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nryrw V“ 1 .-¢ ”-2.‘:'.n~r‘r'v 'n ”" -'
ULN“! [xfifif‘flr .311} 1.;(k'3. [ ' 1‘3}. Jug:

By

fiamld tialvin D'Arcy

A martyr-t

S-‘ubmitted to the Fohool of Gradzmta {Radian of iiichiijtm'z
Stat. College of Agriculture and Applied Science
in partial fulfillment cf the reguiremants
for the dogma of

ENTITY-.2. C? E'TTELEII'CCPYZY

D9339. 1'1;me of CI-mmistry

1951

71/2 7 [5' 3

At" K137i”? if?! '3‘"; 17%;???

The writer wishes ta express his sincere
appreciation to Dr. Ralph C. Ihzston under
mono direction the problem no undcrbnkon.

Dr. Bhutan gave freely of hill fine and
knowledge both in the laboratory and «normal--
tation.

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A. Frepamtion of i3thy1m;‘:neemm Iodidouuuuuu..u
B. Prepamtism of Cthar {griggmni Reflgafltlouoocoo¢000aoo

III Rsactian Of fithylonu fixido Rflfi Crigmard afiafiflntSOOOOOOCAQO
fifllySiB Of Grignarfl geagaattlOOO‘OOOOOOOCOOOOOQOOIOOOOOOO
A. Reaction of One "ole of likinylma Oxide With One) "019
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V The Raaction of (Ema-half “ole of Ethylene Cxlda wiish One
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VI Prepamtion and Analysis of the Intermediate Product From
the Eimction a? ‘rr'ezhyleno {73133 ates-’1 Crimrm’d ffflafiafit-ucoooo

VII Fratominat'lon of Ethylene Imlohydrin and Alcohol Y5. 91:13.. .
VIII Identification 01" ti‘lfi AlfiOhOlcoaotooo‘o 0" 0.00010 to coco-o. 0.

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INTRODUCTION

Ever since the original reaction of Grignard involving magnesium.
these organo-magneeiun reactions have been used for e. variety of organic
synthesis.

Blaine in 1902 (l) etudied the reaction of ethylene oxide with
ethyl magnesium bromide. In 1941 Huston end Agett (2) continued thi-
etndy establishing the nochoniem of the reaction. Huston and Longhorn
in 1943 (3) studied e limiler reaction using cllqumgneeinm chloride
colutionc with ethylene oxide.

This work no undertaken to compare the reactions of ethylene oxide
end elkyl mgneeiun iodide eolutione with those greviouely studied by
Huston end coworkers, md to further substantiate the eerly vork of
Meienheinor (6) by analyzing the precipitate formed when one-half mole

of ethylene aide reuote uith one mole of ethyl magnesium iodide.

HISTORICAL

The first spplicstion in vnthotic organic chemistry with the use
of mgnesiurs was carried out by Berbisr in 1899 (4) using methyl iodide
snd magnesium in other with msthylheptsnons and obtained dimethylheptmol.
Blsise (l) applying his principle in 1902 treated ethyl mgnesiun
bromide with ethylene oxide. the principal predict obtained use ethylene

bronhydrin. He interpreted the results by the following scheme:

i5

/ 0 * Czfifi‘MgBr ...._.’. prbCHzCHz-O"gBr

CH:
The product of the shove resotien upon hydrolysis would give ethylene
bromhydrin.

Grigmrd (5) in 1903 studying the Iork of Blaise (l) in which
ethyl ngnssiun bromide reacted sith ethylene oxide found that after
the initial rssotion had tsksn plsoe heating of the sddition product.
followed by hydrolysis would give n-butanol. He explained the form-
tion of the ethylene bronchydrin through a secondsry rssotion in fluid:
an sddition compound no formed ss shown by the follo'ing formulas

(1%0’
\MZBr
According to Grignsrd it was the mpturing of this "oxcniun salt“ by
heat vith ubssquenos hydrolysis that produced the n—butanol, u out-

lined in the next in reactions.

H
I. NO < C” {- heat .......p CzfismzmzoligBr
CH2 \PflgBr

II. C2H5CH2€HZOMgBr 4- H011 _...yn-C4HOOH

The first analytical data in confirmation of the Grignnrd upland.-
tion of the reaction we given by Moisenheimer (6). He obtained a
precipitate from the reaction of ethylene oxide and ethyl magnesium
bromide at -21° C. Analyzing; the addition product the results corres-

pond to the following assigned formleu

 

 

on (13235 c H
D“ o It -— A O( " 5
C32 gr c235

This addition product we kept for several weeks in a vacuum desiccator.
at the end of which tine it sue found not to have changed. When heated
on a water bath it decomposed. Analysis showed the compound to have a
composition corresponding to the formla. Cgflacfiamizo-Jngr formed as
indicated in equation I. This substance then hydrolyzed gave the
n-butanol ( Equation II). .

In 1932 Ribas and Tapia (8) treated ethyl-magnesium bromide with
ethylene oxide at 40° C. From their experiments and analysis of the
addition product they concluded that it consisted of a mixture of
BrCH368’OMgBr and (Br cnzcnaohng.

The principal reaction in this group of experiments was formlated

by the following equaticnu

ZCzfla‘igBr --—--L Mgr; r2 .9 (03392155

~.....__
+ +
6‘31 on
3 ‘/° 2 '3 0
CH2 ‘ C-
.. a ., . C” .
(3an .«i12C)2‘lg (02,“15CF12CT120)2:.%
+ +
2 TIC-H 2 HOH
z BrCHgCHZOH + Hg(0H)2 scaaficnzcnaon + Mg(0H)2

Huston and Agett (a) in a are oomrehensiye study of the writ of

Ribas md Tapia and of Sohlenk (8) on the equilibrium:

(III) 20235333: -——-b (Czflshldg 4. MgBrz

I

found that if one rule of ethylene oxide was added to one mole of ethyl-

ngnesiun bromide. the min reaction use with mpesium bromide:
(Iv) ligBrz e 2(c32)zo “—9 (BflHgCHzO)zMg

Hydmlysis of the addition product. without heating. gave 60 to 70
perceit yield of ethylene bronchydrin indicating that the reaction had
proceeded by equation (Iv).

Huston and Agett (2) obtained excellent yields of n-butanol either

by heating the reaction mixture:

(v) (03115)”; + (BrCHacHao)z‘<g ....; (043902313 4 Mama

or by the addition of a second mole of ethylene oxide:

(VI) (Czflshllg e2(CH2)20 ...+. (04H90)2M3

Hydrolysis cf the addition product obtained by (VI) gave a mixture of
n-butyl alcohol and ethylene bromohvdrin.

Huston and Agett (2) as well as Huston and Iangham (3) have shown
that the ethylene halohydrin is the product, shun the ethylene oxide
attacks the mgnesiun-halide bond. The alcohol is formed ehm the
ethylme oxide attacks the allql-mgnesium bond. Huston and Langham (3)
also showed that than dialkylmgnesium is added to the mgnesium
alooholate of the ethylene halohydrin, a primary alcohol is famed.

TTI'ZO R; If ICAL

The work of Agett (2) and long-ham (3) in this laboratory has
shown a fundamental difference between bromide and chloride Grignard
reagents with ethylene oxide. Using a similar technique developed by
the above authors, the writer was able with care to obtain good yields
of iodohydrin and n-butyl alcohol.

'v‘men using a mole to mole ratio. without heating. the reactions
followed are similar to that of the chlorides:

(I) (62392115 + 303332 )20 --) (94390592;
or

(II) czrtrigI e (01%)20 ——+ c4ngorrgx
If the reaction follows reaction (II). it would necessitate a subsequent
rearranganent:

(III) 2C41190‘Jg1 -—+ (C4390)2Mg "’4 ugIz
The hydrolysis of (C4flgo)ai-§g would yield the desired n-butyl alcohol.

Ethylene iodohydrin is to mod by the reaction of; ethylene oxide

d

with the alkyl mgncsium iodide reagents:
(IV) Mgr: e 2(cnz)zo .4 (Ionzcszo)2ng
(v) (Icgczazobug e 22:03 ---r chnzcrzzoa 4 Vs (on)2
It has been reported (2) that a good yield of the alcohol my be
obtained by treatment of an alkylmagnesium bromide with one mole of

ethylene oxide and heating the reaction mixture:

1‘ ,. ,. . h
(VI) R235 + (Braiacdgobzfg4%(Rcmacszowu + ”ng‘2

Upon hydrolysis of the addition product formed pith the bromides
and chlorides good yields of the alcohol were obtained. Homer, the
yields were small in the case of the iodides. It in also observed
upon standing rapid decomposition of the addition mduct with the
iodides.

The following scheme of reactions might lead one to expect an in-
crease in the yield at alcohol men a reaction mixture of equal moles
of ethyl magnesium iodide and ethylene oxide were heated (3).

(VII) 202315: + 21% qzCafislfgl :: (Callahlig + 1:512
(VIII) 14312 + 2(cné)zo —+(ICH,CH20),Mg
(Ix) (Czfls)z”€ + (Icnzcnzo)zng ...—) (C‘H90)2Mg + ngxa
(x) (Icnzcnzo)2?.zg + 2320, achnzcnzomian) + 1140102
(XI) (C4H9o),3!g 4- 21120 qzc4ngonuosz) 4 Mon),

Experiments described here give no evidmce of such an increase.
One explanation was that the (I Ii2CK20)ziig might decompose under the
influence or heat into Hgla and ethylene oxide.

If the addition product (ICH2CH20)2?@ was allowed to stand for a
week or longer. decomposition takes place, and the resulting gas as
caught in a container surrounded by dry ice. On analysis the product
was identified as acetaldehydo. A possible explanation for the de-

composition reaction sny be indicated as rollers:

(XII) (ICHZCH20)2‘~Jg ---) 2 [litrmzoj + ‘Tglz

(11:; 1! . -
Eyre . o u -—-+. Cosmo
O. O.
H

A similar type of transtomtion for the magnesium dihalohydrin alcohol-
ates no chem by Huston and Bostwick (10), and by Huston and Brault (ll).

-7...

Theee investigators, propose the intermediate formation of e. protonized
double bond. Itueton and Bmult (11) found that the 2-mothylpropnm1
could be famed only from the mgnesium-bromine bond. For such a re-
ection it was necessary for that ion fox-mod to undergo a preliminary
rearrangement to
CH3
I _ 9.
orig-6.»?! 20: .....+ CHE-(.3
+\(.. . . H
H

The positive port of the molecule being electrophilio ettrnote e.
poi:- of electrone my from the oxygmtrted carbon atom. me ehifting
of the eleotmne thus reenlte in e shifting of e proton to the new nego-
tive carbon with the remltent fomtion of the methyl group. In turn
e peir of eleotrone from the oxygen ehifte to form 11 carbonyl linkage.
The reeulting product In: In eldehyde. It follow! filerefore that the
percentage of alcohol and iodohydrin would decrease as the yield of
aldehydee increases.

The present work eleo eobstaurtiated the remit: of Tdeiemheimer
end Ceeper (6) who etete that "The Grignord reactione can be very neily
underetood if the orgmi‘o ngneeium compounde are regarded as oompluee
with magnesium mnetioning u the centre]. atom with e. coardinetien
number of four tor-ins;

(czHeh‘K /°H5

(c2115),o’ ‘ \I
the elkyl end helogm being bound to the magnesium by principal, the
two ether moleoulee by subsidiary nlenoes. If each e, compound ie

.3...

treated wit: e ketone, aldehyde, etc... the latter possessing for more

motion energy than the other. replaces one of the ether molecules
toning.

R260\,, [€113
/ \
(C 7’. ,3 o 1
within Ihieh there new occurs :1 shifting of unione. the eeoondary
“lance union bctreen the carbonyl oxygen end the ngneeium becoming a
principel nlence union end the elkyl group. displaced from ite union
with the mgneeium by the oxygen, being bound by the principel nlence

let free at the cox-bowl carbon etom. while the cobrdimtion poeitien

1120533 0( 02715 )2

opened on the mgneoium ie occupied by other fomticn.“ The formation
of thie eddition product is supported by the observations of Ahrene
end Stapler (7).

This verificetion we brought about by obecrving the addition of
one-held mole of ethylene oxide to one-mole of the Grigmrd reagent.
This reaction roeulted in e. precipitate {emotion end enelyeie ehowed

the compceition to oorreepond to the following fomle.
0/
02% Pig-I

Io.:'.

It can be assumed that the ethylene amide nae attached to the magnesium
by a weak "subsidiary valence". Upon gentle heating between ninetydtwc
and ninety-four per cent of the ethylene oxide was recovered. Addition
of the ethylene oxide up to one-mole, results in die disappearance of
the precipitate indicating an increase in the solubility of the addition
product. Heating of the solution thus obtained did not give any
ethylene oxide shoving that the bonding had become complete. This type
of behavior ie in accordance with the work of lieieenhoimor and Casper.
It was further found that the addition of two moles of ethylene
oxide to one mole of an alkylmagncsium iodide increased the yield of
both the alcohol and iodohydrin. Assuming according to Huston and co-
workers (2) and (3) that dialkylmgnosium leads to the fomticn of the

alcohol. the reactions may he represented by the following equations:

2

1 A. I . 5'3?"
(XIII) R2515 {I 35512 + 4‘C32)20 .9.) (R..x2
CH 4» ‘*.E.3:(C'H)?

er: (1)279; e (ICIf20TI20)2‘fg
(XIV) ('RC‘IZCL'fizO)2‘!g + 22120 quczzcnz \
(xv) (ICHZCIIzO)23§g + 2:4 0 qzzcriacagcfi + Eig(0;’{)2
I'Zolrover, since the percmtage yield of alcohol and iodohydrin are

not large enough to indicate the course of the above reactions. it
must follow that the treating of the alkylznagnesium iodide with access
ethylene oxide oust of necessity attack both the alkylmagneeium bond
and the mgneeium iodide bond.

(XVI) Czfls‘lsl e a(cnz)zo qczascnzcuzongocuacxax

(XVII) C4H90115002H4I {- 2320 -—-y @1903 4-. 10211403 4! MgCOH)!

-10.

HtiP TIE-ITS??? AL

1. int erials

The following alkyl iodides were prepared by the methods in

Organic Syntheses (12):
ethyl iodide
propyl iodide
norml bu‘tyl iodide

The methyl iodide, iso-propyl iodide, soc-butyl iodide. and iso-
butyl iodide were obtained from the Columbia Organic Chemical Company.

ethylene oxide was obtained from.Dow Chemical Company and dried
only for a short period over soda line. The ethylene oxide was kept
in the refrigerator at 5° c. ’

The mgneoium turning: (free from iron) were obtained from the
Dou'Chemical Company and dried in a desiccator over anhydrous calcium
chloride.

Anhydrous other was dried over sodium ribbon for a period of one
week (or until all water was reacted). Ilt was then distilled leaving
some of the residue which contained any peroxides.- ihe distillate was
also tested at intervals for the presence of peroxides.

The alkyl iodidee'rere fractionated before using for a condensa-
tion through a twelve inch Fenskedtype column. The alkyl iodides were
dried over’anhydroue calcium.chloride and stored in a dark bottle, in
the presence of a 1's! Mp! of clean mercury (13).

The Grignard reagents prepared and studied were:

~11-

methyl magnesium iodide

ethyl magnesium iodide

norml pronyl mrznesiun iodide
iso-propyl magnesium iodide
normal butyl "mmesium iodide
sec—butyl magnesium iodide
iso-butyl magnesium iodide

II. Preparation of Crignard Reagents.
A. Preparation of Ethylmgnesium Iodide.

One mole of magnesium timings was placed in a dry ons-
liter, three-necked. round-bot tom f1s.sk.1 A large reflux con-
denser and s Hershberg dropning funnel were connected to the
side necks of the flask.2 The center neck was fitted with s

mrcury-sealed stirrer and an inlet tube for dry nitrogen.a
The system was flumod out with dry nit mgen and than four--
hundred milliliters of snhyd rous ethyl ether was admitted
through the separatory funnel. To file separately funnel as
added one mole of ethyl iodide and one hundred milliliters of
anhydrous ethyl ether. The mgncsium-srther mixture was stirred
at a moderate rats and the ethyl iodide-ether mixture was added

cautiously. The reaction starts at once and was cooled (2° C.)

in an ice bath to mintain a moderate rate of reaction. After

__ hwy

1 The flask was placed in s. drying oven for twenty-four hours.
It was stoppsrod before removing. to eliminate moisture and
carbon dioxide.

2 The condenser and funnel were closed with tub es containing
anhydrous calcium chloride.

3 The nitrogen used was C. P. water-pumped. This must be dry so

a Geissler Potash Absorption Bulb was used filled with canon-e

trated sulphuric acid C. P. and a anhydrous calcium chloride tubs.

ell the db]! iodide wee added. the ice both In relieved. end
the reeotion mixture stirred until it reeohed roon tanpen‘bure.
The eontente in the reaction the}: me elleled to stead over
night. in the preeenoe of e very eloe flow of dry nitrogen.

B. Preparetion of Other Grignard Rougenbe.

The equipment wee eohetmotod eimiler he thet need in
Experiment II A. The motion the}: wee cooled with e. «It iee
both (~6° c.) in the reaction of methyl iodide. The methyl
ngneeion iodide reegent ‘beoomee vexy violent (18) in ite re-
eotion if “loved to were: up or ehen a. eelveuh mpenteeo
the methyl negneeiun iodide m not elle'eed to land for eny
period of time but en imedietely ruched eith the ethylene
oxide. The preperetiene of the ex» end ieo-butyl meeinn
iodidee an e longer an. end they no elle'eed to etend tor.
forty-eight houre for the reaction to be more complete.

The Grigmtd reagent m treebed in three differnt we:
(A) reaction of one Iele of ethylme oxide with one mole of
reagent: (B) eene ee (A) but followed by heating: (C) motion
of in to!» or dhylce aide with one able or renew. The
three proceduree mentioned above eill be deeeribed end the re-
enlte an! be found in teble IV under hbuleted Reunite.

III. Reaction of Ethylene Oxide end Grignerd Rees-rte.
' mlyeiLof the Guard reagent:

The Grimm reegenb eith m eohent nee forced through

e ghee tube. tide «mum e enll glue renal plug. by

-13-

 

A.

nitrogen under pressure. The Grigmrd reagent no collected in
e. dry nitrogen filled mo ml. graduate cylinder md nee-tired.
Five milliliter eemplee were pipettod out and mined for the
orgenomgneeium content by Gilm's procedure (15). The emplee
more placed in 250 ml. Erlenmeyer fleeke end covered with ’toh
gheeoe. Complete hydrolyeia wee carried out by the cereml
addition of 10 ml. of water. To the hydrolyzed portion I.
measured noose of 0.111 hydrochloric eoid wee added end that
heated on the eteembath until ‘11 of the tonic mgneeinn
chloride no dissolved. The euroose eoid wee titrated with 0.1]!
eodium hydroxide using phenclphthelein no on indioetor.

One milliliter woe pipetted out and analyzed by the
Volherd method for the iodide ion (16).

Reaction of One Hole of Ethylene Oxide with One Hole of Grignerd
Reagent.

The nonmred Grigmrd reagent m added to e. (111 nitrogen
filled one liter three neck flask. The three necked fleck nee
fitted with e reflux condmeer. mchnnioel etirrer. e. enell
glen tube for the ednittence of dry nitrogen. end e eeperetory
funnel equipped eith en enter netel Jocket to pemit me nee
of dry ice ee e. cooling agent. The Grignnrd reegemt nee
cooled in en ice-eelt both («6° 0.). Fifty nillilitere of
enhydrone ether no placed in the «proton funnel end eur-
ronnded by dxy ice. The calculated amount of ethylene aide
for the reaction nee eeighed cut end eddod to the eeperetely

-14-

 

B.

funnel. The separatory funnel one etcppered by the uee of en
enhydroue calcium chloride tube. Cautimsly, the ethylene
oxide other mixture ens added to the Grigmard reagent. The
addition product that me famed from the ethylene oxide end
Grigmnd reagent was allowed to rennin in the reacting flesh
in the ice-salt bath for five or six hours. than the ice hath
no removed and the stirring preceee continued for an hour.
The addition product of the above reaction ens hydrolyzed by
adding a aqueous solution of amino: sulphate in chipped ice.
After hydrolysis the other leyer was decanted. The party
residue was extracted three or four timee rith wall portions
of ether. If the ether-enter extract shoved teeic propertiee
(litme), it no neutralized by e emll amount of dilute
hydrochloric acid and ice. and again extracted with three
(100 m1.) portions of ether. The ether eoctrecte were combined
and dried over anhydroue ecdium sulfate and than fractionated
through a short Faults-type column.

Reaction of One hble of Ethylene Oxide with One lia'ofle of lGrignerd
Reagent Followed by Boating.

The preparation of the Grignard reagent ens accomplished
as outlined in II A and B. Addition of the calculated emunt of
ethylene amide to the Grignerd reagent one accomplished no out-
lined in III A. After completion or the addition reaction the
reflux condenser one set for distillation. The fleck containing
the addition product one placed in a Gino-Col heating mntle !

.15...

 

and about three hundred milliliters of ether ns distilled off.
The alkyl magnesium iodide-ethylene oxide product as allowed
to cool and three hundred milliliters of anhydroua hensene nae
added. The condenser was set for refluxing and a gmtle reflux
continued for six hours with oontinnous stirring. The addition
product was hydrolyzed with aqueous amnion sulphate, extracted
with ether. separated with the use of a separatory funnel. dried

' over anhydrous sodium sulfate and than fractionated as deeorihed

C.

IV} Th.

in III A.
Reaction of Two Melee of Ethylene Oxide with One Vole of Grignard
Reagent.

The procedure was similar to III A with an equivalent eel-
oulated amount of tee soles of ethylene oxide. In order to
have the reaction of two nolee of ethylene oxide with one mole
of the Grignard Reagart go to completion, it no neceeeary to
add the ethylene oxide very slowly and stir the reacting mixture
hriekly. The product was hydrolysed inediately. extracted with
ether. dried, and fractiont'ed as described in III A. The re-
sults of the various eendeneetions can be found in Table 1".
Reaction oi‘ Ethylene Oxide with hgnesiun Iodide.

lodoethoxyngneeiun was prepared by the addition of
ethylene oxide to negnesiun iodide. Analysis shoved sane
impurities. See Table III.

A one-liter three-necked round botton fleek wee fitted

with a mechanical stirrer, reflux condenser, and dropping

-16..

 

bottle (17). Five hundred milliliters of anhydrous ether along
with one-fifth mole of anhydrous mgneeiun were placed in the
one-liter reaction flask described above. “the magnesium ether
mixture was cooled in a salt-ice bath. To the mixture us added
one-firth nole of pure iodine. The systen as protected from
moisture by the use of anhydrous caloiun chloride. Nitrogen we
continually fed into the system as previously described. After
the reaction had goneto completion the iodine dropping bottle
was removed and a dropping funnel surrounded by dry ice was
attached to the flash. To the tunnel was added one hundred
milliliters of anhydrous ether with two-fifths mole of ethylene
oxide. The ethylene oxide-ethen-nixture was added through the
separatory tunnel to the reaction flask ever a period cd’ one
hour with ccntimcus stirring. After complete addition of the
ethylene oxide the ice-salt bath was removed from around the
reaction flask. The stirring was continued until the reaction
flask and addition product reached rccn taprature. The product
we hydrolysed with dilute hydrochloric acid and ice and ex.
tracted with three ens-hundred milliliter portions of ether.

The ether extracts were dried over anhydrous sodiun sulfate and
fractionally «mum. on. ethylene iedohydrin in the aqueous.
layer was determined by a method described by Goober; (18).

The aqueous portion was distilled until the temperature reached
about 60° icon there was apparently no ether ruining in the
distilling flask. The iodchydrin tends to decompose so a partial

-17-

 

vacuum was used until about one-half of the iodohydrin was
distilled from the aqueous solution. This aqueous colution of
iodohydrin was neitralised with a saturated solution of sodium
carbonate. The iodchydrin me separated from the aqueous
solution with the use or a separator? funnel. and distilled at
85° (25 mm). After determining the refractive index of the
iodohydrin solution, the ammut of ethylene iodohydrin was com.-
puted by reference to the curve obtained when plotting; indw: of
refraction against percent icdohydrin. The iodohydrin extracted
from the other and water layer gave a yield of 8.3 percent.

V. The Reaction of One-half Mole of Ethylene Oxide with One Hole of

Ethyl Bhgneeium Iodide.

It was noted that a fine precipitate was formed when
ethylene oxide we allowed to react with the Grim-lard Reagent.
Claudine“ appears when onevfourth mole of ethylene oxide is
added to one mole of the Grigmrd Reagent. As the mount 01‘
ethylene oxide is increased to one-half mole the cloudiness
disappears with the formation of a fine precipitate. Finally
the precipitate dissolves as its remaining portion of one mole
of ethylene oxide was added to the reaction mixture.

The precipitate formed by the reaction of one half mole
of ethylene oxide and of one—mole of ethyl mgnoeium iodide
was separated with a high speed centrifuge.

The addition product of one half mole of ethylene oxide

and one mole of ethyl mgneeium iodide one annlyzed for the

-18...

ngneeiun end iodide content. The reallte are recorded in
Table II.

A portion of the precipitate was hydrolyzed as described
in IIIA. Neither the n-butanol nor iedohydrin were present,
indicating that there was not 9. breaking of the elkylmagn‘eeium
or mgnoaium iodide bond.

A weighed sample of the ethylene oxide ethyl mgneeium
iodide addition product wee placed in e five hundred milliliter
round bottom flask with two hundred and fifty milliliters of
dry ether. the apparatue me eat up as deecribed in the follow-
ing paragraph.

A five hundred milliliter round bottom flack we placed
in e Glee-Col unable. The round bottom flask In coneected to
e reflux condenser, which at the top was connected with con-
densing; bulbe surrounded by chipped dry ice in e lerge theme
bottle. Thetementure in the thermos bottle we meimined
at ~10° to ~15" c. The ethylene oxide ethyl ugneeiun iodide
edditicn product use new heated gently elleeing the ether to
reflux. The refluxing wee ccntimed for ten hours, after inch
time the cendeneer water we perbielly shut off to permit the
tunperature to rice to the boiling point of the ethylene cuticle,
Ethylene oxide with cone ether collected in the condeneing bulbeo
As the condensing bulbs became full their ccntente were emptied
ihte an Erlenmeyer flask (500 m1.) kept cool by refrigereticng

hear the end of the refluxing end condensing of the ethylene

oxide the water in the reflux condeneer eee ehnt off. The

balance of the ethylene oxide with some ether was collected in
the bulbs. About fifty milliliters of other and the ethyl
magnesium iodide remained in the flask.

The ethylene oxide other solution was fractionated twice
and the percentage of ethylene oxide recovered from the ethylene
oxide-ethyl magnesium iodide addition product was calculated as
shown in Table II.

VI. Preparation and Analysis of the Intermediate Product from the
Reaction of Ethylene Oxide and C-rigmlrd Reagent.

The allq'l-mgnes ium iodide was prepared by the procedure
described in II A. With mole to mole ratios of ethylene oxide
and the Grignard reagent no precipitation took place. However.
when the second mole of ethylene oxide was added a precipitate
formed. The reaction mixture, was centrifuged for ten to fifteen
minutes at about 200-3 r.p.m. to separate the precipitate. After
washing with other and centrifuging again, the precipitate was
transferred to a. sample bottle and placed in a vacuum desiccator;1
The other me completely removed by evaporation with a water
pump for three hours. and the oil pump for ten hours. The total
iodine was determined by a Parr bomb fusion (19).

In the Parr bomb cup were placed two-tenths grams of the
sample, twenty-five hundredths grams of powdered potassium

nitmte, foun-tenthe grams of finely ground sucrose, and

w—

: Thie procedure ehould he carried out rapidly as the addition
product precipitate hydrolyzed quickly.

 

fourteen. grnms of sodium peroxide. The cup was assembled with
the top being tightened down and the contentn mixed thoroughly

by shaking. The sample was: ignited over a Picker burner for

about the minutes. After allowing; the bomb to cool, it we opened
and the cap and one transferred to a covered six hundred milli-
liter beaker. Two hundred milliliters of distilled water was

added cautiously to the beaker and its contents. The excess

 

sodium peroxide was decomposed by boiling after which the cap
and mp were rinsed and removed. The resulting solution was
cooled and carefully acidified with concentrated nitric acid.
The solution was boiled to remove all hydrogen peroxide. After
the cooling of the acidified solution, a measured excess of 0.1}!
silver nitrate was added. The silver nitrate no added in emll
q-metities with vigorous choking as the silver iodide formed
will occlude both the iodide solution and silver nitrate. The
solution was heated to complete the fcmtion of silver iodide
and the supernatant liquid becomes colorless. The percent of
iodine was then determined by the Volhard method for iodine (16).
The mgnesinm in the Grignard addition product was deter-
mined by decomposing e. weighed sample into Ugo, with the use
of a .‘iekor burner. The decomposition was carried out in silica
crucibles. which were heated until they were brought to a
constant weight. A weighed nanple was placed in the crucible.

and the crucible and content heated gaitiougll to prevent

 

ignition and lose by spattering. In a few minutes the

.2 l-

 

tonparahwo was 332312101132 IDGY‘GFBGfl uni-11 t..e3 2220151223321 heat
of 1:128 3522?er 22m: 22:22:21.2“- 3220 12.2331... 2‘; ms (:0 12122242321 Fm! (me
hour; 1:12: crucible .222... "1:12 2231 321226421 “12.2 a dosicm‘tor. allowed tr.)
0001,31 and 2': fights-:1. Th2: 021103.741? 22.21:} cart-'33:: 22's: .2 rahatL-ed

£11.11 a 62:2 22813212122: 2:015:21: was 2) “1.22.1.2: 1. 1.2:: '322'03319391223222: .1 .2282

was calculated from 1:129 €23..1‘.o:2122.«; oqrmtiom

1313.01.33?“ x 0.6"” x 100' 9‘2"!!!

-. ~“o nwovvw

22 v. a? ‘dglt 1‘9

 

VII. Detentimtion 02? 32101.1: of 3312:3102: 10101232122122 2321.1 1.1001201.

‘

‘Eha ethylano 102122321110 52221 2:100:23}. tax-222'- 1 by t1 2:: 2‘ 2222:1022

‘ of alkyl mgnesium iodide and ethylene (2:21.13 22:02-22. 21121111225: unfiar
roduaed prmuurc. 'E’no chm/122226 123.101.3321 9.22:2 a102222231 were (".21.-
1002.22! togo‘omr, 3181331021. 0.:3131a2cad 132 2:2 022 23 11t22x't}.2'c2.2 32:21-12:
flask. The flag}: 32.2.2.5 $1152.21 5152 a Minor, an”: 0022212323932. To
the ethylene iadcayiz'r .2, 8.12:0;2221 52131:: .22“: mm £21107; :i‘mrizy grams
of sodium hydroxiéu with vigorous stir-2132.: for 1:22.12" :23 mirmtea,
“A than one hundred 1153;: 3121111111“; 232:5 2'32.“ 1.2212312 22:26 2221210.} {leifiy
over Q period of ninety 21212222122223, '22.:12 comic-.1021 chiming. 731222
resulting mixture was allowed to 2:001, miter 3:221:31. 12". 2.2.22. 2:33-
carved that two layers 1262.1 22:23.22: 33.222221. ”11223 3.13.1531" lay-or 22:2. 3
attracted 32:11:22.2 222215112qu 1203253220. 22120 solver. 1...... £223 . m::m<3+.s
warn 00:2“.an and dr‘wi- cv'ur anhydrous “21111152 G‘ulfi.‘2~.’;.f2.' The
indium hydmxida 1:232:22" was b01161 to 02:32:]. any 21.21068 of banana,
cooled, and 222122-2222 to 0220 11:922. Elva 32.111111122222222 of this

legume 230122411022. ma titratad for 123.111.: 2232 by Verna-.123

a? 22-2

2113:1191 {18 ). $2.9 iodo'wdrin yield was i‘oumi by taking the
ratio of.” '52: 731013 of ‘1 5.1.16 1011 011161 in 11111: 111151131818 of 11116
11:.'d;‘-3..y:.0d ram. 10:1 111151.11 30 to 1:110 mime of 10-3113 10?: Pound
in 1.1113 11 mctmi M1; '16. roagorrt.

Fae abhor-Emnzono solution of 1:210 alcohol m 61181511131 at
atmospheric pressure. The yield of alcoiml was calculated by
taking; 15110 111110 of 1m: weigm’ of 1110111101 o‘fcaineri ”my 41311119.-
tion to 1110 airfarsma in the 11131;;‘111‘5 61‘ t 10 orig, "11ml organic
radical present lacs :19 mar-natal (irrigmlrd reagent.

VIII. Hamillcation of the 9.1001101.

2116 11100::on were identli‘i 21.1 b: mkia—g 11111. (5.5 dini.1:m‘oun~
zoétea (20).

Una-huh“ 1:11.211 of 3.511‘1t1o. may). clioridc 11111:: 11111135
with arm milliliter cf 1311:: 1111101133. in a teas-'1‘; 1311110 11111:! the mit-
ture boiled garfisly for five min~1bea.an mi 111111231‘9 of dia-
1311?. ed mataar 1115 1111114111 and trze 301.1101: (100106. 1111'. '11 the prev
cipita‘so solidifies. 1le pracipibu‘tu was 010119612'311 on a filter.
washed with tan milliliters of two per cent 801111111! carbonate
solution and. muryatalliaufi £111.11 1:21:11: 3.3.1111". tom of a mixture
of ethane}. and water of suci. compositlcn that the aster 1:19.13

dissolved in 1:11 o 1101: 191113103 20111: 1111: se nmwfi 9111: in 32-1311

orys 1.9.13 1:sz 0001121113. “Ina 012,124 11.1.3 quk’g mrwcad by vacuum

£111. ion a wad dried 0119. porous plate.
The 3,5-dinitmb. avacate o1? l-‘imtanul
Wetting: 1301111: 112. ...0 enter 63.80
fixed melting 905.111: 153.99

 

For n mic-i melting; point the 3.5 dinitmbmoato of a
1mm semi-e of: pure 1-'~mm.1 me: made and its mal-‘irug 905111:

fitter-mined. Tia-m 02.331411 amounts of the car-stale on” the human

-1
I

am] urézrwm aimitz'olmzmeata 3331.3 1331mm inwanmq 3:13:34}
by crushing in a mrtar and the melting; point of the mixture
ma actor-mined. .
LT. Iiurztif ication of :..thylena Ioddxy .zrlno
Ethylene iodolwdrin ma pragmrefi (21) by 9. 3331313.: 3331.106
0.43213 pmmrs 5:103 0391;333:213 3 bramf‘qdrin. .5116 proéu :5; 9.03733
the 83.31:: prcpartiea M; the! 9'-§;.?'-.ylane 503051335113 Obtained in the
candonsa‘. ions and that reported by Camera: and Cwok‘iu (21).
"316 r-iligg paint of 61.51.31.338 ioc'derln in 278-175’0, at:
5122.55 tungammm than me a. 3.3-33.5; dml (if 5.330339035535021.
flay-war, f distilled with the use of a 33mm, film 31.333.13.33...
was 3133.: at 850/25 m. If it was 3130;313:3331 tight in a. dam;
but .13 5.5: 3:11 mau~ -n 6133.31'01‘ a perwci of 52333 or t? 4.. WW (3.3.53.
1528- 6.018555)! (.1; 20° C. is“ 1 £43.55.
A further test to prove the gamma cf 8b.1§1ufl0 50301;. rin
33.3 ‘3; using, 133d 5333133333 w 333 5.2” 11:23 21:5 -="-.;;da was
foam. 5.3.3 mar-.111; 3135 1306533533.
The foz°x'.ni:-ion of 3.2333333...» 135.3 113.39 35‘105652133; 1333903123
the 2.3335131145339233 23311132030 for cozf-zmsfison of a :33" 1:213 03 1:21.:

c131“ vative 315.150 with a known 83331-3 02' 3365;31de '19. (33-3 ”$311)

.215;ng moi-.331: c: :13 W'i 3535.33 1.37.” C.
93:31 melting point 137.5° C.

”2 4n-

The methyl ether of ethylene iodohydrin was yrepared.
he methyl—Z-iodoethyl other obtained had a boiling point of
156.90 c. at 750 m1. Butlerow and Osaok‘ln (21) reported the

boiling; point as: methyl-Zniodoefi’nyl ether an 137.80 at 750 m.

~25-

DI SUITS-.810?!

DIS SSION

It in genenlly accepted that the formation of a coordination com-
pound must be the t1 rat step in all Crigmrd reactions (2), (3), (10),
(‘7), (23). "eieeuhelmer (6) proposed the ether is held on the Grigmrd
reagent by subsidiary valence:

c 35 czfis

K 0/
CH /CH

I . é o «35.4%-:
Cilia

H5c2’0\¢2H5
Earlier work by Huston, Agett, and longhorn (2). (3). also Schlenk
and Schlenk (9). end Rib” and Tupi: (8), indicated that the reactions
which take place when one mole of ethylene oxide is added to one mole I
of ethylmgneaium bromide or chloride my be represented by the follow-
1mg equations:
II. 2C2H5M€§3r :1» (CZH5)ztxg q. 24,3732}
III. ”girl: + 2(cnz)zo --—) (Brcnzcazo)zug
If the productc of reaction II and III are heated it is found that
the mount of 11-13qu ulcchcl is increased.
Iv. (0235):.‘15 4. (BrCHZCHZO)2?5g ~—-—> (céagohm + ngRrR
When the coordination compound, (C4390)27!g, ll hydrolyzed nubutyl
alcohol result“ The ulcohcl 1: also formed when two moles of ethylene
oxide react with one mole of cthylmgneeium bromide:
(62%),“; 4 “63250 --—»(C4H90)3*=fg
If the addition product! of this reaction are hydrolyzed a. mixture of

-26a

 

n-vbutanol and othylenebromohydrin ma ohtained. The latter we derived
from reaction III.

The electrophilio attack on the oxygen by mgneeium causes an un-
balanced electronic equilibrium so that one of the carbon-oxygen bonds
no weakened. The following reaction of ethyl magneeitm iodide shows
the mgnesium attacking fine oxygen of the enozide. thus the iodide ml
partial 1y separated from the mgnosium. The iodide val now in the

position to attack the primary carbon of epoxide nucleophilically.

 

H H II If .5} H H
HC--C!i HC-—-C :1: HC -- 6—:
\‘o 0/ H a. ‘ H

0 , ’ i . o
. . :0: i
02:15ng ‘ E33533; .1 (3.235%

 

If iodohydrin alcoholate has the greater stability under the con-
ditiona of the reaction. than the iedohydrin no the chief predict famed
upon hydrolyaia. Thin tact hu hem verified by Huston and Again (2)
and Hutton an! Lenghan (5).

M of the publicized data indicates greater reactivity of epoxidea
with the halogen-mgneeiun bond than with with alkyl-mgneeium bend it
the temperature was kept 10" during addition of the epoxide and the re-
action mixture no not heated before March-in. This greater reactivity
val. indicated by large yields of bromhydrin and email yields of alcohol
vhm the ratio of reactant- ” 1:1 (1). _

Burton and Restrict (10), mi Huston and Brault (11). have recorded
in their atcporimation rearrangement of the addition {redact-

47-

 

Aootaldoiwdo was; obtained in very anal]. tom-unto.- tin-o {oration of which
my be explain-oi by the following modal-.1323 as prof-posed by Cattle and
Kalb-dw- (Sé). Too traction toicoo plow botuoon o’oiylono oxide and

txztyl an {.311 053. 12:: bromd o:

e.‘ e p ‘af-e- f. I‘ .,- . 1.; . ,"A» on- '
(antiwar-fat: ; 4. :3; ___¢ ELM; 4» (331332643)
(ir':::.tt'o)" a r" e i. ' r )"

.- - d .A r w l? :1-

‘E'Ezo investigators furthor mggostod that tim removal of tho comm proton
from ethylono bmmhgdrin 15':th only to auco:-:.;,»1mw under ouch difficulty
that each I. molmlsm tom moat unlikely.

“ohm: e. 1:1 molar ratio of ethylene oxido and othy‘lmgnooium iodide
mo reacted without heating, and than hydrolyzed. tho yi olefin more 53.7
pox-cont of n-tmtonol end 20 par cont or iodohydrin. Considerable
ethylene iodohydrin was lost by dowryosition. ’g‘hoaa results were the
actual amounts of products moovorod £1: tho other layor.

A precipitate me not formed it equal mlomlor quantitioe of
ethylene oxide and the elk}?! mgnoaium iodides were mooted. Homer.
from the results show in Tabla IV, and obsmtrg the ammt of do-
comgaoaition with tho elkyl madam iodide end ot‘hflone oxide. one own
“cum tho reaction follow the name couru as that of the other
halogens.

“the echemo of motions are ee follows:

9235*531 + WW2“ 1..., cgnanzzgczra ‘23:
or

(7237.564 ocrizmzz

(”"73 r?! (117 “We-o" (inf) C .13.?” '(“rv on ””1573:
a 5 .2. .2. u. ‘ , é ”a z .b 2 2,1. ‘ .33..
01‘
("7.7512 + 211.1,}..11 ”+112 *1 1‘1"?" 2P 15:11:11,. 1‘" I
‘1 ‘9 :3 2 2
1: yr" 11, :1 v 21.11 r‘ 1111 11:1" {1'1 1141.121

Hydrolysis of him intamlfmte product mulzi yield the dash-vi

u-‘mztamlo '
111911 the molar ratio of ethyl-.1119 0:11.111 to fishylmgneaium iodide

was normal. to 231. a not-.131 met-1.121319 1.11 the amount of 11411115311101 cor-

rewarding to 72 percemt and 40 parcmrfi of the 911.313.111.311: 1odo‘1ydfln.

By amiycu of the precigzitata fame-:1 3:111 mcordenl 1n TIE-3.110 I. it maid

am «1119111: that the intezaefiiato for the tamtion of the alcohol is

(64'191‘3'111. This intamdiflo could not be isolated in a pure fan: as

2 u
it explodes when 92190211! to air for my Lam-1011 of time.

The 1111;931:2133 111:9 pmduot, 03119 “’13! my 313111 be c0113" 111112111 and an
the sobzticn binaries (tepid-.011 at 11.111511115111111 101111113, the dewmositton
of the sham intozmdiato pmhmt 0cm: x: no mar-cu «1 to tha arm-.1111

8" " afi‘ffl -> (1'41 7963a '11 1 —"'.:;I3
273: this sch m or 2111111031011 1:21-13 embatamfl 1131116 12: roam-11d eitimr from
butwy 1.11.91"? 11.35.50 1ch cf 12.51.13.711 31.11 1.13m) 11:111.

according: to'9chle1-Jr. (25), 31111113111314 ve rte-ream: dissociation
take: place: 17111311 the othylmgnczaian (111.101.2519 11660611113133 into (11631321313.-
Mgnednm £12113. magnesium chloride. ”5110 ”6161:1011 of ethylene oxide with
Mafia-1.111131115111111: appear! more pmba’ole.

I'dllsar and Puffin) (212). have givera airtime-3 t‘s-mt the (£47390. 3313;

00111111183 111111 11:31:15 mm: o! mgnaaium 11111011111111.1111»; have suggested

'29-:

that if C H“ C" 73C! 13 the profiled: 01’ 0216131313313. 13: should Imvo the

4'?
prop rty 3f Earning a cmlorx with mam 351m: chloride), 933333113; by
virtue of t 3 Lnshared electrons on L310 “2:33;: atom. 13:3. 3 the two
“.1131 on prmlacto s muld bolas *3 31133. This mm further verified by
Ihmtoa 3331' {gingham (3). In 33;:3-3r'imunting with two mole-3 (if 32321571339
oxide to one mile a}? 93....5'1 11""0 inn Ladder 3.2311 qwtti 3:139 of 133:3:-

0..

113313323 {edit-1‘0 was 1331330.! and Bf"1388uo

g

In ongorimenting wit 1: tin -331333 usirg m: 34.33.: 3.2313 31’ m! 1333
02130 311:1 one 33013 of atlylvumasmn 1331M (Fable 1:) in firm 32:93 r5.»
M32331 omflmsa't'lcns this iodide content. was found {a be 53.5 93133233
and the 332.323.32.132: cezztenfi 9.9 9333 32.21. This precipiizabe (54239-3 .31;

if heated 0.3 directed in 5301:1013 '3’ 33:51:73 It recovszy ui‘ 3‘3 {screen‘s of
the 33:03:16.3. imicaiirw Liza-t neither 3:333 311-:y1m233312m or mfffiw‘i’m
loéiéa ”033:! have bun uttacked. (6) ’39 33133333331333 this belie-1‘ it

was found that 33.33.3313 231331913333 ‘13:; wax-013133 3'12: 3;: 311.1“ 333333.133
3311:3331: a solution no n-hutancl or fluidly rin m3 prawn-t.

"v

“.3213 are two 230333.313 in" rmciiates for at 35'1323, 3icfiofixyériaz

I. 73312 4. (3.32320 ......+ Ic:..2cz:?zc.=~zgz

01‘

II “3.2: ’13:? 3 1'3""? 332*:

I! the raw ion fallen-3 XI one ebb-3133 r333 133 n.3- ahow 111 {32313 in.
{Widence in Table 11‘: sham 32.3 133333331333 proda 33 (z::.';;3c::z.c)2"§3

1033.3 to the {mi-don of mnylme 13:13:32. r121.

«'50-»

Rocorded in Table IV are the percentaga yields of the various
Grignard reagents reacting with efihylene oxide. It ahdws the general
mechanics of the reactions. The bramchlng of the carban chain in the
Grignard reagent 1:33:33 to decree” the :‘rieli of the 3.1303131. It was
not possible t3 carry out the reaction of tertiary butyl 33531331113
iodide with the epoxidé, duo‘tO'the decomposition of tubutyl iodida.
However, from.the uxperimantal data ani the work of Huston and
Langham (5) and "mum” (2'7). the tertiary bII'tYI magnesium iodide would
yield only ethylene iodohydr‘ln. When methyl magnesium iodidemsused
either in the 1:1 or 1:2 mole ratio great car. must be‘usod udth the
addition products. fiban allowed to become any, or separated from.1ta
solvmt by decantation, the addition proiuct will «1:910:13 with great

violence.

~31-

S71" MARY

1.

2o

3.

4.

5.

6o

7.

Th? 91313”- K‘W'PW'H 30-3.4.3: r3333 5:": o. my similar to the 31}:ng
61Ls¢i-\“ 3., . C323 rule at? 6331513313 3.3153331} one) 91213 of" 4731' {3.123321 r9-
MEL-3 fox-.36. by the trawaat. of 3.3-.51 mloriz‘iaa with 1335315315.... 1.

habitat-1 {:13 6311311313 oxide and 12235:. or 1.9.731.

Analyt’ cal ramlts from 0031:1133an 0." 1:33) m1 3 of 3:11 $19113 with
with one mole of mmmium Sadie-‘33 iridium“ the fonatim; of

71"“? 4-0.

:. _. . '1’

In ”3:33 condmnation of 3m) 30108 (3‘? 33313313313 a??? clan and one mole of
52132.1 mmeaium 3.31133. ramita 3233.113: tn the fomtion of (565335.033733.
_ 3 h

This midit‘ion 3530:1333 in i‘omai in a similm- 3333:3303 33 than 33193-19139.

fmm 1732+{E“3g;€ it is 05595;"?! wide}: rmn‘aagaa givimg ((-55 3.3 Ca) ‘3: and
"33:90
U

Analytical rwulfss hzr’ahezr show that the «33:33:33.3 formia of the 8:1

ratio in C T; C- 2.33.2353;
( ‘3. 9. >2 5,, .__, 2.

The percentage yield of the alcohol and ethylene ioduhyflfin 13 inc.-
craasarl considerably with the a 4.330». of two 330133 of ethylene

oxide am} one mole of alkylmgnasium ibtlidOo

”so precipitate was formd 131m we mils of the: awn-"1&3 .133 was! to

one mic of the art-5:33:31 rimgm.

The Mitten products 3533333311 ethylene oxide and alkylmgnaaium

iodide. are not: 3320.33.13.

8. It was shown that one—half mole of the epoxide does not react fully
with one mole of alkylmagneslum.lodida, and that Weilanheimer'a
suggested subsidiany and principal valence can be used in explaining

the nddition product formed when the epoxido reacts with the Grlgnard

reagent.

~53-

TABLES

TABLE I

AflALVSIS c1 13)r"ION PRO‘"CT PEG 7 ‘332(€I 2)20 and czfis-TEI

__ L J AA

 

—v
-i‘“ w— v" u“ I __ A __

 

 

 

 

Condensatidn No. 573 Iodine 91 33153195111721
1 46.30 9.50
2 47.72 8.66
3 45.92 9.00
4 47.35 8.?5
5 48.21 8.87
6 '49.53 9.28

 

Based upon the production of CzfiscHECIizO“5‘fg-50CI—1201f21
Theoretical Hg 8.921%

I 47.25%

-----

(04’ ') 'V'afid di-ioio‘10+1nx"fipvnnqryq (11

8,5, :axo-Joq ¢~?~- ‘p’ ‘ avg-e tk- ”Ag-1‘“. Whvbnw'fir- (a

l
’1: 5

4

Qt) .

v.14-

tion.

-34~

TABLE II

HALYSIS 03‘ ADDITFOEI mam: mm {3012)20 mo 0225355

 

 

 

 

41

 

 

(72251“ngng inn ‘Jo. - 5i; Iodine fZfiI‘fsgnesium _
1 523.8 10.00
2 55.1 9.85
Theoretical 53.7 10.7
Theoretical formula
02:15

| ’C;
- - . 0
[1g ‘13

I

Recovery of abhylano oxide

1

93%
91.435

TABLE I I

AryrzLYSIS 01? maxim FECT’ICE mm 2(03’ )20 AID V5512

 

 

 

 

_ Cordonsatigg 3T0. V %.I£§gpo 7. maggoaiom m
1 60.35 7.83
2 63.90 7.62
3 1.31 6.91
4 60.96 6.42
5 63.51 6.75

Based upon the production of (ICHZCHZO)21£g
Theoretical Mg 6.55%

I 69.30%

'58-

n. or 3:7“! AT”-

‘
J A~5U

’1‘ !1'3374 If} I 5?

’51-..va l-rv ~2-

YIsnna on A.Comot“ Afj *

IC vvxf'rz-‘I quI 1':

 

 

 

 

 

r A ”I v - .7- ‘ ~ H ’I m: urn -\
5.55.. . pm“, TH" 73‘ )1“! ’3 ( HA ") . C:
s .u' - 2 _:- .a-J ...... ._. . .-..t'.' _.. .n..
__ V. M‘ "— ‘2‘- ... -~.. - .f 4‘. ——~ -
-——- 9- .. .. --. W. -wm—-u~”- u—u—fl.v Much-IL. n~m«¢-”w~m ‘ 4“—_ “ ‘

to
L1”

’cI+(‘"*). _’r1"'_ 1.201"

A...‘ A

THU-$7 (( a“?
.2 ' .3.

‘ 'éz a)”
‘YTHEE 2

 

V

lu?ronanol

1’ 0d ohyd 2’1 :1

larvmtuno 1

Iodohydrin

Inn-mtanol

Iodohydrin

3-"cthy1-l-butanol

Iodohydfin

Infiexanol

Iodoéuyddn

BuMefihyl-vI-ne mono]

Iodoh.yd tin

édMBthy’I‘Il-‘f‘ graham}

Iodohydrin

" :flyl mgnesium 10:11:10
51147-31 (it. 75

13‘s hylm guaslum 10:11 *1 a
53.7% 2;

231 40g

n-Prom'l rngnss $3.1m I ed ‘1 d a

11x :01 or} ad

40E

13.5:

36.8fl 6105i 55%

3‘35"; 537':

. i-Prcpylmgnosium Iodide
32.6.5 4&3}? 30193

210.3: 51::

nuf'mtylm {31183 iota '10:! Mo

35.2% 64.3%

2503 Q“ 56 a1: 3302:

3.7512177 lmgnesmm 103.1710

191 sfi
.1 . ,I
28.2.}. 43'

1-85.13} 1mm onion 1935113.

6

19.55.? 21.193 )

30.1fi 54.3”

*3?-

PHYSICAL CtVSTAFTS OF THE ALCOHOLS

TABLE V

 

 

 

Alcohol n? B.P.°C. Ref.
1-Propanol 1.38543 97.19 18
I-Butanol 1.39931 117.7 18
1-Pentanol 1.40963 137.9 18
S-flethyI-lmbutanol 1.4084 132. 28
luflexanol 1.4161 157.5 19
S-MbthyI-I—Pentanol 1.4115 152.4 38
4-5:ethy141-z>entano1 1.4490 152. as

 

.33-

DERIVKI'IVSS I" THE

TABLE VI

LC GEO-IS

 

 

 

1.1.P.°c. Ref.
1-Propanol
5,5-d1n1trobenzoato 74 18
l-Eutanol
3,5-dinitrobenzoate 64 18
1-Pentanol
3,5-d1nitrobonzoato 46.4 18
S-flbthyl-I-butanol
3,5-d1nitrobenzoato 61 28
léfiaxanol
3,5-d1nitrobenzoato 58.4 28
Z-MathyI-I-Pentanol
3,5-d1n1trobonzoato SB 28
4““!!et‘mr1-1-hn‘banol
72 28

3.5-d1n1trobensonto

 

~39¢

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'41.

 

 

 

   

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