Table Of ContentBEACTIGN3 OF K-^BROMOAMB)BB WISH GLEFI1©
by
Hobart C^^olmsoa
A thesis submitted in partial fulfillm ent of the require-
meats for the degree of Doctor of Philosophy,
in the Department of Chemistry in
the Graduate College of the
State University of Iowa
August 1950
ProQuest Number: 10666174
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T
T u % \
Q- o p . Su
This Investigation was carried out under the
guidance of Dr* Boberfc B* Buckles. The author wishes to
express his deep appreciation and thanks to- Dr. Buckles
fo r his constant in terest and assistance throughout th is
work*
f
u
i i
table of coHTsaras
Page
PURPOSE OF TBS RESEARCH . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
INTRODUCTION .................... 2
DISCUSSION....................................................................................... 20
DPffllMSWAll 48
preparation of Mromo&eetamid© 48
Preparation of H-Bromoeuccinimi&e ****#»#»«»»» 49
Preparation of B~M©thyl-S-hencene ............. 49
Preparation of Sf3^Bitromo^£»jaetB3rlli©xane »,»» 49
Preparation of 1,5-M phenyl-l-propanol »»*«*»• 50
Preparation of 1,3-M pheayl-l-propone «h m m . 51
Preparation of l*S-M ph#nyl-l-propen© Dibro-
mite * * »,«**»«»» *v♦**«*•*#«**«« 52
React ion of N~Br ozao&o ebami&e with Isobutylene* 5 3
Reaction of H-Bromosuecinlmi&e with Xsobutyl-
ene 53
Reaction of il^Rromoaeetami&e w ith Cyclohexene* 54
Reaction of H-Bromoaucoinimide w ith Cyelobex-
©ne .»•««»•*«***',«»•**#«**»«****» 55
Reaction of M-Bromoao©tamide w ith 2-Methy1-
E-hc-xene * * ***«,«* * *«»*«* * * * *« * 56
Reaction Of N-Bromosuocinimide w ith
S-Methyl-S-hexene 57
preparation of N-Bromodlaoetiztd.de ****»*♦**«., 58
Reaction of H^Bromodiacetimide w ith
\ S-Methyl-£-hexane «»**# #*** • f .* 61
Reaction of M%romoaoctEmid© w ith l f3-Di-
phonyl-l-propene »•««••**#*•*»• BE
Reaction of N-Br ctnosuc c inimi&e w ith
1 ,5-Diphenyl-1-propene **««„<,** BE
Q uantitative Study of the Reaction of
N-Bromoaoetaxalde w ith Styrene « 63
Reaction of N-Bromoacotamide w ith
Styrene «*.»,**««* *♦* * * *«*«a«0«* 63
Determ ination of Halogen in the W ater-
soluble Products «»*«+ *• *9 • *«** 64
Determination of Halogen in the carbon.
Tetrachloride Residue 9«»0»* 0», 64
i l l
Pag©
Determ ination of Witrogon in the water-*
soluble Products .* »«**.«,* .«*<*.«» 66
Determ ination of nitrogen in tiie Carbon
fetraefeXorXd© Residue ♦*****»» 66
Reaction of XsopropenyX Acetate and
Acetamlde 67
sxm m m «*«*#**«*#«••»««#**«*»<*««»*»»<»#»»»'***«♦ to
BXBWOOHAPOT ................... ?a
iv
fABLS OF TABLES
Page
/
fable of H^pomoauoolalmiAe 17
fable XX.** Analyst® for Bromine ant Hitro$@& •■***# 41
T
1
FUBP0S! Of' fBS KBB3SAHOH
ham been observed to react w ith
olefins in two ch aracteristic manners# Both N-bromoaeet-
amide and H-bramoaucei nimide are known to give dibromides
w ith certain olefins hut, in general* the la tte r compound
brominates In the a lly lic position of an o lefin and
leaves the double bond unchanged#
The purpose of th is work was to compare these
reactions of W-bromoamides by experimenting w ith o lefin ic
compounds th at were stru ctu rally capable of undergoing
f
both addition and su b stitu tio n reactions and observing
the type of reaction which took place w ith various
N-bromoamides under certain conditions#
In th© reactions of N-bromoacetamide, d iffic u lty
has been encountered In iso latin g the reaction products
derived from the aoetaml&yl portion of the reagent* both
as a q u alitativ e and quantitative reaction# A q u an titat
ive study of the fate of the nitrogen and bromine com
pounds has been carried out in an e ffo rt to shed some
lig h t on th is phase of th© reaction*
B
iwmomoTioM
In the la tte r p art of the nineteenth century,
A*W« Bofman, (1 ) and several others reported the prepare
a t Ion of M:*$iaXog@n derivatives of several amides* How*
ever* they were for the moat p art in terested in the
preparation of these compounds and I t wasnH u n til some
years la te r th a t the chemical reactions of th is type of
compound became of primary in terest* Most of the work
th a t has been don© on N~haloamide© has taken place in
the la s t eleven year© and workers are s t i l l finding an
ever increasing number of applications fo r th is type of
reagent#
Mial©amides have been found to be very good
sources of halogen, both fo r halogenation a t saturated
carbon atoms and addition to unsaturated system s. In
contrast to the well-known addition of halogen to the
oarbon-earbon double bond, i t vj&s only in 1919 th at
Wohl (&) reported on the introduction of a halogen in
the a lly lio position of an olefin# Wohl treated a series
of compounds w ith B-bromoacetamid,e during the course of
an investigation of the mechanism of su b stitu tio n reac
tions and came up w ith an unusual use for th a t reagent*
He reported th a t, w ith the compounds he used, the reaction
was mainly tfc# su b stitu tio n of' bromine for hydrogen#
Some of hi® resu lts are shown below (a*bfc)* fetraraethyl-
ethylene (a) gave th© monbromo o le fin ; no hydrogen bromide
was detected.# fh© reaction of trlm ethylethylene (b) gave
a) {01s}g0«0 (G%)g + A cIB r ^{0% )sC«C-CHsBr
GHg
b) (GH5}eO<5H*G% + AcKHBr-* 0 5B ^ rB
e) ca^-l-OHgOOgCgHg + Acffiffir-------------=»CH3 o & u
a compound of em pirical formula Q$Lg$r% wMoh had some of
the ch aracteristics of an'olefin# Wo rrsonobromo compound
was isolated and only a trace of hydrogen bromide was
observed* wohl reported mainly su b stitu tio n reactions
w ith several other olefins | in some eases a dibromo com
pound was formed but the double bond was always unchanged*
However, the reaction of styrene with N-bromoacetamide
was one of addition to give styrene dibromMe although
no yield or description of the product was reported; no
monobromo styrene was found among the products*
More recent work by Buckles (3) has shown th at
B-bromoaoetumi.de reacts w ith several unsatur&ted com
pounds to form appreciable amounts of the dibromides* At
the time* the general use of N~hal©amides as the sole source
of halogen in addition reactions w ith olefins had not been
4
previously reported as tin© main reaction* In generals,
the l^temoaoetamili© was added to a chloroform or carton
tetrach lo rid e so lu tio n of the o lefin and th is mirfcur© was
heated and/or illum inated w ith u ltra v io le t lig h t. This
author observed th at the reaction was catalysed by heat
and lig h t and th a t there was in the reaction a short in
duction period (especially w ith styrene) followed by a
vigorous reaction In some cases*. So* the reaction of
ethyl einnamat©* cinnamic acid* otilbene, tolan and sty
rene w ith H^bromoacetamid© to form the respective dibrom
ides brings fo rth a second im portant type of reaction
which I^bromoacetamide w ill undergo*
The addition of bromine to these olefins is
believed to take place through free radical interm ediates
which would explain th© effect of u ltra v io le t lig h t on
the reaction* I t is postulated th at N-bromoac e tamide w ill
form a bromine atom which w ill attack the double bond to
AoMBt 4* hr AoMi* + Br«
^G«C^ 4* Br» -------
Br
✓2***9s ^ AeHBBr ---------------------+ AcKH*
Br Br Br
form a free radical* Then N~bromoacetamid © w ill attack
the free radical to form the dibromide of the olefin*
