m REACTION OF SOME

ORGANOMAGNESSUM IODIDES WITH ‘ '

1, 2 - EPOXYPROPANE

Thad. for tha Dagm of Ph. D.
MTCHIGAN STATE COLLEGE
medsE.hmms‘

1955

1". LE)“:

fig? M
”7/19, W/fl?’

 

 

TEE ammx or saw oammmsmn IODIDES
ma 1,2.Eromnoyms

By

Francis E. Etta.

A THESIS

Submitted to the School of Graduata Studias of Michigan
St.te College of Agriculture anfi Applied Science
in partial fulfillment of the requirumanta
for tho degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1955

 

'29
Dr. Ralph 0. mm

 

Acxummm

The author wish” to express his appreciation
for the encouragement and guidance of Dr. Ralph C,
mater: and Dr. Ralph L, Guile, who, after the
untimely death of Dr. Hunter: assumed ti» direction
of tha work and who“ mention. aided materially
1n the completion of the problem.

111

VITA

Francis wgeno mans
candidate for the degree of
Doctor of Philosophy

Datamation: The Reaction of Sana Grammaaim Iodide. with
1,2-epomrcpana

Outline of Studiaa:
Hajom Org-mic Chem-try
Minors: Analytical and Inorganic cranium

Biographical Italic!
Born: June 18, 1928 at Olnay, Illinois
Undergraduate Studies: DePauw Univanity, Groencutle ,
Indiana.
Received 8. A, June, 1950

Graduate Studio” Hickman State College, East Lancing,
Michigan

1?

mamm

1m. Mastic-Mon In. “am an awa- on the mm 61’
ownin- mm" an mm. The obj.“ of m. min an to
My “I. ”have "nativity W lfiwm of th- arcane—-
main baud u «mad ta u- mania-iodine bond. m. m
WM by varying tha ratio. at math: marina, tha flatten
that and tho mum mama. If. was found mucosa-y to human
amt manta” m surfing mums that reaction period in
and” to shun reproducible vault..-

Tb Mum mam m pupa-ad flung usual, aflzyl, mpg-owl ,
brawl, Mutyl, ”bum, an phony]. iodides. A]... W m the
deu Wanda con-amusing to tho MM ”mafia.

Th. yield. 0! mm mm and Wain: «mound. um
«tam um tha 011nm titration 9mm . The Maura mags“
ma waned for mm. to» «mm by the velar. ”thud.

th- mlyasd magnum Hagan: were Mam with both an. we M
as}... o: 1 ,fi-rammmpm mar emmlled condition. , chill. the 61-
owum 0mm um treated filth no no]... or 3.34me.
W m «mm... The alcohol. produced by tho shove muons
were WW by distillation in an ems. Ix: tha manna at organe-
nmm 1M1... with 1,2..me the ldodo—Z‘vpmme WG
m an Wad, ama 1: <1me mrmdly on mm, but was

datum by dmumn with 115311 and. the iodide ion produced
m «m. w the W uthod,

In tha motion of owns-Am iodide. nth on. m1. of
1,2-opowopua, lauded-proposal 10 the min pmt, «an. the
amend decimal 1a produced to the axiom of only on. or m pamont.
Th. run of Liam-proposal ms... with tan. 0: nation. “the
mam )1.ch u of tho one” of 70-8051" at wanton tuna of on to
no boon. & longs: than or ”action gave 1m 3453M. numb only
in oh. «an of othylmmamm iodide and the summary 311513;de
10614” to: tho field decreased substantially.

when tho ratio of orgmomgnoaim iodide to 1,2agpomropm was
1:2, tho yield of 1-1odo-2-propwo1 was of tho! eras? of 954.00% at
short reaction u... (up to um. Mora) and deans-ad to 70-80% after
18 hurt. The yield. of the alcohols produced were of the order of
20-351 omopt the mo of s-butymagneum iodide wash gov. only about
8% of Lao thflufiahannol.

The pmipihto proaeut before .hydrolyoio in one reao non of
”Wu- Wo with m mice of 1,2-epoxypropana ms Mad
as. tho runn- indicated. that. the precipitate probably his a formula
«Win: to a ratio of one mole of organonagnesim iodide to two
no)... of 1,2-opommm.

I rho recolo- panama 5130!! that tho initial rooofion 1. with the
Win-iodine bond, and tho macaw with tho ”Wain bond
1. alone:- than first of the mgmaiaifiodim bond.

vi

TABLE OF CONTENTS

Page

WWMCOOOOOOOODCCQOOOOQOOOOCIOOOO'OOOIODO‘00OOIO00......

”mu....oaaooaaaaaooaaaaaaaaoaoaaaaoaa.aaaan..aoooaaaaaao
”WC-OiiiiOOOCOO0....IICOOIOOOIOOOCCODOOOQIOIOOOOIOOOOIQO
nma......ggggoogaaaanaaaoaoaawbtaaofitooaaaaaloaaalloato

I. Preparation of Grimm Easemennn.................

II. Andy“. of the Grimm Reagent.......................
III. Roaotiona at th‘ Griflnard Rflflfientaoaaaoaaaaoaoaasuaaoaa

A. Reaction of one mole of Grimm reagent. with one
.01. 0‘ 192‘.P°33P’°P339o......o.o....o.oa...¢o..o

B. Benetton of ona :91. of mm reagent with two
mole- of 1,2eaponpropmo.........................

c. The preparation of diallgrmmaim and diaryb
magnolia! from the corresponding Grunt-d reagents

D. The reaction or diorgmamdm with 1,2-epm-

pm...OO‘QOOOOOCO...00.9.0IOOOOOOOOOOOOCOIQ...

IV. Preparation of 1-1060-2-pmpmo1 from 1 ,2-epoxypropana
and ”mm deC aura“.000.00.000.0000I0090000

a. Helm-anon of anomalous iodide in other..........
8. Prvparttion of 1‘1060‘2‘pm0pana1aaaaaaa.aaaaoaaaao

c. The physioal properties and the method of determin-

ation of yield. of 1dodo~2mpmflnuununu
D. “tent. to prepare derivatives of 140604-

FNPWIICOCO.6000...I'D...OOOCOOOCO.OOIQIO.OQIOQO0

V. Analyail of the Intermediate Preoipitate Formed in the
Reaction of One Hole of Grimm-d Reagent with Two
“bl.“ Of 1’2“0P°3yprapangaaaaaaaaaaaaaoaeaooaoaaaaao.

1

2
13
1h
11;

15
16

16

19

19

20

21.
21
22

22

2b

26

mm 6‘ OWNS - Continued . Page

VI, Dotmimtion of a flu: Dance on the Reaction of
n-Pmpylmomsinm Iodide: with 1,2«opoxypropm. .. .. n. 26

A , Rue tion of one min of mpropylmagnooim iodide
filth on- lolo of 1,2v-opoxypmpme 26

3. Reaction of one mole of Wmaim iodide
nth two mien or 1,2-epomropano..............,... 27

VII. Pram-amt: of Alcohol Derivatives"..................... 27

3. 3.5-6in1trobomtos................................ 2?

B. walth................-...................... 28

VIII. Calculation of new: 28
Till-38139711111133 30
Dmsm...........-............................................ M4

WWCOO.UOOOQOOOOOOOIOOOOOOOIOOOOQOQCQOOOQ'OIQ...00.00.00.300. m

mm“...i.fli.OOIOOQOO¢OQCICOIOQIOODOOOIQOIOOOOOOOI.‘QOCOUOOOC 62

viii

 

INTRODUCTION

1151?mele

Thor. ha been me inter-oat in moont yum consuming the
auction of m epoxidee with ormgmoim halide: . The results
of than “adios have been interpreted in var-ion! my. and compute
amount he- not been reached a to us nonunion of the reaction.

The oojeot or this work no to study the relative reactivity of
the «Wam- and mum-iodine bowie. The method and to
«him thin m a. “only or the rotation at ”swam iodides»
with 1,2«pozqrpropane. The products of the reaotiono wore isolated and
a noun" of tho Wale row tidty of the two different bonds In
obtained from tho ratio of the aloe-ho]. (corresponding to ormmeum
bond chance) to 1~iodo~2~pr0pm1 («29”»me to «mm-iodine
bond clung.) . The effect. or changing condition. on m ntio of
promo: wu studied by varying the length of reaction tho, the re-
tation Wramfl , and the mount of 1,2aopoxypropano per m1. of

Grime! rugent .

HISTORICILL

HISI‘ORICFJ-

There he: boon mob controversy over the constitution of the
MM reageni in «lotion since it was first described by 61-13mm (1)
in 1900. 30th.0risnerd (2) and Bleiae (3) have shoun‘oy'enelyeio of the
routine remaining alter enporation of the other evolution that the
«motion lulide retains one molecule of other oven when dried
under rm pressure. Baoyor and Villigor (h) on 1.13 basis oi' the
above date proposed that the formula of tho Grignard reagent (should

be (A). Homer, Grigmrd (5) felt that the formulation (3) was more
noerly'oooeietono with the producte formed from eooh oonpooads when need

CaH°\o/Mgfi 03K /HgI
\ '0
9335/ I 03515.? \R
(A) (B)

in mm. Law, in 1906, Teholinzoff (6) on the basis of his.
audie- of 'diotheratee" of ioopmpylmognosium iodide prepoaod a formula,
o: type (c) . In 1921 fieieenlmimor and Casper (7) advanced the theory

cflfl'flx )433 (533050“ /R
/0\ ‘ . . fie
Cafie 130(C'H&)3 (63%)30 \X
(C) (D)

“abet the Grimm“! tangents be ooneidored not an autumn ante but u
omen» hem e “room of type (E) . Heieenmmer end Caper else

prepeeed um the reunion of albumen: Mid” proceed. by
”plume of one o: the wordinotod other group: by om compound
reacting with the woman:- halido . The inteneduto (E) {mod

£300 (3330.031 8/3 (031%)29‘24 /H' (n Hedge
(c.15330’ugx‘ *9 R300" 3\11‘ be I

(E)

could then neuronge to give the magnesium Inlido salt of the product. (F) .

(snug I3! (0,3930 Joanna,-
/u3 + (Cap.) 30 a ”-3 R,
3300' \X (0335);.0 \X
(F)

The theory that. the Grimm reagent might be other than the specio-
W in :01an was tint advanced by Joliboio (8) in 1912. En had
arm that diothylnagnesimn was insoluble in other but was soluble in
an our: solution of magnesium iodide to giro 43 solution with an the
properties of ethylmagnooimn iodide. .01: the basis of this and othor data
he proposed fleet the wimerd reagent should be shown. a Rg‘dg-Hgiz. There
we ml: oontzoverey over em- tomuleuon or the Grimm reagent and
is W for debunk and Somenk (9) in 1929 to find em pmuemy
an em halogen and wt of tho magnesium oould be precipitated Im a
alum): of Grime-d reagent in eoher by the addition of 1,h~dioxeno.
flay believed on the belie o1 thie emerinent the the Grimm-d reagent
eniete in an equilibrium Mob my be tomnlened ea:

 

 

 

 

 

01‘
Rafis'fizla 3238 * “8'13

 

1'3 193]. Roller (10) unopened. that the moat probable equilibrim
contains no army-aim halide, 1.9.:

Rgflg-ngaz H.243 + M313

FWP work by Roller and era-workers (11) indicated that the dioxana
pmipuauon mthod m not 73114 as a mm of ”mouthing the
equilibrium present in a. (3-in reagent solution. They found that

tho diormommm content increased with 'aixo when the solution was
allow! to stand in contact with the dioxano precipitate from the
original orgmomgnoom halide solution. Tho' gomral conclusion arrived
at in flat furtlnr dispmportionation of tho prooipitato my ocoor- on
extended unmet with the. aolution.

Seblonk (12) in 1932 pmpoood the idea mm the percent 0! din-
wgmgauim and mmesim halide varies summing to the ammo
map present. mint) and Foobargfll (13) advanced tho thaw-y that
olkylumum ammo. are mainly in the tom of alkylmwuinn
«blonds, while alkylumaiuu iodides m be more in tho tom of di-
alkflumm and mounts iodide . &wwr, Kharuh and 301mm
(1h, page 105) have 11M data vision indie“. than in we nun there
in 11%).: difference between dkylmgmaiu- malaria" and allwlumaim
iodide: u for u diallqlmgmlim mum is concerned tad in other

«In m “We“: chlordane contain more: dinkylmgnooim than
do anyhow-dun iodidoo .

Anton and Barnum (15) have noted the ready mammoy or
didlqunmuim ”lotions and an mutual: great. Immhy of the
arrow" divmmaiw halide solutions. tumour, on this om
not they but than conclusion out the atom-.1 percentage of comm.
mum in «lotion is low. They further proposed that the «11111me-
bo tonulotod as follow a

2 my: (law'g-Mgrza):fiang + nga

In was smart m1 Ub’oolohdo (16) almond on theory ow. instead
of the Sohlmk ropruonhuon of the «mum present in «lotion or
on. “pronoun” of “too on! Bog-shard , it. might be better to consider
the «mum-mm u

11 M31; + 01132-132 4- inwaflfiho : n Mgla'CflaflgI'mmafifi) 30

who” a in probably too. They further picture the oomplox as muting

which can be monmtod in this mannor:

Mg“. [cm/\‘Mg/jlfiég] *mfiaflfim
I’ ‘I’ I
one of the «aunt workers to study the wtion of Mantra ro-
man on «room. am My (1?) vb mum Lea-eponymous with
Whom mun. HI mutilated that. tonal mam: produots
«old on Imam-depending on the point of cleavage of fine opoxido

ring and whether or not rearrangement occurred during the relation.

Promct Type
0‘
3131 + chosen; ————> magmas- —> 0539213333 (1)
J )- OH
I H
033mm,, ——> 08333383 (2)
0- H

——> cash-maze- ——» snags—933w (3)

l 1.

0330113933... ——> coacazgmfl (h)
R

In an “tempt to prove his theory, Henry treated ”Minimum
braids with 1,2-opoaqpropano and obtained a 60% 3101:! of 2-ponoahol
(reaction two 1) . Other workers (18) have observed similar results
um other Gama mascots. Norton and hm (19) in a. similar re-
action of oflxymmosiuo bromide and 1,2-opomropans ioolstod 11% of
Maximal, whioh would result from a mutation pooh woondim to typo
(h) . more is also work by 81*.on and HoCouhz-oy (20) who report that
tho product or the reaction hooves): tabutylumosim chloride and l ,2-
opmpropsns 1s 2 ,2-dmthylo3-pontanol vhloh would result main from
a. typo (h) reaction. Tho mjorloy of the nations with 1,2-opoxyfi
pm, honour, appear to follow a typo (1) mutton path.

The loglod conclusion as to tho mom» of the rotation hosed
on tho data in the literature is that oh products formed from tho
much of spend» with Manon! myrrh: ore tho result of melam-
philio attack by a amnion on tho least magnum carbon atom. ‘

m.- probably mom otter the spend. has ooordimtad with the mag-
3901\- (27) .

“3336): 0/6,.“ 52(ch )2
(A) $22ch Q Q His-1‘15 + (0 2-3020
. man 9- A

+2.) c- caxa)
(B) lggIO' o ()(())—-—+!S-g (
9"

 

(+0 (+)C:}~ (-) (_) (+4») (MI-6’}.
.4L ; Hg—«oo—g- + x (R )-—-> X‘s-42*?

It in oloo possible to have management.

a ( )c-
Hug-o + éHH R .c~H (+)(-) .c-H
x \ :Mg-O~C(+)———> 1413.0 at
X .
auto-.14
x~Mg-o.c-R

Tho reaction is not, however, as “male on it would appur, for
mm: as Ag.» (21) hm mom that dmkylumuiun is problbly an
ounotiol mtamt. In their studio: they found that the addition of
on. .010 of oflvlnpooiu bromide to «ma» oxido an: an Mention
complex whioh m idontiool with that obtained by pacing othylm oxide
into on “but solution or ulna-in- bronido. Appanntly the first role
of othylm outdo moot. only with the nun-aim bromide present in the
hip-rd taunt to ton an addition oomph; by mm or the following

rotation:

2033538”: 3831': * (5335):“:

/o\
2 Cfiiflfi. '
|~—-—438(003135o32‘)2 * (0235) a”?!

2 too
2 1903305123:- (60%)

In ordor to obtoin my n-butyl alcohol it no masonry to heat the

nation lixtnro or oloo odd :1 oooond mole of othylooo oxide .

2 830
n—butyl alcohol

02‘

/o\
(631%)“3 * 2 033~C33———> (B‘C‘Haofi) 3M8
\ 2 ““10 % n-butyl alcohol

 

Eoth mun tad mm (21) and hasten and LW (22) have ohm-m
that tho rotation of othylaognuiun holidoo with othylom oxide ludo
to on intomdioto ooupwnd honing tho upiriool formula (mm) ,Hg from
diothylmgnooiun , or an intomdioto compound having tho miriool
formula 0.8901131 rm othylumooim halides. Both or the” int»-
nodiotoo upon Wayne give good yields of l-bntonol.

Boston and D'Arcy (23) a toll to other works" (21, 22) love
reported that tho "action of «magnum holidoo givoo u o hya-
product am mount. of autonomic. Cattle and mayday (-210 in
studying mo rmtion of n-hgtylnagnooixm bromide with othylono oxido
found that on oootoldohyoo- moan m fox-mac! upon heating the product

or the ettvleoe exldomoim bromide reaction in a m. To account
tor thin they patented thet the Bree.ca.o. ion hey, when booted, lose
3 braide ion end reerrmgo to eoetaldohvde.

Mditloul proof of tin tomtion or o oorbooyl conpound upon
mm. the addition «mu: m mum by Eaton and BoetIIiok (25),
who aloe found woo reacting ”Wei“ braid” with 1,2-uepoxyu
propose tbt ecetono m e byproduct 1n ell of file reactions.

(BrCH.CH.O~)aHg——-9——> magma + my '5 M30 + enacxaacmr
03:

However, Huston and Tiefenthol (26) found no evidence of «atom when
they treated elkylnegnoeiuo chloride: with l ,2eopoxypropeno.

mum and BMW: (23) found upon undying the reaction of my}...
mum iodidee with equinoler uncont- o£ ethylene oxide that the
roeotioo no predominately ot the allqlnomooim bond although no the
alkyl group incl-cued in complexity the ethylene lodohydrin we produced
in proportionetely loner noun“. moton end Longhn (22) found in
their otndiee that when elkylnemoim chlorideo were touted with on
equinolor amount of ethylene oxide there m e admiricont reaction at
the elkylupoeion bond which in acne can exceeded the mount of. rou-
ootlon ot the melon-chlorine bond. thatch and Agett (21), how,
found that on treating elkylnegneeim bromide: in e one to m rotio
11th ethylene oxide the indtiel reaction we predominately at the
melon-bromine bond.

10

In elnoet All can when the retio of reectente use one mole of
MM fleegent to tee melee of ethylene oxide , the yields of the
alcohol and ethylene hllotvdrin were banned eppreciebly.

Eaton end Tiefenthel (26) found thet when elkylnegne aim chlorides
were treated nth 1,2.epoxypropene in equimoler quantitiee the yield of
lcohlcmzapropenol tensed tron 35-65% and the yielde of the eloctnle
varied from 0.1415. In the reection of ellqlnegneeiun bronidee with“ an
equinoler mot or 1,2wepoxypropene, meton and Boetuick (25) round
thlt the l-hrouo-aopropanol we produced in yields of 50-67% while the
yielde or the eloohole reused from 14-13%. The meet etriking thing
apparent when cunning the yielde m the much larger over-ell yields
or eloohole out the elkylnemeeiun chloridee. In all once the addition
of two Iolee of oponde to one mole of ellqlnegneeim halide inoroeeed
the yielde of both l-helo-aopncpenol and the eloohole appreciably.

Votie end comm-e (28) hm etudied the relative relativity of
use ellqlnegneeim halides by allowing them to react with l-hexyno and
securing the volue of olkene evolved.

C‘chz-ca + mg...x————ec‘hac~=-cugx + RH (gas)

They tound that methylnemeeiu iodide end nethgrlugneeiun bromide are
of About the em order of reactivity while methyl-omens chloride
mote el-oet three time ee feet, The one other of reactivity holds
for the ethylnegneeiun holidee except that ettvlnegneeimn chloride reecto
only We ee feet no the other two (lee teble below) . Thie would one
to indicete tht the elhyllegneeiu chloridee ehould give better yielde

o: eleohcle tln the ottnr eliqlnaneeiu helidee. end, in general,
thie ie two, One would also emot that the yielde of alcohols from
the reaction of alkyhnagnesim bromides end dlqmgmeim iodidee
would he or them area:- or mom.

Table (Referehoe 282

 

Relative
Rug! thivity
03,1461 . 6
611314 gBr ,6
03;,th 16
533::ng 71
C aflgflgBr 100

cause: , - 155

In summing the reaction of alkyl iodidoe with meeium in other
Oldhen end U‘bbolohdo (29) noted that organic iodides are cepahle of
mting to give various products .

(1)311 + Pig—4mm]:
(2)231 e Mg—efla' 4- 3313

(3) 2R1 + Fig—aim 4» RE 4- MgIa

The «there one to tho omclueion that reactions (2) and (3) are side
”octane which occur more readily with orgonoiodidee than with any
other halide end that one mt‘oe very careful to have an emcee of
magnum meant in the mention at all times.

Later, Rookie and Ubbclchdc (30) studied the reaction of methyl
iodide with new-ion and tom the following roan tione occurring.

2C331 +33 +(C‘H5)30——+C3H. + MgIa'(C.Ha)3O
20331 + M3 $11313 + 2GB}-

 

03,- + Et,O————-> 2cm + caacm + can.

Thy a1» taund that the following reactions occur in the presence or
1mm.

ZCHaHSI “ Iz _—" Cch * “312

It 1. 3100 van Emm thnt appreciable quantities of biphanyl are pro-
ducal 1:: tbs puptration of phonylmmaim mm". The rotation to
give biph-nyl pnmflsly gees by a free radical Muslim (11;, page 59) .

MATERIALS

13

MKTERIJKLS
Lows-opus (3.33. 33-3132). Dov Chemical Company. Used without
further purflioation.
Alivl Iodidea.
Hothyl , Ethyl , n-Propyl , na-Butyl , o-Butyl Iodide: . Eutmn white
label produota.
1~Propy1 and Phony]. Iodidaa. Colmabia Organic Chemicals Com.
Dried over anhydrous sodium or magnesium sulfate , mdutinod, and
flared our freshly acrapod capper who.
Joachim iodide. Mfl’ Analyzed Reagent.
Hague-1m Tut-aim. Merck and Gompany. Mainly for Menard rotations.
Anhydrou- Methyl Etm . Dried over sodium ribbon for at least om week.
Dionne. Purified according to directions of Finer (11h) .
mam WMd.g c. P.
fidim sulfate. tame“.
Woman sulfate. Anhydrous.
Solutions:

311‘"! mm“ . animate]: 0.1 N. Prepared from Balmn'
Analytical made var nitrate .

Potassium Thioomto. Approximately 0.1 N. Standordizod
mutant tin mm nitrate solution.

Sodim Wanda . Approximate” 0 .1 B . standardigod against
potassium «1d ohms-late (Balm-3' Analytical Grade .
Sulfuric Acid . ipproximtoly 0 .1 N. Standudiaed against the
sodium Worms solution.

1b

 

Fifty arm (2.1 a.) of main taming. mo placed in a dry,
two liter, tin-«oncckcd round bottomed flack which was fitted with a
mercury tooled otirmr, a Ibuhhorg dropping tunnel, and a Gram
(gm-:1) comm. The condenser and droppm m1 were new: with
drying tubal fillcd with a fixture of «him chloride and am limo.
Tho flu-k was swept with “water ma“ nitrogen dried by bubbling
W concoututcd sulfuric acid. The flak was placed in a container
no that extol-ml cooling could be mum it doth-ed.

On. Wed milliliters of anhydrous ethyl other and five to ten
arm a: the organic iodide mo addod to start tho reaction. Than
five hundred milliliter: of animirouc ethyl eta-r no added to the
fluk- uti tho ruminant of the two moles of organic iodide no fixed
with than hmxdr‘cd milliliters of Anhydrcuo other and aided it tho rate
a: one to two drops per second thmugh tho drooping m1. In most
om: external cooling in nut! in occur to prevent tco vigorous unu-
ing and the to out don the tm‘ masonry for caution. The- now
ally]. iodides Ind phony]. iodidn m added Int tin rats of two to three
drops par mend with the «condom alloy]. iodides were added ct tho
rate or about can drop poo ”condo Attor addition was combats, stirring
m continuod for an hour and than the MM "agent was canned

15

«comm; to the procedure dcecribcd in (II) and then allotted to react
81th 11,2me imodiatoly. Allowing the Brigham reagent to
am overnight did not appreciably increase the yiclds.

II. M of the Grim“ Regent

The Original regent wee Mien-rod through a glut tube fitted
eith e glueml filter by mm of nitrogen present-o into a graduated »
tiling cylinder which had been fitted with an inlet tube, a safety tfle,
and an outlet tube reacting to the bottom of the cylinder. The value
er the «lotion m mound and a one milliliter aliquot me am and
canned by the cum procedure (31) using phenolphthelein u the
indicator. Author one 11111111th ILliquot was taken and analysed for
iodide by the Volhm nethod (32) . my ether eolction o: the Grimm
‘ fluent me then divided in such a any that from one-third to one-hut
ecle of tor-Wan iodide we. placed in each reaction the]: and
then each portion we treated with either one or We mole-e cuivclenta
or 1,2oepomropm .

The volume or the flatworm: solution remaining after
precipitation of “main iodide and comment! iodiée with
Liz-diam a: measured up deecrihed in (III-G). I; one milliliter
aliquot use than anti enthused by the Man: madam. The other eolu-
tion of Mammalian me then divided into two equal portions and
«oh portion on treated with two mole-equivalents o: 1,2-epoxyprcpmo .

For yields of omens iodides and 411”an com
pond- eee Table I.

16

 

A. Baum of one mole of Mam-d reagent with one mole of 1,2uopoxy»
propane.

About one-thud of e mole of the MM Regent (honed on tin
mm ammo) m mm w m or nitrogen mum to a
m one-«11m, three—meow, m bottomed nun: which had been swept
with on nitrogen. The {leak on fitted with an mm (bulb) Wanner,
a W mled etirrer, em a. dropping tunnel. A thermometer in
«upended through the condenser by mane of e oiohm wire no that the
bulb of the thermometer m covered by the. Iolution in the flock.
em: up «new and drawing m1 were fitted with drying om.
tilledeith a. fixture oi‘ eeloim chloride and sedan-lime to protect the
when rm: both «in vapor and em dioxide. The mount of 1,2.
W necessary to react with the mat of iodide ion titrated
intlnGrimz-dremtinaeohpermle mtiommighedoutm
lined with an equal volm at We other. The revolting solution
m then added to the Mme-d reagent. The reaction temperature we
W et ifs. by external cooling we the reaction was etirred
namely Wt, the 0mm motion time “ml-Wu mar addition
of the cyanide we completed (usually was minutoe) , the reaction
m m maintained at the desired «mature by pleoing the {leak
in . meant mum «to: hath (mtrolled to 3.1%.) and stirring
we continued fat the aeration of the mention.

it the end oi’ the ”notion period, the rotation mixture m hydro»
:1de by 41-min addition or e unturned ”lotion or main: ioéide .

1.7

wooedmliosbyeeene or eeioe hethmrouno toheneeeemy.
Pro?- !oe-ty to sixty milliliters of mine iodide eolutioh were
required to owe onplete preoipitetioo of the nemeeim eel“ em
leave a o1“: ether ”lotion. It we usually neeeuery to etir the
nation mean 539!- vicovonely during woven-in in order to get a
moth deoonpoeitio‘n. The clear ether eolution m decanted from the
precipitate and the precipitate was mixed with tour portions of other.
Voter m then added to the preoipitete until it an e puty one: end
thin pate no em ted onoe with other.

The combined other ”lotion of organic reaction produote m then
dried om We «dim wrote. The other we moved by dietillo
more theme on 18' Vim calm until the Wrote” a: the gm
had ueohed about 50°C . (The omtul control a: pot mum. m
menu-y to prevent deomoeitioo or reaction products.)

The residue running otter moon]. of the other we placed in a
five hundred milliliter, threewneolmd, roundabottoned (leek equipped
with bulb condone” and e glycerol sealed etirrer. Slightly more than
the Mounted mount (hand on the mount of iodide present) of ”dim
hydroxide pellets we added and the mixture was stirred for fifteen
minutes, during WWI: time is demo pmoipitete of sodium iodide M
unelly appeared. sixty to eeventy millilitere of water were mm in
portions , end the neulteat eixture m "fiend for five to six hours
in order to convert the barb-ammo). meant into propylene ‘ oxide
a: ”dim iodide . Stirring wee oontinueue during both the period of
edditionend thepmdofnflux. ‘Phe nutiohmmmdlouedto

18

oool ie no. cementum, the were are «matted, and the voter
ieyer we «treated with other. The combined other portions were dried
over «hadron ”dim mm. The water layer which contained the
eediu iodide produced in the motion we: boiled to expel any die‘eolvcd
orcenic utorial and diluted to tire hundred milliliiere . In order to
«W the yield of luiodo~2~pr0pano1, a two milliliter aliquot of
the solution we: analyzed for iodide ion by the Voltxerd procedure .

The other on Wed from the driotl mixoure of organic products
by dietilhtion through an 18" “gram: calm , etopping the animation .
when the pot temperature had reached 50°C.. The midue m then rm,»
tiom‘bed through eithr an 8.0 inch helix poem column or a 9.0 inch
Vim column fitted with a. mu reflux, pertiel taboo” typo head.
has we applied to all dietillntione and reactions by Gian-col aunties.
After the initial fractionation, all sailor me we combined and
rot mtioneted before my “tempt as made to determine the physical
commie and misc derinti‘roe. For yields coo Table V.

Boeidoe lniooo-n'bpropmol and the alcohols , We]. lay-promote
were iooluod from the roastion mixture. Those identified are listed
in Table II.

 

m: In'ordcr to determine the importance of - . g all 01' the oxygen
from tho reaction the}: it me oooiood to set up dontioal reaction: as
described above—osmopt that com flank was flushed with dry nitrogen
while the second m flushed with dry air. Omaha: mole of ethylmgnee»
1m iodide we: placed in each flask and owed to react. with one mole oi‘
1,2uepomropane for 18 hours under the conditions described above". Upon
working up the reaction mixtmro it we found that the yield of bio-denim
propenol from the rose tion cmiod out under nitrogen we 68% while the
yield of 2~pentano1 me" 28$. The yield of lwiodo-zmropanol from the
mutation corriod out under dry air we 65% and the yield of 2-pont.mo1
m 27%. The“ results vould econ to indicate that. tin pmeenoe of oxygen
bed very little effect on the course or the reaction.

19

B. Rotation of one male of Grignard reagent with two males of
13-090mm.

The undoubted meant (in a ratio of two no}... of tho opezido to
one o: the Grimm reagent) or Lamp»: 1:: ethor m added to
tho Grimm-d reagent «I described in prom (Ind) . The addition
«all: took wont thirty minutes. After addition the reaction was
plane! in 3 amount mum-s bath maintained at 15°C .3106. at!
am tm‘oughout the owns a! the reaction. The nation was usually
characterized by a white pnoipitate which home more dam Ml the
rotation promoted. and in ma cases actually betas a gel wMeh was
very hard to stir.

Tho muons were many set up in o aortas of five and at the
definite tine inns-vols one a: the the ”notions m prone-ad as
follow- .w The mtien mixture no hydrous“! vith uvoaty to ninety
milliliters of «touted mum 19:11:13, The hydrolysed venetian no
then manned as douribad in (III-mt) . For yields nae Table VI.

Besides lawman-prowl and the .10th «wool bwmduou were
“eluted from the reaction fixture . 2m» Montana as listed in
fable II .

C. . The preparation of Mallqumagnosimn and diarylmame 311m from tho
comapcmding Gama roogento (10) .

About one mole of Grigmd reagent was plum in a dry om liter,
three-name , round bottmd flock wider. had bun swept with dry nitrogen
and not up no (inscribed in (III-at) . Approximately m to three teams
male in omen o! the caleulntod meant 6! av 1 Audion-m (on a mole

20

per mole beds) was diluted with about one handrod milliliters of
alum: ethyl other and added dropwiog so that o gentle reflux m
unstained. Stirring as continuous daring addition and m motioned
for 8-12 hour. after addition no amploto . Then the thick solution
was transferred by new of nitrogen pressure to 250 m1. centrifuge
bottles, stopper-ad tightly, and centrifuged at IMO-1500 mp .31. for
fifteen to twenty minutes. The clear supernatant @1513? solution was
Matted by nitrogen pressure to the mixing cylinder doooribed in
(II) and tho'wlm was mesa-mod. One milliliter aliquots Hora analyzed
by tho 611mm prooedaro using phemlphthaloin as the indicator.

D, The rgaotion of diorganomgzosimn compounds with 1,2oepomropano.
The gapornatant other ”lotion (oootaining for the moat port
diorgamgnegiam cmpouncio) m then transferred by mom of utmgon
prooaaro to a one liter, tires-mocked, round bottomed flask oat up as
in (11121-3) . The calculated quantity of 1 ,e-opoxypropam m dissolvod
in an equal volume of “mamas other and added dropwioo with stirring
at 15°C. (maintained by cooling in an ioo bath) . Addition usually was
completed in about ten minatoo. Tho reaction flak m thou plaood in
a constant temporataro water bath maintained as in (III-.3) and stirred
anti]. tho test with Mahler’s kotone (his?) was negative, by wMoh time
the solution tad become milky. In 3.11 canon another tailor reaction
was mama to run at least We as long in order to see if aw

approoiablo increase in yield of the alcohol was obtained .

21

The hydrolysis of the reaction mixture was carried out as duoribod
in (III-A) with about 25-35 321. or the saturated ammonium iodide solac-
tion being and. The Women! mixture was worked up, dried over
13W“! sodium sulfate and tractiomtod as described in (mg).
for ”stats m Table VI.

IV. Pro oration of 1-iodo-2~ 1 from 1 2 one and H elm:
Tofiao Ethan“. - '

A. Preparation of ammonium iodide in othoz' (16).

Thirteen we {0.53 n.) of magnesium were placed in a dry one
liter, moeanooleod, round bottomed flank wept 'with dry nitrogan and
equipped with condemn, glyogrol sealed stirrer and dropping formal.
About the arms or iodine was dissolved in 50 m1. of other and slowly
aided to the uagmsiam with vigorous stirring. The reaction was often
difficult to start, but once started it was necessary to keep the
initial amount or iodine low in order to prevent too vigorous a reaction
from taking place. It was found boat to have an ion both may to oool
the flask rapidly if neceamy. Once the mention had started 1450 n11.
of anhydrous other was added and the dropping tunnel was ropioood by a
powder addition tunnel. The remainder oi‘ the iodine to males 0.5 mole
m added slowly by means of the powder fumol while stirring the re.
action mixture rigorously. It mg necessary to cool the flock intor~
nittontly to prevent the other solvent from refluxing too vigorously.
Addition was usually completed in about two tours. Stirring was con-
timed for about om hoar- dnd the reoction night“ was allowed to stand
overnight.

22

B , Preparation of 1~1odo~2~propmo1 .

Tho mum iodide ethomto (0.5 m.) was transferred by means or
nitrogen pressure to a dry nitrogen-swept one liter, three-mom , room
bottomed flask equipped as in (III-s1) and one 15016158,,0 g.) of 1,2-
epomrcvpane in one mndrod millili tors of Wrong other was added
ovor a period of one hour with stirring. A dense white precipitate
formed as the oxide was added. The reoctioh was placed in a constant
imperaturo water bath maintained at 1531°c . and stirred for twentybzfour
Mrs at that twporaturo . The maotion was madrolyoed as in (III-is.)
using about eighty to ninety milliliters of the saturated monim .
iodide solution, which oomplotoly precipitated the megmslm salts.

The othar aolution of organic reaction products (mainly 1~1odo~2~propmo1)

on dried over anhydrous sodium sulfate and the other no removed by

distillation. The amount of 1-iocto-2-pr0pano1 pronont in. that residue

was than determined by mono of the method discussed in the following

section,

C. Tho physical properties and that method of determination of yields of
1~1odo-2-propanol .

It was found thlt the l-viodo-prropmol was difficult to diam
since a large portion of tho l-iodo-prropaml decomposed during distill-
atioo. Therefore instead of isolating the 1-iodo»2-propamol a method
of analysis which would mm datomination of all the 1~10do-2 —propano1
pro-cent in the reaction mixturo m needed, 31m: tho 311mm decompo-
sition procedure bu boon show to be an acceptable method for determina-
tion or l-iodoneapmpaml it was decided to on it as the method for

23

dot-mun; the fidd a: on. wood; ummuy, on hydrolyzed
«action m m wound «cording to tho procedure duel-lbw in
(ma, page 17) and the yield of laiodan-propanol 1m detonated by
mm or dbl: demolition and than» 0! tbs iodide ion vhloh mm
W. this no dam by new of tho Velma procedure a in
(mus, M18) .

Tho um yield of huh-Ewe}. I’m the reaction of mama-
fun mam. with two moles of 1,2oopomropm m of tho order of 75-83%
band on th- munt ”iodine and in W mumum iodide.

A gummy or lama-2.19m}. m waned (h1~h3°c . at 3 m .)
and tho physiod proportion were detemimd.

Refractive Index Beauty
Fwd ' Lit. Found Lit.
n§°:1.5hsa (533: 1.9359 (13": 1.8999
“foam ng". 1.5365

Tho molecular mxmuon at 30°C. an ammo and round to be 30.19
(«wan mm). m valuou sound tox- both the refractive index and
density remind constant upon repeated distillation of the comma .

In order to determine the purity of the lame-9mm the
percent iodine In dot-mined by both alkali onion and Parr bomb
mm. Both mthods gave the mo results.

 

1-1oao~a-prom1s cum” 68.2% I; Found: 67.9% I.

2h

The precipitate pmont baton W11“. in the mutton a:
W iodide int): two ”In or 1,2-cpomrapm m analysed by the
procedure in (V).

Odom. for (0311.01) .313: 6.19%! Mg; 611.38% I.
Found: 6.115 Mg: 62.03! I.-

D. Attmta to prepare Mutt”. of luiodo-ZoprOP-mol.

An :ttupt m lid. to prepare the 3,5—din1trobmontn of blade-2-
prop-null according to u» procedure daemon 1n (Vic-A). m mm
mun (om vith midino and one without) wood to produce .. dorlutin
Mob could be "amt-111206 to a constant melting point. A. third
trial «I nude using the procedure doooflbod by Stuart and Vandovwlrf
(:5). m: procedure a.» tmod to m. a. pure oer-anon. A North
mu m m using the phonon" described in (v1.4) with the onoption
that no pyridine no used and the reaction was heated only contain!
hour‘- rm 11; um moved to mm overnight. no: procedure gave 3
«Plants which, sitar recrystallisation? to a constant melting point,
squad ot 83 5‘81: .000 . An analyti- of this derivative resulted in the
following nines.

3 ,S-dinitrobmoates
Unmet!!! lemma-prowl l-ohlorocznpmpanol
S found 5 odo'd. % calo‘d.
c . a1.73 31.55 u1.6s
H 3.18 ?.38 3 .12
N 9.11? 7.38 9.70

Halogen 12.19 33.35 % I 12.28 t 01

2-5

‘1‘!» don-inn" can a padfive qualitative test for ahiwim and
a mgatin tut (or name.

From th mini. and tho Minn" mm 1% is evident that
We»: «:3th nomad during no reaction or the 3,5-dinitmbcmoy'1
shim-id. with 1.1“”sz . It in interesting that the uniting
points of thn 3 ,S-dinitmbemutoa at biotic-26mm]. and immora-
anmpanol have been reported an lacing very nearly the me “6).

in Amt. m m to W tho phony). urea-mun o: inimwzn
mm). according to the prooodm described by mum (33) . The
roman: W m a viscous oil which refund to crystalline.

In a. further effort to prepare a derivative of the biode-
20mm). an Ottflpt m undo to prepare the OQ-naphthyl urethane
according to up procedure momma in Muir: (33) . m prams
uniting from in: reaction as recrystallized from 11min until a.
constant uniting point. no obtained. The melting point of this
derivative was 131.8~132.9°c.

okfinaphttwlurethane

% cula'd. % found
c h7.50 hem
H 3 ‘97 h .12
N 3.9h 3.87
I 35.60 3!»?!

26

  

v. 1. of the Proci mm Pomd . '

Gr rd 0 out _.’. Twono co ram 2

The rmfiion mixture watching one mole of ormomgcuiua iodidc
and two moles of 1,2ocpomropm m flit-rod at. 15°C. until tho mm

 

can a captive out with fiichlcr'c Was. The precipitate was thou
concc’ooé on a mug-ca :15” filter mm). (the precipitate no toned
«or into tho tunnel through a. zinc tuba by com or nitrogen prom").
Tho precipitate m quickly freed from no“ of tho cum. by new of an
“pint”; won placed in c m «docum- and, in order to m
tho but traces of other, was dried at 20 III. for czar-halt hour and than
driodcth,tox-anotbrm1hour. .
Tho dry precipitate was Almond for magnesium by 1mm; wished
nlplu to mom oxide . The prcoipitcto m .1» nuance! for iodine
by the man decomposition prooodm uni Volhard titration o: the iodide
present in an aliquot. Some precipitates ohouod a tendency to ignite
if exposed to the Air for periods longer than rm minutes; Micu‘iu-ly
m pmcipihtoc derived from the methyl and ottwl reagent- .
Therefore , it was masonry to mom rapid weighingo on than announces .
For rend“ soc Tobin VII.

VI. Determination of a Hus Balms E tho Reaction of n-Promom

. fl9"'j‘r°“ a: v

      

A. Reaction of one mole of mpropymmcim iodide with one mole of
1 ,2ucpcmropm.

Th. vocation I“ not up u in (III-oi) with the exception this a.
trap inn-rad in i 1327 Icooiccpropyl alcohol mixture on connected to

27

the condenser ia oroor to collect any gases swim during the course
or the ruction cod during ham-chain. The reaction m omiod out
at 153190. for 21; hour- cnd Wlmd by addition or ice cold 25%
mitotic acid dropuicc (80 m1.) until all the “motion colts hid pro-
cipitatod. (Scum-1c acid m and to avoid addition of iodine to the
nation mixture.)

' Tho mtioc on than wot-land up as ascribed in (I‘LL-xi) with the
cmcption ms the pmipioctcd ammonium «it. wore dissolved in mid
and titrated tor iodine ion by tho '10in method. Tho other Minot
m rmwd lad titrated for opoxido mm by tho method list“ in

mam Quantiuoivc m c m: Via Mating any: (£13). The

and“ are listed in table VIII.

B. {inaction of on mole of n-pmpylmagzoaium iodide with two moles of
1.2«pomropm.

The reaction flak was set up as dcmribed in (Vila-i) and tho roe
action was allowed to proceed in tho mnnor described in (III-B) with
tho conception that the relation was hydrolyzed and worked up as described
in (“IL-i). The renal“ m lined in Table 11.

VII. Pmpmtim of Dog-inure:
A, 3 ,5-Diniircoomoam (33 .310 .

Dumper“ “to alcoholvu phoodinadry tonal. room
bottomed flank and to it no mm about one gnu of 3,5adinitrobomoy1
chloridc and m mm. or anhydrous pyridine. The mm: on rum
with a null reflux condom»:- looooly otoppcrcd to prevent moisture

 

28

from entering the flask and han’md on the steam bath. for one to two
hours.

The venetian W was rammed from tha steam bath and wound
to 0901, 31’th which 11‘. was poured into- watar in order to hydrolyze any
excess acid gramme. The mtomrganic mixture ma extracted with
ether and the water layu- m «awarded. The aux-r ax’amt no wind
also with five percent sulfuric acid , W100 with ten pox-cant ”411m
«Manna caution , and one: with water . Then tha ather m evaporated
and tho team was dissolved in hexane . The resulting aolu’aian was
domlorlsad by boiling mm Marita and the Horn "was renown: by rum-
tiara. The 3,5-dmltrobenaoatel Hera allowd to cmtalliu at room
mental—‘9 and than recrystallized from ham to a constant melting
point.

B. Phenylmthnm
The phenylmthmo of loptmzayl-E—propanol in prepared awarding
to the prooodure described in McElvain's maotarintioq o: Carma

W: (33)-
VIII . egg Elation of fields

The alcohol was isolatad by :mmmuon (III-11, page 1.8) . The
per-amt yield of each wow). I!» Mainland by taking tbs raw or the
mole: of alcohol produocd to the males 9: organic radical patent in
mm mm 9W meant. ‘

29

The yield. of l-iodo-Z-propanol Ion download by 11131an
damnation and tits-tum of the iodide ion produced wins the Volhu'd
method . Tho promo yield of lalodo-Z-propml m calculated by um;
tb' noun or the uolu of iodide ion round to tho ml» of iodide ion
found in the mooted Grimm moot.

Yields of lwiom~propaaol taro reproducible to within three
percent or loan oxoopt in tho cue-s of the methyl and o-botyl mm
which our. reproducible to within about four poroont. At longer no-
aouon periods tho yloldo were mount loot roprodnolblo than to
obmr rotation periods. Yields» of the alcohols more reproducible to
«mm: m to three pox-cont. in no“ cocoon-hora again depending on the
Grimm-d mo. Tho yields of the 810013319 from the methyl and ethyl
MW were reproducible to tho extent of about tin-ea to five

percent.

TABLES MD FIGURES

TABLE I

ms or mm) mmms1 m moamumm' amino

 

 

um Ma. ’33?” 3323‘ ”$3?“
Homl 100 100 18 .3
W 96-97 100 h? .5
mm”). 93 100 61:.3
1~Pr0pyl 73-379 100 1:8 .0
WV). 90-91: 100 M .5
o-Botyl 68-75 100 50 . 6
PW]. 911—91: 99 73.6

._._.. _._.__ A M-

‘ Calculator» bond on mat of organic We used.
2 Calculation. band on amount of olkylunumn iodide and.

TEE EMT!“ a H L .. 5

31

TABLEII

 

-:~m morons m3 1,2-EPOIIPROPAIIE

(Br-product: Ieoletod rm the Reaction)

 

A A“.

—.-.—

M

An. , 4 LL

 

mm mom ammmw
mum mm ,1‘ 1mm!- alcohol:
Ethyl Acetone , loamy). alcohol
n-Pmpyl Acetone, WNW]. alcohol, my]. eloohol,"
n-proyyl iodide, impropyl iodide U)

lampyl mm, leoprOpyl alcolnl, ”apropfil 19am"
n-Bntyl loom I 100ny alcohol (We) , nabutyl

. eloohol
mm Acetone, s-outgl maids,“ o—butyl alcohol“
Phony].

"—

* Idanunod by mean of 2 ,badinitmphonyl hydruone.

Acetone , benzene ,3 diphewl‘

'1 Identified by mom or 3,5—din1trobemoato .

i Identified by men- ot boiling points end refractive index.

O Identified by means of boiling point. and melting point.
Trance of maturation were found in all roao flow: and were
outed for with bromine 1n oerbon utreohlorldo.

32

.9593 mm 95“
38.. 8 363 $5 .53 25 .8“ ”3% we :33 «5.33 an Edam a
60.33 .8338. 33 we £3." £3 gang». gaggle“
88 «a 33» g Juana» «a 83%? $3. .33 «8 ha. 3 “333 a
.323 £338 9..., «fig» 353. Ea Adams gag $3qu a

 

 

d“ .93 on «.mm min I. .... 2. mg
,3 $3 an .3 o.~ u- 2.. ..... ”Ram
a: 93 4m .3 0.3 2. I. 2. mafia
.2." £3 E 3 830m .5 I. 3 «gm
3 8a on .i o...“ .5 2. s. 63%
HR Ba on I. o. R I. I. .3 15m
a: .5. on 2. 0.3 .i I .5 33m
a: 93 on 1. 0.3 a... .3 1. d3;
.3 93 em 2. 0.8 93 am 2. aim Edam
.3 95 N a... 9%. pa .3 2. 33 ”BE
3... .2 ad flan 9mm 2. i I “flaw
d... 93 a QR «A» 2. 2. I. .33
are. 2a 3 m. E “.2 .i 2. ...... 3.3%
«.N :3 m4. m5.“ oé. a... .i 1. ”Ham
.3 93 Q. «.3 92. n3 3 m.m~ «.3 .33
a.“ .95 3 flaw Hdm E5 3 0.2 5.2. aha.
dw 2n 3 fimfidmflmébda an 3 Now 4.5 ”his:
a: 3A a: .1. Aofimxaw 2.. am 2. 0.2. ”have:
.3 95 MN .2. 3.83.2. 9a .3 t. 4.2. .353”
3a :3on 25. 3.8.3 25.. 33.3 3&5
no 333 «an; . H“ M -83 m 833$ . em M .6on m g
. «gauge a3 «negobaoo

Enaudmm mflh 8 manHmnou goo be 935 was
masgw H HE gnoH Mawggg a gag mm;

35.232 .

 

 

Hummus

33

T3313 IV

ms mum‘ or WESIUH mums ma 13.127031?me .
was 1mm: or comaoum commons on m awnou

 

 

 

Vfif' w 4}t* N L r , ~— fiw -W ~ w~< «4 ;__ . ~a=
Condition. Conmned' Conditions Not contmnoa’
aouuon mm o ‘ «0
fly: w w _ A x:
o 9&5 ' 11.0 8? .0 9 .9
1/h hr 100.0 11.9 100.0 12.1
3/}; m- 98.7 16.3 88.0 12 .1
3 m 86.1: 22.9 73.0 ll»?

18 hrs 70.7 33.0 68.0 32.h

‘ One ml. of othylnagnuim iodide use! We moles of 1 ,promrepm.

5 Constant Mature (15°C .) and stirring thraughnut m rotation
period.

' Allowed to stir one hour Aftar Mania!) of apexidc, than stand a
room tapemtm throughout tho rut of the manual! period.

3b

.393 «an—egg}. .8 gun 5 v35 .8 33» a
.%%QA no «Ho... £8 and 953 3:823:39 no final 30 a

.figgsfiououofiofianogguflaflafiooduofiié .39..

1

 

agar... EH SE

. .; - : . .WM
g H... . .8.l~lovo.wtfl MO gHoflH

gamma» .8 mmfiqfimfia 9. may... no .595
magaflohsa a 95. 33mg manganamo .6 .aoflfimm Eu.

baa

as. $5939..“

«.mm 0.3 4mm «.2 m.m~ 0.3 ads am mm
p.mo m.- h.mm o.m~ ¢.m4 h.m~ q.- NH mm
do» «.2 4.3. mdm mi.» .33 ”.2. H mm
0.3 mg «.3 3m «2% 93 4.2. .a ma .
«.me m4.“ mam. WE. «:3 9R 9? 2 m”
0:: win «.2. 4% 42. .30 4.8 m ma
0.2. 0.5m 92. GS H5. 3:. «.2. 4 ma
92. «13 v.2. 0.8 42. 5.2. flow N m."
0.2. 9% ad” mam, 9.2.. m5. flow H 3
0.2. 3% 4.2. 9mg 42. 0.2. 0.2. a ma
ed.» 93 “.2. o.$ 98 92. «.9 m m
.8; .03.» ha. : r :3. A55 .9.

35

.3533gfiiaaagfigfifi-finaegigflgfil
a no A9503 33.30.53 no 905» a: .3333 9!. 003 093$ 9.00.203. 33 33- 03.323 0.0! 5000." 3a a
.188? on $3.. .33 803%? day 8.905%”; Me 5333 93...: 83 5.383. a
. 0%an 3 £338 33 8.. 9.33390 a

t
L}

 

  
  

 

      

 

 

«E a... E 3 w as 2.. 0.3 a... as 3. 2.3 3.. as a... hr»... 3
E 3. 5 i 0.3 a: 3.5 «.2 as Sn 3 3. 3.3 3: .Bauwm 3
. . a. «.33. .

gag

 

t“. , r . , . .l: ,..L . . I .!f 1 lull!
'. - . .xiFrmll,

388.3. Eu .8 mg no «was. .8 98.5 Bu
mfiamgcfia .8 3.30 0.2. m5. gfigamfin .8 555.00 Ea

 

Ruin W5 3.8: 0.3 “3:10 «d 33.3 0.3 “305 an. 833... «.3 3305 3..” 3 u a E

 

 

      

 

  

     

     

 

 

 

 

083 2....
3.39.? «.5 3.30.» 98 amuXJu ”.8 “3.9.3 0.3 Afivflen m.$§.3m.mm 0.2. 33.3 «.3 99’3“”: A3
a
den «.8 a.» 043 0.3 0.2. v.5 W3 0....“ .fi 0.? ”.2. «.3 .20 5 mm
0.3 0.8 0... ”.mm 33 4:. «.3 50.3 0:: .8 0.3 4.3 «Rm 9% 0.3 m
0:8 13 «A 0.00 a...“ 4.8 «an 0.9.. 4.0 «.ma Q3 ~23 0.3 040 h .3
flag 0.3“ mg... 4.8 0....” 9mm .2 0.8 4m 0.00 «A.» 0.03 0.3. «.3 .3 .5
«.0 mama 0.“ ad» a; dam «A. 0.8a «.u 0.3 0.4." mi“ «.3 «:3 o
tilt-Inf. . lflwl *1 .w 0.0 .. ,, n .. .1 n - .
Emu - .3.“ 0.8% - 9n . a.“ Na
#83? 5.. E... n5 H8? . 30.83..“ «o 33» 5800

 

 

man 8 «mg .3 gag Eh
Ag 033 magagIaufl Hg 3% mnov magma 533%.“... .8 33mm gs

ND 39.9

.3033?" 2955.6 05 M0 :30 5 anon 93

03.00.... B- 70.03.» 0.35% an 033..» 3330.300 3» no 03»: 83 3 830009800

tn; .3 00.3: 0.5 .353 conga-.00 03.03 55903!- 05 0:186:91“; no 90MB.

25 5? 035008 0303 Siofiaguuo «.3 00 23x? a 3. 3503800 93 ma
Swag pad—00.08 05 00.5 03.90.5900 33 no 0003 0.3 030.03% 003.4» 30000 05. t

 

 

0 an .mMuMWHMMWH “Mu Em Ex :3 g: .530
0.30 o£3%ma.§.o $0 .20 :4. 03 En:
H.000 «Newman? an»: 0me 0.3 .73 00.0 40.0 «003..
«083.8. Huxomvo “2. ..
0.400 Exam-$25.0 0.2 «.00 2.6 cm; ”0000..
0.8... amp-”MMWmmmmww” “WWW 0.3 4.3 00.0 3.0 gar—£04
0.30 800,004.00. H033 0.04 0.3 8.0 8.0 102.3
0.0% «mumuamuw. .0me mm W . . . .
amumvamowénmgdno n00 m an m «a «n m 4H m tangl—
ndfi «00.6.08. H0306 0.00 0.2 «0.0 8.0 “0020....
«.23 «among? H053 do; 0.2 00.0 «0.0 03.5
0.80 «0.000308. H058 «.3 43 .36 8.0 «2::
3...... 00%.. . 0.00..

 

 

050520.“; .6 was: an. 0.8..
MESH 0300848038 no 08030.0 a: 5 35830 00200 30000 mfihfififi 8 mag

Bah

rm VIII
W8 W mm WE
Ono Ila),- n—Pnpyhnmuu loud. and One 1191. 1341;030:0193»

 

 

 

 

 

 

 

 

 

rbncount hr A Yogi“: T. ‘ b V “a. w
1. n-Propyl road. 26.h g. roams Emma“. all“)
c. 76.5 3. India. 38.0 5. 1mm lama-WWW)
b. 2h.2 g. n-Propyl Rum 17.0 t. W (15m. of propane)
2. 35.1! 3. #01163 29.0 a. Brand: (lama-prowl)
22 .3 5. Organic Residue
135.8 a. Total 132.7 5. Tom
To bal Maury! about 97%
kw * W Bream or 953m Residue (lo 019» Out {ML M
_ 3.19:0, mt # w _ mum. mutant.
501-78 7.0 L3. Antone} mint-nos ,' We of ,mm’
was 6.15 g. Mmpym aeom,‘ tar-pram). 1mm 1)“:
85.98 h .6513. when]. doom ,‘ mama. ,' nwpropyl iodide“

98.135 0.50 3'. We of mm.
1.25.136 ’ 1.10 g. flammal ,‘ firm of iodine
n m 2 m

" Idon’oifiod by name at tho 2 I,h~din1tmphenylhydruane ,

3 Tested for by mam or bromine in carbon tetrachloride .

3 rented for by means of: the 3011mm but.

‘ Identified by means of Mae 3 ,Scdinitmbonzoato.

O Identiflod by ms at boiling point and mu“ index.

38

T3313 IX
RESULT-8 or no: 8.11.1803
an. Role of n-Propwlugnodm Iodide tad M 1!qu of Law

_.. 1 L

A “ _ w r 1 p.— T.-

30 Account For tong f f__ A A __

1. n-Pnpyl Iodido ‘ 7
a. 76. 2 ;. Iodine 12.1 g. Iodine (magnum: an.)

113.6 3. zoom (1-1049-2upropm1)

b. 214.2 3. WI 2.0 g. Pmpnno
"Imus

2. 67.8 a. W Huh I. We (um-and opoxido £31323
25.7 s. W60 (lam-prowl)
50 .05 8. Orr-Ania Rum.
168.2 g. Total 1117.85 3. Tom
rug Roomy; oboutjfi}
Memo: 0. o 20.1% . f 1

 

 

 

 

ngfc . haunt ¢_ M mum. Constituents
50-60 13 .1 g. Acetono,’ unsaturabos, trace of iodim’
30-85 2.85 g. 1~Propy1 alcohol, ‘ ioprOpyl iodide “(7)5
85-100 5.6 g. n-Propyl alcohol, ‘ nvpropyl iodide“
100.12? 3.6 5. true: of Q-Inmnol't and main."
127432 1.7 g. 2-hoxano1, ¢ trace of iodine (7)
4-1112 13.1 g. 2-hour»).
24% 1:2 ,0 g. mambo: , trans of iodine
new! 1.7 3. two of iodine
“go-“lam E: .0 5. w

._ 5‘

 

_‘ Identified by moans of the 2 ,h-dinitroplnnynwdruom .

3 Tented for by memo or bromine in carbon tobraohlorido.

3 Tested for by mom of the Beilatoin boot.

4 Identified by means of the 3,5-din1tmbomoabu.

o Idontfliod by mm of the boiling point ind refractive index.

TABLE I
PfiSIGAL CONSTAITS W In moms

WA—A— A .._

.7. fi

 

 

Alcohol n.P.’°c. n33 Rom-mo
w (it: 1 Pressure) * or a
2m}. 97-99 1.3937 .33 .11? .38
banana 117-419 1.1961: 33 36,19
mom-no: 137-139 1.1.152 26.37
Mica-pontoon 128-130 1 .1115}: ‘ 26 ,38
nun-pm 157-159 1.h225 26,37,39
batman-ham 151453 1 Jam 26,110

1»?hony1~2-propano1 211-»2114 1 .3294 36

* A13. boiling pom. max-mud.

All boiling points agreed with the nines reported in the
literature to within one to m domes.

TABLE XI
DMATIVES C? on moms

w ____L_
, WV , v o a ‘ . 7w .» w.— a
_._._ r ‘ . , __ ' , -1 _..

 

 

 

Aloohol Berivntiwee igaggins POinfizgi: Reteroboe
2m}. 3 ,S-dinibrobmoabe 75-76 76 33 .35
1mm 3.5-d1n1omomato 60.5~61.5 62 33,26,39
2.39m 35mmbmobe 37.5-68.0 38 26,141
hmtm-Z-pontanol 3,5-dinibmbemmbo 62.5-63.5 rah-65 26,33,131
ZbEbpbamol, 3,5-dinibrfibeneonte h8.8~h9.5 h? 33.3?
halole-deoml 3 ,S-dinitmbamabe 50.51 50-51 ho

lafmlazopmml Phonylurethane 87.8—88.2 88.2-88.8 36

An— A fl. _.._.4_

w... ‘v— r w . "—1.7 r . vw v—v

' All melting points: max-mood.

 

0Ao_k<m _”_v uz<oomo>xoom-m._ zk.3 muo_oo_ z=_muzo<zoz<omo do zo_ko<mx um» unumao_m
. Ammaoxvuz.H

111

om

mm

ma

m.

¢_

m. m.

o.

m

m

b

w

m

o m N

 

V

 

I g

" v 'w

‘A

 

‘_ ‘_—_‘A

_

 

d

d‘

4>kamam
4>oomon_

J>Ikw

.J>F:mlz

4>Qomalz

J>zwza

 

J>Ihw2

‘

1

‘

‘

1

1

d d d

 

 

 

 

 

 

 

 

 

0
L0

00

on

om

'10NVdoad-z-000I-I Lwaoaad

1|?

 

 

\O
C)

 

       
    

N-BUTka

*
‘N-PR

.3
Ln
1

 

\‘l
<3
I

PERCENT l-Iooo-Z-PROPANOL
(D
C)
l

Ch
(n
1

O\
(D
Y

 

55 ' S-BUTYL

50 *

35 :Iaa—"_aV‘v~"~—’—-uv‘v-dfl--._'~—..——_’_-fl"’~a_"T
30 f

25 -

20 ' N—PROPYET

    
    
  

 

 

i‘PROPYL

S-BUTYL

PERCENT ALCOHOL

 

 

 

 

o?ééiéé7‘89‘1’o {
TIME(HouRs)
FlouaéII. THE REACTwoN or ORGANOMAGNES{UM loozoes WITH

-rnn nyvonnonur l 9 QATIn 7 , ggiigil

 

 

h3

ma

4H

(Y‘\

.HochOLQINIOUOflIH mo E:Lpomgy QOfipmhompm woodpmcH

mcopoflfl ca smemq m>mw

HH OH

Eu CH mpmnsdz why,

.1
I

.HHH wooden

 

queoaeg

sutJ;

uopsstm~

13159938101!

131in 8310!

when mania halidee are «need to react with nemeiue in the
preeenoe of other, on ergememeeiu halide (Grimm! magent) ie the
product. 1 annoy o: the literature (it, page 32) bu ehevn em, in
generel, the Orianard reagente derived from arsenic ohloridee ere pro-
duced in better yielde than thoee derived from organic bromidee , while
organic iodidee give the pooreet yield of Grimm reagent. In the
We of thie work it he been found that, it they were properly
purified, the organic iodidee gave md yielde of orgenonegneeim
iodidee (Table I). Only in the ease of iwl end e-butyl Grimm
reesente we the yield below 901. The yield or iodine (Volherd some)
wee found to be 1001 tor all can except the phenylnegneeiu iodide
and in tide one it wee 99$. Thie indicated thet even it prt or the
Maui-d reagent deoonpeeed the halogen mined in the ionic torn
premebly 3e upeeim iodide.

The yields of diergenomemeiun oonpoumle remaining in eolutien
otter the preoiyitation of the «magnesia iodide and mmeiun
iodide are listed in Table I. It is felt that the yielde listed ere
probebly not the maximal poeeible einee both the temperature of the
mention mixture and the time of digestion of the preoipiteto with the
ether eolution hm been reported to effect the yield at cum-mo
magneeium compounds (see MSIORICAL, page 1;). Re attempt me made to

145

find the optimu- oenditione for the motion of the diet-Want
We from the magneeiu iodide and mweiun iodide.

In order to etudy the eti’eet of own on the dome of the rev-
eotion of «swam: iodidee tee different portione of ethyl-
Imelda iodide (0.5 mole each) were oaoeed to react with one mole of
1,2-epoxapropene3 one under a dry nitrogen emephere end the other mder
en etuoephere of dry eir. lo eiuitioent ditterenoee in yielde of
either luiede~a~propenel or 2-»li were found. i'hie would one to
iodieete thet oxygen doee not etteet the omee or the reaction etudied.

In “tidying the reaction of Oflvmlitl iodide with 1,2-vepozr
propene the initial neotione were stirred for one hour after addition
ottheepoxide,endthenellovedtoetendetrooltelpereturei’orthe
duration or the reaction period . 2h produote ieoleted were 1-wee-
2—po-opm1, Zwtml, end eeeerel byproduct. (eee Tobie II) .

when the reaction eixt‘ure oi’ etlwlmemeeiwl iodide mag-epoxy—
propane m etirred contimouely during the omee of the reeotion and
mm the reaction wee maintained at e oonetent temeretm or 15"; . ,
there wee e definite decree." in the qt‘len‘titieo~ and number! of by»
preduote . Only treoee or eoetone and ieopropyl eloohol were found ad
the low boiling traction (below the boiling point of 2-pentenol) no in
ma eubetentielly «mm in wine . Poeeibly controlling the
temperature to 15°C. eloue down the decomposition or on. iodolydrin
intemediotee preeent. It ie eleo pouible that oontimoue etirring
w prevent l'hot epote" end loos). action widoh oould reeult in deeme-
eition of the intemedietee end polymerization of 1‘,2-epoxypropane

I46

initiated by cations formed according to the following reaction scheme.

CH3 9H3 933 (4" g.)
(Eastman flxcnchg-onH—cnz + I

Cf? on, sea
ICHJJ + on; <——— xogenous“) + (econ-03.9"

i

0 cu,
ICE-CH—CH, + I!" orifices e— l-D-C-CH,
(9)

Trace or polymere were cbeerwed when the reactions were ellcued
to etend at room tenpereture. Ieopropyl alcohol cmld be formed in
the reection by remaotion oi the acetone by hydrogen, hydrogen iodide,
or colloidal magnesium ell of which are undoubtedly present in the
Grimm reagent. Aloe it could conceivably be produced tron the iodo-
inch-in intemediate by reduction.

Qaa 0H
(19330504353 1) are ' amass,

In all of the reactions of crcunonognooiun iodidee with 1,2-epoawpropene
under controlled conditions treoee of acetone were found and in meet
reactione (phewl and e-butyl Gdgnarde were exceptions) ieopropyl

elcohol we found . In the one or the reaction of phenylnegneeiun iodide
with 1,2-epoxypropene , benzene end diphenwl were ieoleted in coneidereble
mute. Thou revolts were not unexpected (See moronic», page 12).

The one of the reeotion or ncpropylnemeim iodide with l ,z—epemrcpene
wee etudied nore oloeely than the other reeotione o! cranes-melon '
iodidee with 1,2-epomropene for the purpose of determining e. no"
belunoe. In carrying out the reaction of n-pmpylnegneeiun iodide with

it?

one III. or 1,2oepewopefne (fable VIII) it we: found thet on We
19min: the reaction We eehetmtiel mate of propane me toned.
Mew-lb): the temtion e: propene could here «be plece according
to the following "action.

33-63% e 'HQH ——->nw6,H-yfl 4» 83(03”:

em. who-mum iodide was mated with two hole- of 1,2wepoaw-
premonlyatmeotproponemtom Fronthiedetemoendrew
tin-munch thetintheomefthereeotiooofonenoleofcrgmoa
menial iodide with one mile of 1“?me most of the 1,2»
epowopmeietiedwmeettn iodotvdrinintemdietewinmeothor
w I. thet it ie‘ not tree to attack the omeim how. Home,
1.: the iodehwdrin mum» We (u u obviouely «a since
tb yield of lwiodo-Z-propenol decrees" with time) the epoxide in me-
me {on it my be doee not reeot with the wweeim bond to
mom on alcohol.

The dete in Table 1;): marine: the results obtained under con-
trolled conditions (1..., metant mum and continuoue stirring)
em the revolts obtained when the oonditiom were not committed. This
data. indicates the and toe oerei‘elly oonh'olled reaction conditions.

It is appmnt from the uide variance of iodohydrin yielde thet new
tutors we probably influencing the come of the reaction when the
reaction conditions we not meteet, and for this: reason the mention
We no etixred contimmelymdtho tomerotnreand lengthof re-
eotion tine were oontrolled as carefully as poesible, when this: was

158

m- not“. were ”mandible to within 26! «Wine on the
Maud nag-at and (m RENEWAL, W29).

who «Wm load” m emod b ram with 13W
m tbs yum: of the alcohol: m amm- no sum whatnot- um
mam war. annulled Or not (Table. m and IV). m, m
mm o: low-2W}. val-10d noticeably. Th1: variant nu
01m in the cm 0: the ammonia iodide at abort mama
poms: (Table 11') and for this added rowan be“: mature and mt»
action all. we continued an 610001: a possible and tho reaction
m m turn: continuously mm the own at the mutton.

n» “to“ a but an us?- "much of maintain: “didn’t with
13-090mm no swam in the me or immoum-maa. It
as round that hunting at tho "nu: «apex-mu or am m.- tm m"
«and mama lav-ring at the mm o: 1~mem1 by; m not
Mam: inmate m yum o: swam (Table In) . m- u in
wt rub on work of m m Maine): (25) who few ma;-
“macs.” mum in tho can of dbhngmaim braid“. m tho
0th!!- hlnd m and autumn: .( 26) found that heating “tonal-11 inh-
gnum yield- or sham while damning 36.0163 at homered-prowl.

'1‘!» mm or kinda-2W from the reaction of OMB
We with 1,3?”me (Tabla V}. are similar mt 10v Wuhan
(5%.) and mm rowan that. m ani- a night um um. than
a.- "hunk little autumn“ batman the ”mains-iodine bonds in
either em. when th- tmpumtm m mamma- to Ifc. to:- em ham-

h?

the fields were um mar one)» in the one or Immanu-
iodide, when the yielde e: bade-2W}. eere levee. However, a
the reaction time norm" (temperature oonetent at 15°C.) the yields
of lauded-propane). decrease in no regula- nenner. The decree» in
yield ooee , however, become more rapid with leer-need e130 end branch»
in; of the am group. It would one peeeihle then thet the am
group might pley em part in the deempoeition of the iodolwdrtn
intermediate.

Slniler reactions at 25°C. ehow thet at highr temperature the one
or deco-pounce». of the iodehydrm intermediate is encoded up, an night
he expected, except in the one of. the methyl Grimm-d reagent which
ehove little ohmge in yield of iodohydrin with either time or tapere-
tnre. It is ewes-eat 2m 3. etudy or the eeriee of reaction of one
mole of ergenonemeim made with one mole of 1,2490er whieh
were hydrolyzed at one, two, tour, and six hours that the methyl em
phony]. Grim show little change in yield of iodohydrzln with the ._
On the other hand the n-prepyl end n-hntyl Grumm- show en imam
yield of 1~1ede~2~propenol at two inure and then a deereeee inflating
that the mentions ere slower than those of the methyl end ethyl
Grime-do with 1.2-epomropane. The impropyl and e~huty1 Edgardo
chew e marked decrease or idem yield indicating that the mum!
' yield was probably reached before the first reaction in the series wee
W131“.

Ithe come in Figure I hand on the reaction of one mole of enema

magnesium iodide with one pole of 1,2-epexypropane , represent the

SO

Weition of luiodo-z-orepanel with respect to tine. Beeed on the
Woe or the 1-iede-2-poopeno1 produoed in the reeotion or one
mile of orxenmgneeiue iodide with one mole of 1,2-epoxywopane , one
on any em. the methyl mm reagent 1. unique in that it anae-
not. change no; u... and that phenyl, rat-prowl, and Mum. Griwd
remote ere emvhet einiler. Ethyl, on the other hend, ie very no-
wind in that it has IO aide e range between tn madman and final yield.
Ieopropyl and e-bntyl also exhibit einiler ourvee . In general one can
any thet after ehont twelve henre the rate of deooupoeition of iodohydrin
intermediate eom to decrease and elmet level off concept in two euee
(ethyl and n-hntyl) . Yields of alcohol in all ouee were of the order
of one to two percent.

It would he wrioult to more the reunite of thie inveetigetion
with thet or previous eorkere (25,26) since all experiments reported
here were carried out under conditions of mutant tmeretm , continu-
ous stirring ttmghout the course of the reaction, end controlled
reeetion time, while those of the preview vorhre «ere not run under
men oenditione. _

The reunite or a series of reaotiene of ammonium iodides
with two melee of lfiwmpme are emerized in hole 7!. A series
of five rewtione was not up end one reaotion wee hydrolyzed et eeoh of.
rm set time intervele. In e11 oeeee emept the reution or ieepropyl
and e~tnty1 Grimm remote with two melee of 1,2-‘epomropene the _
iedohgydrin yield exhibited en increase and than a decrease: the m
yield at indohyddn in eeveral om: being close to 100%. The mention

of ieepnwlneneeiu iodide with tee melee oi’ l ,2-epoxypropene eheved
1003 iodohydrin yield at zero tile while the maxim yield of iodo-
lvdrin from the reaction or e-butyleepeeim iodide with two eolee or
1,2..me an only 853. Here u in the reaction of one mole of
”we“: iodide eith one mole of 1,2-epoxypropeoe we find
deoomeition of the iodohydrin internediete occurring with tine. In
ell owe the eloobl yield inoreeeee steadily until ehout 18 were
who there ie e tendency for the yielde of the eloohole to level off.

Tb tile neeeeeery for the reaction of the orgenomgneeium iodides
eith tee eelee or l,2~epequropene to five a negative teet ie very
intereeting (eee Table VI). The relative time for obtaining e negotive
teet em to depend on the tau-her of oerbooe present in the alley]. groupe
eith the leap:- ohein nor-e1 ellql mepe meeting et the donut rate.
03 thie hull nethyl (negative at eight hour-e), ethyl (negetive et 6.7
We), end phony]. (negative et 9.5 hours) heve about the eene order of
reactivity , while the n-propyl (negetive at 12 hours) and the n-hutyl
(negotiate at 25 henre) react eoeeehat nore elevly. The ieopropyl
(negative at 5 more) and e-hutyl (negative It h.s houre) tend to reset
are rapidly to give e negative teat but not aeoeeeerily to give the
beet yields of the eloohol. Prue-ably there weld be more poeeibiliw
for eide reactione with e more reaotive hindered elkyl group.

It ie intereeting to. note else that in the reeotione of the di-
orWeiue withjteo Iolee of 1,2-epoxypropene All the reactions
ave e. negative teet eith mohler'e ketone et ehout the me tile
(diallqlnogneeiom h.5—6.0 heed diphenylnegneeim: 7 hre.). Thie

52

would eeen to indicate thet there ie reletively little difference hec-
teeen the "We-in bond in the canoe studied.

The effect or etanding exter ohteining 0. negative Hiehler'e intone
tut wee etudied for eeoh Maud reagent. It was found that in alnoet
ell «no there no en inorme in alcohol yield with increased tile
elthough only with n-propylnegneeiun iodide did the immune appear to
he sub-tunnel. The phenylugneeim iodide actually exhibited e de-
ereeee in yield with inoreeeed reeotim tine but the enell difference
in yield (three percent) could be duo to oxperiaental error.

The reaction of dint-magnesium with two nolee of 1,2-epmpropene
(eve yielde which vere of the em order as those obtained for the
reaction of the elicit-emolu- iodide with 1,2-epompropeno. Four or
the diorgenenegneeiun omponnde (ethyl , nopropyl , ieopropyl , and phenyl)

when reacted with two mole: of 1,2 . ~« ‘ ene geve lerger yielded:

 

the emoted doable then did the organomameeim iodidee upon stand-
in; for periode of time up to double the tine mum to? the tut
with liehler'e ketom to beoone negative. on the other head three of
the diormneeinn coupounde (netm , n-butyl , e-bntyl) than reacted
with two nolee et 1,2«pomr0pmo gnu lower yields of the expected
alcohole then did the corresponding alkylnagneeinm indidee. there is
me tale for ”quoting this lowered yielduat lent in the due or
the Mauritania-aim mm; (1:6) has done to the conclusion
that dinethylnegneeim ie lees reactive toward carbonyl gmpe than
”Wain iodidee . The reaction of dinormlmpylnegnoeim with

_ two lolee of l,2~epoxypropene sinned the greatest inoreaso in doohol

53

yield on standing (tree 12% at nix hours to 33% it. 12 hum) , but a
ainilar reaction allowed to run for 214 hours more only e 385 yield of
alcohol. It appears from this fact that there one very little reaction
occurring (hiring the period Iron 12 to 22; more.

From the data dimeeed above one can at leaet drew the oonclueionc. .
that in the reaction of orgenonegneeime iodidee with l ,2-epcxypropene
the first reaction (fact) in to give the iodotodrin intermediate. This
reaction is acocmanied by little if any precipitation of solid material.

[CU-7:30): 0 9((3333):
magi + mach-‘03. ———+ my 4. 003321.),
be j 00
( one): 03,01!“be ;( 1336)::
mwgwm
' Ho

‘5 (0 one) a
(.1) (soluble)

The intemodiate (A) is somewhat unstable and will decompose on
standing. Tho rate of its decomposition is much greater at high:-
temporatm. The products of its Weition may he acetone, unpopfl
alcohol, propylene oxide , or unsaturated . “than a eccond min of tin
epcxidc is preeont the clamor reaction to give the alcohol intermediate
will occur in appreciable mounts and a thick white precipitate is
famed during tho course of the reaction.

51:

“Gene“ ‘P‘ceEh
Mme; . among—sawing § 0(cfi).
a a
0(02H5)2 Cflfimn.
mmwmg-o-cmng
ca, d3,
(imluhle)

It ie intending to note thet it we neoeeeery to hue the new Iole
er epoxide preeent in order to get an: eppteoieble count of the eloohole
and thet only in the reaction 0: orpncnegneeinn iodidee with two nolee
of 1,2a-epowopene did a heavy precipitate eppecr. It ie eleo note-
worth that in the reaction or diormonuneeim with two nolee of
l ,2oepoaqpropene e white precipitate gradually appeared , which continued
to increaee even after e negetive flichler'e ketone teet woe ohteined.
Figure 11 ie e eeriee of graphs ehowing how the yielde of l-iodoa-R»
propenol end the alcohole very with tine. Since only four pointe were
eveilehle theee grephe on: do no more than give en indioetion of the
overall rete of increeee of the elcohol yield and deoreeee in iOdo-u
mm yield. In more]. 1|er, icopropyl, and e-bntyl ehow ehout the
use type of curve for rate of production of the eloohole while all the
reet are eclewhet dike. In ell ceeee there ie e tendency for the reto
of production of the elcohcle to level of! otter 18 honre or leee.
The mph or iodolvdrin yielde ehowe that in general ethyl end n-propyl
prohehly torn lore metehle intemediatee than the rest, for they do

55

not level oft otter ehont three hoot-e no the not de. m of the other
some are eeeentielly eililer otter three heure eltbugh the initiel
rote of deooepoeition of iodohadrin intemediete varies .

the reaction of mania iodide with 1,2-epomropene could,
theoretical: et lent , produce 1-ioGou-2vpropenol or 2-iodo-l-peopenel
or e mixture or the tee . Both Zaiodoal-propmel end laiodo-z-propenol
have ohereoterietio eheorption own in the infrared epeotm. the
primary eloehol cine en eheorption peek at about 980 a.“ while the
meadow doohol given on eheorption peek at ehout 935 om“. Free
the relative heighte o! eeeh of then peela th peroentege of eeeh o:
the imerio helolvdrine preeent in a mixture could he detenined “6).
Free on eel-inetion of the infrared ebeorption epeotm e: e pure «mole
of the product obtained from: the rotation of negneeim iodide with too
melee of l,2~epo:qpropene it see detemined by seem or the nethod cited
above thet et leoet 905 of the iodohydrin wee preeont ee l-iodo~2-
propenol, and noted]; the value was probably closer to 1005 (on
Figure III) .

The plveioel proportion; were detox-mind end it one found that there
me me dismount with the values listed in th literature. Both
the refractive index end the density found were higher than thoee
reported by sum and Yuan-war: (eoe Enmmmu, xv-o) .

An ettenpt me made to prepere the 3,5—dinitrobeneoate of the
1-W2~W1 but the only product ohteined iron the reaction or
J meeneoyl chloride nth leiodo~2~propenol no the 3 ,S—dimm-
beheoete of homered-propane]. . It it believed that halogen interehenge

56

occurred during the reaction or the eeid chloride with the iodohydrin.
Binoe the ulting point: ct the two derivetivee ere eeeentielly the
are, one emot nee tide oriterion to differentiete between then. The
work doee, hoeewr, tend to indicate that the iodine ie in the l-poeition
of the helohdrin.

The precipitate preeent in the reaction of crmemmeeim iodidee
with too echo of 13-me hoe been mlyeed (see table VII)
for ell ceeee emept the reecticn of nuhntylnemeeim iodide eith too
nice ot 1,2-epomr0pene which set to a gel that :1th other eo
tmoiooely flat the precipitate began to decompoee hetero all the other
could he removed.

The reeulte of the enelmeee ecu to indicate that the tomole of
the precipitate ie probebly (A) . in ie, or own, poeeible that no
ectoel epeoiee preeent could take mend fem (B, c, D) and en: one
or on of theec night he preeent.

o o
max-203.6%. Ems-O-QPEHJ 303.6%]: normqmw-cmw
:' on. i on; én.
,0\ p. /9 ,
mama, anaemia,

(A) (B) (C) (D)

,0 0
(new cmcrhna + 14313.2 03.61333.)
(E)
Moreover, wt of the precipitate night he the result of the epoxide

meeting with the other two epeoiee preeent in the Schlenk equilibriu (E).
However, einoe the reaction of l ,R-epomropone with neweim iodide

57

(nightly eolehle in ether) gives a demo precipitate and the reaction
of “Walt: We with one sole or epondde 1e tut end given
no preelpltete, one mld probably be ehle to etete thtt root or the
pneipatete in in the for: of (D) or peeelhly (B).

It to interesting that a recalculation or the theoretical molecular
weight at the preeipltate in em cam shoe 3 better emu-lean or
the calculated percentage of 38de end iodine with that actually
rm. This recalculation 1e based m the rm that to em Mann!
reagents m titreted am (3“) ”mung. 1. much 1.» then the
utmted iodine percentage and therefore em or the iodine not to
present ee newline iodide (1n emee of that produced by memo of the
Schlenk equilihrlm) metered ot armament: mam. . Accordingly,
it no eon-ed {or the eehntwlnemeeim iodide, for temple, that county
meat of the iodine wee preeent as e-butyhaghealm iodide (ellql found
was 68-75%) end the other thirty meat or the iodine wee preeent to
mania: iodide. rm- Iem thet fifteeu pemnt of one hole or (F)
and emnty percent of one ale of (a) looulo he meldered to he
preterit tn the preoipltete .

Mala-2 63:93:11: 8~°¢Ha~flslo2 “kW“:
0’ o
(F) (a)

In the one of the precipitate from the reaction of ethylnegnulm
iodide with two Iolee or l,2~epomropane the poor agreement or the
meta analyele (9.67%) with m odouleted (8.22;) m not exploitable.

58

m repeated onelyeeo for magnolia for this preoipitete son the em
mute. In metal it w felt that a: the two enalyeee pertomd
(up-sin end iodine) the nonunion Wee were the loot eoemte
einoe the manor percentage of meme malted in a greater eeneiu
tldty.

matuuptmudo tornnamehflmeon thereaction or
owl-enema iodide with 1,2-0Wano. lthe malt-e of the re-
ootion oi' n-propylnagne ciun iodide with one mole of 'epoxide are listed
in Table VIII. about 97% of the reacting material: were recovered with
31% being definitely identified and the remaining 1633 being qualitatively
identified (nos Table VIII). It 13 evident rm the remlte indicated
in the table that most of the n-vpropyl residue is Wood to give propane
during lvdrolyeis. Also much of tho iodino is lost to the nogneoim
salts during hydrolysis.

The reaction of Miameoium iodide with two moles of epofide
was also etodied and the results or the mo: balance are given in Tobie IX.
Kore only 88% of the reacting materiale were recovered with 67% being
definitely identified and the ramming 21% being qualitatively identic-
tied (eee Table 110. It ie evident that a mall portion or the iodine
in lost to the nemeeim colts end that about 203 of the epoxide ie on.
mooted. It in eleo apparent thet iodine in not limited to the zomtion
of leiodo-a-pmpmol einco traces of iodine could he found in most of
the Irwtim.

Pweical constants and derivatives of the alcohols produced in the

react-ion of. Wenonah iodides with 1,2.epoxypropane were deter-ind

59

and are listed in Tables I md XI. Thom amen-s to be one arm: in
reporting the melting point or the 3,5~din1trobomate of h—Iethyl-z-
hannol in earlier studies (25,26) of the reaction or err-annulment
halides with 1,2-0poxypr0pana . Tho nolting point or 50-51% . obtainod
for the 3 ,S-dinitrobomoate of tho Methyl-antenna}. from the reaction
of a-butylmgnoeiun iodide with l ,zwaponqpmpm cheeks with tho value
reported in the literatm'e (110) for this derivative .

WAR!

1. It has been show: that oxygen probably has little effect on the
course of the reaotion of «31-3me iodides with 1,2-opowopano.

2. In order to get reproducible ”cults in the reaction of ergono-
mnuim iodidu with 1 ,provpropm it no found necessary to oontrol
tho reaction condition carefully with reopeot to temperature , reaction
time , and curring.

3. It was found that refluxing the roaotio‘n mixture containing an
ammonia iodide and l ,2-opoowpropano gave no approoioblo increase
in the yield of the alcohol and that the yield of him-propane}. was
many reduced .

h. The results presented slow that in the reaction of orgamagnooim
iodide: with 11.2-3me the reaction at the crammmaim bond
in slow and tint on initial fast reaction takes place at tho magnesia-
iodine bond.

5. Won orgmogoooiuo iodides are oausod to react with two min
or 1,2nopoquropaoo the yields of both the aloohol and loiodouaopropmol

are increased.

6. The plasma pmrtieo of luiodo~2~propanol have been dotominod
and the ot-naphthyl urethane has boon prepared .

7. man:- of the prooipitato want before hydrolysis in the
rmtion or orxmmsim iodides with tan mloa oi l ,mem
indium: thot tho prooipitato probably has a. formula corresponding to
‘ ratio of one mole of 01‘de mum. to tvo moles of 1,2aopoxy—

pm.

8. Han hams um detornimd for tho nation of n-propylo
magnum iodido with both one and taro moles of Lemma.

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63

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H

M7HWflifilfijfllnfilflfliflfflfijflfluflm(Iii/Tn]?ES

460