Ra‘—
.
a . a. .
9.. \ 0.1 .m
.Q o . .04.
1.... . ‘
An.» 4» x.
.3...” r‘.’ .
u 2..
... ~ . _
I u. .3 L: We.» 6 «m .
t w. r a: r . .MJ
. .«p .. ... ... a _
z : .. . .. c
«\m “at . 5 Pk.“ an
t... - .. 4 ‘4...

r ‘ .

O

“'..“
.\..‘.;
0“. .
V“‘ "t e:
.-
‘

. ._ w. a. 9.. rm...”

fig '1
p
i-
. "t
3
ml
q

rIu-H . &- tin—s 1..» A”)

v v I .M‘ ., I. V; .
:2“ . q . a . 6. .81 . 4' .
n ‘. . ¢ ”1‘“ . “¢
.u w .... . a .
a. u no A v Iy\.. H.‘.‘ a
. u , . 3 H .e. .
uh I— .)‘c‘. a ...-- O I'Wwa SO~M~
I 9~ I o g. .. It.
. . fl 7-» v.‘ a \
a N n g I». a » A. 6 u
H ‘ . 1.5- . g a“.
.‘ sf. 0‘ 5 '31& J 0.. ’u?‘
n :6. a" F .u a ‘
F u m... .. . . . N
x , as: .. ... .o 5
CW iv. - . Sub .
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a! o I,
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i
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51:35,E _f___:__:_,:_é__,__._

 

 

 

LIBRARY

Michigan State
University

 

PROPERTY OF

MICHiGAN spars: urmzmw

DICZEORGKALEIO mmms AS A am FOR TEE
DETTRIHATION OF 603:?me 21mm

33

Janet Bradford Van Dom

A THESIS

subdued to the Con-go of am. at! Art.
Wm Stat. University or Agricultnn and
Appliad 361m. in W W‘ of
the W for the deer“ of

EASTER 0330mm

Wt of Chemistry

={»/%V” - i

(I;
i
x

Ammammn

Thomflwrweltothanknr. K. G. 3mm-
hil gum. md ”ultimo throughmt this We
mum. Dr. Stone'- helpthl “amnion- and whole-

heartod cooperation-woof putvalnomoowloung
the project.

EICE‘L RELALEIC £32me A3 A B." ”BET ma TEE
EE’i’fifiIfi'iA'I‘ION CI? CWIJU‘GATTSD DIGILIFIE‘IS

3.?

Janet Bradford Van Dorm

NABSTRAC'!

Submitted to thc Colleg- or Guiana. and Arts

mmmummwotmmm

AppndSoimompnmhMMot
mwmmmu

MASTm OF semica
W or W

Year 1356

The use of dichloromlaie admirida as I. replacement for chloro-
mldo We in tin mutant“ detendmtion of conjugated
dial-fins m mmgam. The proposed matiwd is based on the
Dion-Alder rsaotion a! dichlommlaio afiwdzide with only the conjugated
olefin, own in tin We at other “taunted and unsaturated hydro-
ou‘banl. cum» on the akinct u that converted to ciaondo by
naming 1n diver. nitrate collation. The chloride» in dammed by the
Yolhud method. Chlorine on the meted mivdrido 3mm! not in
round by m- procacmo.

Bunk: indicate dichloromlaio unmade react: with mono
oonjuptoddiolofim: homer, themetimfldnotappoartoboqumu-n
can“ for ch. mm Mod. Both Volhard and unmet-rig determin-
mon of amends m refluxing tho purified mint 0: 2,3-dimatimo
1.3411th in film min-nu Minuet: indicated only on. o: (in tun
mum. chlorine atom 'IBI removed by reflmdna. Racavory of chlorine
In mm gmfitatiw nox- minim“

Starla tundra. Ind mm" 61'th of tho 0221011!» “on. of
the dichloromlaio mbydrido mm m mania-d. Tho addition of
the mad Wanamaker. Wommbmiorotdichlom-
Mama-“Whammy“ Wanda. Itilmlnfiad
mutual-11mm Wnumtummhrepmmrorcblmo
tilde Md. 1:: this type of amines.

11

231?: '2? 3322"”; EETB
kw

unnafisanIa
nuns» U4» Uncoocoooocoocooooooooo00000000000000000000000000.0000.

. m m- i i ‘
A~r-31nooooOCOOOOQOOOQOOQOQOOOCQtOD oqoao-ooogoccuou con-coo

Preparation 0: moocoaoouvuounoooooo¢oo¢né¢oc000voooooo
Purification 0f Dichlorommlaic Afihydr1d0¢0.0.9.0000.00000000
1'18th of Cthfld-i Dmmuononooooaoocooooooouoocoatin-
Reanlts “1th 2,3~Eim0thyipl,3!ButflfiiflnlAldduct..........gg.o

S Saar r P

DISCUSSIOKOOOCOOOOOOCCOOOOOO.0....O...60.000.00.00.OOOOCOOOOOOOOO

'0
U1

mwm ‘
Ji G 0.00....9...!0......OOOOI...COOCCOCOOD00.00.000.000...

6*

LITEFATJPE 0mg.o-oooooooooc00.00.000.000.coo-.ooncuooooccoouoo 2

3

‘PPEgDIKIOI0.0.0.00.00.00000...OIOOOOQCOOOOI.0.0.0.00000000000IOO

MFH‘E

Emmwcr‘zcz‘:

The Dials-«mar reaction offers a aligns mtimd far qamtitatively
6.3th oom’ugatad diolei‘ *6 -. 51:13:: the reaction 13 specific for
conjugated ayatans, it is pasaibla to analyze for the canfigated
define in the presence of both mturatsd am! minimized byfiocaz’oom.
numerous analytical asthma have been ciwalnpad using both 3211810 and
ciflnromleio mntdda as tins dimptila.

lialaio ammirido was first utmzed for the estimation of. momma
by Bassett and wmxm (1) in 1332. Ai‘ter alum rial-«31¢ min-dude
to react with the mph at 100°C, the gain in “Eight or tha crystalline
m’rwdride wanted the amt o: 1509mm Went.

Birch and Scott (2) utilised tho name reaction for the identifi-
ation of warm“ 333011213 fmtiom . In this mama's tbs uniting
point! of the crystallim adducha with mlaia an‘mh‘ida identified the
"rims 63.019me present.

Amtim variation at the name mastitis Ian developed by Trapwh
Ind Ratio: (8) for tho dettmafination cf but-am“ in 38938. A W
”mammmmmmwumlmmmmmde. mo
Ian at minim duo to tbmrption a! the butaiiom by mlaia anhydride
than indicated the mat of dim pram 1n the sample.

mm, moan and Hall (7) developed n method in which ehlcmmleic
“Md. in: and u the awn-ma 1n the Dislu—Alder reaction.
81m. tho chloro group of tho uddnct 10 attached to I tertiary when,

itupoadblctormothomumxidobydmhnfmxing
with um" um. Th9 $10313» in the means amoromidn Inimh'me
in the reaction mxmz'a, homer, in a wiry]. chlorine: tin-atom, silver
nitrate“ nttuttnkthtmmgmt. flan quantityorailver
nitrate W rape-unto thqémtotdiohfinm.
mun-maguhmmrmamammmnm
mormimmmmmmmmmua, m;-
momumtmmwmmmwmrm.
Iii-avenues. are:

(DWWlnbydridoha-gmtingpom at

32-3k°c; slight iapuritiec man the amen-151 to 11m.-

(2) Purification 1- (Efficult‘, rewiring 73mm distillation

and yields are low.
(3) Th. prom in “any Inflated; tharafora, it m be handled
'undornitmgeaorcarbondmcnmdmmdinomed
W9.

(a) sun mat: a: ckfiamnleia acid ammo polymerization

of the «malaria.

Diohhrmloio cigar-ids is a likely alternative reagent for a
quantitativ- Dim-nder rmtian with conjugated diolofim. This
mmmmumpoanbmtiuuehlmmleiommide,but
has additional W.

(1) Worm-Jain anhydrida is a W cow melting

in n7-1zo°o.

(2) muse of diamomleie acid are easily reamed bur
minimum, recovering tho mwnda from the acid.
(3) ho amoun- atmu W be «m1. for titratim, thus
increasing tho Imitiflty h: the method.
The pan-pose or this investigation ma, therefore, to stab» the
m or diohlormaleio avarice) u I mag-gent for the cgmntitative
damnation of omjugated elm and dmlap a method utilizing this
meant for tha dmmtim or butadime am related WWI.

The course of this ctufiy wan directod at times main objectives.

(1) Eco: dichloronulaic arfivdrido undergo a Dials-Alder reaction
with the common conjugated olefina?

(2) In the reaction with dichloromloio azibyc’rida q‘outitativc,
or can the reaction be Jada quntitafiive?

(3) what conditions are necessary for tho quantitative removal of
chlorine from the admict without affecting the chlorine of the
mounted minorido? .

In order to mentor those questions a series of coxzxpmmds was
synthesized using diobloromaleic anhydrido on tho dionophilo for
motion with various dionoc. The most mitablc of thooo adduoto was
than prepared in quantity and used for the systematic study or conditions
necessary for couplets removal of chlorine from the adduct.

Wondidducts
m_mmm(k)nomtmuwtmumm

mum with W mbydrido. my comma mutt»
nmummmmummmmuowm
mod together at 170%. More notably, Clifford a: 61m (3) formed
«mm o: nobleman-1o crumb-id. Ilth botadim, walnut-dim,
dimlopmtodim, gig-pipwylono, Mum—hm” and dipwtono.
Inmhomfliqu'dbmmuthllolmwporwwo

nation annual." ct Boo-WOW”... Reaction

immune: varied from room tombwo for ofilopontodiooo to 210°C
for butadimm.

In view or on; previous ooziz, no solvent woo nood in tho prop-
ration of the (2:15- ‘Joroz-nal-sio an? 3231:: addicts: and tho roomtion

amino was varied from 133-3003.

 

Furoio Acid Minot: Cno grain of fluoic acid (Summon, Sol. '
and Ball) and 1.3 goo-sis of dichlommloio mtzyz‘iflda (Z-Jomaoo {311.92%
Alkali) We onion“? taga't‘nor in a presto-two bottle. Tho toizpomtura was
mind to lmrm": em nminioflnod trim for 30 wanton. in tho coin-
non cooled, oryatnlliaation occurred at 130%. The mochct m
Wood first from dry other am} that afiin from carton intran-
We. 1-231ng point a: the piano: :1:an was 29—13%.

Ranting 0. am worms in an oven at 135°C :02.- 3 hours, than
15 mm at "5°C yielded no promot.

Limo-gimp?!» ctiono mm Swen ml. of gamma-2,1;-
hmtiono (1-30;me signer) of: 1C mm: or condo diohlomoolaio
umydrido m hoatod together in o W bottle. The tmpomtnro
”vafiommmmthmmrmmm. Adorkmd
liquid as obtained that orgmtmizod upon coolim. The W W
Wood from carbon tranchbrido. 1'21. first crop of mania
obtained V had I. nolting point of 100-11000. After Moor 6:31th
motion crystals air-o obtained that had a melting point or ammziu
natal? 75°C.

finco it appeared like}: that oolvmt me still present in both
any: of Wt, ‘32: Meta mo dried at room tormoratnro under

m {or 3 hour... The waiting point of the tint crop of cry-toll
on and a 122.12%. The second crop of crystal. mu malted a.
5‘6.

Km and m (6) round that 2,5-dimthy1-2,h-huodiono «no not
for. . nomi Diolooildor .ddu'ct with mom anhydrido, but yioldod
only an mrphoua high melting product. rm and Warren (5') round
tho am to ho true or other olefin: which had doubly substituted
terminal whom. Therefore, it is pooaiblo that the material isolated
from tho "action with diohloromloio onhydrido is o polymr of com
nor-t, than accounting for the inoonlittont melting pointo.

2,5-Dimttv1 Fur-n Adduotc Ono ll. of 2,5-dinotkv1 Man (En-tun-
Ihito label) cod 2 mm. and. diohloronoloio uuvdrido mo booted
topthor in o prawn bottlo. At 120°C «tannin Vaporiaation Occurred.
Routing «a oontirmod to 160% mm tho upon oondmod onto the
an. o: the bottlo. After 10 mm at 160°o o black 011 m obtoinod
Union In rudily oolnblo in other; Lita convict. evaporation of tho
othu,odarkoflrminodthatdidmtoryotnmuwmortorpro-
longed owning.

Improno mounts Three :1. o: iooprono (known-Pom). 5 arm
or and. diohloromloio momma. and h dropl or p—(t-hummmi '
no hated tagothor in o prawn bottlo. m teapot-stun nu rained
tolBO°Conduintoinodthmtorls mm. Thodorkoilyproduot
obtain-d In roomtdliood tron 11min (60-90%) after Ittnding
overnight. Editing point no lab-125°C.

a,3-nmw1-1,3-mud1m Adductt m1" :1. of 2,3-dimothyl-
1J-hntodim (Web-nor) and 16 gnu of crud. diohloromloio

Mo wot-o hootod toasthor in o pressure bottle. Tho tow-oratm
no mud to 150-1660 and maintained there for is minutes. A m
timid no obtomod that omtollizod coagulate]: on it cooled. Tho
product was remained from 11min (&3—90°o). m off-white pom
as obtained Ifi’doh maltod at loo-135°C.

{urigggtéon oflifllorgfigoig Axfirljmjg

Putnam, Hose and 21.211 (7) ram: that small amounts of acid impuri-
tioo in ohbroMloio antigmiv‘ido catalyzed polynorisation of diolefino ,
111mm: Iimiflmt more into their method. Some trace of d1“-
ooommuo acid on “8;,th to bo prooont in tho dioi‘zloromloio
“hydrido obtoinod from Hootvooo Color-Alkali. Therefore, too oethodo
of pnrifiootion mo attempted.

Roogont pod. carbon tetrachloride was booted to boiling, than
Durand with crude dimHloromloio onm'drido . um tho oolution had
otood W, largo Moo crystallised out. Tho cryotalo voro
tuba tiltorod m1 named with carbon tetrachloride. when o muting
pom loo «mm, the notoriol loot oolvont ot 100°C and than aub-
linod commonly.

Sinoo diohloromloio ooid io know to loco mater upon mhlimtion
to (or: diohloromoloio onfixydrida‘, the orndo material was mblimoo
noon mod prooom'o ot anomaly 115°C. Pure unite plotoo taro
obtoinod mm halted ot n7-120°c .

Both tho mo and rmblinod diohloromoloio mfiydrido varo
titrotod with on oqooouo oolntion or potaooiim moxido using phmol-
phtholoin indicator. Tho erode material uoasrod 99.01 percent

diohloromlelo mkwdrida. Tho romblimad Mot. (”raged 99 .19 pm
sent diohloromloio mummido. (Complete data in Alma-mu.) In both
me! tho neutralization oquivalmt was 83.3} than theoretical noutrol-
intion ogfivalwt for dichlommloio We 13 83.5. for dichlnroc
maleia acid 92.5.

Sublimation ital adapted n 9213 SW mined of purification of
dichlommlmo We. mammmonn-upu,mauo
are high yield- ot para dicnlmnloio anhydrido.

Methods of Chloride Eotarmimtion

Putnam, Ham and Hall‘- nathod utilisu tho Vol'nard procedure to
dot-amino the quantity of silver consumed by tho chlorido present.
In their mthod a moamred cocoon of 311m aunt. in refluxed with
the reaction mixture, than the moon silver nitrate in back titrated
with potasalnm thiocyamta using ferric ulna u the indicator. In this
cm 1.110 mm we used in an attempt to wtitativoly W. the
ohlorim from the adduct. The: ma (1) refluxing in 006.1111: M.-
carbomte colution, and (2) reflmdng 1n luv” nitrate solution.

Sodium Bicarbonate (0.533): A1: mmw 0.51! solution or
Indium him“ an pupal-odor dissolving M gram of sodium
bicarbonate 1n 1 lit-car of distillad mter.

Silver Nitrate (0.23): am hundred unity grams of reagent. grade
mum nitrite var. dissolved in 3.5 Elton a: distilled voter.

' Petunia: Thing-unto (6.2m): rut-y eight grams of magmt we

potassium thiccyfinato were dissolved-11:6 liters of distilled water.

Ferric Alma Ixfllcator: Ono ranked emu-3y rive mm of ream

grado ionic amoniwa mxlfzi‘oe-r‘Mecahw:at-o mm disaolrod in a mixture
1’ 3450 ml. water and 5'0 ml. commtramd nitric: acid.

The silver Mira-ta and potassium t: docmuto solu‘dons mro 1'th
(towered to each other and firm the silver nitrato sciatica ma
”anaemia-ad with x‘zaagan‘t grade sac-limo ailerida.

I?) the ”dim bicarbomita method, £32111 83.“le of; adimct were
first dissolved in (110mm, than varying 32mm“ of 0. 57:! sodium bicarbonatc
Iolution vars W. “he ooh-him Hora heated to hem and held just
balm! the boiling point for l to 2 hours. anew cooling to room
Marmara, the aolutions wore acidified with nitric acid. and a Imam
excess 6 silver nitrate solution added. The silver chloride was!
allowed to cattle, than was filtered from: the solution. Tho roaming
silver in Iolnti-on uaa titratod with potassinzn thiocg'amto using ferric
3.11m cha‘bor.

In tho alive? nitrate mailed, 89.352138 of addwt warm dissolved in ‘
acetone. A known cocoa: of silver moms solution and varying mount:
otm’oormnddod, thathoulnflmmdflnrnflnodtara
Mawuflufir-mmnurumumo
that Ian by mum. After cooling, tho precipitated silver
Mommtondtmthammtimugthomluummmdiflod
umumwmmmmmmmmmw
titration dth W Wm“.

Results with 2 ”oEmMEWI-v ~§atafii one midget

The edchxct of 2,3—dimetlv1-lfiobutmliono Idth dichloromloio
anhydrido a. round to be neat mum. for We: may. T‘nil adduct
mWfideldhrmyaWtoyicldap-odmtot
good parity. In addition, the ndduet had 1: relatively high mung
point. 31m 2,3-d1mawm.3-bumdim u . liquid (bomng point 70%),
ittoooouldboueighadumutelytormymrkbogimingdththil
compound. .

Tho mm}. Dials-Alder reaction of didmloromloio anhydrido with
. 2,3-dBwflwlol,3-butadimo am yield 1,6-d1eh1oro-2,s.d1hydro-3.h-
mum. mum mam-1d. (I).

   

c3, 01 o (:1 o
// \ ll 03%| //
nae—o o— \ ch—c/ c—o
nae-c cq-c not \ c—c
\\ / \\ 9311' \\
or, c1 0 o

I

in WI for carbon, lydrogm and chlorine and the mtnliaation
miralmt of the reaction promct of dichloromloio “world. and
2,3-dimotm'l-lJ-butadiano Hm obtained. Table I ohm analytical
"cult- t'or the adduct.

The mtrdiution «walnut indicate! tho Adda“ 11 the mcpoctod
maria-3 hot-var, tho mm nullylil chock- uith the percentage:
WUthomrvdridombydrolrndtoitlcoid. Simothoatart-
ins mural In over 99 percent dichlomlaio mhydrido and this

um I
comm norms m mausm or 2,3.om1g-oormms Ammo:

Results Wis Thom-ct. moor-rt.

 

W0 told
lontroliootioa Equivalent 12h 121:3 133.5
Elmtcl mum
' Carbon 5.0050 h3.2.‘3 345.0%
Rydrogcn 15.56254 14.1.93 b.5315

A... —_..4. _ _. _-—_ _‘_._._—_‘-— *‘AA—

'myuo by Him-“root: loborstorios, 81:01:10, 11113101..

reaction occurred moor snhwdrms condition, it my be warned that
mommtobtunodmmuwmdo. Thomllsoomlouscdtortétc
olmtsl analysis could hnvo om hydrolysed in tho stinocphcro axon it
on W and shipped for may—m. Tho product unto in all aperi-
mtaimmovandriedmdkepttnodeaimtor. _
ran 2,3-dilnot‘vl-l,3-butodiono contact as first booted in sodimn
bicarbonate solution in on attempt to remove tho chlorine from tho
mt. aonlts of pram Wt; ore given in ram. :1.

In sll cues tho perccutcgo recovery mo low. Some correlation io
awn-ant between tho may. concentration of bicarbonate and the
porccntogo recovery in that the higher too ratio or bicarbonate to
ssqlo, tho higher tho. parentage recovery. Tho amount of bicorbomto
nododtorloo moat rscovoryontmbcoiowouldbo 60mm-
oqxivolonts of bicarbomto por limoqoivalont of chlorine. This
rsquirod moon of bicarbbnoto would bo impractical for o. moral loathed.
Moro, no mrthor sork was down uith sodium bicarbonate media.

rm II

mm! D? CEEOELEE Fiiifl 2 ,ynm'r: 33,-1.3-mmmzs Efidfl
I?! 331313?! BIGARLLEIAW

 

Addnct m. Meg? Admot Flag. 01' Pm ant Maggi-arms

 

 

 

grams Taken Found Recovery mg. Adduot
0.0621 ' 0.2299 0.120 2h.1 15
0.03556 0.3? 0.120 30.7 1?
o.cL;17 0.335 0.115 324.34 22
0.0563 ‘ 0.156 0.130 39.5 ‘ 22
m # A “‘- ““ A . ‘ M . A‘“ “

 

 

 

mums: memwslfo: 1.81 08mm“: mm, mung
sine-1 hour, heating mums-130 G . ,

.Hoq. n. . nolooulsr we. of want/2000.

hot his. «apartment: mum that, 1:: sum solution, the.
manhunwmmwunu
mwcumnmum. mam-mm.“
mmmntmnmuoummm. mum.
Wan ton Winn. 011!!! ton mania-sum, and tho We
crummumuuowmuthmm-unm.
A‘mamm-umnmmmmuwgm
“Wammnmwwmwmm
HWMIQOJM mmumgmnnmm.
nmmwmwwmmohm
mmmm1uam‘. Hauntn3housmso
wuwmmuuusumummm
mmqurk. .
nmmmmumorwdmmmm
thomdthsmfioumodumfimmofimsnd.m

 

Esq. Mthzot Hag. 01‘' Patent Boating

 

 

 

 

 

Takm Foam Rowmry mgr,

0.320 0.205 75.1 3 12.2

0.33:”; _ 0.231; 88.2 2 12.0

0.292 0.170 553.2 1 10.0
Wm

0.27? 0.220 80.0 3 124015

0.33.2 0.29? 80.0 2 12.8
m; “ ‘ w:urw“ * :: 1:w ‘Lfim* ': t w ‘:_::‘_w::v

0.190 0.220 15.0 3. 10.2

 

 

 

 

WWW“

iView. st. . molecular wt. of «mot/2000.

the mutt-ago war: of chlom. It as found that it tho hydrom
1mmtroflon,buadon100wommotthsohlom,m
whammommmdcmmwdmupmm
Mummaumotthosflvwm

Esrly W result showed the concentration of silver ion
mummwmnwmomum.
mmmmwampmmormsmw~
Ink]: 20 «1111mm of am» pa mmvnm 0: ohm»,
mhwwobmlthmwot’W. 1min
uwmmwuzmmormvumm
mgnmummmmmwmmm m,
mmummtmmmuumqu-mm
wmmotdmtmummngsppmnmm

 

 

unmoqnwalsnts of silver pox- mumvalmt of chlorine. Remus
at those (imam mo all above: 100 pmb of the onlmlstod
mat of chlorine present. A Wt linear relationship, as show
in Ham 1, as found to can batman the silver ion omcrmtratlon
and the pom-cam recovery. (Somlm dots 11: 133%.) W this
3-me m nm- sbovo 100 Wis, n wagon-ad the minty
out oi: ailflr m Waving mm- mum in addition to am;
um: 05. mm oft-.219 madam. ‘

Careful emotion of the reaction as it proceeded revealed that
s Mmuu toned madman upon addition or aqueous mm
mmu to um um solution or m m; his mum»- au-
mlvdumwphumwmrmnmmmdmm
WMmawmamcipit-stow. men-mm.uth°
solution cooled, In sodium precipits‘bo spin append tn sons
wins. his mm was. as filtered from the solution
it): the silver fluoride.

mummumuammmuum
sum, sauna solvents vars triad in so now to dissolve the
mum wipluto «1mm dissolving tho sllnr ohlorids. I: the
umwwmmvwnrdW-nmmmm
filtration, a W doomed tbs tramway or m Wes“.
'nuwlsuldnssddsdto momma, 1‘ mm mm
momentum. memuwuomm
ad the annual precipitate 1101 saw did dissoln tho addition-1
WstpdmwmmmmoWth

5 E5801. hzuomua 20 292323200 22 5.35 .lo Swim dud

wm¢nunommuww¢NNNON29$$0.0w

5:34 32504 cm:

 

 

a

-

J

q

q

1

d

-

.\
o .
‘\\\

d

\n.

l

n

AHBAOO

 

sootono wash solution. From the oboorvations sad. It soon: rsasonabls
to suggest that the proclpitata was an insolublo silver 831% of the
organic £213 prosent in solution.

fleaulta dbteinod.by*tho'?olhard method after‘uaahing the raoiduo
uifih acetone were still high. It was proposed that the silver might
be oat-"upland in 80:00 ammo: in the resulting acetone-state: W.

In s final effort to obtain whiten“ “mm, s series or determin-
ations was made in which the silver ohlorids obtainad'lss dried.snn
”M.

For the gra'rmetrla determination or «florid» tho «5910' as
dissolve-:1 in 20 ml. of acetone, 100 ml. or 0.21! squms silver nitrate
mod, and the solution roflwcad for 2 hours. we Mg 17h.
silver chloride formed.waa filtered froatths+s61uhion, indhod.lifih
azaoona Ind water, dried, and uniéhad. Results torus sarias of determin-
stigma are givaa.1n.f3bla IV.

TABLE I?
RECOVERI'OF CHLOBINE'USIN3*GRKVIHETRIO CHLORIDE DETEREINATIOR

 

mm: in. Haqumt 36:1. 01" Pox-cont

 

 

m Taken Found Emery
0.0539 O.h73 0.261: 55.8
0.0657 0.528 0.326 61.3
0.0975 0.703 0.390 56.1
0.1021; 0.742 0.157 61.5
0.1032 0.823 0.26 5.3 .5
0.1131 1.196 0.592 53.5
0.314!!! 2.768 1.67 60.5

“.m— 44‘ AM A A“ ,M , A; ##4-

 

v—vv—w w—y

.Hoq; :0. I submit. ofsdchcvtr/ZOGG.

17

No correlation is evident batman the pore entago memory and the
relative ccmmtrnticn of silver: ion, tins mgpating the correlation
in the previous work could be duo almost mtirely to the pmccncc of
sn aflfiificml sum? cmzpmmd. In all cases the pcrccntagc recovery
is mghtb chum 50 percent, but rccultc vary meek uith no apparent
runon based on ailvcr ion concentration, rvdrc‘jm ion concmtraticn,
or heating tins. The read“ 0.155308% that only one clflnrino atom is
imwmmmnthccddnct untiroly, simcSOpcrcmtI-oconry
mm inflicnc corblc‘ea rcamwal 01‘ cm chlorins. The mu of. nuns
chlorins am, hon-wow, is not ctoichiomotric antic the condition
W. .

to data-zinc mama. or not the rmticn ct achhmlodc afivdrido
nith 2,3-dimtrvlplfi-hxtndimc Ins quantitative, sccuratcly magma
min or 2,3-diaat'v1-1e3-huudiem m mm to rust with In
mammals W. mmmfimmw,
thcnsctionnithousdissclvod inmotomsmthochlcrinsmsud
by “flung in silver dtrsto column and weighing the silver chloride
proclpitstcd. Table 7 than that and-r the reaction conditions used,
2.!“ than 50 pcmmt rec-ova? was obtained. Thrace data imlicatc, than-
fcrn, that the reaction or dichloromleic We with 2 away].-
lg-butadicnn is not mauve under thccc conditions.

may. Wotmmnnmmomwum
rum-made solution see ’2 hours, than the chlorine which had ionized was
precipitated as silva' chlorido w ”aimed. Evan under than ccnéitions

TATILE V
3433517371 (I‘TLT‘I‘ PM?! 2 ,3-1. CUM...»
1,3-uJLADm... MACH fulfil .5

  
             

 

- '--~.L—O ..- -- um...” w-cn H -'-~ —-.- ‘4“...

fit. 2,3s~BLeotE-vl- Esq. semis ‘ Meg. an." Force-ant '

~vo'. a..."

 

o
- 1,3-Butaditmo, Taken Found Emory , ,,
gm '
l. L A” ‘ ““ A :1 A "“ “‘ W i... —“_ “‘ * _: “‘ ”no
0’706 I 1702 7021 ’42 .
C,::‘:‘1:;.5 - 60;]— 145.1;

A ”A M# A _-..__ A...

“foo. wt. . Inlmlar wt. or 2 ,Whigwm/zow.

it as impoulolo to obtain 130 pox-omit mama? of tho chi-arias.

Results one shown in '3me VI.

$531.3 VI
830%! OF SEWER mm LOWS? “TE ammo

IN 0.223 33035.: 1.1.3.333

 

 

 

Ww%.~,Wg—Q‘W
cm at. neq.‘ ms Mag. 01" Poo-cult
arm Taken Foam! Recovery
0.0177 0.62}. 0.1.5? 73. 5
D .0097 ‘ 0.5:" 0.2415 724.1

“‘“ “‘4‘ ”‘* “ ”#Mwm:“ ..._ w. ..w“ “4‘ 3:; A '; A “‘ “Am

 

whim. wt. - comm wt. of acme/coco.

Sinoo tho chlorino could not bu quantitatively men not: tho
mt lit?! mono octane: Woo, it is unlikely that any W
using oilvoc- nitrate could amorous: this moi.

19

1313385331013

mom, no" and Hall ( 7) allowed 190mm to react. with chloro-
mlaio migrant! o to yield a mixture of 1-cflom—2,;-oimm~hdwtv1
phthano anhsflrido ( 11) am 1-daloro-Zfi-dihyfiroa3-m’chy1 phfimlic
mw‘ifléa (III) .

CH. 61 o 01 o 61 o
I \ I m.\‘ I ,C“fl\l ll
a-c c—c\ 3-0 a -c Has—0’ c—c\o
304': . I 0’0 ”ac-0| Adtnfi n' (Ii—00’

a " a "
“ca. / \\ can \ ‘6:th \\
H o n o 0

II It:

By ramming thin W in 0.2}: silver nitrate solution using
a ratio or 2 mmmuivalentu of oilvm- ion par mniqmmm of
Impl- they obtained wtitativo removal of W. The 1,6-dichloroo
LS-dilvdz'o-B,b-dj.nm‘v1 momma deo (I) used in this may has
u 0113118: We accept for tho replacmmt of rumba-gm by chlorine
on tho budge-“mad carbon. Kama“, tho tomato of this study indicate
fiatmlymchhflnenmummuulabhhlfi-dmruzfic
6W3,h~dimtw1 phthalio atom-ids in removed «an utter «tannin
Mining in diver nitrate or Indium hydroadda solution. This decrease
in unfit: mat be duo in some manner to the Winona. chlorine atom
in the moors.

Scale mdolc var. constructed of mam-mum
phthalio «worms (1:) and 1,6-d1oizloro-2g5‘dflvdrO-3;h-dimfiwl
Mama-(I). monohmwdbothmlaoulu tab.
Wamummmmbmkwuumny.mm
piano W for on SR. unboutaztion motion. The dgdity at“ the
mmmummntootmmmnmmm.
mrmumomm mmmthommmummdmm'
“Michnfirmootflummwlmofiddmmm-
aeolian-anon.

.mmmmuummummmurmmsth.
macaroni-ion. mw.mumum6nmowumhnnim
mammmun involved. Wm, momma
mwmwnw1mmmumu,nruumm
mmwammmmmmimuuwu
brothel-optimum.

m- 1mms-dmrm-u-auw1pom «warm. (1:) 1n
Wmmumuthomuonmmodn

03.01 0 011.01 0 CH. 0
1. /\|// lxI/I I'\ //
n—o c-c‘ 3-0 8-666 a-c B—c .
II I 0-". II A )3 ------O [1» l .01
330-0 c-c’ no—c -c 3,0-0 c-
\ l’ \x \/ I \\ \ /| \\
ca.a (32.3 0 011.3 0
0 an o
[011”. I ,CHaJ? //
2. 3-6 0-0 3—0 .0—0
II I b 0 H30 0—9 (I! I
{1364‘ 341-0; E o- /ci:—c{\
c .
'3 o en's o

h. 61.9 “.Mm .

nmummsoummmwmbm
WhWMWCMMWWW
Mama-um“... hump-awn;-
mmmmnmammuuwu
“autumn-mu.

mmMM,m-3Wm¢m
many-mom.

» 610 010 ‘ o
I '\/ 4 MFKJJ 10"» //
1. u.c-c o- 3.6-0 o—o
II I , --. “2.45 ---b l ,bocl'
"M\ /°\—°\\ "' \ \ \\ ”A °’°\
on. no org/010 \cm./o \al\o
1° //
2° “kiwi-ct: 3.0-» 2:3] MICE-kw“)
0
0-0 —d
3' ‘cm{\ \g ‘wm \\
on Ron I7 03% lo
3. n.o-a’ '36 - nae-f CH-"d —c‘
II I b M £ 6;) 4- a.
B’M‘wax' \\ n'M‘ ’ \—\\
. «no on,
V

he 61.. ‘8.” ‘30)-

Again in thin motion the cm}. group could furnish electrons
“Marthe-11mins. Homer, the effect weldbelaeemd
hmdtlmmeothnchlemnommhwgzgfleomm
M30011. The-3mm affectlotoiflorinemwt transferred
W the alpha carbon. therefore, there. mum be new cmtribution
ddmtmtranomchlorimntutomom. Simateoohlorino
mefilable,wam£tortlne@flibrimwuldmm
mumeandatopelflmauwBeNMWcmr.

mummflfimwmtthntthe‘mmtofmmuu
Whyfimwdtheneoandcmotmmammlmfle,
Msmmwmmmmummwuwum
mfimflrmdotfimdzhflm. Thedeuuhoethettheutant
ormotmmmczmmumnmw,mw
mayoMothI-mtion.

Wdhanodrwt-mpmmnmnam
ammmumforthcmmfitMtofrmfionafiertm
mumamm

(Cl ° 03.. In;
W’flfié naafi’ cl:- Cb
' rd 3‘! 0-0 Co'-
H o 030
. II v

Inmatheoiaermmdrumtmmowmcmt
Mmuumammmummmwmgm

23

nwmmmm remunevmweagonhubom
what! with a worm). group mm: has a strong attraction for
W.euom~1e effects or electron contribution by the worm-1
m 00 mt traiwfee'eed through the carbon chain, lea-ring may the
inductive mm'ofthntvdrwlm. This matition for W
mammumnrmmmbamm,wwimm
Watumemmwomwom
sanctum. upland. ,

W W pond to be 1 W W to
We. Itmabtunodrdativohmomnfinmfummda
mmmnmodumo «mammal. 31300th
mmwwum.mmwmm
We
”mumummuum,mmzmm,fi
Int-dim. WWtsmWMtfi-flfiWfi
handin- md 2,5-dimthy1 farm, but that bender would lead to the
apposition that the reaction had yielded only polymeric natural.
611mm: and cum (3) obtained reaction Met. a: diohiomuleio
W with butac‘imo, mimics), dioyulopmtadime, 215..
W. Eastman-1 ,Mmtmmo and dim-them.

m reaction promote obtained by Clifford and 6191:: and in those
Wmdtfl‘imlttomtcufimry. Manama”
m polnerieatim, asking it dirflmlt to obtain 0. mama"
reaction. Data for the 2,3-diroefiv1—1J-butadim mt show that

«mow the maxim pone oodofi mommy, tho when we not quanti-
totive.

Tim 1,6-c'iahlom—2 ,W‘Q'IiW-B ,huéizitehl'g'l phflzflic wfivflrida
m1 elm Emu-oi that tour who} to carboxw 2 mm! 5 of, the six
mobertd r313, as in the case of the 2,S¢m¢l§"l-2,Lvhmzulimee Wt,
Mild who the mmtion difficult home of the steric i-fimh~once
intowdacad by the two cliwz'ino stem-n3 an the brblgfihaai car‘m.

The reactivity of dichleromloio anhydric‘ae for the Melt-m
reaction memo also be considered. Sim->3 the Dials-Alder mention is
believed to have an ionic mochmdm, the notation of a Iinglo chlorine
atom to the mime, u in «marmalade morons, W assist this
ionisation by month. affect: and m... the reactivity. The 1m
Wammmmmmmwmdwum
cum and mm: to cancel any Motive affects. Prose this domino,
tho motivity of (ti—chloromloio wool-ma amid be mom to that or
M1810 31mm with the added static Moos caused by too chlorine
new. I

6313313. 5102*? 7

The mdualone of this “My my be stated briefly:

(1) Dichlomealeie ufiwfirida a a convenient material to purify
and handle. '

(2) Wmumronmuuumor
mm. but 1tl nddition to restricted to mm which offer no
Item-13 difflmltiu, 1.0., no substitution on the terminal carbon or
the conjugated system.

(3) The reaction of fiohloromleio «hydride with the com
€101.13» 1- not manna m the reaction conditions amend.

(Urhotwnmwrwthemofdiwm
murm- um. ammu- u in the rug. arose-180°C. Butadim at.
such elevated W pram a 'ui'oty has-rd.

(5) Emory o! chin-1m from the 2,3-dmuv1-1J-butadim «mat
in not mauve or Mable-atria ulna and reaction conditional.

Although diommmloio anhydridi often «ruin Mg“ our
chlorate-.1019 mom-1a. an 3 reagent to: the mama «mm
of conjugated dieleflm, thou unfit: Mute it is not a suitable
Wt. rho M10 factor! and mm“ afloat. introduced by
the second chlorin- etc: in the molecule vastly alter the hermit):-
of dichloromleio «hydride to mod to ammonium: defio

2'5

LIT '. "an“ 'L'd 3.13 CITED

1. Basaatt, H. 1.. and i=‘illiazw, H. 6., J. Chm. Soc. .3523, 2321;.
2. Birch, S. F. and Scott, W. 12., Ind. Eng. 33mm." .23: L3 {1932).

3. Clifford, A. 2%. and 61313, C. 3., U. S. Patant No. 2, :31, 2.. ”.6,

a. Dials, o. and T111310, w. 12.; nor. 1;, 1173 (1938).
5. Farm, 3. E1. and Karma, 1‘. I... J. Chen. Soc. 1921, 3221.
6. 33111.9, A. L. Ind Mk. ‘0. J. “0 Ohm. 500. fig, 826 (193-02).

7.?“ w‘m'n", 8. To, 1‘08,’Hg R. m F311, R. 1., I111. mg. “13“.,
Anal.“ “:1. 1’3 628 (19146).

8.W.0h.agm1£3tm. W. J0. Ind. Eng. Chm" but Ed. 5
10: (1931.).

I. M31331: of Dichloromlaio Amman
Samples dissolved in mm, 121th with 0.86173 potassium
max-oxide, mlpntham indicator.
ggajichlofimleig Arz‘wdl. ride

 

SaWIO ”fight’ gm 205212

m. of Potassium Emma. 3h.70

Percent. Eiclnoromlaic m‘vfinde 99.01

Nautraliution mvalmt 6h.)

Ramblimeg Mcwmflc m do

Samplo Weight, gran 2.6818 2.0930

Kl. of Pomaimn was 37.00 28.83

Percent. Dic‘nlpromleic ”Rwanda 99.2? 99.3.1

Bmmmn mvalm 81": 51303
Calculations

Percent manor-ambit! Anhydrids :-

 

Neutralization mm c

83- 19 361' 14.51000]
.K . O.‘

 

 

 

28

II . Effect. of Silver Ion Commtration on Percent. Recovery

 

Routing rim . 2 hour-
qurogan ion concentration Ion than 0.01!

w

”A...

 

 

2100.. mm 1400. 01‘ Percent

Takm I‘m Recovery

0.305 0.132 h3.1

0.337 0.270 71.0

0.398 0.333 80.0

0.L11 0.329 70.5

0.063 0.393 85.0

0.600 0.370 62.3

Wfi::‘ 4““. “*tno

0.182 0.276 151 33.0
0.180 0.269 126 32.6
0.185 0.233 125 32.2
0.201 0.233 123 29.6
0.206 0.280 136 29.0
0.209 0.275 132 28.7
0.222 0.230 129 27.0
0.223 0.320 123 26.7
0.230 0.300 127 25.0
0.220 0.292 122 25.0
0.263 0.315 125 22.1;
0.273 0.210 150 22.0
0.273 0.383 no. 22.0
0.278 0.290 100 21.3
0.236 0.230 97.9 20.9
0.292 0.290 99.3 20.0
0.320 0.310 96.9 18.5
0.336 0.233 85.7 17.8
0.303 0.329 90.5 17.2
001-0136 00335 7501 13.5
0.522 0.008 76.6 11.1
0.580 0.081 83.0 10.0

29

2121

138216! June: Bradfard Van Bar-an
Born: 2300003), 111113012, June 23;, 1933
Academe Caz-00m

1905-42? Table Grove Comaty High School
Tabla Grove, Illinois

1907-50 m 823.1% High School .
Table Grove, 111121011

1950-51 Western 111111012 State 6011030
250001010, 111111019

1931-52.; Univmity of Illinois

Degree: Hold: Bachelor of 8010000, 19515
Univmity of Illinois

Date Due

 

Demco-293

 

 

PROPCMY CF

  
      

MICH STATE UNIV E33!"

   

CHEMISTRY IJIBHARY C. 2

Van Doren, Janet B.

Dichloromaleic anhydride aS“a
reagent for the determination of
conjugated diolefins.

4.5. Thesis 1956

CHEMISTRY 1.1895133“
Van Doren, Janet E. c.

Dichloromaleic anhydride as
a reagent for the determination
of conjugated dielefine.

K. S. Thesis 1956

 

:"A _”~_— —‘

 

 

Batedhe. Name. 'SSUED To

 

 

 

 

 

 

 

C7. r f '1 ~ n'i‘F. 3 LIFE 33.2

 

 

”TITI'I‘HHIHIIMMHflfifllflfflTfll'lflliMflW