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PREPARATION AND CHARACTERSZATMN
OF SALTS OF TRIAMiNC‘GUANiDlNE

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PREPARATION AND CHARACTERIZATION
OF
SALTS 0F TRIAMINOGUANIDINE

3!
JOHN PAUL OLATTA

A THESIS

Submitted to the School of Graduate Studies or Elohlgan‘
State College of Agriculture and Applied Solonoe~x
1n partial fulfillment of the requiremente ‘
for the degree of

MASTER OF SCIENCE

Department of Chemietry
1951

2‘" {J / . .1

we;

1" (f 3 ‘f‘ C) ‘)
‘|"'TA"}\;‘) "‘

gcmonmcmm'r

Tho author respectfully aoknovladgaa

the guidanoa and enthusiasm of Dr. John
J. Pitha during tho period or research
and the preparation or thia thoaia. Ian:
thanks are axtandad to the Naval Taat
Station or China Lake, California, for
its financial aaaiatanoa.

1h. author ia alao grateful to hia vita
tornhar anoouragonant and aaaiatanaa in
producing thia thnaia.

EABLE OF CONTENTS

I - Introduction

11 - Preparation of Salt:
A. Trianinoguanidoniun Nitrate
B. Triaminoguanidoniun Bromide
C. Triaminoguanidonium Chloride
D. Triaminoguanidoniun Sulfate

III - Propertiee
A. Solubility Deteninatione
1. EXperimentel Procedure
2. Triaminoguenidonium Halidee
3. Triaminoguanidoniun Nitrate
d. Hydraeine Sulfate

B. X~Ray Diffraotion Studies
0. Study of Di-Aoid Salte
1. Preparation
2. Neutralization Curvee
IV - 'Dieoueeion

Bibliography

PAGE

dance.

15
17
19
21
23
24
29

31

guraonucrggn

I - INTRODUCTION

Current interest in the uses of hydrazine and
various other higher nitrogen content compounds has
prompted a more detailed study of trieninoguanidine
and its salts.

Salts of triaminoguanidine here been prepared

by the hydrazinolysie of carbon tetrachloride 1,
aminoguanidine 2, isothicuree ethers 8‘ dichloro-
fornoxine 4, and more recently of guanyl aside 5.
Of these methods, the first has been atte-pted but
never successfully repeated; and the synthesis from
dichlcrofornoxine is somewhat complicated. The re-
naining syntheses are nore or less similar.

the purpose of the research reported herein was
to prepare several salts of triaminoguanidine and to
study their characteristics.

a study of salts of aninoguanidine6 his sheen
that both Ione- and di-aeid salts can be prepared,
including the bromide, chloride and nitrate. Two
different sulfates can also be prepared, a ”normal”
sulfate and a "bieulfate'.

Recent studies of diaminoguanidine7 indicate that
di-aoid salts can easily be prepared. As with amino-
guanidinep two different sulfates were prepared,

(DAGH*)230 '

+4. 8
‘ and (D‘GBE ’ 30‘ e

-2-

An explanation can be given for the above
observations by noting the possible structures of
ethese guanidine derivatives and their unshared pairs

of electrons.

-.

 

Aminoggggidine 'Qianinoguanidine
32!: H I:
\-. 2|

C - ER HR:
/ \

EN: 0 : KB
I 1/
HQH: HT:
32]:

In each.cf the above compounds the inino
nitrogen would be surrounded by the greatest
electron density because of the carbonpnitrogen
'double bond; therefore, the first proton to beccne
attached to the nolecule would probably be held by
the imino nitrogen. After this first proton is
accepted the resulting ion would still be unsymmetrical
with regard to the groups attached to the carbon atol.
This condition would favor the addition of another
proton giving rise to the di-acid salts and explaining
the existence of two different sulfates, (DAGH')2804’
and (many) so“.

By the sane reasoning, the behavior of trianinc-
guanidine can.be explained. A possible electronic

configuration with the unshared pairs of electrons

is shown.
n din
H2l\s
all
\
0 3 ”0'32
/
H/lt
Hal:

As in aninoguanidine and diasinoguanidine the
am proton would probably become am». to the
nitrogen etc- with the greatest electron density.
In this can it would also be the nitrogen doubly
bonded to the carbon atol. Once a proton was
accepted, there would be three equivalent groups
attached to the carbon atom. ‘i'he electronic charge
will then be distributed sy-etrieally over the
nolecule and the nonc-pretcnated compound would be
very stable. This belief is supported by failure
to prepare dinacid salts of trianineguanidine.

EPA AT

igr SALTS

II. ‘- PREPARATIOI 0F SALTS

The nitrate, chloride, and bromide salts of
tria-incguanidine were prepared according to the
nothod of Pellissari and o.1c.:.9

)3: . 3' "' ‘32
c\: II + ”211‘ ——-> o\ 3 s-sn, e 2N3:
: " '32 El " “g

A - TRIAHINOGUANIDONIUH HITRATE

Twenty-seven grans, (0.2 .01.), of clinc-
guanidcniun bicarbonate was suspended in 250 ll.
of water. To this was added slowly 13.5 ll. (0.2 ncle),
of concentrated nitric said, then 24 ll. of lay-H20
(0.4 nole) as an 85$ aqueous solution.

the reaction mixture was heated to boiling for
three hours, water being added to naintain a constant
volunex it was then evaporated to about one-half its
volune on the steal bath. Upon cooling, use solution
took on a pink color and long needle-like crystals
formed. he naterial was filtered and washed with
ethanol and ether. After concentrating the filtrate
and cooling again several tines, acre of the product
could be obtained. The collected fractions were then
rocrystallised fro- wster, washed with ethanol and

dried in vacuo over porous barium oxide. The material
omelted at 215. 0., with decomposition, in agreement
with that of 216° 0. reported by Pellissari.

The salt was analysed for hydrasine content
according to the empirical method developed by

8 When using iodate solution

Keim, Henry and Smith.
as an oxidant for the analysis of hydrazine these
workers found that it was necessary tovgpply a
correction factor of a/2.b in order to explain their
experimental data. This factor was used in all
hydrssine analyses herein reported except as noted.
Calculated for triaminogusnidonius nitrate:
57.36% 123,
round: 86.85% 'gfl‘

3 '- TRIAHIHOGUANIDONIUI BROMIDE

The bromide salt of triaminoguanidine was pre-
pared the same wsy as the nitrate except that hydro-
bromic acid was used in place of the nitric acid.
Upon cooling the reaction solution the pink color
was again developed together with similar‘white,
long needle-like crystals. the product was filtered,
‘ washed with ethanol and dried over barium oxide. The
observed melting point was 223° 0., with decomposition,

I

as compared to 232’ 0. reported by Pelliasari.
Il'his melting point, however, could not be raised

appreciably by recrystallisation. Calculated for
triaminoguanidonium bromide:

0 - TRIAMIHOGUANIDOHIUH CHLORIDE

32.03
45.191
52.2%

«.29;

”2‘4

31.?

on.

I!"

the chloride salt of triaminoguanidine was
prepared as described above for the nitrate and

bromide.

the product again was a mess of white, needle-
lihe crystals. after drying, the salt nelted with
decomposition at 223° 0., compared to 231' c. as

reported by Pellissari.
raise the melting point.

guanidonium chloride:

Found:

so.“
25. 23s
68.2fi
24.99%

Recrystallisation did not
Calculated for triamino-

'234

01
'234

01

D - TRIAEEIEOGUANIDONIUK SULFATE

Following the procedure described above an
attempt was made ate prepare triaminoguanidoniun
sulfate.

One-third of a mole of aminoguanidonium bi-
carbonate was neutralised with one-third mole of .
sulfuric acid after which was added two-thirds mole
of hydrasine hydrate. The reaction mixture was then
heated on the steam bath for a few hours. Upon
allowing the water to evaporate no crystals of any
kind could be obtained, even with cooling. Finally.
a pink viscous liquid was forned which when cooled
with an ice-Lsalt mixture produced a mass of micro
crystals anon were filtered with difficulty. The
material was very soluble and could be recrystallised
only «from a 50% alcohol-water mixture. The product
which still had a pinkish color was found to contain
approximately 48% 804:, indicating a compound of
probably. composition 110.3280... The actual yield was
very small. '

When the preparation was repeated, the thick
syrup was again obtained. With the addition of excess
sulfuric said, however, a white crystalline material
was formed which was easily crystallised from water.
the product was analysed for H230 with the value of

29.66fi‘being obtained as an average of several
determinations. This value was obtained by using
the factor s/2.5 described in Section II-A.

Sulfate analyses indicated a percentage of
73.84. However, the hydrasine and sulfate content
would not fit any theoretical, possible salt. A
sample was then analysed for total nitrogen and
found to contain 22.2%..’ the sulfate and nitrogen
content indicated a salt of the composition TAG-33230,,
which would have the following percentage composition:

1 s2 ‘ 21.4 x
was, 24.14%
so" 72.5 s

If the factor s/2.e is not used, the percentage .
hydrasine is 24.83, in good agreement with the cal-
culated value. The material melted with decomposi-
tion at 240° c.

After solubility determinations had been com-
pleted, a marked similarity was noted between the
percentages found for this salt and those of hydrasine
sulfate. The similarity is shown in the following
table. .

* Analysis done by Klara-Tech Laboratories, Skokie,
Illinois.

 

 

12393950“ TAGOSHQSO‘
s2 ~ 21.56% 21.403
so: 73.35 72.50 .
H23, 2c.” . 24.83 (without factor)

Ieray diffraction patterns of the two salts
were then made. since they were identical, it can
be stated that the salt presumed to be triamino-
guanidonium tri-sulfate was actually hydrasine
sulfate.

Because the hydrasine sulfate was so easily
precipitated on acidification it was reasoned that
very little hydrasinolysis had occurred. Accordingly,
when the preparation was repeated, instead of heating
on a steam bath, the solution was boiled for one hour
with meals being liberated as usual in large quan-
tities. After concentrating and cooling, white
crystals could be obtained which were filtered and
washed with ethanol and other. This material was
analysed for sea“ and a percentage of 62.7 was ob-
tained, using the factor of 3/25. Since the yield
was small the preparation was repeated and the
crystals obtained were found to contain 52. 2% hydra-
sine. A sulfate analysis of either product indicated
36.56% so".

-10-

All fractions from the two preparations were
then recrystallised from an approximately 50%
alcohol-water mixture. Repetition of the hydrasine
and sulfate analyses showed no change in composition.
The percentages indicate a compound containing three
TAO molecules and two 3230, molecules or 5TAG-23280‘.
The calculated percentages however are 56.7%»H23‘
and 37.781 30". Nitrogen analysis showed 45.315

n1 tfogue .

Upon drying a sample over barium oxide at
80° C. a loss of weight, presumably water, was found
to be 6.25%. This latter determination indicates a
possible hydrated salt. If the triaminoguanidonium

sulfate were hydrated the calculated percentages

would be:
' Calculated for 3TA0023280‘02320 Found
Ian, 52.97; 32.23% (with
g . factor)
so, 33.285 35.32
'2 46.285 46.51
sec e.1 s c.2s

The presence of triaminoguanidine was verified
by treating a sample of the sulfate salt with the
calculated amount of barium nitrate. The barium
sulfate was removed by filtration and the filtrate

evaporated almost to dryness. Upon cooling, long

i Analysis done by Micro-Tech Laboratories, Skokie,
Illinois.

needle-like crystals were obtained which had the
characteristic fie-ability of the triaminoguani-
dcnium nitrate. The x-ray diffraction pattern of
the material was identical with that of the known
nitrate salt. ' v...

If the aminoguanidine, sulfuric acid, and
hydrasine mixture is heated at reflux temperature
for eighteen hours awhite crystalline material can
be isolated which is 51.8% hydrasinc, using the
factor. his material, however, does not appear
to have any sulfate present.

The achotte method of preparation was then
tried, treating s-nethyl, isothiourea sulfate with
the calculated amount of hydrasine hydrate. .The
reaction mixture was refluxed for three hours and
than? evaperated under reduced pressure. Upon cool-
ing, a crystalline material was formed which also
gave negative results when tested for the sulfate
ion.

Another quantity of the thiourea ether was
then treated with an excess of hydrasine and the
reaction mixture heated only one hour and then con-
centrated on the steam bath. lThe material which
crystallised out upon cooling was found to contain
81.81 '28,. A portion of this material was

recrystallised from a slowly evaporated water solu-
tion. as crystals obtained by this method were
found to contain 52.861 hydrasine, with the factor,
indicating again the compound auc- essay-cage.

by treating a weighed quantity of this salt with
barium nitrate, filtering the bariun sulfate, and
then evaporating. tria-inoguanidonium nitrate was
produced. this was again verified by the x-ray

V diffraction pattern.

Pro. the above series of preparations a number
of sclples of small yield were obtained. loch sample
had at least 52$ hydrasine and some detectable sul-
fate. These preparations were combined and dissolved
in a snail volusc of water and the solution allowed '
to evaporate slowly. Crystals were for-ed which
could easily be removed, washed and dried. Titration
with iodate indicated a percentage hydrasine of 52.34.
Further concentration of the filtrate again produced
large crystals which contained 52.23% hydrasine.

X-ray diffractionpatterns of these recrystal-
liscd fractions were identical with the pattern
obtained from the first salt of composition
suc. 23280” 2320.

Trialinoguanidoniun sulfate appears to lose its

'15-

water of crystallisation when heated to oo-cs° a.
no material them dcconposed when heated to 145-100“ a.
After dehydration a sample of the sulfate salt nelted
with decomposition in the range of 150.185. 0.

Ittempts were also made to prepare triamino-
guanidonium sulfate, using the double decaposition
reaction of silver sulfate with triaminoguanidonium
bromide. First, a hot suspension of silver sulfate
was added to a warm selution cf the bromide salt.
there was a violent evolution of gas and the mixture
bubbled over the sides of the beaker. When the
reaction had subsided, I evidence could be seen of
silver reduction. after several hours the beaker
was seated with a silver mirror.

the reaction was then run in the sold with the
silver sulfate being added to a cold solution of the
bromide salt. the slurry was then stirred three
hours at the end of which tine the precipitate had
turned completely black. The mixture was then
filtered and upon concentrating and cooling the
filtrate a mass of white crystals was obtained.
These were found to contain 501 hydrasine, but only
3% sulfate. The x-ray diffraction pattern for this
meterial was identical with that of the original
bromide salt. ,h'l'he reaction evidently had taken
place to only a slight extent.

PROPERTIES

-1‘-

III - PROPERTIES

A - Solubility Determinations

1. Experimental Procedure

In order to determine the solubilitics of
the triaminoguanidonium salts, saturated solutions
were prepared in all-glass system fitted with a
stirrer, thermometer, and an exit port for with-
drawal of samples and the addition of water, as
needed. All joints were ground glass.

The solubility samples were suspended in a
water bath maintained at constant temperature, with-
in.0.2‘ 0., by a mercury regulator switch and an
electronic relay.

After sufficient time for equilibrium.to be
attained, at least three hours at the desired tempera-
ture, a sample of the saturated solution was with,
drawn, placed in a tared 100 ml. volumetric flask and
weighed. In all cases excess solute was present.
After diluting to the mark, aliquots were analysed
for either anion or cation content. From the data
thus obtained, the solubility of the salt was easily
calculated and expressed as grams of salt per 100 g.

of solvent.

2. Triaminoguanidcnium Chloride and bromide

In determining the solubilities of these salts
the aliquots were analysed for halide content.
Analysis. for l2fl‘was not done in order to eliminate
using the factor described ‘in Section II-A. Titra-
ticns using silver nitrate and an absorption indica-
tor were not successful in that a definite end-point
could not be observed. The lohr titration was then
tried but the triaminoguanidine was evidently oxidised
by the dichromato ion and again no end-point could be
obtained. In the Volhard method, the sample solution
slowly became colored long before the end-point.

The method finally used to determine the anion
concentration, from which the solubilities were cal-
culated, was a potentiometric precipitation titration,
using c Ccnco lino-operated pH meter, with a platinum
and a silver, silver-chloride electrode. Potential
measurements were taken in the usual manner, ti trating
with silver nitratc.solution. Plots were then made of
Al/ml in order to get the well known, maximm differ-
ential curve. The silver nitrate solution which was
used had been previously standardised against c.P.
sodium chloride, using the potentiometric method.

The results are listed in Tables I and II, and
graphically in Figure l.

-15-

TABLE I
solubility of triaminoguanidonium bromide in water

Grams of 219-1132

fenperaturc 0° per 100 g. water

10.0 . 4.37
21.7 0. 01
80.1 7.68
50.7 10.74
45.5 13.“
00.0 15.40
57.0 10.50
01.0 23.70

i'ABLE ll
Solubility of triaminoguanidcnium chloride is water

Grams of RAG-[cl

fuperaturc 0° per 100 g. water

10.0 a.s

22.0 0."
25.0 10.10
23.0 11.00
00.0 14.00
40.7 1s.c1
46.0 1a.sv
47.0 10. as
00.0 21.00
53.0 22.71
55.0 23.23
00.0 20.04

p 17-

3. Triaminoguanidonium nitrate

In determining the solubility of the nitrate
salt, the aliquots were analysed for hydrasine con!
tent according to the method described in Section
II-A. the potassium iodate solution was prepared
from 0.P. potassium iodate and standardised against
hydrasine sulfate which had been.doubly recrystal-
lised. the results are shown in Table III and

”6111'. Is

TABLE III
solubility of triaminoguanidonium nitrate in water
drame of fAdoHNO;

Temperature 0° per 100 g. water

16.1 8.66
21.6 -' 12. 3‘
25.0 10.0

30.1 10.13
35.1 , 23.92
60.0 80.66
45.0 89.43
47.6 44.61

60.0 60.00

60

So

40

30

20

10

:lg'

n——~-~.—,---_—."._._ i- -7 _..~__.._.,1

 

FIGURE I

SOLUBILITY OF TRIAMINOGUANIDONIUM SALTS

 

 

Temnerntnre 1n “banana n

_. f
H
m ,
+3 /
w /
3 TAG‘HNO ,5
e 3 ,‘l
u) g
C) I
p—CD ‘
H d
/
H J
m ,
g. .
.p
H ,
w »
m /
g. ,
— o f
/
m A
a // ,
w , /
{S //
4/ TAG'HCl//
/ ” J
// ’,
/ // / I
P“ ,/ 00 .0
p' // ,'TAG'HBr
1 // L
,/ X
5/ ”//p H
_x- 9" ///C) ’/l ,(J//
>—— 0 /fi’/0 /// /,/
3/1} 7/‘
ow///’
l l 1 i L J.
20 30 4O 50 0 6O 7O

-19-

4. Hydrasine Sulfate

As mentioned in Section 11-0, the solubility
of a salt believed to be triaminoguanidonium sul-
fate was determined for water and 1.008 nonmal sul-
furio acid solution. this salt was proven to be
hydrasine sulfate. the solubility data was recal-
culated on this basis with the results being listed
in Table IV and shown graphically in Figure 11.

the solubilities cf’hydrasine sulfate in water
agree with those reported in theolitcrature.10

TABLE IV
Solubilities of Hydrasine Sulfate

 

 

 

 

Tcmpera- Grams per , tempera- Grams per '
turc 0° 100 g 820 ture 0° ‘ 100 g acid
21.50 3.06 18.8° . 0.87
23.1 3.42 21.3 0.92
30.1 3.94 23.5 1.06
34.5 4.60 27.5 1.11
38.9 5.08 28.8 1.21
42.5 5.57 31.0 1.35
47.5 6.49 34.3 1.55
49.5 6.83 36.0 1.69
52.5 7.38 37.7 1.90
54.1 7.68 38.8 1.95
38.3 8.67 41.3 2.20
61.2 9.39 43.6 2.50
64.0 10.04 45.7 2.62
48.8 2.99
51.6 3.32
53.7 3.61
57.9 4.34
61.0 5.08
64.0 5.74
65.9 6.22

10

\O

 

 

FIGURE II

SOLUBILITY OF HYDRAZINE SULFATE

 

Upper Curve - Water
Lower Curve - 1.008 N H2804
F_ p
O

__‘D ,

g 0

,3 7
*_ o ,

0) Q
—— u? L/

O .. O

S: ,U/ n
__ 3 /

.. /
__:: _o” O”

3'; 9 " /
$-—- ‘8 O r_//

m G ”

E _
- 23 O //

(5 ,29/y/fi/
P— O/ (WILD/OM/

1 1 J I i i
10 20 3O 4O 50 60

Temperature in Degrees Co

B 7- X-ray Diffraction Studies

For purposes of identification, x-ray diffraction
patterns of the powdered salts were made. Because of
the complex nature of the patterns no attempt was
made to determine the specific structures of the
products. The diagrams were used only for comparative
purposes.

The patterns were made on a North American Philips
instrument, ..... 0n, x.gradiation and . 01 filter.
cameras of a 114.59 -. diameter were used. Exposure
times were fourihours each, using 35,000 volts and 15
milliamps.

The ten most prominent lines together with their
relative intensities are listed in the following tables
for each salt. The 'd' distance for the Bragg equation
was determined fro. a previously prepared graph.

TABLE v J
TRIAHNOGUANIDONIUM HITRA’I’E

Intensity '0'
'0 7 O 1.
t. 0.4 4
7.0. 0.52
7.0. - 4.17
I. 5.70
7.8. 3.00
a. ' 3.00
0. 2.00
v". 2. 88
0. 2.74

TABLE VI
TRIAIIHOGUANIDOHIUI CHLORIDE
TAGOHG1
Lntensity 'd'

5. 6.62
7.0. 5.16
r '0“. ‘0“
. I. 3.72
W. 3.24
3. 3.13
S. 2.90
V.'.W. 2.40
W. 2.30
vc'sa'e 1.88
TABLE VII
TRIAMIHOGUAHIDONIUI BROMDDE
TAGOHBr
Intensity ' 'd'
'08. ‘0”
3. 4.06
W. 3.36
s. 3.1.
7.8. 2.96
I. 2.45
8. 2.56
7.W. 2.31
W. 1.78
W. 1.54
TABLE VIII
TRIAMINOGUANIDONIUH SULFATE
3TA0-28280‘-2820
Intensity I'd"
.0 a.“
W. 6.64
a. 5. 28
W. 3.05
S. 4.75
I. 4.66
w. ‘0“
W. 4.18
8. 3.66

Yes. 3.2.,

0 ~ Study of Di-Acid 3.1:.

Since di-acid salts of aminoguanidine and
diaminoguanidine can be prepared it was assumed
-that.multi-protonatcd salts of triaminoguanidine
could also be prepared.

1. Preparation

The procedure for the preparation was the acme
as previously described in Section II-A, except that
an extra mole of the desired acid was added. The
material subsequently obtained by evaporation and
cooling was very similar to the mono-acid salts. For
quick identification, x-ray diffraction patterns
were made. The patterns of the supposed di-acid
salts were in each case identical with those of the
mono-acid salts.

During an investigation of arsenic-organic com-
pounds’, August Albert in Germany reported the prep-
aration of materials containing a 030 group, not in
a ring, by condensation with compounds containing
several hydrasine groups. One of these compounds was
reportedly triaminoguanidonium dinitrate. Ho refer-
once, however, is made to the preparation of the

triaminoguanidinc salt.

-24-

2. Neutralization Curves

Tenthrmelar solutions or the mono-acid and
supposedly dinacid salts of triaminoguanidine were
prepared. Ten milliliter samples in 100 ml. of
water were then titrated with 0.0891 N. NaOH solu-
-tion. The changes in pH were followed by a line-
operated Canoe Titration pH later, using a saturated
calomel and glass clectrode. These changes were
plotted as usual and Iron the plot or pH versus
volume or alkali it is evident that the none-acid
salts had no titratable proton. It is also evident
that the di-scid salts were actually mono-acid.

Ten milliliters of tenthenolar trianinoguani-
donium sulfate were also diluted with 100 ll. of
water and then titrated with 6.1 I sodiun.hydroxide.
the resulting curve has the appearance of a buffering
action. This night be expected since the triamino-.
Guanidonium ion fiflfigfl' would act as a weak acid.

pH

14L.

13r—

12>—

11+—

10~—

 

O.

 

FIGURE III

TITRATION CURVES OF
TRIAMINOGUANIDONIUM NITRATES

o - TAG~HNO3

c - TAG-2HN03

(Actually TAG-Enos)

.0

J I L l I J Ll

 

6 8 10 12 14 16 18

NaOH milliliters

 

pH
14

13

12

ll

10

 

FIGURE IV

TITRATION CURVES OF
TRIAMINOGUANIDONIUM BROMIDES

0 - TAG'HBr

e - TAGoZHBr
(Actually TAG-HBr)

 

o 9 3 O 9

OO

O

O

O

O

O
O

O

l 1 I 1 l J l 1 L J l
o 6 8 10 12 14 16 18 20 22 24

NaOH millilitnro

 

pH

14

13

12

11

10

\O

 

FIGURE V

TITRATION CURVES 0F
TRIAMINOGUANIDONIUM CHLORIDES

o - TAG°HCl

O - TAG'ZHCI
(Actually TAG-H01)

O\r—-—
m
H
O
H
N
H
4)
H
0‘
H
CD
N
O
N
N

 

pH
11

10

C}
r +

 

# L.__._

 

FIGURE VI

TITRATION CURVE 0F
TRIAMINOGUANIDONIUM SULFATE

1 l J i J 1
8 10 12 14 16 18

NaOH milliliters

1 l
20 22

-- -— L——-—— _.

24

._ H...‘ A

26

DISCUSSION

-29-

IV - 1318008810!

. The nitrate, chloride and bromidesalts cf
triaminoguanidine can be easily prepared by the
hydrasinolysis of aminoguanidine. These salts are
stable in water or acid solutions. Only the nono-
protonated salts could be prepared and titrations
with base indicate that the salts do not act as
'acids" in water solution.

me difficulties and reactions encountered in
preparing triaminoguanidoniun sulfate were described
in Section Ila-D. These difficulties require sons
explanation. The sulfate salt finally isolated
had the sonpcsition STAG-282804021120; if a solution
of this naterial is acidified with sulfuric acid
hydrasine sulfate is formed and precipitates in
white crystals which are easily filtered. Evapora-
tion and cooling of the filtrate produces a '
crystalline material which can be identified as
aninoguanidonium sulfate. This reaction might be
expressed as an equilibrium as shown below:

- 1L

(TAG) 2 3280‘ + 3280‘

Thus crystallisation of an equimolar mixture
of the two different salts would produce a laterial
which upon analysis would agree with a compound
of composition 3TAG-2H2804-2820. Addition of base
would then favor fonsation of the compound (TAG)2H250‘,
liberating in the process one.nole of sulfuric acid.
A solution of the salt BTAGOEHZSO‘02320 would then be
expected to be acidic and this is actually the ease.
a.hundredth-molar solution has a pH of six and titration
with base (sodium.hydrcxide) indicates.neutralisaticn,
at a nolar ratio of two moles base/one.mo1e salt, as
would also be expected. lhe low nelting point of the
trianinoguanidonium sulfate also indicates that the
nmterial is probably not a pure compound.

The pH of'a triaminoguanidoniun sulfate solution
can be considered as due to the following dissociation:
T1032" : TAGH’ 4 3+

Choosing three different points on the titration
curve and applying the buffer equation, 3’ :Lgs K.,
gives the following results for apparent K. and px.
of this dissociation:

Ka pKa
2.1 x 10" 8.32
2.0 x 10-8 8.30
2.4 x 10"3 8.38

1.
2.

5.

4.

5.

6.

7.

8.

9.

10.

BIBLIOGRAPHY

StollO, Re, Bare £1. 5548 (1.90".

Pellissari, 0., and Gaiter, A., Gasz. chin.
ital. 44, II, 78 (1914).

Schotte, 3., German Patent 501,389 (1926):
Chem. Abstract.gg 4524.

Prandtl, R., and Dollfus, 2., Ber. 65 754
(1952).

O'Connor, T.E., Bergen, 1., and Reilly, J.,
J. Appl. Chem. A, 91, (1951).

aw.. JOJO' Hugh... Jro' He. .nd saw,
0.3.1“, Jo “e ChOIe SOC. 19-. 2823 (1948)e

Unpublished results by Pitha, J.J., and
01.tta’ J. P0

Keim, 0., Henry, R.A., and Smith, G. B. L.,
Je “a ChOIe 300a L2. 49“ (1950’s

“bCI‘t' ‘e. Chem. Zentr. II. 158‘ (1928’ Oh.le. x
Abltttflfi, 22, 41291. .

8onmer, F., and Weiss, K., 2. snorg. allgon.
Chen. 2’- 51. (1916).

ABSTRACT OF A THESIS

51
John P. ULaTiA

'PREPARATIOR AND CHAhAClEhIZATIUfi Ck SALTS 0} lRiAtheGdAfilDINE"

Currant interest in the uses of hydrazine and other high
nitrogen content compounds has prompted a more detailed study
of the salts of triaminoguanidine. The purpose of the re-
search was to prepare several salts of triamineguanidine and
study their characteristics.

The chloride, bromide, nitrate and sulfate salts were
prepared by the hydrazinolysie of the corresponding amino-
gusnidinc salts. Triamineguanidonium sulfate was also pre-
pared by the hydrasinolysis of S-mcthyl isothiourea sulfate.

Solubility determinations as a function of temperature
were made of the nitrate, chloride and bromide salts in
water. The solubility of hydrasine sulfate was determined,
both in water and in one normal sulfuric acid.

For purposes of identification, powder x-ray diffraction
patterns were made of the salts. The ten most prominent
lines of each pattern are listed with their relative inten-
sities and corresponding 'd” distances for the bragg equation.

attempts were made to prepare di-acid salts of triamino-
guanidine. leray diffraction studies and titrations with
alkali show that only the mono-acid salts can easily be
prepared.

JOhn Pa Olfltt.

From the reactions and properties of triaminoguani-
doniun sulfate it was deduced that the salt isolated
was actually an equimolar mixture of two different com-
pounds ahieh form an equilibrium in neutral water

solution.

 

 

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