AD-AO08 949

ULTRAVIOLET AND VISIBLE SPECTRA OF TACOT(TETRANITRODIBENZO-l,3a,4,6a-TETRAAZAPENTALENE)IN VARIOUS SOLVENTS

George Norwitz, et al

Frankford ArsenalPhiladelphia, Pennsylvania

December 1974

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REPORT DOCUMENTATION PAG IrCN___CN FR

tTREPORT NUMIE 1 GOVY ACCM..ON... 0-54 A. AREC01OFCATALOG NUMB ER

FA-TT-74C39 AlY- c 2(ZJ.TTL'.MdibtJ)SYPOFRPIT & PEW 00 COVEHES

ULTRAVIOLET ANTD VISIBLE SPECTRA OF TACOT(I:ETRANITRODIBENZO-1,3a,. 6it-TETRAAZAPENTZALENE) Technical Test Report

IN VARIOUS SOLVENTS C.EFRrORNINO OWG REPORT %M

7. AUTI4OR(a) 5. CONTRACT ofROANT 005148E1(s)

GEORGE NORWITZHERMAN GORDON

Sf. -PRFORNIING OANIZATttCH NAMC AND ADORES 10. PORMEEET RJCrSCommander ARCA & WORK UNIT NUM9ERS

FRANKFORD ARSENAL, ATTN: SARFA-TSE--M-64-l AMS Code: 53970146350Philadelphia, PA 191W7 PRON: Al-5-(A005-F6-NII11, CONTitOLLING OFFICE NAME AND A015RE1111 iii. REPORT OATE

Co~mmander December 19.Army Materials anid Mechanict. Research Center .MUDROPAS

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It. SUPPLFMENTARY NOTES

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It. KEY WORDS (Caenu. on reverse &Ida If necessary amd Identify by blach nmbut)

TacotTetranitrodibenzo-1,3a,4,6a-tetraazapent daneDibenzo- , 3a, 4,6a-tetraazapentalene

20. ABSTRACT (Centi.. me art reverse .do Of necteeary OW IduiI'f by block mnw.)

The ultraviolet and visible spectra of Tacot (tetranitrodibenzo-l,3a,4,6a-tetraazapentalene) were determined in nine solvents in which the materialwas significantly soiuble. These solvents were sulfuric acid, perchioricacid, nitric acid, glycerin, dimethylsulfoxide, ammoniumi hydroxide, morplio--line, piperidine, triethanolamine, and N,N-dimethylfor'amide. The firstfive of these solvents gave orange solutions while the last four gave amber

(continued)

DD %JAN72 1473 EDITI"OF 09R OV 55 IS OSSOLKTE IJNCLASSIFIEDSECURITY CLASIC ATIC04 OF TKIS1 PAGE (U9ten Data DnA e*d)

UNCLAS SIFIEDWCMT C LAMI WeA;1GW V THIS PAQW& 4qft 110M4

2 0. ABSTRACT: (continued)

r rdark-clored hever, the colors of all the solutions

after aliquoting and diluting prior to the spectral measurements wereyellowish. The study in the ultraviolet region was limited by the rela-

tive' y high cut-off pointr of some of the solvents. The molar absorprivi-ties of zhe 3eaks were c.iculated. A somewhat arbitrary grouping of thepeaks according to location showed that peaks occurred for Tacot in allsolvents at 450 to 506 no except for piperidine which showed a rising slopeand signiiant absorption in this region. Sulfuric acid showed a strongpeak at 416 rim. Sulfur.l. acid, morpholine, anid piperidine showed peaks inthe area of 395 to 403 nm (peaks did not occur in this region in the othersolventsi. A peak occurred at 318 to 350 nm for all the solvents exceptnitric acid and piperidine (which were not useable in this range). A peakoccurred at 248 to 281 tim in sulfuric acid, perchloric acid, and ammoni-umvhydroxide (the only solve-'ts useable in this range). The solvents thatoriginally gave orange solutions were inclined to give sharper peaks, w~ile

Sthe solutions that originally gave amber and other dark-colored 6-:lu'lions

were frequently inclined to give shoulders and plateaus. Tbe col..jrs ob-talned from the orange solutions tenjed to be more stable. 'The extraor-dinary effect of the solvent on the .pectrum of Tacot is probab-Ly related'K to the tendency of Tacot to form complexes with the solvent Experimentsindicated that Tacot could be determined quantitatively by measur nent ofthe color in sulfuric acid, perchloric acid, nitric acid, and dimethyl-sulfoxide at 416, 486, 487, and 506 ran, respectively. The method could notbe applied to the determination of Tacot 'n primers because of the diffi-culty of completely extracting the Tacot from the primers and also becausethe other ingredients of primers interfered with the color.

[I

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Destroy this report when it Is no longer needed.

I.M.4 0

.. .. ....

DISCLAIMER

The findings in this report are not to be construed as4 an official Department of the Army position, unless so

designated by other authorlzal documents.

TABLE OF CONTENTS

I~e

INTRODUCTION ............................................... 3

EXPERIMENTAL ................................................ 3

DISCUSSION AND RESULTS ...................................... 5

SUMMARY ..................................................... 6

RECOMMENDATIONS .............................................. 7

REFERENCES .................................................. 25

DISTRIBUTION ................................................. 26

LIST OF ILLUSTRATION(S

Figure

I. Spectrum of Tacot in Sulfuric Acid (vs Sulfuric Acid) 8

2. Spectrum of Tacot in Perchloric Acid (vs PerchloricAcid ........................................... . ... 9

3. Spectrum of Tacot in Nitric Acid (vs Nitric Acid) .... 10

.s. Spectrum of Tacot in Glycerin (,"t Glycerin) .......... 11

5. Spectrum of Tacot in Dimethylsulfoxide (vs Dimethyl-sulfoxide) ........................................... 12

6. Spectrum of Tacot .i Anonium Hydroxide (vS AmmoniumHydroxide) ....... ......................... ......... 13

7. Spectrum of Tacot .n Morpholine (ve Morpholine) ...... 14

i 8. Spectrum of Tacot in Pireridine (vs Piperidins,) ...... 15

9. Spectrum of Taco* in Ttilethanolamine (vs Triethanol-amine) ............................................... 16

10. Spectrun, of Tacot in N,N-Dimethylformamide (vs N,N-Ditaethylform-mi de) ................ 17

11. Spectrum )i Sulf :ric Acid (vs Water) ................. 18SpctumofTaoti F~~tiin (s ierdis~.......

~ -.

LIST OF ILLUSTRATIONS (continued)

~:.Figure Page

12. Spectrum of Perchloric Acid (vs Water) ............... 19

13. Spectrum of Nitric Acid (vs Water) ................... 20

14. Spec vum of Glycerin (vs Water) ...................... 20

15. Spectrum of Dimethylsulfoxide (vs Water) ............. 21

16. Spectrum of Ammonium Hydroxide (vs Water) ............ 21

17. Spectrum of Morpholine (vs Water) .................... 22

18. Spectrum of Piperidine (vs Water) .................... 22

19. Spectrum of Triethanolamine (vs WLter) .................. 23

20. Spectrum if N,N-Dimethylformamide (vs Water) .......... 23

LIST OF TABLES

Table

I. Peaks of Tacot in Different Solvents ................. 24

2

INTRODUCTION

Tacot is tetranitrodibenzo-l,3a,4,6i-tetraazapentalene. 1- Themolecular formula of the material is C. 2H4N808 and its structuralformula is as follows:

In appearance Tacot is an oxang7 powder. It it used in primingcompositions and detonators that are subject to nigh temperatures 8sin rockets and space vehicles. - 3 Tacot Is effective for such a pur-pose because it continues to function as an explosive even when heatedto as high r temperature e.s 4000C (the melting point of the materia].)- 3

Tacot is made by a process patented by duPont Co. 1-3 that involvesnitration of dibenzo-1,3a,4,6a-tetraazapentalene with fuming nitricacid. The production of the parent compour, dibenzo-l,3a,4,6a-tetraazapentalene, is also covered by duPont Co. patents.

3- !

Not much has been reported on the solubility of Tacot. It hasbeen stated2 that the material is soluble in 95% nitric acid and thatit is insoluble ii water, most acids, and organic solvents and onlyslightly soluble in nitrobenzenu, dimethylformamide, and acetone.Apparently, there is little information in the literature on theultraviolet and visible spectra.

XPERIMENTAL

The solubilitie; of Tacot in various solvents was investigated byadding 0.01 g of Tacot to about 75 ml of the solvent and notingwhether the Tacot diisolved after a few minutes occasional stirring.

Thiimcal and Engineering News, Nov 5, 1962, 49-50.E. I. duPont de Nemours and Co., "Technical Information on duPont~Explosives Specialties, Tacot, Properties," New York, N. Y.3R. A. Carboni (to L, I. duPont de Nemours and Co.) U. S. Patent

2,904,544, Sept 15, 1959: RE 25,238, Sept 11, 1962.4R. A. Garboni, J. C. Kauer, W. R. Hatchard, and R. J. Harder, J. Am.

Chem. So(.., 89, 2626 (1967).s_ . r ni^ , J. C. K'aucr, i. F. Caa.. .. and H. E. So n -- J. Aui.

Chem. Soc. 89, 2618 (1967).3

by this means it wzs found that Thc'ot was not significantly solublein the following sclvents: water, hydrochloric acid, phosphoric acid,

ethyl ether, petroleum etler, carbon tetrachloride, and isopropylalcohol. Tacot was only slightly soluble in the following solvents,with the production of a yellowish or yellowish-green fluoresence:

methyl alcohol, ethyl alcohol, butyl alcohol, acetone, methyl ethylketone, methyl isobutyl ketoiuz, acetophenone, dioxane, methylenechloride, chloroform, bromoform, benzene, toluene, -ylene, ethylacetate, butyl acetate, amyl acetate, triacetin, tricresyl phosphate,formic acid, acetic acid, acetic anhydride, nitrobenzene, amyl nitrate,acetaldehyde, aniline, thiophene, acetonitrile, and pyridine. The0.01 g of Tacot dissolved in the following solvents with the produr:-tion of the indicated colors:

sulfuric acid - orangeperchloric acid - orangenitric acid -- orangeglycerin (C 3 5 (r;") ) (rqL,1red heatin, to about 50Cc)- orangedimethylsulfoxide {(C'i3-203} - orangesodiiiim hydroxide solution (207) - amberammon'um hydroxide - ambermorpho Line O C 2 - amber

(OcCH T2 N11CH 2CH 2)piperidine V i - amber

( 2 CH 2 2CH 2 2 2N)tri(!tbanolamiae { (HOCTI CH2 ) N} - brownish-redN,N.-dimethylformamide (HCON(CU) 2 ) - ye]lowish-brown with

olive-green tint

The visible and ultraviolet spectra "or Thcot were determined forall the above solvents in which Tacot was soluble except the sodiumhydroxide solution (no spectral work was done with the latter solutionbecause of the danger of attackinj: the spectrophotometer cells). Thesulfuric acid, perchloric acid, Fc. ammonium hydroxide used for thespectral studies were r~igent grade, while the other solvents wereFisher Certified Reagentj. The Tacot was obtained from duPont Co.The spectra were prepared using a Cary Modei 15 spectrophotometer(1-cm cell) with the solvent in the reference cell. For all thesolvents except glycerin, 0.000g of Tacot was weighed on a seml-microbalance into a 100-ml beaker, then about 75 ml of the selvent wasadded and the Tacot was dissolved by stirrin', with a stirring rod atroom temperature. The solution was diluted to ion] ml Ir. a volumetric-lask with the sclvent, an appropriate aliquot (or sub-aliquot) waspipetted into a 50-ml vctumetric flask, the volune ; as brought up to50 ml, and the spectrum uas determined. In the case of the glycerin,the Tacot was dissolved by warming at abouL 500 C, the solution was

dilited to 200 TO, and the aliquot was taken. All the solutions afterthe final. dilution prior to th2 spectral readings were yellowish incolor.

!4

The spectra obtained for Tacot in the different solvents are shownin Figures I to 10. The spectra are given from the cut-off point ofthe solvent to 600 nm (no significant absorbance was obtained above600 nm). The cut-off points of the solvent were determined by obtain-ing the spectra of the solvents against water (Fibures 11 to 20) andascertaining the wave length at which the absorbance was approximately0.5.6 The cut-off points of the solvents are given in Table I.

A surmary of the data concerning the location of the peaks and the

mclar absorptivities (e - molecular weight of Tacot/cell width x ccnc.in g/1) are shown in Table I.

DISCUSSION AND RESULTS

There was no clear-cut pattern as to why Tacot was soluble in

some solvents and insoluble in others. It wouid setm that some strongincrganic acids are solvents for the material as are certain alkalinereegents (both inorganic and orgcnic). The solvents glycerin anddiuethylsulfoxide are ordinarily not considered to be acidic or basic.All the solvents in which Tacot is soluble can be considered to bepolar.

As indicated in Table I, the peaks in many cases were not clear-cut but occur as shoulders and plateaus. In order to assess possiblepatterns, the peaks were grouped together somewhat arbitrarily accord--ing to location. By this means it is seer that peaks occurred at 450to 506 nm in all the solvents except piperidine which showed a risingslope and significant absorbarce in this region. Sulfuric acid sLowed

a strong peak at 416 n. Sulfuric acid, morpholine, and piperidineshowed peaks at 395 to 4Gs2 trn (peaks did not occur in this region withthe other solvents). A peak occurred at 318 to 350 n for all thesolvents except nitric acid and piperidine (which were not usable inthis range). A peak occurrel at 248 to 281 nm in sulfuric acid, per-chloric acid, and ammonium h)droxide (the only solvents usable in thisrange).

An attempt was made to compare the spectra obtained from thesolvents that gave oraige solutions with the solvents that gave amberor other dark-colorel solutions (all the solutions firally used forthis spectral work were yellowish as previously noted'. The only con-clusion that could be drawn was that the solvents that originally gaveorange solutions were inclined to give 6harper peaks while the solu-

tions that originally go--: amber or other dark-colored solutions were

6G. W. Ewing, "Instrumental Methods of Chemical Analysis," 2nd ed.,5v--,

5 ~ f~kM ~ ~ -~-

frequently inclined to give shoulders and plateaus. The colorsobtained with the orange solutions were more stable than the colorsobtained with the amber and other dark-colored solutions.

Tacat and its parent conpound are hybrids of several dipolarresonanc: structures, - 5

'7 hence the interpretation of the spectrum of: Tacot from the viewpoint of electronic configuration would be ve7.3,

difficult. Probably the diversity of the spectra is due to the tend-

ency of Tacot to form complexes with the solvents.

A study was made of the possible application of the color obtainedwith Tacot in solution to the determination of Tacot. It was foundthat satisfactory straight-line calibration curves (using a Beckman

Model B spectrophotometer) were obtained for sulfuric acid, perchloricacid, nitric acid, and dimethylsulfoAide at 416, 486, 487, and 506 nm,respecr 4-.-ly. Glycerin was not satisfactory because of its viscosity.~The colors obtained with the other solvents uere not satiafactory forquantitative work since the colors changed somewhat wth time.

The spectrophotometric determination of Tacot. in primers wasinvestigated. It was found that Tacot could not be completely extrac-ted from the primers by sulfuric acid, nitric acid, or dimethylsulf-oxide (perth_!ric acid was lot used because of possible hazard).Also, it was found that the other ingredients of the primers (potas-sium chlorate, antimony sulfide, and calciurm silicide) seemed to effectthe color somewhat. Prior extraction of the primers with water (toremve the potassium chlorate) was not helpful. Possibly, the spectro-photometric technique could be used co determine Tacot in materialsother than primers.

SUTMARY

The ultraviolet and visible spectra of Tacot (tetranitrodbenzo-1,3a,4,6a-tetraazapentalene) were determined in nine solvents in whichthe material was significantly soluble. These solvents were sulfuricacid, perchloric acid, nitric acid, glycerin, dimethylsulfoxide,ammonium hydroxide, morpholine, piberidine, triethanolamine, and N,N-dimethylformamide. The first five )f these solvents gave orange

3T. A. Carboni (to F. I. duPont de Nemours and Co.) U. S. Patent2,904,544, Sept 15, 1959; RE 25,238, Sept 11, 1962.'R. 4. Carboni, J. C. Kauer, W. R. Hatchard, and R. j. Harder, J. Am.Chem. Soc., 89, 2626 (1967).5R. A. Carboni, J. C. Kauer, J. F. Castle, and H. E. Sinmions, 3. Am.Chem. Soc.5 89, 2618 (1967).7Y. T. Chia aid H. E. Simmons, j. Am. Chem. Soc., 39, 2638 (1967).

6

solutions while the last four gave amber or other dark-colored solu-tions; however, the colors of all the solutiuns after aliqucting anddiluting prior to the spectral measurements were yellowish. The study

in the ultraviolet region was limited by the relatively high cut-offpoints of the solents. The molar absorptivities of the peaks werecalculated. A somewhat arbitrary grouping of the peaks according tolocation showed that peaks occurred for Tacot in il1 solvents at 450to 506 nm except for piperidine which showed a rising slope and signi-ficant absorption in this region. Suifuric acid showed a strong peakat 416 nm. Sulfuric acid, morpholine, and piperidine showed peaks inthe area of 395 to 403 nm (peaks did not occur in this region in theother solvents). A peak occurred at 318 to 350 nm for all the solventsexcept nitric acid and piperidine (which were not usable in this range).A peak occurred at 248 to 281 nm in sulfuric acid, perchloric ezid,and ammonium hydroxide (the only solvents usable in this range). Thesolvents that originally gave orange solutions were inclined to give

sharper peaks, while the solutions that originally gave amber andother dark-colored solutions were frequcntly inclined to give shouldersand plateaus. The colors obtained from tlle orange solutions tended tobe more stable. The extraordinary effect of the solvent on the spec-Lrum of Tacot is probably related to the tendency of Tacot to formcomplexes with the solvent. Experiments indicated that Tacot could bedetermined quantitatively by measurement of the color in sulfuricacid, perchloric acid, nitric acid, and dimethylsulfoxide at 416, 486,487, and 506 nm, respectively. The method could not be applied to thedetermination of Tacot in primers because of the difficulty of com-pletely extracting the Tacot from the primers and also because theother ingredients of primers interfered with the color.

RECOMNENDATIONS

It is recommended that the investigatory work on Tacot be continuedin order to establish a method for the assay of the material using wetchemical or instrumental techniques. Also, it is recommended that theinfrared spectrum and thermal properties (using differential scanningcolorimetry and thermogrametric analysis) be studied.

L7

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REFERENCES

1. Chemical and Engineering News, Nov 5, 1962, 49-50.

2. E. I. duPont de Nemours and Co., "Technical Information on duPontExplosives Specialties, Tacot, Properties," New York, N. Y.

3. R. A. Carboni (to E. I. duPont de Nemours and Co.) U. S. Patent2,904,544, Sept 15, 1959; RE 25,238, Sept 11, 1962.

4. R. A. Carboni, J. C. Kauer, W. R. Hatchard, and R. J. Harder,J. Am. Chan. Soc., 89, 2626 (1967).

5. R. A. Carboni, J. C. Kauer, J. r. Castle, and H. E. Simmons,J. Am. Chem. Soc., 89, 2618 (3967).

6. G. W. Ewing, "Instrumental Methods of Chemical Analysis," 2nd ed.,p. 61, McGraw-Hill, New York.

7. Y. T. Chia and H. E. Simmons, J. Am. Chem. Soc., 89, 2638 (1967).

! I.

25