. . . . . . . . .

3.27

:2

. . . . . . . . .3.’23K27

3.303.40

----- ...3.49

3.433.ms

.---.-.---

. . . . . . ..------.---

3.Y3S

3.&s---------3.33

. . . . . . . . .

. . . . . . . . .--.------------------------

-----------------. .........

3.37hfetb IOYCIOmpylmbhol ----------------------Dime~ylcy$opmpyIcublnol .. . . . . . . . . . . . . . . . _;_;._bltibylethyl 10 mpylmrblnoL..._ . . . . . . . . .hfethyl rop OY opmp karbhml------------ _.:----

E rT~ TMethyl n~qti~py ~bhol ----------------bftiybpmpyl~dopmpylwbhol ------------ . . . . . . . . .

--.------

----- ...3.423.423

.........------- --

3.373.40

—..-.-. .........----------

3.52--.------

---------3-423.41

........-........- .........

3.32 ------------------.--------

Oycle m yl~tide ---------------------------- 3.3.1, l-D!~owdopro&-----------------------tranu-1,2-D1cidomY mwe------------------ 3.25s

........-

........-........- ---------

-----------.------

........-3.348

........------------.------

IMotbyloyclopmp Ibtie --------------------- 3.24

/’EtbyloyolopmpY hone -----------------------Prop leyelopmp Idebne -----------------------

. . . . . . ..-

YfButy oyclopmpy Wm------------------------ %24---------

kPmPYl O~O~PYIMM -------------------- an

a34;:3.40

3&%o

%44sX438

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

3.518--.------. . . . . . ..-

. . . . . . ..-

-------- :3.ma

........-3.43s

--------- ---------a32

..----.--

........-3.433.43

----------.--—-.

---------........-

3.42 ..- ....—3.338........-

s The 6ynriM 8 denotesband which @howeonly fw a shotddmon a strmw= alWPtkOL

.

3~loo&_55_s

98 RDPORT 11l>NATIONAL ADtiORY COM&UTTED FOR ADRONAIXMCS

TABLE 11.-CHARACTERlSTIC ABSORPTION IN INFRAREDFOR CYCLOPROPYL RING

TABLE ILL—MOLECULAR REFRACTIONSCYCLOPROPANE DERIVATIVES

OF

Oycloprqmmederivetivo Cyelopropne dezfvative

+—l-=oYdomwl~m ------------------ ~=2-Oyolopmpyl we--------------------------;*&~l&m..-...-_-.-- ::

--- — ---- —. . ----------- .>C~mpyl+mtiylbnti ---------------- KG

2-cy&Jprepyl pine. -.--. __.. ______RX3ycIepropyl tene..-.._ . . . . ..__. . . . . . .

:ptiyg~p_-””---””””””””””””””””””M3ydopropyl+methy.

nyltimm -------------------------->@dqm~l~---------------------2-Oyclopropyl-l-bnteoo.. . . . . . . . . . . . . . . . . .*dmPY1-l-pm --------------------Klyelopropyl-1- ~--------------------->mmwWmetiyl-l-butie. _.–._.-...

0.4.5%E a%37.18 a?. 61 :%$: 42.16 ,s.3

a7. 57 .19le------------------------

ibatano_-- ----------rv@l@mOm --------------------km-mmlPPm ------------------------- s. 77*dommkl-titi ----------------------2-g#eel-&ti ----- -.--.-.__.--.--- ;:

---------------------- 9.7s .>@do~yl+metifl-lbbe ------------- 9.7s

2276 2a. m27.406206 wao. m a7. 1241. a4 4L 76aam a7. 00

0.86

::.42.41.2a. .

- ~ ------------- =lE!z!&Oyclopmpyl->bntene (1. b.)----------- 2206%OyrJoprop@2-~tene (1 b)~aytiwmp> -e (1. b.)--------------5

XlycloprepyMbntene (1. b.)--..______–. QS2

2-OyclePrePyL.2 exene (L b.)__________

>OyclOpmpyl-2-bnbme (b. b.)___________~@OProPY1-~~W (b. b.)------------2-OydoProPyI-> exene @. b.)__________ RSO

sphmti --------------------------------a 64Dl~wPyL ------------------------------ Q&2 I I%w:%ltene- . . . -------------------- 2L18

W%WYl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ma

~@yI~#pykbboL ------------------- ;2

Dbnetby w p~ylwbtil ----------------Methylethyloyclo PYlcddnoL_________ 8.77Me*yl~P &Wp~tibbl---..----.--- ~g(Methyl tYrcYc40ProPymrbinOl_-._-._..-M*-mpyl@owwlwbtiL-------- 17

~h~~&m~mb*nd..._... 24.76 “$~ 0..ylmrbfnol -. . . . -------- !23.40

Methyletbyl do pykarbfneL._-_. . . . . 24.06hfethYl~P~#v~lmbhd ----------- 2&~ g; . :fiMethyl nty oyoleprepy mrbInol. . . . . . . . . . . 42.a4 .14MetbylLwpmp@oyelopropykarblnoL . . . ..-. am 3104 -.06

Oyeloprepyl Wdti..-- . . . . . . . . . . . . . . . . . . . . gg ~.wlJ-Df~-om&--------------------

1907 Iual.40

fmnd-1,2-DieldnmuY o~~e ....--. . . . . . . ~.m ~Cdl .49 Ihfetb 1eydo~op 1Atone.-.____._-_–_ Q@Etby OydOpMpy h+OnO__.... . . .._.. ___Prop 1cycloprop 1htie --------------------

;;;E

Bnty oydopmpy kehme______________ .Q75Imprupyl Oydoprepyl ketone___________ Q7s

,

1*I

Methyl oydopmpyl hone ------------------ 29.34

Dlethyl oydoprop3nelJ-dlcarlmylote...._ 44.WI I I J

.Atornfc end SIWP refractfvftf~ of reference 64were used

b~x+.MB (observed).

CYCLOPROPYL RINGTABLE IV.—CONTRIB’IJTION OFTO MOLECULAR REFRACTION

\ CHi R’

Mngcontrfbntfon- \O/ + !2HG

1

CTO$R’

$r ‘R” 1 Ha ‘R” 1“Oyclopmpne derivatfwI

(%)I

Alfplmffa mmpnndsI

(%&) %3mn -butlon

2-@IJwwYl rewm------ m=E!N3ydopmpylnti___ am :E%$r=??:;;: g: 0.44.44

~_r$propyK3-methylbn-2-fJyclopropylp3ntan&-- 37.61 4-Methylbepbme _____ w. 12 .4s

27.a7 ~ 2-Dfmethylbexene___ Sa.w .44

I >GiGpropYlhemae__.J 4214 I 4-Metby~_.-...J KL7?’ I .43 I

I DIoydepmpyL-______l 23.62 I u-H— —-... ------1 n91 I .a7 I

~Abmiamfmetkmf mbydregent akenfrmnreferenm64.b Rem refczenca66.● Inclndm ring mntribnti PII19rmy oreJt.9tionaccompanying wnJngiUon.d Frem mferencaM.● Frem refemnm 67.