RESEARCH AND DEVELOPMENT DEPARTMENT

J. E. Wilson, Director

NavWeps Report 7109

Technical Report 116

11 May 1962

SYNTHESIS AND PROPERTIES OF

SOME CYANURIC CHLORIDE DERIVATIVES

By
M. S. Chang
A. J. Matuszko

U. S. NAVAL PROPELLANT PLANT

Indian Head, Maryland
0. A. WESCHE J. E. DODGEN
Captain, USNavy Commander, USNR
Commanding Officer Technical Director
r
NAVWEPS REPORT 7109

FOREWORD

This report combines a summary of significant accomplish-

P ments of foundational research task assignments of the Fundamental
Processes Division during the period from September 1959 to
September 1961.
r This report is transmitted for information only. It does not

i' represent the official views or final judgment of the Naval Propellant
Plant. It represents Information released at the working level that
is still subject to modification and withdrawal.
The work was performed under Tasks NPP-00-213/32015/07041,
R-360-FRO9/RO1101/001, and R-360-FR109/RO1101/001/286/1,
and data are recorded on laboratory notebook pages 71176-71250
and 61201-61275.

A. J. Matuszko
Head, Polymer Division

Approved by:

Bodoiartocha

Associate Director for

Research

Released by:

0. A. WESCHE
Captain, USNavy
Commanding Officer

l iii

., - _ . ....
 CNAVWEPS REPORT 7109

CONTENTfS

Heading: Page no.

<5 Forewordiit
Abstract vi
Historical
Discussion 3
Ricperimental Details 10
Rierences- 19,

I-

v
 NAVWEPS.REPORT 7109

ABSTRACT

Cyanuric chloride was reacted with several negatively ,

substituted primary alcohols with fiuoro, bromo, nitro, or
nitroxy groups as electronegative substituents. Completely
substituted reaction products were obtained with trifluoro-
ethanol, tribromoethanol, pentaerythritol trinitrate, and
pentaerythritol dinitrate. Di- and tri-substituted products
were obtained with 2-methyl-2-nitro--1-propanol which has a
tertiary nitro group, whereas alcohols with primary and
secondary nitro groups did not react. The reaction with the
potassium salt of nitroform gave a product which gradually
H
decomposed on standing. The monoperchlorate salt of
trhydrazino-s-triazine was obtained, but attempts at the .4.
preparation of perchlorate derivatives of amincazido-s-
triazines were unsuccessful. Sensitivity and stability data
are reported on some of the products.

vi
 NAVWEPS REPORT 7109

SYNTHESIS AND PROPERTIES OF SOME CYANURIC

CHLORIDE DERIVATIVES

A project involving the synthesis of cyanuric chloride

derivatives was undertaken with the purpose of preparing heat-
stable materials which might be useful as propellant ingredients.
Because of certain similarities in structure between cyanuric
chloride and trimeric phosphonitrilic chloride, an investigation of
the reactions with these two compounds was undertaken concurrently.
The study with trimeric phosphonitrilic chloride will appear in a
later report.
Reactions of cyanuric chloride (2,4,6-trichloro-s-triazine)
with hydroxyl compounds to give alkoxy-s-triazines and aryloxy-
s-triazines have been studied extensively by F. C. Schaefer's
group at American Cyanamid Company. (1, 2) However, reactions
with alcohols and alkanes containing nitroxy or nitro groups have
not to our knowledge been reported. Therefore, as part of our
study we undertook acquiring information on the reactivity of
negatively substituted alcohols and alkanes with cyanuric chloride.
Azido and hydrazino derivatives of cyanuric chloride proved of
sufficient interest in gas-generator applications to warrant their
inclusion in this investigation.

HISTORICAL
Cyanuric chloride has been known since 1827, (3) although for
some time it was considered to be the trichloride of cyanogen.
Liebg( 4 ) determined its composition after preparing the compound
by passing chlorine over dry potassium thiocyanate.
Impure cyanogen chloride was converted to cyanuric chloride
with sunlight by Serullas. (3) However, the product was believed for
many years to be an isomer rather than the trimer of cyanogen
chloride. As late as 1867,(5) the trimer to monomer relationship
of cyanuric chloride and cyanogen chloride was not clearly under-
stood. Infrared and ultraviolet spectra( 6 ) now support the triazine

I1
 NAVWEPS REPORT 7109

structure and indicate that the chlorines are located on the

carbon atoms.
Cyanuric chloride is readily hydrolyzed by water vapor
to cyanuric acid and hydrochloric acid. Treating cyanuric
chloride with hot alcohols produces cyanuric acid(7 ) and the
corresponding alkyl halide with almost no esterification. Mono-,
K di-, and tri-alkyl esters of cyanuric acid have been made by
reacting cyanuric chloride with alkaline earth alkoxides( 8 , 9 ) or
with alcohols in the presence of basic acceptors. (9) To carry out
a stepwise substitution, the preferred base is either sodium
carbonate or sodium hydroxide. (10)
Primary and secondary amines, hydrazines, and related j
compounds react with cyanuric chloride in three steps. The
oversimplified rule of thumb, expressed frequently in the litera-
ture,( 1 0 -19 ) that the first chlorine atom is replaced at 0* C, the
second at 30*-50* C, and the third at 900-100 ° C cannot be used .4
generally. This rule applies only to water solutions and not to
other solvents. Some amines react to replace all three chlorine
atoms at 0* C; others do not react at all, or react with the replace-
ment of only one of the chlorines even at 1000 C.
Certain mercaptans or their alkali metal salts react with
cyanuric chloride( 2 0 ) indicating that the chlorine atoms are
sufficiently active.
Cyanuric triazide is produced( 2 1 ) by the reaction of sodium
azide and cyanuric chloride in aqueous acetone solution.
Cyanuric chloride has been reported( 2 2 ) to react vigorously
with silver nitrate in acetonitrile solution to form a trinitro-s-
triazine which has not been well characterized.
Alkyl Grignard reagents react with one of the chlorine atoms
of cyanuric chloride( 2 3 ,24), whereas, with some aryl Grigard
reagents, two chlorine atoms( 2 4 ,25) undergo replacement. The
products are 2-alkyl-4, 6-dichlorc-s-triazines and 2,4-diaryl-6-
chloro-s-triazines, respectively.
8
Cyanuric. chloride reacts( 2 6 ) with iodo- or bromobenzene( , 27)
or with bromophenetole and sodium to give mixtures of di- and
tri-aryl-s-triazines. A mixture of cyanuric iodide and 2-chloro-
4, 6-dilodo-s-triazine is produced when a cold 56% hydrolodic
acid solution is mixed with cyanuric chloride. (7) This again is

2
 NAVWEPSREPORT 7109

essentially a simple exchange reaction wherein iodine replaces

chlorine on the triazine ring.
Tris-(hydroxyaryl)-s-triazines(l 0 ) are formed by-the reactions
of phenols with cyanuric chloride in the presence of aluminum chloride
catalyst. Cyanuric cldoride reacts with sodium salts of organic
carboxylic acids,( 2 8 ) as well as with the free acids, to form sodium
cynurate and the corresponding acyl halides.
The active hydrogen of diethyl malonate reacts with one
chlorine atom in cyanuric chloride(2 9 ) to form the (4, 6-dichloro-
s-triazinyl)-dietbyl malciate. The primary reaction is base-
catalyzed. In order to have a reaction with all three of the chlorines
of cyanuric chloride at least three equivalents of sodium malonic
ester and vigorous conditions are required. (29)
When cyanuric chloride is heated with benzamide, the-cyanuric
chloride is hydrolyzed to cyanuric acid as benzanide is dehydrated
to benzonitrfle. (28)
Cyanuric chloride is resistant to the action of most reducing
agents. With lithium aluminum hydride in ether, Grundmann and
Beyer(3 0 ) found only the 'inorganic products lithium chloride (LiCl),
aluminum chloride (AICI3), and lithium aluminum cyanide (LiAJ(CN)4)
in the reaction mixture; hydrogen was evolved during the reaction.

DISCUSSION

Cyanuric chloride, the starting material in the synthesis of

s-triazine derivatives, is the acid chloride of cyanuric acid.
OH C1

CC

\/C\
Hv-L Cl-CC

Cyanuric Acid Cyanuric 'Chloride.

3
-:-,3- ' [i
NAVWEPS REPORT 7109

According to Paullng( 3 1 ) the s-triazine ring is stabilized by a

resonance energy of 82.5 kcal/mole compared to 39 kcal/mole
for benzene. The high resonance energy is probably due to the
six nonbonding electrons on the three ring n. trogens which contri-
bute to the resonating system. Because of the high stability of the
ring, much of the chemistry of s-triazines is simply the chemistry
of the substituent groups. The ring is not often Involved in the
reactions except for its effect on the charge distribution.
This study was initiated with the purpose of synthesizing and
determining the properties of nitro and nitroxy derivatives having
the s-triazine nucleus. It was hoped that the reactivity of the
cblorines in cyanuric chloride together with the high ring stability
would result in the preparation of highly stable products. Halogen
derivatives were included in the study because of the electron
withdrawing properties (electronegativities) of the halogens which
are similar to those of the nitro and nitroxy groups. Hydrazino
and azido compounds were synthesized as potential gas generator
ingredients.

Reactions of Cyanuric Chloride with Polyhalogen Alcohols:

Trifluoroethanol and tribromoethanol were reacted with
cyanuric chloride. These alcohols were used to determine whether
electron withdrawing halogen substituents affected the reactivity of
the alcohol with cyanuric chloride or the stability of the final product.
B jth reactions proceeded smoothly to form the corresponding esters
in good yields indicating that the electronegative groups did not hinder
ester formation. The products appeared to be thermally stable up
to and above 1900 C.

41
II
/ C C 7 OCH 2CX 3

CI + HOCH2CX3----o. X3CCH2OC COCH2CX3

where X F or Br.

F4
 j 'V
NAVWEPS REPORT 7109

Reactions of Cyanuric Chloride with Nitroxyalcohols:

Reactions were carried out to determine whether nitroxy
groups-affected esterification or the subsequent stability of the
products; Pentaerythrtl trinitrate (PETriN) and pentaeryth-
ritol dinitrate2 were the nitroxyalcohols used in these reactions.

The cyanuric tri-ester was successfully obtained by the reaction

ofpentaerythritol trinitrate and cyanuric chloride in aqueous
acetone solution with potassium hydroxide as the acid acceptor.
This, to our knowledge, isthe first nitrate ester reported in the
~s-triazine series.

1-l
IC
N NN
+ HOCH 2 C)-CH 2 2 ONO

Cl-C\C~ClCH 2 0N0 2 ;

OCH2(CH2ONO 2)3

N\N
(O2NOCH 2 )0
3 CCH2OC COCH 2C(CH 2ONO2 ) 3

iN

Pentaerythritol dinitrate was reacted as aboveto form the

corresponding tri-ester. The second hydroxyl group of pentaeryth-
ritol dinitrate underwent esterification as did the first hydroxyl
group. Elemental analyses and molecular weight data indicate a
reaction between two molecules of cyanuric chloride and three

S12,2-Bis(nitroxymethyl)3-nitroxy-l-propanol.
-r i2 2,2-Bis(nitroxymethyl)-1,3-propanediol.

--

-[',-
i NAVWEPS REPORT 7109

molecules of pentafnrythritol dinitrate. A possible structure for the

product is shown below.
.

Cl

~' \ C 2 ON0 2
N NI
N C-Cl + HOCH 2 -C-CH 2OH -

C~h2 ONO2

CH2 ONO 2

COC 2 -C-CH 2 O- C

19 N ciL2ONO2 N N

OCH2 00H 2O C 2 C 2
OC2CH2 0~)

Reacionsof Cyanuric Chloride with Mononitroalcohols and with

Reactions with Mononitroalcohols: Reactions of cyanuric

chloride with nitroethanol, 2-nitro-i-butanol, and 2-methyl-2-
nitro-1-propanol were tried. Corresponding esters were not
obtained by attempted reactions of nitroetbanol (and 2-nitro-1-
butanol) with cyanuric chloride, (i.) in aqueous solutiou with an
acid acceptor, (2) by suspension of potassium hydroxide in the
nitroethanol with slow addition of cyanuric chloride, or (3) by
fusion of nitro ethanol and cyanuric chloride. However, 2-methyl-
2-nitro-1-propanol did react in aqueous alkali solution to give the
di- and the tri-esters in low yields.

6
 NAVWEPS REPORT 7109

Cl
C¢

CH3
N NI.
I III
I + CH1
--
3 C-CH2OH
I , cl-C C-Cl
TO2
N
OH3

COCI{2 0-0H 3

CH3 Nj N2 H3

CH 3 -CCH 2 00 COCI C-CH

2 3 + HC1

NO 2 ~N NO 2

The above may be at least partially explained on the basis of

a tautomeric shift to the aci-form of primary and secondary nitro
compounds. Nitroethanol with a primary nitro group and 2-nitro-
1-butanol with a secondary nitro group can exist in both tautomeric
forms. In basic solution the equilibrium shifts in the direction of
the aci-form.
RCH 2NO 2 RCH=NO2 H KOH- RCH-NO2K

nitro form aci-form

Under the reaction conditions used, the cyanuric chloride
probably reacted with the aci-forms in these two instances to form
the corresponding nitronic esters which then decomposed on
attempted isolation. A tertiary nitro compound, such as 2-methyl-
2-nitro-1-propanol, has no hydrogen alpha to the nitro group and,
therefore, can have no aci-form. The reaction with cyanuric
chloride would result in esterification through the alcohol group
of the nitroalcohol.

Reaction with Trinitroethanol: Methods of carrying out the re-

action of cyanuric chloride with trinitroethanol were .limited because

7
 NAVWEPS REPORT 7109

of the decomposition of trinitroethanol in basic solution as well

as at high temperatures. Hence, it was not possible to fuse the
two components at elevated temperatures. Attempted fusion at
a relatively low temperature yielded an oil which was probably
a mixture of di- and tr-substituted derivatives. When ferric
chloride (or aluminum chloride) was .used as a catalyst in carbon
tetrachloride solution, the main product was trinitroethylortho-
carbonate (TNEOC).

Reactions with Nitroalkanes:

Reactions with Nitromethane: The reactions were tried
(1) in aqueous alkali solution, (2) in suspension of potassium
hydroxide in nitromethane with addition of cyanuric chloride, and
K
(3) in a refluxing mixture of cyanuric chloride and nitromethane.
However, no expected product was obtained. Nitromethane, com- i
pared to other nitroparaffins, is uniquely sensitive to the action of
alkali. (31) Also, as in the case of the nitroalcohols, the formation
of an unstable nitronic ester may have taken place when the reaction
was carried out in alkaline solution. When cyanuric chloride was
almostquanin ntromethane, the starting material was recovered

Reactions with Potassium Nitroform: An attempt was made

to react potassium nitroform with cyanuric chloride according to
the following reaction:

C] C(NO0 3

I
+ KC(NO0)s------*

Cl-C -Cl (N02) 3C-C C-C(NO) 3 + KC1

N
Based on the quantitative yield of KC1 obtained, the reaction appeared
to have proceeded smoothly. However, an accurate microanalysis
was not obtained, probably due to instability of the product formed.
Once again, the instability may be due to the formation of the
nitronic ester whIch gradually decomposed following isolation.

*8
 NAVWEPS REPORT 7109

On the other hand, if the reaction proceeded as given above, the

instability of the product could be due to the electropositive nature I
of the ring carbon as well as. the carbon with the three electron
withdrawing nitro groups resulting in weak C-C linkages. Attempts
at removing residual quantities of solvent from the n-hexane
soluble portion of the reaction mixture proved difficult. Gradual
decomposition was apparent from changing microanalysis on
standing.

Reactions with Trihydrazino-s-trazne4 -

The trihydrazino-s-triazine was made with the hope that the
triperchlorate could be prepared. However, the experimental I
results indicate th.t only the monoperchlorate was obtained.
Trihydrazino-s-triazine did react with 3 moles of acetone to give i
the corresponding hydrazone derivative. Apparently, the trihydra-
zino-s-triazne was not basic enough to form the stable triper-
chlorate. Upon diazotization of trlhydrazino-s-triazine, 2-azido-
4, 6-dihydrazino-s-triazine was isolated. (21)

*
H2NHNC
41\
CNHH N
/ \
CNHNH 2
NU
i
11 + HONO H20, 00 C

\\C/ 'C/ + H20

NHNH 2 NHNH2

This compound decomposed upon addition of perchloric acid and

therefore no perchlorate was obtained.

Reaction of Cyanuric Chloride with Ammonia Followed by Sodium

Azide:
Cyanuric chloride was reacted with ammonia to give 2-amino-
4, 6-dichloro- and 2-chloro-4,6-diamino-s-triazine by varying the
conditions according to Thurston, Dudley, Kaiser, Hechenbleikner,
Schaefer, and Holm-Hansen. (33) Treating sodium azide with 2-
amiho-4, 6-dichloro-s-triazine produced 2-amino-4, 6-diazido-s-
t.riazine which was identical with an authentic sample synthesized
by another route (passing ammonia gas into an ether solution of
cyanuric triazide).

9
 NAVWEPS REPORT 7109

Cl/%-lN 3 -C CN
I + NaN----- I 3

\C/ N
\/ N

NH2 NH2

N N

N3 °I

This former route for making 2-amino-4, 6-diazldo-s-triazine was

less hazardous than the latter. Attempts at making the perchlorate
of the 2-amino-4, 6-diazido-s-triazine were unsuccessful and only
starting material was recovered in all cases. Treatment of 2-chloro-
4, 6-diamino-s-triazne with sodium azide gave none of the corre-
sponding azide. The limited solubility of the 2-chloro-4, 6-diamino-
s-triazine In common organic solvents might explain this.

EXPERIMENTAL DETAILS1
2,4, 6-Tris(trfluoroethoxy)-s-triazine.:

A suspension of 0. 85 g (0. 015 mole) of potassium hydroxide

i 10 Al Of trlfuoroethanol -was stirred at room temperature while
0. 9 g (0. 005 mole) of cyanuric chloride was added gradually; the
reaction temperature was held at 30o-35 °C. After all the cyanuric
chloride was added, the mixture was refluxed for 5 hours. A
solid (potassium chloride) was separated by filtration. The filtrate
was washed with water, and the excess trifluoroethanol removed by
distillation. The residue was washed with water and then dried.
Recrystallizations from petroleum ether gave colorless crystals;
mp 450-460 C; yield 1. 2 g (64%).
IA11 melting points are uncorrected.

10
 NAVWEPS REPORT 7109

Anal for CqHEFiN 30 3 :I

C H F N I
Calcd 28.80 1.60 45. 60 11.20
Found 28.96 1.'54 45.67 11.60 'i
Ignition temperature: 3250+ (slight fuming 1920-2900 C). A

2,4, 6-Tris(tribromoethoxy)-s-triazine: A

A solution of 0. 9 g (0. 005 mole) of cyanuric chloride in 15 ml

of acetone was mixed with 4.4 g (0.015 mole) of tribromoethanol in
.15 -ml of-acetone. A solution of 0. 85 g (0. 015 mole) of potassium
hydroxide in 10 ml water was then added slowly in order to keep 'the
reaction temperature around 450 C. After all the solution was

4. 1
added, the mixture-was stirred for 20 min. The solid was separated
by filtration and washed with water, alcohol, and then acetone.
Repeated recrystallizations from methylene chloride and n-hexane
? yielded the pure product weighing 4. 0 g (86%); p 280-281 ° C (d).

Anal for C9 4BrNSO3 :oI

C H N Br I
Calcd 11.70 0.65 4.56 77.89
Found 11.57 0.57 4.64 78.38 '

~Tripetryl cyanurate (or 2, 4, 6-tris [2, 2, 2-tris (nitroxymethyl)

! ethxy -s-triazine).

A solution of 3.0 g (0. 011 mole) of PETriN in 5 ml of acetone

and 10 ml of 5% potassium hydroxide solution was stirred at room
temperature. The mixture was added to a solution of 0.7 g
(0. 00379 mole) of cyanuric chloride in 10 ml of acetone. There was
an immediate rise in temperature up to 450 C. Stirring was con-
tinued for 20 min. The mixture was then placed under an air
stream to evaporate the acetone. Upon removal of the acetone the
aqueous solution was decanted. The residue was washed with por-
tions of water, alcohol, and benzene, and then recrystallized from
acetone and alcohol to form small needles; mp 131°-132 ° C;
yield 3. 0 g (0..00337 mole, 88%).
'Anal for ClOH 24N120 30 :
C H N
Calcd 24.32 2.71 18.91
Found 24.30 2.89 18. 79

11
 NAVWEPS REPORT 7109

Ignition temperature: 1750 C

Vacuum stability: 0.34 cc gas at 1000 C for 40 hours
Heat of combustion at constant volume at 250 C: 2437 cal/g

Reaction of cyanuric chloride with pentaerythritol dinitrate:

A solution of 0.9 g (0. 005 mole) of cyanuric chloride in 20 ml
of acetone and 3.4 g (0.015 mole) of pentaerythritol dinitrate was
stirred at room temperature. A solution of 0. 9 g of potassium
hydroxide in 10 ml of water was added dropwise to the mixture while
keeping the temperature at approximately 450 C. When all the
aqueous solution had been added the mixture was continuously stirred
at 45° C for 30 minutes and then at room temperature for 15 minutes.
After evaporating the solvent, the oily residue was washed with
1
water several times and then evaporated to dryness. The oily
material was, crystallized from n-butanol; yield 1. 1 g (0. 0011 mole,
22%); mp 94°-95 ° C. The crystallized material was assumed to
have 1 mole of residual butanol.
Anal for C 2MH24N 2 0 24 C4H100: I
a. C H N
Caled 33.25 3.77 17.51
Found 32.88 3.98 17.52
Recrystallization from dioxane and methanol yielded a white
solid in which a mole of methanol was retained; mp 1850-186 ° C (d).
Anal for C 21H24N120 24 • CH40:
C H N
Calcd 30.69 3.25 19.53
Found 31.05 3.62 19.14
The pentaerythritol dinitrate was made by conversion of
pentaerythritol dibromide to the dinitrate according to Cragle and
Pistera. (34)

Reactions of cyanuric chloride with 2-methyl-2-nitro-l-prpanol:

A solution of 1. 8 g (0. 01 mole) of cyanuric chloride and 3. 7 g
(0. 03 mole) of 2-methyl-2-nitro-l-propanol in 30 ml of acetone was

a12
 NAVWEPS REPORT -7109
slowly added to a solution of 1. 7 g of KOH in 15 ml of water keeoing
the temperature at approxinately 450 C. After the addition was
completed,the mixture was stirred continuously for 30 minutes.
Evaporation of the acetone yielded a solid which was recrystallized
frommethanol-water mixture;rmp 103°-104 ° C. Analysis indicated
that 2 moles of the alcohol reacted with 1 mole of cyanuric chloride
to form the disubstitution product, 2-chloro-4, 6-di(2-methyl-2-nitro-
propoxy)-s-triazine, yield 0.6 g (0.0017 mole, 17%).

Anal for CIIHION 5 0SCl:

C. H N Cl
Calcd 37.76 4.57 20.28 10.15
Found 38. 16 5.27 20.33 10.52
A solution of 1. 8 g (0.01 mole) of cyanuric chloride and
3.7 g (0.03 mole) of 2-methyl-2-nitro-1-propanol in 30 ml of j
acetone was added to a solution of 1. 7 g of KOH in 15 ml of water.
The temperature rose immediately to 550 C, and then the mixture
was allowed to reflux for' 1-1/2 hours. Evaporation of the acetone
gave a white solid which was recrystallized from nitromethane-
methanol mixture; mp 248°-249o C. Analysis indicated the formation
of the triester, 2,4, 6-tris (2-methyl-2-nitropropoxy)-s-triazine,
yield 0. 7 g (0.0015 mole, 16%).
Anal for C15HUNBOS:
C H N
Calcd 41.64 5.55 19.44
Found 41.98 5.65 19.85

Attempted reactions of cyanuric chloride with nitroethanol and

2-nitro-l-butanol:
The attempted reactions of cyanuric chloride with nitroethanol
and 2-nitro-l-butanol were carried out as above. Cyanuric acid was
the only product isolated.

Attempted reactions of cyanuric chloride and trinitroethanol:

(a) A mixture of 0. 7 g of cyanuric chloride and 2. 2 g of trinitro-
ethanol was placed in a flask and allowed to stand at room temperature
for 3 days. When the trinitroethanol was extracted with water
cyanuric chloride was recovered almost quantitatively.

13
 NAVWEPS REPORT 7109

(b) To a solution of 0.5 g of cyanuric chloride in 10 ml of acetone

was added 2.0 g of trinitroethanol and i0 ml of 10% K2CO. After
stirring at 30*-356 C for 20 minutes the mixture was evaporated to
dryness and the residue extracted with ethyl acetate. The ethyl acetate
insoluble material was a mixture of potassium nitroform and potassium
chloride. When the ethyl acetate solution was added to p-ether, a
yellow solid was obtained which decomposed upon standing. An
accurate analysis on this material was not obtained.
(c) When a mixture of 1.0 g of trinitroethanol and 0. 3 g of cyanuric
chloride was heated slowly in an oil bath at 130°-1350 C, the evolution
of brown fumes was observed. After heating for 1 hour, cyanuric acid
was the only product isolated.
(d) A mixture of 4. 5 g of trinitroethanol and 0.9 g of cyanuric
chloride and 0.45 g of anhrdrous ferric chloride was heated to
750-80 ° C for 13 hours followed by 850-90 ° C for 1 hour, 95°-100 ° C
for 2 hours, and finally 950-100 ° C for an additional 8 hours. The
mixture was cooled and washed with dilute HC1 and then with H20. .U
Only a yellow oil was obtained. Attempts at crystallization were not
successful. The crude oil was washed with H20 until the yellow
color disappeared. It was then dried in a vacuum desiccator. Assuming
a mononitroform adduct to cyanuric acid, the following analysis was
obtained.
Anal for C4 H4 HOS:
C H N
Calcd 18.46 1.54 24.61
Found 18.47 1.72 24.56
(e) To a suspension of 0.9 g of cyanuric chloride and 2.8 g of
trinitroethanol in 30 ml of CC14 was added 0.3 g of anhydrous FeC13 .
The mixture was heated in an oil bath at 75-80° C for 20 hours.
Upon cooling, a solid separated. The solid was washed with dilute
HCland H20 and then recrystallized from aqueous alcohol. The
major product was identified as TNEOC by a mixed melting point
with an authentic sample.

2,4, 6-Tris-itrinitromethyl)-s-triazine:
A solution of 1. 84 g (0.01 mole) of cyanuric chloride and 5.7 g
(0.03 mole) of freshly made potassium nitroform, prepared according
to MacBeth and Orr (35) in 50 ml of acetonitrile,was heated gently
for about 30 minutes and then allowed to cool to room temperature.
14

Co- ,
 NAVWEPS REPORT 7109

The suspended insoluble material (KCl) was separated by filtration, -

1. 69 g (0. 0262 mole, 87%). The filtrate was evaporated under

vacuum. The residue was extracted with n-hexane and dried with
anhydrous sodium sulfate. The n-hexane solution was allowed to
stand In a dry ice acetone bathovernight. A solid separated; mp
75°V-890 C. After recrystallization from n-hexane the product was

immediately sent for microanalysis without trying to -emove residual

n-hexane.
Anal for C6N1 20 18 :
C N
Calcd 13.64 31.81
Anal for CON12018 •1/2. CGH,4:

C H N
Calcd 18. 91 1.22 29.42
Found 19.43 1.23 28. 10
Analysis after drying in a vacuum desiccator for 2 hours-gave
the following results: C, 19.78; H, 1. 39.
Analysis after storing in an ice box for 1 week gave the following
results: C, 20.57; H, 1. 49; N, 30.53.
2,4, 6-Trihydrazino-s-triazine perchlorate:
To a solution of 1. 7 g (0. 01 mole of-trihydrazino-s-triazine
in 15 ml of acetic acid was slowly added 1Nperchloric acid. After
standing at room temperature for a few-minutes, the mixture upon
addition of ether gave a white solid which was recrystallized from
alcohol and dried in a desiccator: p 1700-1750C (d). The analytical
results suggest that only the monoperchlorate was formed.
Anal for C3 H1 0NS0
4CI:

C H N Cl
Calcd 13.26 3.68 46.40 12.70
Found 13.23 4.20 45.99 13.13
Attempted preparation of the triperchlorate by using 70%
perchloric acid-or by prolonged standing of the mixture was
unsuccessful.

15

.1
 NAVWEPS REPORT 7109

Reaction of 2,4,6-trhi ydrazino-s-triazine with acetone:

A solution of 1. 7 g (0. 01 mole) of trihydrazino-s-triazine and 7'
17.4 g (0. 3,mole) acetone in 7 ml of acetic acid was heated gently
for 15 minutes. Upon cooling to room temperature a solid separated
which was filtered and recrystallized from methanol; mp 163*-164* C.
Anal for C12H21NS. 2H20:
C H N
Calcd 44. 03 7.67 38. 53
Found 44.35 6.75 38.82

Diazotization of 2,4, 6-trihydrazino-s-triazine:

The diazotization of 2,4, 6-trihydrazino-s-triazine was carried
out according to Ott and Ohse. (21)

2-Amino-4, 6-dichloro-s-triazine and 2-chloro-4, 6-diamino-s-

triazine:
These compounds were made according to Thurston, Dudley,
Kaiser, Hechenbleikner, Schaefer, and Holm-Hansen. (33)

2-Amino-4,6-diazido-s-triazine:
A solution of 0.7 g (0. 002 mole) of 2-amino-4, 6-dichloro-s-
triazine in 10 ml of acetone was added to a solution of 0.2 g (0. 003
mole) of sodium azide in 5 ml of water. The mixture was stirred for
30 minutes at room temperature. Evaporation of the acetone yielded
a white solid which gave the same physical properties as the product
prepared from the treatment of cyanuric trilzide with ammonia.

Attempted synthesis of 2-amino-4, 6-diazido-s-triazine perchlorate: L

A suspension of 0.36 g (0.002 mole) of 2-amino-4,6-diazido-s-
triazine in alcohol was added to 1N perchloric acid at 00 C. No
reaction was observed. The mixture was allowed to stand at room
temperature for several hours, but still no reaction was observed.
Upon evaporation of the solvent the starting material was recovered.
Whtm acetic acid was used instead of alcohol as a solvent, no per-
chlojrate was obtained.

Attempted synthesis of 2-azido-4, 6-diamtno-s-triazine:

A suspension of 2.9 g (0.02 mole) of 2-cbloro-4, 6-diamino-s-
triazine and 1.95 g (0.03 mole) of sodium azide in 100 ml of dioxane

16
 NAVWEPS REPORT 7109

was heated to reflux for 3 hours. No 2-azido-4,6-dianino-s-triazine

was obtained. The solvent was changed from dioxane to o-xylene,
- H but still no azide was formed.

Cyahurie triazide:
Cyanuric triazide was made according to Ott and Ohse. (21)
Ignition temperature: 1820 C.
Vacuum stability at 800 C for 24 hours: 0. 57 cc gas
40 hours: 0. 58 be gas. ,

IiI 1i

I. [I

17
 NAVWEPS REPORT 7109

REFERENCES

(1) James R. Dudley, eta4 J. Am. Chem. Soc., 73: 2986-90

(1951).
(2) Frederic C. Schaefer, 1., J. Am. Chem. Soc., 73: 2990-2
(1951).
(3) Seruflas., Ann. chim. et phys., (2), 43: 76 (1828).
(4) J. Liebig, Pogg. Ann., 15: 359, 622 (1829).
(5) A. Gautier, Ann., 141: 122 (1867).
(6) Irving M. Klotz and Themis Askounis, J. Am. Chem. Soc.
69: 801-3 (1947).
(7) P. Klason, J. prakt. Chem., (2), 34:152 (1886).
(8) 0. Diels and M. Liebermann, Ber., 36: 3191 (1903).
(9) A. Hofmann, Ber., 19: 2061 (1886).
(10) H. E. Fierz-David and M. Matter, J. Soc. Dyers Colourists, ]
53: 424-36 (1937).
(11) H. Fries, Ber., 19: 2056 (1886).
(12) C. K. Banks, etal, J. Am. Chem. Soc., 66: 1771-5 (1944).
(13) W. W. Cuthbertson and S. S. Moffatt, J. Chem. Soc.,
561-4 (1948).
(14) E. A. H. Friedheim, J. Am. Chem. Soc. 66: 1775-8 (1944).
(15) Ernest A. H. Friedheim, U. S. Patent 2, 295, 574 (1942),
through Chem. Abstract 37: 1228 (1943); U. S. Pateit 2, 390, 092
(1945), through Chem. Abstract 41: 160-2 (1947); U. S. Patent
2, 390, 090 (1945), through Chem. Abstract 41:160-2 (1947).
(16) Ernest A. H. Friedheim, U. S. Patent 2, 390, 529 (1945),
through Chem. Abstract 40: 5070 (1946).
(17) Ernest A. H. Friedheim, U. S. Patent 2,422, 724 (1947),
through Chem. Abstract 41: 6900 (1947).
(18) H. Fries, Ber., 19: 242 (1886).
(19) H. Fritzsche, et al, U. S. Patent 1, 625, 530 (1927), through
Chem. Abstract 21: 2193 (1927).

19
NAVWEPS REPORT 7109

(20) A. Hofmann, Ber., 18: 2196 (1885).

(21) E. Ott and E. Obse, Ber., 54B: 179-86 (1921).
(22) H. Finger, J. Pr. Chem. 75: 103-4 (1907).
(23) Winfrid Hentrich and Max Hard tmann, U. S. Patent 1, 911,689
(1933), through Chem. Abstract 27: 3952 (1933). j
(24) R. Hirt, etal, Helv. Chem. Acta., 33: 1365-9 (1950).
(25) A. Ostrogovich, Ciem. Ztg., 36: 738-9 (1912).
(26) F. Kraftt, Ber., 22: 1759 (1889).
(27) P. Klason, J. prakt. Chem., 35: 82 (1887).
(28) A. Senier, Ber., 19: 311 (1886).
(29) W. Kolb, J. prakt. Chem., (2) 49: 90 (1894).
(30) Christoph Grundmann and Elfriede Bieyer, J. Am. Chem.
Soc., 76: 1948-9 (1954).
(31) Linus Pauling and J. H. Sturdivant, Proc. Natl. Acad. Sct.,
23: 615-20 (1937).
(32) H. B. Hass and Elizabeth F. Riley, Chem. Review, 32-34:
373-430 (1943).
(33) Jack T. Thurston, et al, J. Am. Chem. Soc., 73: 2981-3
(1951).
(34) Picatinny Arsenal. "Preparation and Analysis of the Di-,
Tri-, and Tetranitrates of Pentaerythritol", by Delbert J. Cragle
and Frank Pristera, Progress Report for Feltman Research and
Engineering Laboratories, (1960).
(35) Alexander K. Macbeth and W. B. Orr, J. Chem. Soc.,
534-43 (1932).

20
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