AD-R122 049 SYNTHESIS OF R NEW ENERGETIC MATERIAL /i458-TETRRNITRO-i458-TETRARZADIFURRZRNO-(34-C)(34-H)DEC(CL-i5)(U) NAVAL NEAPONS CENTER CHINA LAKE CA

UNCLASSIFIED R L MILLER NOV 82 NNC-TP-6397 F/G 7/3 NL

EI-EBBBBBBBNIEIIIIIIIIIIIII/ll/l/ll ,

1.0 12Q=8I3-2

LA L.2

NATMW& AI.S~u OF MOMig-g4-A

NWC TP 6387

Synheis of a New En ietcSMaterial, I ,4.5.8-Tetranitro-I 1,4, ,

Tetreazadifurazano-[3,4c13,4hDecalin (CL-I 5)

byRodney L. Willer

Resaerc Department

NOVEMBER 1982

NAVAL WEAPONS CENTERCHINA.LAKE, CALIFORNIA 93555

Approved for pubic release; disbtton unlimite.

DTICCL ELECTE

BB

.2 06 069

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'1ECURIT'v CLASSIFICATION OF T141S PAGE (Whom Doto EWro*e)_________________REPOR DOCMEHTAIOH AGE REAo UIUTrUlcTrIOSREPORT DOCUMENTAT PAGE BEFORE COMPLETING FORM

1. REPORT NUMBER 12. GOVT ACCESSION NO: . RECIPIENTS CATALOG NUMBER

AL TITLE (owd Sublftle) S. OF REPORT A PERIOD COVERED

SYNTHESIS OF A NEW ENERGETIC MATERIAL, Interim - Mar 1981-Jan 19821,4,5,8-TETRANITRO-1,4,5,8-TETRAAZADIFURAZANO- 6 PERFORMING ORG. REPORT NUMER[3.4-C 1r3.4-hlDECAL1N (CL-15___

7. AUTNOR(@) S. CONTRACT OR GRANT NUMBER'e)

Rodney L. Willer

PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAME,.EMENTPRJT TASKAREA & W UIT NUMERSNaval Weapons Center PE-61153N, Project-SR02402,"-China Lake, CA 93555 Task Area-SR02402, Work Unit

Number 138509II. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE

November 1982 LNaval Weapons Center IS. NUMBER OF PAGESChina Lake, CA 93555 32

14. MONITORING AGENCY NAME A ADDRESS(i'dilferent boo Conirollh&4 Office) IS. SECURITY CLASS. (of this repet)

UNCLASSIFIED

IS. ICftAUIFI CATON/DOWNGRADING

IS. DISTRIEUTION STATEMENT (of this Report)

Approved for public release; distribution unlimited.

17. DISTRIBUTION STATEMENT (of ie abstract nle.edi Moak", I d1afurent hem Repe)

IS. SUPPLEMENTARY NOTES

IS. KEY WORDS (Cethis on oeve~re aide it necese. ,mad WWIby block sm'ber)

Polynitramines C-

High Energy CompoundsHigh Density Compounds

2. ABSTRACT (Cuw...w anrevers, .@e14s 1i neses wd -dSr bpblock rmb.

See back of form.

DOD , CO1S ITION OF I NOV O S OBSOLETE UNCLASSIFIEDSeCUflTY LASIFICATIO OP THis PAGE (When Da FWW

UNCLASSIFIED3mVwV? cLaw"A s or -rw *Aa Ei bo soe,,

()Synitheis of a Nowu Energetic Material,45.08-Tetranitro-1,4,5.,8-tetraazadifur'azawo-

5,4-eilS,4-hJde=a1in (C-1i), by Rodney L.ller, China Lake, Calif.,, Naval Weapons Center,,ier 1982. 32 pp. (WC tP 6397.pu~blca-

i =,nU sI'DM.)( The synthesis and characterization of

.new energetic material, 1,4,5,8-tetranitro-,,5, 8-tetraazadifurazano[3, 4-c] [3, 4-bdecalin

(CL-15) is described. The compound Is calculatedrom its measured heat of formation and densityo be the most energetic compound synthesized toate

Accession Fop

NTIS GRAH&

DTIC TAB o3Unannounced 3Just ificatio.

Di stributio '

Availability Codes

fAval and/or

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NWC TP 6397

CONTENTS

Introduction .... ..... .... ............................ 3

Results .......... ...... ........................... 8

3,4-Diaminofurazan(Q) .......... . .. .8Reaction of 3,4-Diaminofurazan with Glyoxal

(Preparation of )..................... 9Nitration of 1,4,5,8-Tetraazadifurazano [3,4-c] [3 ,4-h]-

decalin (Preparation of , CL-15) .... .............. 10

Properties of CL-15 ......................... 11

Experimental . . . . . . ....................... 12

Diaminoglyoxime(k,) . .. ........ .... .... . ... 123,4-DiaminofurazanQ) . .. ......... .......... 121,4,5,8-Tetraazadifurazano[3,4-c][3,4-h]decalin (Q).. ..... 121,4,5,8-Tetranitro-1,4,5,8-Tetraazadifurazano[3,4-c1-

[3,4-hdecalin (, CL-15) .... .. .................. ... 13

Appendixes:A. Abstract of Chinese Work . . ................ 15B. Russian Synthesis of 4,5-Diaminofurazane .. ......... ... 19

C. Infrared Spectra of Compounds ...... ... ....... 23

D. 1H NMR Spectra of Compounds ..... . . . . .. . . . . . 27

ACKNOWLEDGMENT

The author would like to thank Nate Sipple for running the heat of

formation on CL-15 and Ronald L. Atkins, Arnold T. Nielsen, and Andrew P.

Chafin for numerous helpful suggestions.

NWC TP 6397

INTRODUCTION

The Navy has a need for new energetic materials which have higherperformance than those currently available for use as ingredients in newexplosive and propellent formulations which could, for example, increasethe kill radius of a missile warhead and increase the speed and/or rangeof a missile. We have been involved for several years in a program thathas as a long range goal the synthesis of such materials. We have chosento concentrate our efforts in the area of polycyclic polynitraminessince this class of compounds seems to hold the greatest promise ofyielding compounds with the desired properties.

This report describes the synthesis and preliminary characterizationof a new energetic material which has the chemical name 1,4,5,8-tetra-nitro-l,4,5,8-tetraazadifurazano[3,4-c] [3,4-h]decalin and to which wehave assigned the name CL-15. Although this compound proved to be toothermally unstable for weapons use, it is calculated to be the mostpowerful explosive compound synthesized to date.

N02 NO2I I N

0

CL-15,

In January 1981, we received a letter from Everett Gilbert of theArmy Research and Development Command, Picatinny Arsenal, Dover, NewJersey, which contained a copy of an abstract of a paper entitled "Studiesin the Synthesis of Furazano-Aza-Condensed Ring Compounds." The paperwas authored by several People's Republic of China chemists and hadbeen submitted to Dr. Lyle I. Albright of Purdue University for considera-tion for presentation at the 181st National Meeting of the AmericanChemical Society in March 1981. The paper was ultimately rejected

3

.*.*~*.*.7-

NWC TP 6397

because none of the authors were members of the American Chemical Socety.A copy of the abstract is included as Appendix A.

In this paper, the Chinese chemists claimed to have synthesized

several furazano-fuzed cyclic nitramino compounds by the general routeoutlined in Scheme 1. The structures of several of the compounds are

shown below the scheme. The compounds described should be quite ener-getic. The density and detonation properties of these materials were

SCHEME 1. General Route for the Synthesis of Furazano-FusedNitramino compounds.

H H HHNC .NR H2N ,+ Nitration

HO-' , H2 N R'H H H

02N l02

02N

N02 2 02 NO2

01 0

N024 --

4

~ ,t* *A.

NWC TP 6397

Calculated Properties of Compounds __d 4 n

Density (g/cc) 2.00 1.88 1.96

Detonation Velocity (mm/Ps) 9.12 9.06 9.50

Detonation Pressure (kbar) 395.00 390.00 430.00

calculated using the methods of Holden I and Rothstein.2 The calculateddensities and detonation properties are summarized below the structures.Indeed, the compounds were predicted to be very dense and powerful. Infact, one of them, 4, calculates to be more dense and energetic thanboth 1,3,5,7-tetranltro-1, 3,5, 7-tetraazacyclooctane (HMX, ,), 3a currentlythe most powerful explosive in use, and hexapitrobenzene (XNB, k) themost powerful explosive known at that time. 3o

NO 2 No2 o2 21 02N NO2

02N-N N-N02 0

N02 NO2 NO2

HMHNB, TNAD, Z

INaval Surface Weapons Center. Estimation of Normal Densities of

Explosive Compounds from Empirical Atomic Volumes, by D. A. Cichra, J. R.Holden and C. Dickinson. Silver Spring, Md., NSWC, 1980. 39 pp. (NSWC

Report TR-79-273, publication UNCLASSIFIED.)2aL. R. Rothstein and R. Petersen, "Predicting High Explosive

Detonation Velocities from their Composition and Structure," Prop. and

Explo Vol. 4 (1979), pp. 56-60.AL. R. Rothstein, "Predicting High Explosive Detonation Velocities

from their Composition and Structure (II)," Prop. and Explo., Vol. 6(1981), pp. 91-93.

3aLawrence Livermore National Laboratory, University of California.LLNL Explosive Handbook. Properties of Chemical Explosives and ExplosiveSimulants, by B. M. Dobratz. Livermore, Calif., LLNL, March 1981.(Report No. UCRL-52997, publication UNCLASSIFIED.)

3bLawrence Livermore National Laboratory, University of California.

Energy and Teohnologj Review, Livermore, Calif., LLNL, November 1978.(Report No. UCRL-52000-78-11, publication UNCLASSIFIED.)

5

NWC TP 6397

Measured Properties of Compounds and

Density (g/cc) 1 .9 0 3a 2.01 3b 1.804

Detonation Velocity (mm/us) 9.15 9.33 8.65Detonation Pressure (kbar) 393.00 406.00 365.00

When this abstract of the work of the Chinese arrived we had justfinished our work on the sznthesis of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin (TNAD. V. The relationship between the two pieces ofwork was obvious. We easily formulated two related structures andwhich calculate to be even more dense and more powerful.

*N 0 N 02/ Y0 0N

N02 NO2 NO2

1

Calculated Propeties of Compounds and

Density (g/cc) 2.00 2.00Detonation Velocity (mm/us) 9.57 9.70Detonation Pressure (kbar) 437.00 450.00

We decided to explore the synthesis of compounds k-4 and 8 with theobjective being to see if we could repeat and confirm the work of theChinese and/or extend it to the new compounds which we had formulated.Schemes 2 and 3 show possible synthetic routes for the synthesis ofCompounds k and

4Naval Weapons Center. Synthe8is of a New Explosive Compound,Trans-1,4,5,8-tetranitro-1, 4,5, 8-tetraazadecatin, by Rodney L. Willer.China Lake, Calif., NWC, August 1981. 16 pp. (NWC TP 6303, publicationUNCLASSIFIED.)

6

-or - |,--aK-. . L n-m *- I 1,,-_ ! J --m'! .u N

"C TP 6397

SCHEME 2. Proposed Synthesis of Compound L.

I I2 % + :

t* I!

SCHEME 3. Proposed Synthesis of Compound .

II I

M2 stiO .0. O

[AA

1 3r2

0/

TI-

NWC TP 6397

RESULTS

3,4-DIAMINOFURAZAN (Q)

Since the Chinese workers did not mention how they had synthesized3,4-diaminofurazan, we did a literature survey on the synthesis of thiscompound. There are three literature references to the synthesis of3,4-diaminofurazan.5- 7 The first reported synthesis was by M. Coburnof the Los Alamos Scientific Laboratory, Los Alamos, New Mexico. Thissynthetic route is outlined in Scheme 4. This route involved the dehydra-tion of the known diaminoglyoximine, ,,8 with an aqueous base. Thesecond synthesis of was by Carmack and coworkers6 and was only a

SCHEME 4. Synthesis of 3,4-Diaminofurazan, .

I

H 2N\p"OH OH- H2N

NBC-CEN + 2NH20H 0

HXN' %11H H2N 4l

slight modification of Coburn's method. The third synthesis was by twoRussian workers7 and involves a somewhat different route which is sum-marized in Scheme 5. A copy of the Russian paper and a translation of

Vthe experimental part is included in Appendix B.

*. Mainly because we had a great deal of difficulty obtaining a copyof the Russian paper, we chose Carmack's method for making 3,4-diamino-furazan. Our yield for the recrystallized product was consistently50-55% of material with a m.p. of 179-180*C. However, the Russianprocedure may be better.

5M. Coburn, "Picryl-substituted Heterocycles. II. Furazans (1, 2),"el. HeterocyclZc Chem., Vol. 5 (1968), pp. 83-87.6A. P. Komin, R. W. Street, and M. Carmnack, "The Chemistry of

1,2,5-Thiadiazoles. III. [l,2,5]Thiadiazolo[3,4-c][l,2,5]thiadiazole,J. Orq. Chem., Vol. 40 (1975), pp. 2749-2752.

4I. V. Visalok and A. V. Ostrovskoya, "Preparation of Diamino-furazan," Khimiya i Tekhnol Eementoorgan Suedin, Vol. 78 (1978),pp. 48-49.

8E. Fischer, "Ueber einige Reactionen des Phenylhydrazines andHydroxylamins, Ber., Vol. 22 (1889), pp. 1930-1936.

8

? : ,- ,,,,,, , "~~... ... . .. .. ...-... .•. . ........ ,. ...... .,-, .- .. ...- -, . . ..,,.,,,.,,.- .. ,,. •..: -, i -, . • •,,.-. .,. . . ... . . . -. ,.-. . . ., ,. . . . .. - .'-

NWC TP 6397

SCHEME 5. Russian Synthesis of 3,4-Diaminofurazan.

SS11 11

(1) H2 N-C-C-NH 2 + 2NH2 OH'HCl + 2NaCO2 CH3

* NOH NOH

H2N-C- C-NH 2 + H2S+ + NaCI + 2CH 3COOH

*OH NOH H2 N,N

(2) H2N-C- C-NH 2 + NaOH HOCH2CH20H, DH 2 N AN

/

HO H N

HO JCX N NH

REACTION OF 3,4-DIAMINOFURAZAN WITH GLYOXAL (PREPARATION OF 10)

The reaction of 3,4-diaminofurazan, ,, with glyoxal was initiallyexamined by adding the appropriate amount of to a well-stirred solutionof 40% glyoxal. The 3,4-diaminofurazan would quickly dissolve to givea clear solution, then the product would precipitate. Using this method,the results were variable. The product seemed to vary from the desired1p to a mixture of 3,4-diaminofurazan and the dihydroxy compound .owever, when one equivalent of hydrochloric acid was added the product

was consistently the desired V. Compound 1t was completelycharacterized by spectroscopic techniques an gave a good elementalanalysis (see Experimental Section).

9

NWC TP 6397

NITRATION OF 1,4,5,8-TETRAAZADIFURAZANO[3,4-c] [3,4-h]DECALIN(PREPARATION OF , CL-15)

The Chinese workers indicated that they had used a mixture of nitricacid/acetic anhydride for the direct nitration of their 3,4-diaminofurazanadducts. Our attempts to use this procedure for the nitration of compound1Q proved fruitless. We then turned to a procedure developed at SRITnternational, Menlo Park, California, for the nitration of glycouril totetranitroglycouril9 (Scheme 6) which involved the use of a mixture oftrifluoroacetic anhydride/nitric acid as a source of N205. When thisprocedure was applied to an essentially quantitative yield of(CL-15) was obtained as an off-white amorphous powder.

SCHEME 6. Nitration of Glycouril.

H N02 NO2I I INN

1O2 L02

The LH NMR and IR spectra of is entirely consistent with thestructure (see Appendices C and D).

H FI NO2 102N N

0' HN03/TFAA 0

H N2 0O2

LC C-15

7 Numerous attempts were made to develop a good recrystallizationprocedure for compound 1~. In most cases, the compound crystallized as asolvate (1:1 complex). This was particularly true in the cases of

9M. Kamlet and S. Jacobs, "Chemistry of Detonation. I," J. of Chem.Phyc_'cs, Vol. 48 (1968), pp. 23-35.

10

-,- ~~. . ..................-........-...........-. -............. ...................-..... .

NWC TP 6397

acetonitrile and 1,2-dichloroethane. It was, however, possible torecrystallize the material by dissolving it in 100% nitric acid andadding trifluoroacetic acid followed by cooling. The procedure gavesmall crystals of CL-15.

It was noted very early that the compound seemed to be ratherthermally unstable. Samples of the material left at room temperaturesoon emit a red gas. Upon prolonged standing, the material turnsgummy. It is thought that this decomposition might be due to thepresence of trace amounts of acid; however, even recrystallized materialshows this behavior.

PROPERTIES OF CL-15

The low thermal stability of CL-15 made the determination of itsphysical and chemical properties very difficult, and in some cases,impossible.

We determined the density of the compound to be greater than1.987 g/cc because crystals of the material sink in 1,3-dibromopropane(d = 1.987 g/cc).

The heat of formation cf CL-15 was measured to be +185 kcal/mole bythe standard technique of back calculation from the heat of combustion.Since some time elapsed between weighing the samples and the combustion,this should be considered a minimum value. From the heat of formationand the density we have calculated detonation and velocity pressure tobe 9.41 mm/us and 413 kbar using the method of Kamlet and Jacobs.9 InTable 1, these values are compared to those of HNB and HMX. It can beseen that CL-15 is calculated to be more powerful than both HNB and HMX.Since the heat of formation ef CL-15 could easily be off 5-10% due todecomposition during weighing and handling, the actual performance ofCL-15 could be even better.

TABLE 1. Predicted and Measured Properties of CL-15, HI, snd HIN.

CL-15 11 M1z

Predicted Measured Predicted Measured Predicted Measured

Density, g/c 3 2.00 1.98 1.85 1.90 1.97 2.01Detonation pressure, kbar 437 413a 388 393 393 406bDetonation velocity, am/us 9.57 9.41 9.05 9.15 9.10 9.33

aCalculated by the Kamt-Short method based on a measured heat of formation ofb +187 keal/mole.Measured at a loading density of 1.97 gl/n 3 .

"he impact sensitivity of CL-15 was measured to be 20 cm on a Model

12 impact machine (2.5 kg drop weight).

11

NWC TP 6397

EXPERIMENTAL

NMR spectra were determined on a Varian E4 360 (routine 1H) andVarian XL-100-15 (1H and 1 3C) spectrometers and are reported on the 6scale. IR spectra were determined on a Perkin Elmer 137 spectrometer.

DIAMINOGLYOXIME (1) 8

The procedure of E. Fisher was used to prepare this compound. 8 Theproduct was recrystallized from H20 to give crystals with a m.p. of 200-201*C (lit 2000C).

IR (See Appendix C, Figure C-I).

NMR (See Appendix D, Figure D-l).

3,4-DIAMINOFURAZAN (Q)

The procedure of Carmack and coworkers 6 was used to prepare thiscompound. After recrystallization from water it melted at 179-180*C(lit 5 1800C).

IR (See Appendix C, Figure C-2).

NMR (See Appendix D, Figure D-2).

1,4,5,8-TETRAAZADIFURAZANO[3,4-cJ[3,4-h]DECALIN (Q)

A 10-gram portion (0.1 mole) of 3,4-diaminofurazan was added to asolution of 10 g of 37% hydrochloric acid in 20 ml of distilled water.This slurry was stirred at 60*C while 7.25 g of 40% aqueous glyoxal wasadded. The mixture was stirred for one additional hour then cooled.The product was collected and washed well with water. After drying, itweighed 10.86 g (0.049 moles, 98%). The material can be recrystallizedfrom 50:50 DMF/H20 to give plates with a m.p. of 230-231*C.

Analysis calculated for C6H6N802: C, 32.43; H, 2.72; N, 50.44.Found: C, 32.26; H, 2.74; N, 50.19.

IR (See Appendix C, Figure C-3).

NMR (See Appendix D, Figure D-3).

12

'N6' r'F " "' "'' ." ;" " " ," '. . , . .

NWC TP 6397

1,4,5,8-TETRANITRO-I,4,5,8-TETRAAZADIFURAZANO[3,4-c] [3,4-hiDECALINCL-15)

Fourteen ml of trifluoroacetic anhydride and a magnetic stirringbar were placed in a 100-ml round-bottom flask. The solution was cooledto -5*C (salt-ice bath) and 6.0 ml of 100% nitric acid was added dropwise,with stirring, over a period of 20 minutes. This mixture was allowed tobriefly warm to room temperature then it was recooled and 2.22 g ofwas added in small portions over a period of 10 minutes. The mixturewas allowed to slowly come to room temperature over 4 hours. The productwas collected by vacuum filtration under a blanket of nitrogen and washedwell with methylene chloride. The last traces of solvent were removedunder vacuum.

IR (See Appendix C, Figure C-4).

NMR (See Appendix D, Figure D-4).

The compound can be recrystallized by dissolving it in 100% nitricacid then adding an equal volume of trifluoroaceLic acid followed bycooling.

..--.-.. .... ... .-. -. . ... ..........................

NUC TP 6397

Appendix A

ABSTRACT OF CHINESE WORK

15

Lorl,

MV Tf 6397

Studios in the gynthesis of Furasao-Ama-ondesed Ring Mpoundsf

(2h. First Report)

3,9 4-41mnf~a (1) provides a good Intermediate forthe preparation 'of furazano-aza-condeneed ring compounds.The reaction of (1) with dibydroythylonediamine dihydro-chloride (11) in an acid mediu and then by dehydration, eye-lirzation and condensation gives 2,3-diamino-5,6-furazano bpiperazine dihydrochioride (111). It can be converted, in ni-tric acid, into*2,34.dimino-5.6--furazano EbJ piperazine dl-

* nitrate (IV). On formylaztion of (III) gives 2.3-di(S-formyl-amino)-15,6-furazenotbj piperazine (V),9 and -it. is then nitra-ted to ob~tain 1,. 4-4init r-.2,9 3-di{IN-nitro-4-foraylamia) -5,6-furazano ("bl piperazin* (VI).

0'OIWA

'I2,NAa.

'VE .. j C _

I~\m + (P1V)A W S

NC TP 6397

The condensation of (1) with 4,5-dihydroxyimidazolone-2 (VII) in an acid medi um gives 2.3-1.uidazolono(b-5,6-furaza-

no(b] piperazine (VIII), and it is then nitrated to obtain 1--

nitro-2,3-(l' ,3' -dinitroizidazolono-2) (bJ -5, 6-furaz'ano LW pi-perazine (IX)

0EO A= 'Irmo

The condensation of (I) with l,4-diformyl-2,3-dihyo1roxy-

piperazine (X) in aui acid medium gives l,4,5,8-tetraaza-2,3-furazano(bJ octahydronaphthalene hydrochloride (XU)t and it

is then nitrated to obtain l,4,5,8-tetranitro-l,4,5,B-tetra-

aza-2, 3-f urazano (b] octahydronaphthalene(XII).

MM CAD

CI)Arc Cl . (OCl

The condensation of (1) with l,3-diformyl-4.5-dihydroxy-

imidazolidine (XIII) in an acid medium gives 2,3-imidazolidi-

no Ebi -5,6-furazano [b) piperazine hydrochloride (XIV), and

it is then nitrated to obtain l,4-dinitro-2,3-(i',31-dinitro-

imidazolidino) EbI piperazine (XV).

17

WC TP 6397

A

The given structures of the above-m-entioned compoundsare proved by elementary analysis, and by .IR and M spetra

examinations.

-'i..c(\ c \~

~ AO 8

ft

NWC TP 6397

Appendix B

RUSSIAN SYNTHESIS OF 4,5-DIAMINOFURAZAN

19

I . ,,; ' ' 'W ~~~~~~~~~. .. .. . . .. , ". " ,"... . ....- ..... . -"...... ,".. . - ,.-...••.,,.--.-. . .,,

NWC TP 6397

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NWC TP 6397

spew peamxzu o uimeura smaxemin ocamca (40-60 wim). To mmU0 ANAm.2H0ypfl3ss soupe~naC? 2%~. Oft apucca. uuC aa3WIE N AOC?P7XUKM, 80O-5AO MOT BOJUJIHALflOOx .rmanualbm odm~J2W?cx 3a 3.5-4 qaca. Upojan towu~3sc no lIC-cucrp aIeaMPm'yp masotaw eWrwq~eH JIARBMNyPBSJNY. cMMeaPoaaWos 33300?TU 05000 -

k~anuo~moact.B Tpen'pmq udy16 emqommb X A. Cademwo' 128510k. M0W -.i'Mmx. OTSOAnol TPYdROt. MiUMAo a peorsop xopnorO N0Ae38 v U OTeyol'vPM aa-

rpyaw 5W00 mmo. 278 r coamomcAoz rxapoxczsam a 38 r yxcy0RoxmC..0ro 33-ypaa. B pocluOP NOCreneiaio nomaamu 120 r pydeaoHqiAoL& "xi" xicv1ou Tax, rroUnwepOp Oama a npe~eiwx 3o.ie'. 3oreu peaxamioya imaccy narpnaur xo 50-6eo x

Aew saimep.W up *rOft TowlpaTYPe 2 Telveau 2-3 neoC0 (moneit peamnu. PCA6ASU? noodecime'naaowu peaxwio maccad. CoAepvxo xoxds ducTpo marxpenawT xo 90-95P a@maupyr Ha Popoamo Ewaepa OT anamuI c6pU. OM&?PB? oZJwm8WI -exw2 olOApF aanamf ocazoit AmauNmorAmom. a olqaabponwmau iff cm53 us soSAY. Damoi 88.5 r

___________ B Tpxo~ xcd ekom 50 arzdemy mxt ep -uMaOVOPOu. MX~imm~aot4 novemar 78 r jwauaaorimoxcaua. 26.4 r V~,aONI a 3CO L-A

mmemnauom~. Ck-ecs marpebavr ups 155-16O0 2 T656U0e 3.5 whCOn it NOISE OTrGRXDpeCTsopmabI S zamyyxe 9oAoeTpyAmoro 300001. OCTITOR cuemnum co 100 P nom v01 307-Ounrposumw. hmoA jauuoWama 40.5 r (61%).'T on. I79q180O (us mmi), no .-teP~raPwi a 1mm (73 r na. 18&'. Rabteno. %: C 23.53. -H 4.44. X 56.28. Eaaqwcj..-so AMM C2M4AP16O 4%: C 24,00; H 4.00. 11 56.00. Mcnairp: 160D cWi" (C-1l a

4rpsa~ae).3200-3400 cu1 (-As/u,).

L. L.Kennetil. Stuaxt. IMte-cocyetes , 1975, v* -v8. 651 - 690.2. M. Russo, V.GuidoUi * L .AfO-tdtao, getnan .temt. W2.IJ6.931 .

3. L.N'eddli G.Blaguri. Af.flusso. Ce-n-oor Abtent.-v2.26. 774 . (iq,'j).Ckrm. Ass.. 1973. v.?79, £iMlff.

4. Buwea m .BD., 0aovp 9sau a aA. B. An~. e.C= a522re0.X90ms60.9 27. 19.5. E.FLisckes, Chain. e-... lug. Odc. 29, S. MO30- 1936 .L. G. A. Pea's. ,R.T. Pjtacw. Asalyt.- Chum. . 1060 . v. 32p. 003.7. .com. I Met. Chan. 19fi5. V, S p 83 -IV.

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49

21

NWC TP 6397

TRANUATION EXPERITAL PART OF PAPER

Di In a 1-liter three-necked flash fitted with a stirrer,a cooler, a dri tube rinsed tn an iron chloride solution, and a ther-mometer, place 500 ml water, 278 g hydroxylamine hydrochloride, and328 g sedium acetate. Crskmtly add 120 g of rubeanic acid so that thetemerature stays between 30 and 35'. Then heat the reaction mass to50-60* and hold it there for 2-3 hours (the end of the reaction issignaled by bleachng of the um). The contents are then rapidlyheated. to. 90- 95* and run throigha Blehner filter to remove the sulfurpreeipitate. The precipitate is .cooled in ice water and the precipitateddiamnoSlyouim is filtered out and dried in air. Yield - 88.5 g (75%),196-19r melting point (out of water). iUterature value [5] for meltingpoint - 196".

DiaiWnfurazan: In a 500-roi three-necked flask fitted with a stirrer, athermometer, apd a cooler, place 78 g of diaainoglyoxime, 26.4 g NaO,and 300 ml etylem glycol. heat the mixture to 155-160Q for 3.5 hoursand then distll the solut4.n in a wqter let vacuum. Mix the residuewith 100 ml water anitfilter Yield of diaminofurazan - 40.5 g (61%)melting temperature 179-180 (out of weter); *zacrdfng to 17] the meltingpoint is 180* . C 23.53%, H 4.44%, N 56.28%. Values calculated fromC2H4N4O are: C 24%, H 4, N 5. Ii spectra: 1600 cm-I (C-N in thefurazan ring), 3 -34M0 ca 2 (-32).

22

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NWC TP 6397

Appendix C

INFRARED SPECTRA OF COMPOUNDS

23

$ q , ', -",5 , , :',' ,' :, -, ".,,, ., :, , ..-. .] .. , -. , .. . , ., . . -. . -. .. . ., ... . . .. .. .. .. . .... .. . ... .. ....- ,,.,. , -4, ,. ,.' , ., .E ... , .-. -,"..-'.".'-- ." ....- °-'..,.". . .'-L .".Lo . .".42 .,..-"--... '. .,

NWC TP 6397

4000 3000 20U~0 1500 CMl 1000 900 S00 700

__ 60 -- - 0

*~j4 SAC - - '--- 40

02

3 4 5 6 7 8 9 10 11 12 13 14 1WAVELENGTH (MICRONS)

SPECTRUM NO.___ ORIGIN_____ LEGEND - REMARKS____

SAMPLE - _ _ _ _ _ _ _ ._ _ _ _ _ _

__________PHAS Kbr. DATE 31 L J,

____________THICKNESS - fWIRATOJa&I________

PANl ~O.W.111111 THE PERKWNELMIER COWPORAICON NOWAMC COWL.

FIGURE C-1. IR Spectrum of Diaminoglyaxime.

4000 3000 2000 1500 CM't 1000 900 800 700

.10

-. 4

MA CRMN._ RII -2 L~6AEENT (MCRNS

P AVEAENGT (AMICRONS) _______

THCRMNO - OIINES --- LEEND-- ---- ~-- REMARKS.

V 24

SA PE- .4 . . .n

NWC TP 6397

4000 3000 2000 1500 CM' 1000 900 800 700

___ ___00

60 1 A 1 1 A__~60-60

~40 40_

3 4 5 6 7 8 9 10 11 12 13 14 15WAVELENGTH (MICRONS)

SPECTRUM NO.___ ORIGIN___ LEGEND_____ REMARKS-____

SAMPLE - - - __________ _______

zP

___________THICKNESS__ _ IOpERATORjakwLIM. _ _____

.... ~ .w.,a~ ITM PWIIN-ELMN COMORAON. MOIWAIK. CONM.

FIGURE C-3. IR Spectrum of 1,4,5,8-Tetraazadifurazano-13,4-cl13,4-hidecalin.

4000 3000 2000 1500 CM'1 1000 900 8oo 700

WAEEGH AMICROnS~STrRU NRU ORGN__44LGN __ EAK

80 PE _ _ _ _ .__ _ __ _ _ _ _ _ _ _ _*- 1 4 Z UIY- _ _0__ _ _ _ _ _ _* ~ ~ ~ ~ i M:-iS PHAXi. J:EL~J

- ~ ~ ~ ~ ~ ~ ~ ~ - ?wCNS PIAO.~.....60 R 'O 13.21 M PKNKMRCWOAIN.N W tK O M

FIGUE C-. IRSpetrumof '60525/P?

..............0.*. . 40. . . . . . . . . . . . . . . . . . . . . . . .. . . .

I

NWC TP 6397

Appendix D

1 H NMR SPECTRA OF COMPOUNDS

27

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C. I 428

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