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Masters Theses Student Theses and Dissertations

1950

Ammonium and alkylammonium salts of carboxylic acids as Ammonium and alkylammonium salts of carboxylic acids as

characterizing derivatives characterizing derivatives

Hal Gilbert Lankford

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Recommended Citation Recommended Citation Lankford, Hal Gilbert, "Ammonium and alkylammonium salts of carboxylic acids as characterizing derivatives" (1950). Masters Theses. 4830. https://scholarsmine.mst.edu/masters_theses/4830

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A..lJtMOJ.IUM AND KYL.uaWNIUM SALTS

OF CAJ'Ut~XnI 0 .;\ "ID AS '-;HARA~fF..RI ZI NG D'll' VA/rIV~'

BX

PiAL <Hl.B: RT LANKFORD

... - ---

'rH I

4 to tho

~CH OL 0 )l{I' F.S AND "'u;lI"'~_.

l~ of t

EMITY

1 ultl11

•

..h1'!'he

Rob rt

ur thi

uthor 1 to xp

ell for the h lpful

1nv etlgatl n.

th t

Out.;p;c,utlon m

1

T

Work •••••, .

Introduot1on ••

R w 0

• •• • • • • • • • •vlou

• •• • • • <.i t1 .. " •

••

1

4

p rlmento.l ••• " ••••••••••• i •••••••••••••••• IIi • • • •• 9

~onQlu ion ••••••••••.•.•••••• • •• •••••••••• !t, •••• 11

B1blloe;r phy " ••••••••••••••21

1t t ~ •• , illi iJ 22

1

I R DU 10

of th Il1 thod w1d ly u to t bll h th

ld ntlty nd purity of an organic co pound 1 to pr •

arious d rivativo9, the prop rti of whioh ha

b report d 1n th literature.

obJ ot of thle in t1gation to p

lkyl onium o.lt ot ca.rboxy11 e

in th lr utility ohar at rlz tion d r-

1 tiv • hould the ltB m t th r qulrElm nt

of otory d r1 tl • b u1d e p rtloul r

val ..bl from t ndpolnt of tl • h '1

roy qulckly fo d.

o 'b otory for 1d nt t1 10n pu 0 ,004 of gl n d r1 tl hould 11

lnab , It hould h P P 1 th t will 1

t f 10n b 11 or the0

10 w n

bil1tl h 1t ho

b quiokly d d 11 purl i d.

1<1 rl tl r ~ u d

1 t

1 11 q tl 1 b

r 11 P r1fl

point r 111

11 bl h 1 p nt •

cord1 to 1 b rg r!2) for o11da

(2) 'II • b rg r; hy 10 1 t.h d of 0 an1 Jll r"J.Vol. I, • Y.. Int r 01 no , 1945. p. p. -5.

without decompo 1t1on, the It1no po1nt 1 tho t

1mport t phy 10 1 property in praotic 1 organic oh m­

1 t.I7.

Tn org nie chem1 t u8ually d termln

point by th o p1ll ry m thad, in which 8. gl

ill ry oo·nt 1ning the finely <11 1dod a plG 1 pl d

in bath who t- 11y

th u'D t 0 t , th tu J 0

e pill oord d th It1 p int.

t mper tur hou1d b inore d at t no g0

th 1 p r mlnut 1n th olnlty or th Iting oint.G

Pur oompaund 111 U lly m lt w1th1n 0.5

rng n th m It1ng po1nt 1s d termln d by th be

m th 0 o nru lon d d G P nlan r·..a d- 1n th lit r tur : 1 , orton(') t t

m lti a,int 1 t n the po1nt ( t h1 h)

the...

fir t pp r nc of 11 u.f otlan oocur , wh &

3) orton. ., L bar tory T oh 1 u in Cl

h try, .. Y. , Gr w - H1ll, 193 , p • 1.

1 b4) 1nt 1 t Pr

(4) 1 b r r' .P. olt ., p. 19

1 th 1 t t 1 d1 01 1 u u 11 t t

lting pa1n ub t 0 that elt ov r rng

dlf1'lou1t to work lth, ino th 1nitial 1 1

point 1 not 8. 11y d 48 in d, and var10u xp rlment r

wl11 u u 11y report d ff nt lnltl 1 elting po1nt •

o e ub tanco m It 1.th d. oompo ltlon, tho

a ur ~r' 1 d p nd upon the r t of heat1 or the

b h t d ~a~ldl1. In order th t on may

Iting point a h. In th 1n tanoe the ple hould

pro...

duo b1 ulte, th oompl t det 11 of th m thod u

nd h r t or heat1ng t 'b .1 n.

r

o

1

u1p nt d 1 d t

on r 1 1

adequat.e

m~Q(lIl~flOry •

"VI}:; .,)

Nt re n b r of of p P ct~

t1 of 0 xyli 01 Wh1Gh t t

of ~h bo • m t10n d qua11fl0 t10n • emo 00 only

u d r1vat1v r th mid , b t1 ·ut d 1d

0114 tel" •

1dea a qulte 1 pl to prep re •. o d

h1or14 1 flr pr p 1" d by h t1ng or •01d and thlo1 ehlorid und r r flux tor tift en to

h1 Y inu • l'h 0 oid hlo

into col , noent hyd x14.,

h pI" 0 pit t 1 d d

w th aold 1 1 to

hl .ride, he ,.1 1 w111 b uo

bl du to hydrol ooourr1ng along with

th ono1ytJ1 •

l11d o

dUN.

"""Ii"'.J~\4......1n.

pt

r

d

d

:y b

0114 ter

u

r h

o

b r t1 phont"oyl b~vlu.L\,I~". pnGl1aoyl

1)- ];mony:Lptl.enlllOyl

d

dlum

D.',.UU of h

o r ...Q]Jlu~ ••

h lid 1 h

r th

1'ul n

ron41•

11

rA xtu

b d

1 1

under r lux f r on , t.v, r hr e haur I oor n

1ng to on , two, d thr e roup. It r

y be ry t 111zed from lcahol.

Th r otions dl au 8 d thu tar hell b n

d1splacement r etlen. Thl 18 a1 0 tru of the m J­

arlty of re otlon eneount r d ln org nle ch 1 try.

rh r otlen of 8od1umcetat with p-bro Ophenao11

bra 1<1 r. to 11lu trat thl typ of r otlanl

",H C ONa + ~··O OCH.Br~aH.C00 H . nO r * Br

p-br~mophen c 1 oet t

org, n1 'b s h b en u o p P

It of o r xyl 0 cld r r lei nt1tloatlon pu~o "Th rg 1 b e u ed beo u or the trl

nit 8 n whloh th c nt 1n. N1 rog nh r1 Ion

1. tron , and thu h pa r or un8h r d 81 otron 1n

th compounds which 1 v 11 ble for haring. w1 t.h

oid. our or t.h nlt gan bonds t

are 1 r e y 0 1 nt, h b n 1. t •

(5 • R., El ctronl0 ,echanl me of r n1erl n . 0 0., 1950, p. 20.

etlon ,

Ph flY ydr zln torm ph nylhydr zon1um It or

phenylhy r .14 , 4 P nd1ng upon th typ of 1d u d

1 en- ub tl ut d I1ph t c 1 nd al1ph t1c 1.

b 10 old fo It , wher 1 p1 ub ltu d

lpbat 0 1d g v ph nylhydr zld 6)

6 hr1 nd on, 0 olt •• p. 1 9.

Bu hl r, ron, d Edd , (7) found th t b nzyl min

7) Bu hI r, v reon. and Edd , J.21 1 (1935).

~-ph ny1 thy1 mino form d t1sf ctory d 1vat1V with

n b r of 0 d. Th in 'II add d to a hot thy1

& t t 1ution of th oid, ftar whloh the olution

pour d nto w tah 51 tor cry t l11z t1on. the

uthor ere b1e to purify th r ultlng Ite by r

ory t 111z1ng them from ethyl a et te or ethyl alo hoI.

H---J-

oni It of rb~x 1 i h

\udled by v rlou lnv t! t t1m .. c.u:un,or 10)

(lO) Mo or 4. L., J. . Oh oOo , '6, 742-7J~7f 19'.6.-1925 . 191 ) ..

prep red and tudlec1 the propertl of gr t nu b r

or on It • Th It were p clp1.tat d fro

loohol, or o tones lutlon or the old b P

1nto thsm. & t r n

1nt r t d 1n the po alb111ty that the alt ~t b

u d r at rlz1n d rl atlv • ina roly po

poUlte.

1 In(ll) t.ud th on u ot

11) lk n. J. ..he • ... ndo • 1 " ,

r t l' 1 oont lnln fro 0 lfptc n 0

1 fund th t It. prealplt ted r oh 1,

Oont~on 1 nc!

ntIt

a11. tM thpllr[louUr ;

p1

oro p r tl 11 t bl nd It d t rply.

1y h wed th t th 1 •

1y noh a

1

o ~n 1

r th 11. th o uld b dHLI.rr'~'1n d w1

au do~a:ol'J~81 1 n

1 of

hlgro op1a, ng 1t 1tf1cult to ob 1n ~l1 1 mel 1

po1nt • tt t1(12) vi • hod or the

•

(12) ~utt nt1, S." J .' t' Ohern .. 80 ., 6', :5 23 1 1)

..........-o 1t the m 1" ng po1nt , w1thout xpo ur

to tb tom ph r • H1 m thcd, how ver, 1s not r ad11y

apt d o qu 11 t1ve wol"k.

F.

10 14 H - oJ -......... J" H

/I II hO'/'

H .. ... ... ."1 0oJ", oJ -..

/0

or1"0 te p olp1 t

r b bubb

t r

h r

n vaC)UU~r.2 d t.or 0 r lor de.

·1

d uncio.r~o ~te

oxt,l'8lor41n 1:"1 Bmc)unt or1s

to

1.

1

1t 1n' t llnt])el'At

o ob•• I!"Vl}

th

d,l

{,\umo b

brown

molino4

neloeC10.kI"Y . 0

a.l)an~lorlOa..

2

H fluorobutyr 0 01 , F 0[ I;.... u ... o ... "H- ,.J -

I I IF F "i'

oid i a oolorlo liquid wlth ry un-

pl e- n • It 1 n5 aold, laolbla with t r

and o ton I>

1 tot mpt t.o pr o1p1t t h a onl alt fro

th r and o t()ne olution t lIed. Th alt may b

pr red. from a- nt ne Bolut1.m of old; how r, the

Glu ion turns red whor} the -old 1 dd d to the pontan ,

cl th alt e Dl d wn ro e :)olor d. he It ell

ry ~t n 1y r th c d. Th odor nd

en r r ro W 8hinge with ntan • tt r 1

d '1 ln va 1 or it w no 1 <1 th t th alt

, 'dh1 h 11'1 o t d th t it ght be purl!!

bf thl thode wo tt mpt t how ar, g • n

ult • v r 1 h 0 n

pu if h It, b t wlt ut. u e " I

0 b th lt t b pr p r d in r lat ly

t by ubbl n nla into th r a i

hl or"! I11n I1d 0 by th

lz rr t d

uo • nt it nc•

t h cop101ty r d 1

d 0 .. 1

on pl 1t th wn blow 1 fl ur

1 010 h P ro t or pon 1 to b ld

1 , h w r., he r ult 1. n t r 11 1 , 1 h

p rh p indio tlve of aold It orm tlon.

The th onium nIt waa 1 0 pr p r d b bubbl

tho as 1 ctI] into the &clG., It h mu h the a

&Pp. r &s the mmonlu It. but 1, qulte hygro epic.

Thr no odor or tho old 1n thi 1t

1y1 min' form mo t t o 1

obutyrlc ld. ~oo11rl5 in r ing lxture of ry

10e d ohlorofo even tall d to produc 0l"1 t 111 tl n.

% in

d r

H.

o H •HI- ~

I

- 99 4 7'7 lf no • 4 9,.e, lf old

• t bI 011

1

ot- T 6- no .- y- 1 1'01 ton

p. or 01 9 .5 - 7.

H H HG>- I

I I

~ ~ 0 - <;-- c- C-H 0I I //

H o H-C - C -OH" /C

II

0

alt of thi~ n .... ld w 1"0

I is w"nlt , tablo. d nl::>t hy roe ,ap c.

11' r run on D ple tha.t W B pr pared are

th on • It 1;' pelt t r pl

th p1 •

11 n. 1t lao pr r d fr.::>J:D •po1nt or hi It 1, d nt. on h

0 b tin nli t th t t1m in th R u t

n 'lA'''' ....''..'' d t rl u

1 • l'\W""l7nr, th tin pint rcpor ad bolo

o

1 d

r 1 d o 1 ot on ot,enUr\.ll,10

5 1th

, 1

d0100::lpCl 0 it10

5

nn 1 Ac H H 0

<-P- I I 1/= ..., - - OR m.p. 33

The rf ~t 0 a~l<i aolv nt <>0 th 'roportl r

the alflmonlum salt wa stud-led ith t.hl aoid. A:u onium

c1nn te s pre 1plt t d from th r, o ton, nd

chloroform. Eh ob rvod ar1a.tlon 1n m ltln3 point

1 t h o 1:1 en d to 00 lud d 01 nt.

th r

1 mmonlu olnn t p, c1p1tat d fro

I

ther 171.2... -...... 1 h a lnt174 4 bra h lor

H chlo fo 17'.2- brown178 d

~H c ton 172.0-H H 179.4

-;1 NN. th 1 .' 7 1.35H

1v.8

p - nltrob neale, JOOR

o•

, m.p. 240 - 242

1

Allyl onlum p-n1trobonzo te is p e yello~ olid

th t w P p red by ding 1111 mine to n ther olu-

tlon of th aid. It melt from 152.4 - 155. it r

reery t lliz tlon from ethyl 1coho1.

er 1 other a ld w re inv tig ted, but g va

1 11 un tl r otory r& ult •#'- II /f

II - b n oylprop1onl0 ld,~ ':l ... J .... - OH,

r 41 y form It w1th mmonl. h t m It d OV r

wid r ng., 90 - 9 , and turn d y l~QW a it m 1t d.

Th thyl in It 011 out of th r oluti n, but

y e pr lplt. ted fro \) ton. I 10m It 'JV r

a rang , - 99 , and turn d old n brown

Tn onl 1t f non 01 id,

H CH3 H CHJ H 0J I I I J /1

H-C-C-C-C-C-C-OHI J I I I

H CH3 H H H

b oa l1qu1 1n th d 1 tor, probably du t 100 or

m nia t.h oid s l1qu d) or it m1 t h va b orb d

'II t pore R HI I

mmonium It of n 1.1 . aCid/, = v -: - H,/ I

0 .vV H

0w pr 1plt d m b lut laohol. .p. 133 - 138

~onQ1U ion

n b r of ne and 8

oarboxyll0 oid a.mo u ~nd

p lou ly r ported

It hav be n pr p r

nd th lr p op rti

vest1 t d.

S oharact rl zing rlv tl • 1n-

• 1 ted b cu.Th.

or the

in. ho en to ork with

w1th wh10h they re 41 p n e4 nd th pld t;y

r p

with wh h they form

attempt o 1 ot nt t1v group

..._.......1 y of t •

m Jor dlfr culty IlCOun d pur1rl0 il n ot

nt 1

•

,

10

OOU d b 1d ntltled.

In eonolu lon, it ~QY be nld that th1 meth d 1

not t 8 n ral p 11~abl11ty. but might be u etul n

more or leas leo1 ted caeoa.

19

ltlno point PI' r tu us i;)1t mod -

f10 r that d 10n d by H r h".J (1' b h•

(13)(~9~).

B 4, Ind. En Jh m. , &1. ,• • , _.

'12

l1q 1 i n th 1n no ooncentr ted ulfur1.o & 1 , 1

1roul ta hro th tub by ot 1 r unt 4

on .. b 1 ... b ariJ18 aa mbly. eotrio 1 he tl or t.he

b t fford e 111 c ntrolled t per ture. Total

1 r ion th t gr du t d in t nb or a

es • w re u d to det 1n 11 melting point '.

o p 1 ry tub r tho e .,0 01&111

• 11 fro the Kl ble 1 l'h. 0

oft n are b tw n on done h It to two

i111 t6 1n 1 m t r.

d t d by t1tr tlng lth net 1'<1 Id.

1

ot1 n •

»

HY

ron, and Mid J~,

otron1c oh 18mo.n Book ., 1950, p •

I B. , Ind.. g. Oh m An 1.! 4 t

en h ln, Ji hem. Soc. (London), 193 • 2'0

• 0)1 t r L., J. • vh " 01' 6, 742-747, 911925 191 ).

6 ~orton. • in Ore; 10Ch mi try, N. 21

7. 011 lon, J Am. ah O. f 6, 150( 9 ,,)

8. d n, J. ., •

9. riner, R L.Id ntlfic ion or!. Y., ' lIe , 19

•pound

1 •

11 ..

1Vol"

r r, Phy 11M tho~ anL: 0hcmlst, N. Y. Int r' 1 n a, 1945, pp. 1.45~

• J h • 0 It'" 3123(19 1

,

![2

VI

H 1 G. lAnktord w born in xb r , I 0, on

Jun 1 • 1925. Upon campI t1n;;.) high C 00 h J01 d

th ~ , V...U~ prog m and w nt to th Unlv r tty•

of the South, c Tenn. Aft r bel d,fro th }l h ontlnued 0011 8 tr in1

ourl Sohool or 1ln and 81:. llurgy, Roll, 1 ourl,

h r h obt ln d hi B oh lor or S01 nc d. 1 9.