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AN INVESI‘IGATION OF THE DIPOLE 1434st OF SEVERAL
SERIES OF UNSATURATED CLMPOUNDS

By

Horton B . Penieh

A THESIS

subdued to the School of fluctuate Studies of Michigan
State College of Agriculture and Applied Science
in partial fulfillnent of the requimente
for the degree of

MASTER OF SJIENCE

Depart-eat of Chemistry

1952

Mi IIN 3:31 m..,:..TICZ~I 02'“ T2273 DIVL; EHL'LE’2‘3 0"? 5.1.29 323-21.. 5225:1133
a? wontrm co;- mm
A23 A332"? QRCT
Despite the great theoretical mportanco of the electric ciipolo
mom. int‘ae manner-him properties «mmolamlos,
mntflnwrkofummflhaabemdomflthfliphatiomnm
www.mmmummmmmu
town this property in several nodes or substituted alloy-me
and related nuance, and to present a timoretical Motion of
thenmlteoithoeenoamom.mmmasumdmohdedm
amamlandmparwlwpehalidoa. 62.11923. Malcolm. and
e for other closely related compmnda.
A brief outlim at the procedure vhifi: was used in this work is
ea fallout
1) Preparation and Mioation of the WW.
2) Mex-ammo or the refraction indium or the pure liquids
at 25': 11th on Abba ”Imam-motor.
nmmmnuaamummmummm
in ham and the denomination of the demitiee of these solutions.
h) monument of the amt: comm of the solutiom by
the notes-Wont mum}
S) Nation of the dipole mama at the wpounds by the
we suggested w 8.33.va and Malena
mom-memathepmpmwlmdanylhalmoe wretmmd
to be appreciably lower than the momenta of the mmspondim, saturated
mm} It me also found that there in an appreciable increase
in the dipole manta 31mg the series

150320 "621231‘ 12:: 0 631‘ 110 c 3‘3”

12 0213

Mob 13 greater than can be accounted for by polarisation of the
mwa-mmm

In 00:31.60th or this momma the follow Motion
Mummdumdmwnuflmmflmmmrm

Wormwood:

B 6 > 2
taught—x irgcrovd

6' ‘ 3m
A similar strum we proposed for the 3113']. W. This ism of
851110121113 has been mozrhiomd provimoiiy for motivl acetylene. 4"

The WW foundfowtho proparwlvpohlidmmmtaloo
be We! all balm yummy due to tho greater dwbmmgativity
at the carbon atone in the aootylonio amp. Home: tin evidence
Wed in; mm to permit the mom of definite W810!!!
raga-dim this. .

An attanpt me made to calmlato the dipole mm of poop-11mg).
cum. ether and the alcohol: cox-room to the bmicbs mentioned
above w naming Mar-conjugation structures similar to tint almacv
W. andby woes-amazing tint the manimdoor the contribution
dtmmmtmwmtmmgnitudoorflmmof
WW1“. m resulta- ot these adulation were Win
inthe oomofthoetzm.mtmmmgoodagmaom withtlwmnbe
Mined for the alooholl.

1) J. cum. 3. Ohm. Won 33” 32%(19327fi
2) I. ?. rflwm and E. D. W: J. Eon. mm. 300., Egg 29:8(191’2).
3) W as; 313019 games; Trans. From Soc” $1923).

1;) I. K. Syrldn and 1-2.3. mam. mo Stmomm of molsaculeo, Inher-
ocurm mblisimrs 1m" how 29-, page-112.

   

ACKHOWLEDGKENT

The writer wishes to express his sincere
appreciation to Profeseor H. 1'. Rogers for his
guidnnce and helpfulness throughout the oourse
of this work.

{*Wfi'

TABLE OF CONTENTS

PAGE

mnowcnou................................................. 1
moon 2
CHEW-known”............................................. 7
EXPERDCMAL 10
moms 16
oxacussm 20
mm: 314

gafldaafin

TABLES AND GRAPES
TABLES PAGE

I Dielectric Constente end Specific Volumes of the Benzene
glam” ‘t 25°C....OOQCOOOO.0...............OO..C....'.. 1'6

II Dipole Homentsmd Bupirical Constants......................... 18

III Other Dipole Moments Used in the EvaluAtion of the Reeulte of
Th1,w.rk0000DOOOOCIOODOOOOOOO.'....OOOIOOOOOOOOOCOOI0.... 19

I? mm and Calculated Dipole Honente of Acetylenio Alcohols . . 31

W33
Compound Graph ( 6 Vs I.) Q'eph (l/d Vs I.)
W1 m‘eeeeeeeeeeeeem VII
Allyl BNIido...........II XII
Allyl Cyanide...........II XI
‘uyl Ewl Bth”.......m X
W1 Imdeeeeeeeeueeeen XI
3033']. moeeeeeeeeeeeen VIII
2 Mm-}Mtyue........m VII
3 html.aleeeeeeeeeoee'| XII
3 htmqueeeeeeeeeeeev . VII
1 Chloro-h-oetyne.......fl VIII
1 Dietkvlsnino-z-propynelv VIII
2 lethyl-a-bme-J-

-butyn‘eeeeeeeeeeeem
a Hethyl-3-butyn-2-ol . . .W
3 mtyn’1‘o10e0000000000n
Propergyl Alcohol.......V
Propergyl Bronide.......I
hwuglmmlRMLuI
Propu‘g‘l Imdfl....nu1

Hufifié“”

INTRODUCTION

I INTROIXICTION

Despite the greet theoretic“. importance or the electric dipole
latent and the large umber of leesurenents which have been nede , very
little work hes boon done with aliphatic compounds conteming triple
bonds. the purpose or'this work is to unsure this preperty in e series
of substituted tlkynes end the related elkenes , end to present s theoreti-

cnl interpretation of the results of these measurement...

THEORY

II Triblsarl’s

For this discussion we say consider s molecule es s system of stone
in which the electrons set es it they were hosted in certsin definite
positions. I! the centers of cation at the positive and negative charges
do not coincide the molecule is ssid to be paler end it tends to orient
itself in en electric field es would any object centsining sepsrsted
electric chsrzes . The dipole accent is s qusntitstive neesnre of the
pol-fit: of s mlesule of e snbstsnce end is defined by

x‘é-Er

I

vehere 1-1 represents the naitude of the dipole moment , E the totel
neaitnde of one “the surges (either positive or negative) end r
represents the distance between the centers of scties or the chases.
This definition seen-es thst the sclecule is electrical: neutrsl .
Since this discussion is concerned only with neutrsl solecules end not
with ions the sssunpticn is vslid.

It is obvious tron the definition that the dipole element is s vector
“tit: possessing Ill the osusl sttributes end being subject to ell
the naval unipulstions which nsy be applied to such s quantity. Thus
the tots]. dipole sosent of my molecule may be considered to be the
meter m of the sonents of ill the individnel bends in the nolecule.
Since the cherges on s solecule era of the order of 10""9 em and the

intrholeenlsr distences ere of the order of one engstron unit, the

menitude of the dipole moment is of the order of 10"“ esu, or one
W (13).

lost of the common methods of neesuring the dipole moment of s
substsnce depend upon s measurement of dielectric constant. The
electrons end nuclei of s molecule ere displaced from their mean
positions in en electric field so that both polar and non-polar molecules
will become polsrised. This polarization will correspond to individusl
moments In end mA where an is the moment induced by the displace-
ment of the electrons end nA is the moment induced by the displecenent
of the nuclei by so electric field. If s unit field induces the nonents

mi end mi in s non-poles molecule, and if f is the field strength

;‘('i*‘i)’

where :1 is the moment due to polsrisstion.

I! the nolecules in the field also hsve s permanent dipole moment
they will orient themselves in such It way thst s slight excess of them
will be directed sgeinst the field st W time. The magnitude of this
effect vsries inversely with tempereture. These molecules produce s
further lament 1:9 , which is the orientation polsrisstion. This was

evslueted by Debye‘ !‘-° ss

where k is the Boltznsn constsnt end '1‘ is the sbsolute tempereture.

m, ‘totsl I (1% e mi e .345) I,

To obtsin 2"!- we must hsve snother expression for eat/F. This can be
obtsisedn by s eonsiderstion of the definition of the dielectric constsnt
sad the force toting upon 0. unit charge in s sphericsl csvity in e di-

electric which has been plsced in an electric field.

at a M 3 6 - 1 9
T 83" T e e 5
where 5 is the dielectric constant, H is the molecular weight, (I is
the density end I is Avogsdros umber.
Combining the last two caustione it now follows that

c-1.H
5+

- 5...?!- (llé + IA' e lieu. ).

The left an equstion 1- the totsl molecular polarisation (Pt) of the
We end is the sum of three terns which ere the electronic, stomic
end orientstion polsrizstionsc PE, PA’ end Po. It should be pointed
out thst in the shove derivstion the “emption is made that the electric
ehsrge is in s vecuun end thus these calculetions apply best to s gsseous
dielectric.

It is obvious thst 1t instesd of using e may field in these
cslsulstione sn slternsting field is used, es the frequency is incressed
it will reseh I: point st which the inertia of the molecules prevents them
from routing with the field. Thus the term for 50 will eventually
dislppefl‘. Similsrly, the moment due to stcmic polsrizstion will slso
dissppesr. Using Hmolls relation 6 - n', where n is the refractive

index st infinite wavelength.

n' - l I!
~----- - The soler refraction (HR) .
n. e 2 d

r.

 

In ectusl prectiee when the refractivity method is used it is usually
seemed that '

PE+PA ' MRD“

nan is the moler "mun meesured et the frequency of the sodim 'D'
line. The error introduced by the inclusion of PA in this equetion tends
to csneel thst introduced by the feilure to extrepolete n to infinite
wavelength. P is obteined from dielectric constent messur-ents sede st

lower frequencies . It follows that:

I
POOP -HRD. ”I

it 25%;- . ,u. . .0123 We .

is en spproxiletion the shove fo rules can be spplisd to dilute
solutions of polsr solutes in nonpolsr solvents. When this is done the
polarisetion of the solute st s particulsr concentretion is obtained es
fellows:

‘51s " 1 “if; " l"ere
en t 2 dis

 

Where 1 refers to the solvent, 2 to the solute, 12 to the solution
and f is the sole fraction. 1’, is the totel polsrisstion tern for

the nonpolsr solvent. When e series of P, veluee ere obteined st
”riots concentrations they on be extrapolated to infinite dilution (Po) .

Being this nice A is celculeted es indiceted previously.

In dipole nonents obtained fro: neesurenents of this type In error
is introduced by the sssunptions in the derivation of the equstions which
is usually sssumed to heve s nsxinus velue of e few tenths of s Debye
unit6 elthough in some can it is eppreciebly higher, especially if the
compound whose moment is being determined ferns solutions which ere
slightly conducting. '

The precision of this nethed is O.lD or less. The difference between
the sllus of the wonent determined by neesurelents in the see phase end
those ads by neesurenents in dilute solutions of nonpoler solvents is
usually not pester then 0.213,“ the gee pom mount ordinsrily being
higher. It is obvious thet couperisons of dipole muents which heve
been determined by the sac nethod ere much more velid then coupes-icons
sf moments which heve been determined by different methods . In this work
it hes been necesssry to refer to new dipole moments deter-iced previously.
Wherever possible velues were selected which were determined in bensens

solution st 23°C.

amour IONS

III CALCULATIONS

)‘or the purposes of this work the calculetione were nodified
slightly «cording to the method suggested by Halverstsdt end luller18
who here shown thst plots of 6 end l/d versus the role freotion of
solute Ire essentidly strsight linee in dilute solutions and have sug-
gested that the nlue of Ptoo calculsted Iron these extrqoleted values
will be eseentislly free of error due to swell haunts of impurity in

the solmt. the actual equation used is determined es follows:

P is " 3-53-23- ' -1- . P“ is the specific solute
61. + 2 d

polsrisstion st s specific ooncentretion. This emotion follows inedistely
from those presented previously.

The equstions

Ind
V is " v + ’96).

follow
from the strsight line relstionships mentioned above. e ' Ind v' ere
the dielectric constsnt end specific volme st infinite dilution. The
slopes of the strsight lines ere e ' end ’0' , end to) is the weight
Motion of solute. .

Solving end elilinsting e u and r“ , then

d'V'
Ptoo' C + s + (V'+f')-e-,-;-§-.

Or, in tons of mole fraction

OLV 6:01
Pm. 6,. HI '0' (MaV‘t‘H‘F)??? ’

where e , v , x , ,0 here the some significance en the primed veluee in
the previous equation. IThis equstion is the one which in used in the
calculetions in this work.

A brief outline of the Ictuel procedure in cslculetion is as follows:

1) The nolsr refrection is culculsted from the neuured values of
the refrective index end density for the pure solute by the
equsticn indiceted previously .

2) The cell conetsnt, relative to benzene es standard, is determined
by liming the cepscity of the cell at 25°C with eir, then
benzene, es the dielectric.

Cell constant . Cu;- 31 C
5m: r 1
The vslue 2.2725 for the dielectrie constent of benzene is used
throughout.

3) The nlues of e u at various concentretions ere determined by
sessuring the especity of the cell with eir end then the solution
es the dielectric st 25°C.

(Cw " 0301“) ‘0‘ 3.11 Bout.
cell const.

 

6'" e

h) The density of the solutions is determined st 25°C.
5) The nlues obtained for ‘6 13 end V“ are plotted against the
nole frsction of solute (1.) end the slopee at and p are

determined. These graphs we shown et the end of the experimental

section .

6) Ptoo is calculated by the use of the equation indicsted above.

7) The dipole moment is celculated from-

EXPERIMENTAL

10

IV EXPI‘LRMDJTAL

gefrsctive Indices
The refrsctive indices of the pure liquids were determined st 25°C
with en Abb‘ refrectoneter.

Densities
Densities were determined with a modified Ostweld pycnoneter at

25""0.28

Dielectric Constents

The dielectric constent neesurenente were node by the heterodyne-
best nethod. In this nethed two redio frequency simels ere combined
by ilpressing then scross m an. grids of i ninr tube (can). This
introduces e frequency, which is equal to the difference between the
frequencies of the two oscillators, into the output of the 1131‘ tube.
When the frequencies of the oscilletors ere nesrly sees]. the output or
the linsr tube is in the audio range and one be heerd if the signll is
slplified end put through e loudspeehr. The pitch beeoses lower es the
frequencies of the oscillators become more nearly elike end finally
assess when the freQuencies ere equal. In this work the null point from
the liner wss observed roughly es above, end It fine sdjustnent nsde by
inn-seeing the amplified liner signfl. on the grid at s 6E5 'Hegic Eye"
indicator tube.

In this equipment, which is einiler to that described by Chien ,19
the fixed frequency oscillstor is crystal controlled by use of s. 200

ll

kilocycle quartz crystsl. . A General Radio precision condenser, type
722D, is in perellel with the dielectric constant cell in the L—C circuit
of the verieble newency oscillator. Since the frequency of the

verilble frequency oscillator is given approxinetely by

f - l/ZZTV'E',

it is obvious thet shy change in the especity of the cell must be cor-
rooted for by s corresponding change in the precision condenser in order
to keep the frequencies of the two oscillators equal.

freq.

F ._-....-
0.0 .

I'" ..__..__._.._..

_ Min }:——-—r—~—--M—) beet detector

 

 

 

b fret.

'EL...

Verieblej

 

Cell Precision
condenser

A disgres of the cell any be found st the end of this section.

mmg of Compounds

Motion of the senpounds whose dipole moments were uncured.
The finel purificstion of nest of the following compounds wee ecocnplished
by distinction through e 60 an. helix peeked colun until succesein one
ll. portions showed s constant "frectivc index.

A lamina -- Eastman mute Label compound was dried and redistilled,
b.p. 53°C (YhSMJ, .155. 1.1225, dff- 0.7597.

Am}. Mide .. The compound obtained comercially was dried over
calcium chloride and distilled, b.p. 71°C (714%.) , rigs- l.h6€x’), dfiE- 1.14201.

Ml Czsnide -- This compound was prepared by the action of cuprous
cyanide upon sllyl bromide by the procedure given in Organic Syntheses ,20
mp. 116°C (7h5m.), “1235, 1.1.039, aff- 0.8267.

A1121 Eml Ether -- Eastman White Label compound was dried and re-
distilled, b.p. 67°C (7hm.), 25- 1.3892, diS- 0.7596.

5211 Iodide -- This compound was prepared from ellyl bromide by
refluxing the pure sllyl bromide with methyl slcohol and oodiun iodide.
The rotation mixture wss decanted from the solid residue end fractiondly
distilled through s 60 on helix peeked colmm under reduced pressure.

The distillste wee redistilled as described shove, b.p. 102°C (71:51:31.) ,
1:35- 1.5h62, dfi5- 1.7955.

Since ellyl iodide is extrenely sensitive to 113m.”

the dis tillstions

were performed in the dnrk so were detexninetions of the dielectric con-

stsnts end densities of the solutions. When it wee necesssry to hm

lifit s hell red ”pencil light” wee used since the decomposition has

been shown to be slower in light of longer wsnlengths. It was noted

thet otter e tour hour storsge in couplete den-knees the retreative index

We content but hegsn to change soon otter exposure to white light.
321nm. - The W White Lobe]. compound was distilled es

described won, b.p. 183°C (new), 311235 - 1.51407, dfis - 0.9798.

13

flung-phage - l'hil compound m prepu-ed in low yield by the
addition or phoephom tribrmide to e alight ensue at 3-butyn-2-el et
45°C in the presence at 0.1 mole at pyridine. The reution In very
vigorou- end m: was given off. When the addition the complete the mix-
ture Ill uuhed with Inter and the organic layer m moved end dried
em «loin chloride. The arsenic layer m then distilled W e
.60 a helix peeked calm at reduced memo and then redlltflled u
demibed then, b. p. 28-30% (8km), n35 - 1.1066, dis - 1.3815.
It it believed that the ujer produntl or this reection ere the eaten
at phnpheroul mid.

flag-Ibo]. - Ihh me! It: obteined hm the Puebla Belem}:
mantel-tee. The compound wee dried over Iodine sulfate and then eeleiun
eultete end dietmed u the“, hp. 128°C (7mm), $5 - 1.1093,
4,”? - 0.9198.

m—z-ol ~ Th1- cupound m chitin“! and purified in the nine
lemu- u 3-bntyn-l-ol, b. 9. 107°C (film). as; . 1.h238, dis - 0.8890.
1-Chlero-h-eetyne - ‘rm cal-pone m chum from m. run-om
Helen-eh Lehman", dried over «lama chloride and (ii-tilled u ebove ,

h.p. 99.5 (Mm), 18h (Ha-J, n§5 - 1.1551, «1,? - 0.9139;
l-gtgtgludeL-zrome «n- this mum! no obtained tra the
lmhlu Beeeereh 'uboretoriee and dietllled u ehove, b.p. 119°C (7%“) ,

lags - 1.h291, 4&5 - 0.7982.

Wbbmo-fi-butm e- thy hydrogen bmide m weed through
the we alcohol (2-methyld-butyn32-el) et 0°C until the rotation mixture
In. “meted . The ”genie layer the then separated from the henier

1h

layer of hydrobroeie laid . The organic layer was washed three times with

ueter (the new. we. metreliecd with we, in the first washing),

lepereted end allowed to etend for twenty-four hours over dry 111360, at

0°C. The nation mixture wee distilled from fresh K420, under reduced

preemre. Two frectione were obtained, the smaller high boiling one

nae no rotation with elooholio eelair not rate end rapidly polymerized.

It in thought to have been l-bromo-3ometkvl-butediene-l ,3 or a similar

compound. Thie nethod ie eieilar to that of Campbell and Key,”

b.p. , n35 - 1.h631, dfi5 - 1.2657.
equal-penny.“ - Thie compound m obtained and purified in

the one sinner ee Mutyn-l-ol, b.p. 103°C (YhSmJ, n55 - 1.1mm,

dfis - 0.8566.

fistula-cl - Thie chpound was obtained and purified in the cane
Iemer ee 3-butyn-l-ol, b.p. lea-109°C (37mm), n35 - 1.15m, dfi5- 0.8767.

m1 Alcohol «4 This compound was obtained end purified in the
cue leaner ee 3-butyn-l-ol, b.p. 11h°c (71:51:13.) , 113235 - 1.14393, dfis- 0.9106.

Propel-g1 Bromide .. This compound was obtained end pm'ified in the
flue leaner u l-ohloro-h-octyn, b.p. 88°C (7140mm) , n55 - l.h9h5,
dis - 1.5657.

Progugl £1th]. Ether - To one gram molecular weight of propargyl
eloohol 0.2 gren atomic weight of sodium m edded in small pieces. Each
piece of eodiul wee edded when the previous one bed almost completely
rented. Cere must be taken not to allow the reaction mixture to get
too hot (above 70%) or to try to force lore eodiun to react by vex-hing.
When either of the above it done the reaction mixture decomposes violently.

15

When the sodium had reacted 0.2 you molecular weights of ethyl iodide
were edded end the mixture was refluxed for two hours. The reaction
mixture m then distilled through a 60 on packed column. A mall
frlction of ethyl iodide came over first at 72°C. The desired product
distilled et 80-81%. The yield m approximately 50%. The emcee
eloohol ranaining could have been recovered or used directly to prepare
more ether.

The crude ether m redietilled an above, b.p. 80°C (750mm,),
n35 - 1.1.019, eff - 0.8m.

Pmpggl Iodide - Thie compound was propered tree: the bromide in
the cane manner as Ally). iodide. Decompoeition in light did not seem
to preeent e eerioue problem here, b.p. 11h°c (7140mm) , n55 - 1.59111,
dis I 2.02134. \

CELL

1‘
‘7

TO OSCILLATOR
CIRCUIT

 

 

 

TO AIR 0R VAC. I

 

 

 

 

 

 

 

 

 

 

 

 

/ 1
SOLUTION . TOP VIEW
PLATES' PLATES
5 Emma: ' ~
> F

I

I

I

ENTRANCE .

 

 

 

 

 

 

TOTAL VOLUME. OF
SOLUTION HELD

j .50 ml

 

 

 

 

RESJLTS

16

V RESILTS

TABLE I

DIELEIRIC comm-ms AND 52201210 70110123 or THE
BENZENE 30117210113 12 25°C

A _._.

Aggluine 4 f 111;]. Bromide

 

 

 

 

 

 

 

 

 

1.. e“ '1. It- 61" VI.
0 £28119 2.3128 1 .1192 0 .0939) 2 .6885 1 .0831
.0198? 2 .3111? 1.1179 .06031 2.5285 1.0989
.01505 2.3015 1.1272 .03108 2.11055 1.12171
.0100? 2 .2939 1.11465 .01660 2.311119 1.13314
.00176 2.2818 1.1155 .01010 2.31142 1.1377
.00L20 2.2930 1.1118
11111 6:31:1de . . 1 11w; Ether
0.03376 2.8272 1.11161 0.02921 2.3371 1.1502
.020h7 2 .6059 1 .1163 .0209? 2 .3202 1 .1118?
.01276 2.11786 1.11451; .0152} 2.3068 1.1h75
.00681 2.38171 1.1150 .00906 2.2926 1.1h65
.00h96 2.3561 1.11119 .oohoa 2.2822 1.115?
.00281 2.31711 1.11118 .00390 2.2811 1.11155
M20 1 - - mg 1.1.. -
0.05258 2.16171 1.0825 0.02573 2.3128 1.11106
.01790 2 .3382 1 .1226 .01809 2 .3207 1.1118
.01126 2.3231: 1.1270 .01070 2.3001 1.1100
009.96 2 .3095 1 .1323 . .00552 2 .2857 1 .1109
.oo3h5 2 .2865 l .1h02 .00285 2 .2786 1.117113
.00130 2.2789 1.11133 .00126 2.27119 1.11119
z-Bmo- but A . WL-Ol __
0.02300 2.1711 1.1279 0.01869 2.31112 1.1113
mm. 2. 1.1326 .0129? 2.3178 1.1112
.01210 2 .3233 1.1362 .007935 2.3032 1.11116
.00678 2 .3020 1.1396 .003302 2.2837 1.11.1.6

7 TABLE I - Continued

M

1?

 

 

 

 

 

 

 

 

 

2-Butyn-2-ol l-Chloro-h—octyne
0.01761 2.h760 1.1158 0.01570 2.3h89 1.1127
.03501 2.1055 1.1156 .01051 2.3235 1.1131
.01957 2.3127 1.1152 .00591 2.3021 1.1139
.0092} 2 .3039 1 .1850 .00336 2 .2890 1 .111143
.00510 2 .2903 1 .1150 .00315 2 .2579 1 .1th
.00179 2.2775 1.1189 .00116 2.2786 1.1116

1431017111021 ino-2-pr0gzne z-Metlwl-t-brono-g-butm

0 .01729 2 .2801 1 .1878 0 .01173 2 .3170 1 .1350
.01308 2 .2 790 1 .1171 .00910 2 .3181 1 .1386
.0095? 2 .2773 1.1h65 .001116 2 .2936 1.11718
.0059? 2 .2756 1 .1858 .00305 2 .2878 1 .1826
.00190 2 .2707 1.1151; .00183 2.2 827 1 .1831:
.00110 2.2731 1.1889 .00108 2.2775 1.1110

24601111. 2-butyn-2-ol wrl;01 11
0 .01876 2 .3311 1 .1161 0 131712 2 .3100 1 .1850
.01282 2.3126 1.1159 .01320 2.3260 1.1150
.0079h 2 .2965 1 .1175 6 .00915 2 .3095 1 .lhh9
.00512 2.2878 1.1152 .OOShh 2.2937 1.1888
.0039h 2 .2 850 1 .1851 .00319 2 .2852 1 .lhh8
.00199 2.2787 1.1850 .00160 2.2791 1.1853

Preparggl Alcohol. Pmpargl Bromide
0.03259 2.1125 1.1133 0.02267 2.3817 1.1278
.01676 2.3106 1.1112 .01669 2.3285 1.1322
.00757 2.3038- 1.114117 .00976 2.3023 1.1376
.00133 2.2928 1.1811 .00622 2.2902 1.1800
. .00312 2 .2822 1.1122
.0022? 2 .2800 l .1h33

Proper g1 Ethyl Ether

.01276
.008LS
.0051?
.00390
.00272
.00069

2.3019
2.2930
2.2876
2.2829
2.2798
2.2712

1.1151
1.1151
1.1152
1.1152
1.1150
1.1119

Propargyl Iodide

0 .022 53
.017L5
.0116?
000607
.00h7h
.00190

2.3218
2.3106
2.2977
2.2853
2 .2825
2.2761

1.1185
1.1213
1 .1288
1.1360
1.1387
1.1121

18

 

 

 

 

0.344 02.0.... 405 .. 00.0 m0.0~ 2.40. 0040 404 6303 4.002080
0.344 mus.“ 00.0 $4 $.40 34... 5.5 34 850 4050 4002080
2344 mus.“ 40.0.. 40.0 «04... 44. «0 00.00 0m4 .3120 4.3.2020
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0.344 02.0.0 40.0 «44 8.00 00. an 40.004 004 477036070
0.1344 ~03. N 00.0 94 4040 8.8 00.2. $4 40-070000004036010
0.1344 405.0 00.0.. ~0.m .0040 00. mm 0.004 .34 E03707§107074306¥~
0.344 3.54 5.0 0.0.0 04.00 00.00 Q43 00.0 00008070184542.2374
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0.344 334 30.0.. 3.4 mn.m~ 00.3 4040 004 604.810 13
2.24 «2.04 3.0 44.... «0.04 5.04 3% R4 00454.42
p 0 0K 3 .ommw am: comm 4\ 390.0300
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.4 .0 :0 05 3» 3 00.480 638520.00 030: .0822“; .30.. .0550 388

HH Hand“.

19

TABLE III”

DIPOLE EMFNTS NOT DETERME‘IED HERE, BUT WHICH WILL AID IN THE;
EVALUATION OF THE RESULTS OF THIS WORK

A A *—

 

Compound ' /A (D) Compound M (D)
Bx'muoaaectylenvzal3 O .O‘“ n-Propylam ins 1 . 39*“
2-Bronobuune 2.12 (20%) » n-PrOpyl bromide ‘ 1.9h (20°C)
Chlowwe'l’grlesme13 O.hl¢** n-Propyl chloride 1.9h (20°C)
Ethyl. nfipropyl other2h 1.16 n-Propyl qyanide 3.5725,h.05**17
Z-Hydroxy butane 1.79 Propylenel3 0.35”

Methyl Acotylenels 0,77 n-Propyl iodide 1.85 (20°C)

2-Methy1-2-brono butane 2.25 (20%) Vinyl bromide13 1,151“

2-Motmr1-2-hydroxy butane 1.66 Vinyl chm-ids13 1M“
1—Ootanol 1.614 Vinyl Iodide13 1.26“
noPropyl alcohol 1.66 (22°C)

A. 4;. A __

9 Union otherwise stated these values are in benzene at. 25°C
and are tron reference 23.

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DIS3USSION

20

VI DISCUSSION

Polerizetion Eigecte

It has been established prev-lmuiilylh that the reeultant moment of
the -CH, you}: ie equal to that of e C-H bond, therefore the replacement
or e hydrogen by e methyl group ehould cause no chenge in the total
lament of e molecule . Actually, however, the replacement or a hydrOgen
by e -CH. poop will often canoe e noticeeble change in the dipole
meat of e molecule. Thie effect in thought to be due to the palm“-
tion of the hydrocarbon redial by the DO!" paler :1er map. An
example of thin ie ethyl chloride which he e meat which ie 0.15 D
higher then thet of uttvl chloride. _.‘1'he mt due to polerieetion ie
in the one direction u thet of the 0-61 bond, the carbon etcu being
lede lore negative by polarization.

To illuetrete thin we ney draw hm representetive etmtmen

H H
h) Kr) (r) (+) I
H C - Cl and H C - Cl
I i
a (A) a (B)

the ettect of the 0-01 bond being to increue the etebility at etruoture A.

ie the chain increeee'e in length the increeee in the dipole meat
beau-u negligible. However, it ie um noticeable in edding eeeondlry
end tertiery gronpe , the imreeee tron n-propyl bronide to 2—nethyl-2o
bronze butane being ebout 0.11 D. Thin ie because the groups edded ere
cloee to the 0431' bond.

21

In this work the dipole nonente of e series of acetylenic coupounde
were run. Since these ere comparable to the groupe mentioned ebove it
is interesting to no hot the dipole nomnts vary on replecing H by -CH..

We heve:
a on,
302 0-03.13: HOE c-L'Br HOE 0-333;-
63. . an.
- 1.501) - 1.7713 ’ - 1.9M)

The total change in nonent from the primary to the tertiery compound is
(3.th which is considerably larger than thet or the setureted eeriee .
This eeons to indicete that the .03 c- group which is known to be more
polarizeble itself also tends to lake the whole lvdrocerbon redial more
polerieeble. Another explsnetion of this effect is that the increase in
dipole moment in the eoetylonic series is pertielly due to the supreseion
of Imperconjugetion etrncture VII (in the following discussion) upon

replecenent of H by 433..

Resonance end Wtion Effects

For compounds such ee the vinyl helidee‘ve would exput to find
higher dipole nolente then for the correeponding eetnreted halides it
poleriution were the only effect. Actually the dipole moments of these
coelpounde ere law- by about 0.7 to 0.8D than the unsetnreted wide-.7
A einiler effect is eleo noticed in the haloscetylenee where the moment
is 1.7 to 2.2D lower then the velue for the setureted halides. These
effecte ere explained by resonance “natures? such “I

3.0-0}! - I end 83 - C . I

Q + n +

22

If the dipole lonents of compounds similsr to the shone but with s
-ca.- mm between the unsaturated bond and the halogen ere amend
the renounce or hyperconjngetion effects in these compounds could be
studied else. In this work the dipole mounts of cone dlyl end propel-girl
eonpoends heve been determined and competed with the sstursted helides
for this purpose.

The dipole accent of nopropyl bromide is 1.9hD23 which motley
be considered to be (In. only to the noment of the C-Br bond and polarise-
ticn of the hydroccrbon redicel.

the mat of ellyl bromide was determined in this work to be 1.821).
This represents e lowering of 0.121) with respect to the utursted con-
ponnd despite the fact thet the double bond would. be expected to be more
polsriuble end therefore to incresse the dipole nesent. This effect
can be psi-tielly esplsined on the besis of s hyperecnjngstion structure
which hes not previously been nentioned for these cospounds.

a i . I;1 a! Ii! 1? .
H28 H: «3-H H,c - 0 73-3 11.0 - c -c a”)
Br H3;- .. “'3 r
H 393
HID ~32 eQ-H
C") fir
I - II III

The suggested twperconjugetion structures III would sccount for s lower-
in; of the dipole moment. It is interesting to note thet if we consider
the hydroan propylene which has I. dipole moment of 0.35D, the follow-

in; met-conduction etrcchire which is enelogous to III has been proposed:15

H ‘ H ll! M

3,0 oowa, Hfi-C-CH.H
IV

It should be noted that structure III would have to be only e very smell
contributing {later to have s distinct effect upon the dipole moment
because of its lsrge shes-gs separstion. Not much con be sold shout the
extent te which structure III lowers the tots]. moment or the molecule since
there Ire too neny‘unknovn quantities insolvod.- Its Iotuol contribution
would depend mag ether things upon the negmtune end direction of the
polarisation scant end upon whether or not there is tree rotstion er
the «ma:- group. ‘ ‘

The nonent of proposal bromide wee determined in this work es 1.501).
The drop in the ugnitnde or the meat with respect to the sstm-eted
helide is 0m in this use. Since polarisetion or the eoetylenio
poop is eien greater then in the sllylio group s substantisuy larger
‘ dipole meat would be ensued if herpes-commotion were not token into
consideration. the hyperconjnption structu'ss proposed (m) we
enclogons to structure III and es with the prsvions cm s sisilss stmo-
tore use he proposed for the hydrocarbon itself (m!) .15 The dipole

moment or sethl-soctylene (solution nesenrenent) is 0.77D.

(0.)

hr 231‘ (-) hr
sci: - 241 mic «fit-H moc— a”
H l‘) r
v u 3°30 '3
EM
0') )
30:0ch *

3‘.)
puss

It should be noted that even s. rough attempt at calculation of the
contribution of structure VII would indicate immediately that the dipole
moments of propugl bromide and iodide are lower than can be explained
on the basis of the indicated structures. The most probable explanation
for this becones evident if one considers the work of '1'. L. Jacobo"?6
which was reported after the above experimental work was done. Jacobs
hes shown that if propergl bromide is heated to 110°C in the presence
of cuprous bronide e nixtm'e of propergrl bromide and brompropsdienc is
obtained. Jscohs has also shown thet the 'propsryl iodide' reported
in the literature is ectunlly s mixture of propel-9'1 iodide and iodo-
propsdiene. These facts give an immediate explenation of the extremely
low dipole Ionent found for propsrgyl iodide end it is possible that they
partially explein the low value obtained for the moment of proper yl
bromide.

It has not yet been possible to ascertain whether or not the pro-
psrgyl bromide obtsined from the Forehen Research storstories wss sub-
Jectod to such conditions as to have undergone the shore mentioned
isomerissl. However, the physicll constants of the propsryl bromide used
in this work Are in reasonably close agreement with those found for the
pure propergl bromide by Jacobs.26

The dipole moment of propsrgl bromide has also been determined
using material prepared by treating the alcohol with phosphorus tri-
bromide. The value found was identical with that reported here (1.501)),
although the physical constants of the propargyl bromides (111235 1.1t90h, (if?
- 1.576) differed. The physical constants reported by emcee“ for
materiel free Iron bronoellene were n? - 1.14896, dis - 1.562.

25

The shove {sets out some doubt upon the validity of the results of
this work with respect to the propugl type halides and, in particulsr,
prepsrgyl iodide . In the use of the bromides the results of this work
In probsbly valid, especially in light of the eonuniestion with
Dr. Jacobs. In addition, the sllylio halides ulso show dipole moments
which ere lower thsn expected. Since the myl halides are better known
than the propsrgl hslides, end since s similar isomerisn has not been
reported to occur in these compounds , it cannot be sssuned thet isomerism
would be e valid explsnstion for their low dipole moment.

A study hes been nsde of the bond lengths of the 0-1 bonds in the
propsrgyl helides by Pulling end coworkers.” The bond lengths measured
were slightly longer then the normal C-X bond lengths and the authors
proposed the following resonance structure:

'0-
-

EC - C - CH, I
II.
It is obvious thet in order to sccount even partially for the lowering
of the dipole moments this structure must be sssuned to contribute even
less the structure VII. It should be noted here that the indioeted work
of Peeling is subject to some doubt es s result of Jacob's work.

The dipole moments at two other ecstylenie helides have been
determined in this work. These compounds are 2 nethyl~2~brono-3~butyne
(XIV) , end 2 bronc-B-butyne (X) whose dipole moments sre,respectively,

O .311) end 0.351) lower then those of the corresponding saturated compounds.
Taking structures I? end VII into eonsiderstion the following resonance

and hyper-conjugation structures sly be drawn:

26

a . £3 3“)
3036-83-03. 302032-03, m-c-c-cn,
31‘ 17,-? C.) Br
I n m
4H
l
m . C . C "' CH.
6)..
311-)
XIII
9"- 9:. ‘ ”“-
HcEc-e-cn. eczema-cu. goo-g-cn,
Br .. BIL) Br
m xv XVI
93a
33 . C . C " CH,
(n
3%
In:

It should he noted thet although structure HI 1- not considered probable
there ll ltlll In Ippreoiehle lowering of the dipole meat elthough not
to greet u in the ~px'opergyl compounds. This would new to inflate thet
m inductive effect oluud by the grater eleotronegetidty of the olrbon
etc” in the triple bond night eleo contribute to the lowering of the
dipole nmnt.’ Thin induetive effect. prohebly portion: aeoounte for
the very 10' ment of prepergyl bro-me .

The dipole team“ of two of the ethyl ethere oorreeponding to the
helogene diamond above have been detemined in this work. The lament
or ellyl ethyl ether m found to be 0.221) higher then thet‘Iethyl,

27

nopropyl ether , end the nonent of propuyl ethyl other ie 0 .30D hiaxer
then tilt of the utureted ether. Since the ugnitudee of the nonentl
inoreeeed in thie eeriee e rough oelouletion will he node to determine
whether e nonelt in the direotion indioeted by hyperoonjugation etruoturee
of the one type to III and '11 would account for thie.

In the following emulation” on propel-9'1 ethyl ether polariletion
ie neglected, tree rotltion ehout the 0-0 bond ie named, the nonent
or the reeonence etruoture corresponding to '11 ie named to be the
me u that of the hydrocarbon (0.771)) , end the nonent of the 0-0-1!

group to "mod to he the one u the meat of ethyl, n-propyl ether.

 

 

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* See next pogo,

28

‘u " 'u " '-
I; e Week - I: ,
new - 1-,.
lg," - n: + I}, + hunquoe + fincoe't + nhySin‘t
.'.: + 3'! +11% 4- hallway

277

n'on: on; enhy+2nunuy [Coetdt
fr
0

Id! - ht; I32 *flga 0% +‘h
" I': + ‘: ‘ bit “he
- (0.77)' + (1.16)' - 2(o.77)(1.16) Coed Coo/3

I! 5-1100. at .700’ fl ""550 Then A ' -1.59

.’w 01.261)
It 5 -12u°, .t-56°, p ~55° than ,u ‘ -1.39
A 01.181)

Dnetothelergen-herotmtionevhiehhedtehenedeitiedoubtful
whether thie emulation in very Canine-at.

minitione 01157 eyabole need in the previouo eelenletion ere a follow:
II, 1,, nl ere the totll Innate dong the x,y, end I nee.
n; .- The meat due to the C-O-gt group lament (1.160).
n. - l'he Intent due to the hypereonjngetion etruoture (0.7m) .
M~fhenmntintheayplene due to thee-O-Etmnoeent.
In - The meat elong the 1 Mil due to the hypereonjugetion etruoture.
I“ «- ‘rhe ment dong the I llil due to the C-O-Et group moment.
I” -- The moment along the z exie due to the hyperoonjugetion etruoture .
gnu .- The inetenteneoue haunt .
e -- The .1th or ,«c (Average).
Anglel o( , f , x , 5 m ee indioeted in the calculation.

 

29

It annexation of free rotation were not velid, we could name the
orientation ehown in the folloeing oaleuletion.fi

‘12 " '1 00’?

I", - 13.0er

‘1 “ fizz-‘5“
- 0.39 if e: e70° ( I - 110°)
-o.22 1: .z -ss°( 1-121?)

 

 

 

In . .3 C03“ . 0.725 1: :5 C 20° (5‘ . 110°)

-o.6h1 11‘ x ~3h°( f-12h°)
In - I; 00- 35° «2.951
.'.nx-1.6811‘5-110° ‘
-1.59 116‘ ~12h°
. 1.73 1: a -110°
-1.61 1: :-12h°

Both of theee veluee ere biwer then the expert-onto]. value (1.h69) .
Although the reeulte or theee oelculltione depend upon new euunptione
which render thu very eppronnete, they night indioete thet the rotetion

 

mitione of the eynbole need in the previoue oeleuletion are In follow”
nxp, .. The total nonente don; the x and I amen.

e11 - The moment of the 0.0.: t group (1.161)) .

n. - l‘he eemed lament for the hyperoenjuption Mitre (0.77) .

nu - l'he noment of the 0-Oeft groug along the x axia,’

an - The meat due to the hyperconjugation etruoture along the 3 1x18.

(Sinner for 3 exit.)
Anglee ¢ , e , I are ee indicated above.

30

ebout the 6-0 bond ie eonewhet restricted in the orientetion indicated.
Thie ie not very probeble end there is probably cone other effect which
has not been eoneidered here. Siniler celculetione heve not been
ettempted for lllyl ethyl ether heoeuee even nore eeeunptione would be
neoeeenry.

When the dipole nouente of eloohole containing on eoetylenio group
no ooneidered it ie found thet in.the eerie"

on, ca,

m§c~ca.on HcEc-é-n 305043-011.
on 011
mu xxx xx

the dipole mom decreeeee very elightly (0.19) Iron xVIII to xx. this
in not like the bmnidee where there we on inoreeee of 0J4“). It ehould
be noted thet the elcohole would be expected to eat nore like the ethere
then the hronidee end tree rotation would be expected in the eloohole.
Couperieon of the nine: obteined for the uneetureted elcohole with re-
ported valuee of the mount. of the corresponding eetureted alcohcle ehowe‘
no definite trend tron the eetureted to the unsaturated ceeee, however ell
are within 0.12D of one another. I! we name tree rotation about the
0-0 bond end ”lune that the orientation of the rent of the molecule is
eimiler to:

no 3 c '2 on.

Egoo-H

Thin orientetion eeene not probable beceuee bond length neuurenente
in nethylloetylene indicete that the bond between the methyl cerbon

31

and the ecetylenio carbon atom hae e great deal of double bond
8 .

character .

It I calculation identicel to that for the others, where free rote-

%
tion wee deemed, ie node we obtain as before the equation:

I? - n: +n: - hung:

A sample oelculetion with 3 butyn-Zool ie no follow"

5' - M - (0.77)’ + (1.79)2 - 2(0.77)(1.19)Coa56°Co-s5°.
- 2.91

M a 1.70

mm xv
consume an cnmuum 9mm HOHENTS a 10mm ALCOHOLS

g...— __-._ A . .

 

Alcohol fl Celc'd. A Determined Difference
Propergl eleohol 1.591) 1 .78D 0 .191)
3 ButynoZ-ol 1.70 1.69 0.01

2 Hethyl—J-hutyn-fi-ol .. 1.59 1.59 0.00

——

It would one thet from the eenellent egreenent between the calculated
and actual veluee thet the eemptione node were eeeentielly reuoneble.

 

fl"I. " The lmnt due to the 0-0-3 group taken no thet of the oorreepond-

* ing eetureted alcohol. .
All other eynbole ere identieel with thoee in the previoue derivetion

involving free rotation.

32

It ehould.bo noted that Ill values for the alcohole are subject to e
greater error than the other compounds because their solution behavior
is extranely non-ideal.

The dipole moment of 3-octynPl-ol was determined and found to be
0.1hD higher than that of the eetureted elcohol. This obserntion wee
not expected. This elcohol would be expected to have s moment essentially
the some as that of the corresponding eetureted elcohol. The difference
of 0.1hD is not very greet, however, end.light‘be due to experimental
error.

In the case of Illyl cyanide the dipole moment is found.to drop
about 0.13 fro- the vllue for anropyl eyenide. It ie difficultlto drew
eny definite eonelusione ebout this due to the lerge diaerepeneiee between
reported veluee for nepropyl cyanide. However, the following resonance

structures new be drawn:

9') N)
11,0 ~CHoCH,-C§H CH,-CHfCH3-C-N
mu m
on.-ca-cn-c§n caz-CH-ca-c-N“)
Gd Hie) » d”)
xx xx:

Structure 11 corresponds to the previously mentioned hyperconjugation
etruoturee and would eocount for e lowering of the dipole moment in this
compound. Unfortunately’propergyl cyanide seemed to decompose when
nttenpte were made to prepare it. lo measurements on that compound could

be:nede.

The dipole momenta of e few mince were run in this work. Due to
the large member of eeemnptione which would have to be made in the
interpretation of these momenta, and the great variation in reported

mace for nines , no conclusions can be drawn regarding them.

33

SUMMARY

WI

The dipole nonente of eeverel eeriee of unsaturated aliphatic
eonpounde have been determined by the refrectivity method . Then momenta
provide evidence that hyperconjugetion in important in ellyl end prOplrgyl
derivativee. Reeonence in the helidee, the elcohole, end the cymidee
ha been dieoueeed in deteil. No conclusione could be drewn from the

mute neeeured for the ethere end the mines.

3‘s

momma es

1. II. V. Sidgwiok, The Covtlent Link in Chmietr , Cornell Univereity
Preee, Ithece, fiew York, 15%, Che-Etu— 7.
2. c. P. Nth, Dielectric Cement end Molecular Structure Chalice].
- Cetelog 50., Ear lurk, E. 5., 1351.

3. P. Debye, gale; Holeeulee, Chemical Cetelog 60., lee Iork, N. 1., 1929.

h. 21:21., plan 29.

'5. G. H. Whelefié The Theo of Reeonenoe, John Wiley I: Sane, flew Iork,
‘e re, 1 e . '

‘6. 1253., page 168.
7. £13., plge 132.
8. M” plge 298.
9. gig... peso 131'.

10. R. J. W. wevre Dipole been“ (2nd Edition), Hethuen 8: Co., London,
19118, p8 S‘ée

ne Ibido’ 9“. 1-9e

12. I. I. Syrnn end 1!. E. Dyetkine, The Structure of Holecnlee, Inter-
eeience Publiehere Inc., New Tori, fl. 1., 1355, page I97.

13. My, page 21?.

11:. 3333., peso 211.

15. M09 page 212.

16. $339., pege 180.

17. £933., page 219.

18. Le. Selveretedt end 14. D. Keller, J.-A-. Chem. Soc., g, 2988 (191m).
19. J. Chien, J. on... Educ., .23, use (19M).

20. I. Gill-en end A. B. Blett, Or 0 theeie (2nd. Edition), Collective
Velma I, Wiley, New Ierk, . ., .

36

21. H. West and B. Poul, Trina. Faraday Soc., _2_§, 688-97 (1932).

22. x. mounpben end J. r. Eby, J. Are. on... 800., 3g, 1798-1600 (191.0).

23. Amndix cg Dipole Moments, Tram. Emmy 800., ‘19 (191.3) .

21;. R. A. Spun- 1nd H. Zoitlen, J. Am. Chem. 500., 2, 1.832 (1950).

25. E. o. Cowley and J. R. rmington, J. Chem. Soc., 601. (1935).

26. 1'. L. .1qu and W. F. Brill. Abetrtote of Pope” Presented at
Am. Chem. Soc. Nationd Meeting Atlantic City, N. J., Division
or Orgmio Chem, Sept. 113-19, 1952, Ind printe commotion.

21. L. P13111123, H. Gordy, J. H. Seylor, J. in. Chen. Soo., gg, 1753—6
19

28. o. R. Robertson, Ind. Eng. Chem. Anal. 134., g, 1.61. (1936).

29. ll. 1. Roget-I and H. Petepott, unpublished reenlte.

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