The Reactions of Morpholine and Sulfur with Various Acid Anhydrides

86 Pages·4.408 MB·English

by  Peters, Edward M

THE REACTIONS OF MORPHGLINE AND 3UXCTR
WITH VARIOUS ACID ANHYDRIDES
by
Edward Myron Peters
A thesis submitted In p artial fulfillm ent of the re­
quirements for the degree of Doctor of Philosophy,
in the Department of Chemistry in the
Graduate College of the State
University of Iowa
August 1951
ProQuest Number: 10666206
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The author extends his most sincere gratitude and
appreciation to Dr* W* T* Smith, Jr*# for the suggestion of
th is problem, his inspiring guidance and particu larly for
patience through th is research# Thanks are also due to the
entire faculty and sta ff of the Department of Chemistry and
Chemical Engineering for th eir many helpful suggestions and
assistance*
i i i
tm m of oow m m
m m m xm m m * # * * * * # ♦ * * • ♦ * * » * * * # * * * a
m m & w n m * * * * « * * # # » » * » * » * # » # « * * » i
wmvmzma** * * # * * * " • * # * ♦ * * # * * * - * * * *
0 4
mmm sxot* ***•.**«»#* * * * * #***## ** • 22
m & m twm & u * * . * * ♦ * * * * * # # * * ♦ .....................*
44
Dlthio^^^uio^phollnosuocindliiiorpholide (I) « « * « • 44
Degradation of Oithlo-O* -morphollnasuceindimorph-
olide (X)* * * # • * » » * * » » * * « + * « * * » * 44
fhe Morpholonlw Salt of ^(H^orphalinomortomorph-*
olidosuceinio A d d (IX)* * * * * * « « * • * . . . * 45
oC-MorpholinomonomorpholidesuccInie Acid (XV)
from the saorpholonim salt of ^^morphollno*
monoiaorpholidosuccinic acid (II) * * * » # « « » # • 4$
o(*Moi?ph linc«aonoBiorpholidosueeinlc Acid (XV)
0
t$ m marpholine and maleie anhydride * * . * # • * 47
M thlo- oC-morphoXinosttocXn&imorphoXide (I) from
the Biorpholonlum salt of oc^morphollnomonomorph*
olldosuooinic acid (II) * # * * * « « » » * . * * * #40
Of-Morpholinoruccin&Imorphollde {III) from the
morpholonium salt of o^norphol inomonomorpho-
lldosuccinlo acid (XX) * * • « • * » * » * « * » « « 4#
pC-MorpholInosucc indimorpholid© (XIX) from di­
methyl maleat and morpholine * * * # * « * * * # * # 49
o^-Morpholinodimothylsuccinat© (V) * * # » * « # < , # 50
oC*?iperi&inodim©t]^lsue©Xnate (VI)# * « « • « „ « #51
fhe Morpholonium Salt of p-Morphollnobutyrl©
Acid (VII)# * • • # # . • * * # « * • • « # * * ' » 51
p-Morphollnobutryie Acid (VIII)# # « » » » # . . « # 51
iw
DTinhi m&leat© m d
diofchfI mAm w M e th y l » ilto ^ * * * * * * * * * §5
3
&$t#»$tt©d erf ®c <*i©rphDlinomm©**
»ppli®3L14o^ii@^lmie A@M * « « * » « * # » * « • * * S4
FoXarOfWisifcl# B M w tlm ®f *4§0rph**
MM* * * * « * * * « *> 55
totm ftlw ftteia T itration curvM for Qoms&m&m
n»'XV* ?XX m d VIM* * * * t * « .............. as
**mothsfX«* oO ^orptoXino©ueo iM taorph*
©im© (ix)* * * * * * * * * * * * * * * * * * * * *
00
Moti© AnhfdrM© with Morphollno tod Sulfur • » • «
§1
ftuauXsil© &nh$€rM© -with JSorptellxti and Sulfur - * * * 62
fhth&ll© AtifcfMM© with tto^tolin© and sulfur * * * 62
Orotcml© tohfteM # with HorpholM# md Sulfur * * * 64
Mrpl&lM© $hJ,©*ul£*t© ( ) r txM Morpholln# and
1 1
SulfurJ * * * * * * * ^ * * * » #. * . * « * * * * * m
MorphoXi**# IM oaulfat# (II) [from MorphoXte© Sul*
im md sulfur » « » + # « # + # » * * » * 65
X dw tifloatlon of Morpholin© thlowXfut© ( ) * * *
1 1 66
SWt&Bf • * « « « * # * * , « « * « * » • • « • « • « * « 74
BXBLXOUUAm* * • « * # « • # * * « * « • • • * • * « • « 7»
BIOSBAITO * « , * • » « * « , » # » « * * * * * * * » * * 77
V
TABLE OF FIGUBES
1 T itration Curve for the Merpholonium Salt of
©rphol in ©m on om o rphol 1 do sue c in i c Acid * * a » » « • SB
2 T itration Curve for the AiCrphoXonium S alt of
»iBOrph©linomonomoj-ph©lid©succinic Acid
pH 7*3 to 11 *3 .............................. 69
3 T itration Curve X‘or ^orpholinoraonomorpholido-
succinic Acid {IV) from Compound I I ' « « * « « « » « « 70
4 Titration Curve for «*morpheiinomononiorpholldoauc«
cinic Acid (I?) from. maleic anhycride and
morpholin© • « • • • • • • • • • 71
5 T itration Curve for the Morpholonium sa lt of
-morpholinobutyrlc Acid ( VII) • a * ® » * » 9 « a *72
Titration Curve x^or -morpholinobutyrlc Acid (V III) «. 73
6
IWTBOPUCTIOH
The W illgerodt Reaction (1) has been shown to be
a general method for the preparation of amides* thio amides*
and acid salts* This is accomplished by the action of sul-
fur and ammonia or some amine on various types of carbonyl
compounds*
( f r - C H ^ C - N Hz
O
>- -C H -C -/V
0 2 /? (2
The reaction has been extended to include imines
(2), olefins* acetylenes, and thiols (3) (4)* The la st
three have been postulated as interm ediates in the reaction
(3)(4)* Carmack and DeTar (3) have demonstrated that certain
alcohols, specifically methylphenylcarbinol, p-phenyl©thy *
1
alcohol and methylbenaylcarbinol, do not react under the con­
ditions of the W illgerodt reaction* They also point out
that ethyl-p~phenyiacetate does not yield phenylacetamlde
2
when treated with ammonium polysulfide as would b© expected*
!&rn©r-Jaur@gg and Huckley (5) claim to have Isolated
dlpbenylurea and both ethyl anllocrotonat© and ethyl anilo-
butryrat© from the reaction between © thylcrotonate, aniline
and sulfur. These products however cannot be considered as
the normal products of a W illgerodt reaction* It therefor©
seems likely that only carbonyl compounds and the actual in**
term edlates of this reaction can undergo a W lllgerodt reac­
tion*
I t seemed of in terest to us to study the nature of
an observed reaction between sulfur* morpholln® and malele
anhydride* and to determine whether or not the reaction Is
general for a ll anhydrides* The us© of malelc anhydride and
morphollne in th is reaction led to a ©tudy of the addition
of primary and secondary amines to the efchenoid linkage of
maleic and fumarlc acid derivatives* This was necessary
sine© th© early lite ratu re concerning the nature of this ad­
dition was not clear and presented some seemingly anomalous
results* In th is report* an attempt Is made to correlate
much of the early work*
Th© work of King and McMillan (4)(13) on th© mech­
anism of th© W illgerodt reaction has focused attention on
the reaction between th© amine and sulfur* This report,
therefore, also concerns its e lf with th© isolation and Ident-
3
ific& tion of one of the products from the reaction between
liiorpholine and sulfur#
HISTORICAL
The reaction of aliphatic aromatic ketones with
ammonium polysulfide to produce (o*-aryl amides is known as
the W lllgerodt reaction {!)•
In 1887, Conrad W illgerodt ( ) found that 1-acetyl-
6
naphthalene was converted to -naphthylacetamid© by the
1
action of ammonium polysulfide at elevated temperatures in
a sealed tube#
QHl-C ^ H z
CD
This discovery led him to extend his Investigations to other
methyl ketones# He showed that In each case a mixture of an
acid amide and an acid sa lt was the main product of the re«
action* Later he found that this reaction could be extended
to Include ketones other than just methyl ketones* Thus
when propiophenone and valerophenon© were subjected to the
conditions of the ?ilillgerodt reaction, the corresponding
G&«*a©i& amide® and dJ^&cid salts were obtained#.
W illgerodt studied this reaction for over twenty-
five years and investigated more than forty ketones# Although