NSWC TR 80-111

AN INVESTIGATION OF THE SHIPP

HEXANITROSTILBENE (HNS) PROCESS

BY ELEONORE G. KAYSER

C RESEARCH AND TECHNOLOGY DEPARTMENT

25 AUGUST 1980

DTICELECTEDEC 9 1980 E

Approved for public release, distribution unlimited. UB

1 4 NAVAL SURFACE WEAPONS CENTER

'! Dahlgren, Virginia 22448 0 Silver Spring, Maryland 20910

80 09 0

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REPORT DOCUMENTATION PAGE READ :NSTRUCrrcO4SBEFCRE --. %PL TT NG FCRMl

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An Investigation of the Shipp Fri 'A l n--Hexanitrostilbene (HNS) Process. RPT.M8l

7. A U :oNRqAj-OR 3AAN- %IJI1UER11(f)

Eleonore G. ,"Kayser

3. 2ERFOMMINO ORGANIZA-ION 'fAME AND ACC14ESS PR OGGAJi !.EMEN, ORCJE: -ASKAREA A NOR~ JNIT NjUMERS

Naval Surface Weapons Center NASA; 31223;

White Oak, Silver Spring, Maryland 20910;,SO R2'1 1 OmT..L.NG OFFICE NAME AND AOORE5S .2 QEgDQ- ;,Aj-----

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UNCLASSIFIEDISa. OGECLASSI~iCATION. OowmGRAGIG

SCN4EOULE

IS. DISTRIBUTION STATEMENT 'of this Report)

Approved for public release; distribution unlimited.

17. DISTRIBUTION STATEMENT 'of the absteract enteedo In Stock 20, If di fferent from Report)

Ill. SUPPL.EMENTARY NOTES

f9. <EY WORDS (Continue on reverse aide di necessary and Identify by block rnumrbr)

HNSHexanitrostilbeneHPLC Analysis of ExplosivesProduct Analysis of the HNS (Shipp) Process

20. ABSTRACT fContinuo an *. erse side It necessary end identify by block number)

->This report describes the separation, characterization, andanalysis of the products which the Shipp hexarnitrostilbene (HNS)process yields. In this process, trinitrotoluene (TNT) , dis-solved in a mixture of tetrahydrofuran (THF) and nethanol kmeoH)is reacted with commnercial bleach (NaOCl) to form HNS. Theisolated products include: hexanitrosti'lbene (HNS) awl

DO ::M, 143 KO T

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SEC~qA-v --?;'CIN 4S -aA41 wp *,i Zaera Setreo,

SE s,; .ASSlrIZA-1z11 Or '-!S DAGE MWhet, Data Entered,

20. (continued)

-5 hexanitrobibenzyl (HNBiB) , t6rinitrobenzene (TNB), trinitrobenzoi*:acid (PiCOOH) , trinitrobenzaldehyde (PiCHO) , trinitrobenzylchloride (PiCH2Cl) , picryl chloride (piCi) , picric acid (15iOH),trinitrobenzyl alcohol CPiCH20H), 4,6-dinitroL,7benzisoxazole(Anil), and trichioronitromethane (chloropicrin) as well as someunreacted TNT. Approximately 5-10% of the red-tar fraction ofthe reaction mixture remains unidentified. Solvent effects onthe yield of several of the above by-products are discussed;however, no other solvent examined displayed the pronouncedspecificity of tetrahydrofuran (THF) for this reaction.

EJNCLASSI 'EES(ECURITY CLASSIFICA?10k Or~YKIS PAGE("an Date Egntered,

NSWC TR 80-111

II

FOREWORD

This report describes the identification, characterization,and analysis of several of the by-products of the Shipp hexani-trostilbene (HNS) process. This work was sponsored by theStrategic Systems Project Office under Task B00035B0OI;R12 KUand the Lyndon B. Johnson Manned Spacecraft Center under TaskNASA RI2ZB. The identification of vendors or commercial productsimplies neither criticism nor endorsement by the Naval SurfaceWeapons Center.

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NSWC TR 80-111

CONTENTS

Page

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

EXPERIMENTAL ............................................... 5Reaction Conditions and Work-Up Procedures .................. 5Analysis Procedures ...................................... 6Results and Discussion ................................... 7

CONCLUSIONS ................................................ 21

ILLUSTRATIONS

Figure Page

1 HPLC TRACE OF COMPOUNDS ISOLATED FROM THETNT-NaOCl REACTION ............................... 11

TABLES

Table Page

1 NMR DATA FOR COMPOUNDS ISOLATED FROM THETNT-NaOCl REACTION ............................... 8

2 TLC DATA OF IDENTIFIED COMPOUNDS FROM THEHNS REACTION ........................................... 9

3 HPLC DATA OF COMPOUNDS ISOLATED FROM THETNT-NaOCl REACTION ............................... 10

4 COMPOUNDS IDENTIFIED FROM THE TNT-NaOC1 REACTION ... 12

5 BY-PRODUCT REACTIONS WITH BASE INSEVERAL SOLVENTS ................................. 17

6 TNT REACTIONS ......... ............................. 19

2

NSWC TR 80-111

INTRODUCTION

Since its discovery in the early 1960's by Kathryn G. Shipp,thermally stable 2,2',4,4',6,6'-hexanitrostilbenj (HNS) has foundnumerous applications in military ordnance items and throughoutthe aerospace industry 2 ,3 ,4 .

HNS is currently prepared commercially5 by reacting 2,4,6-trinitrotoluene (TNT) with a 5% aqueous sodium hypochlorite solu-tion (household bleach) in the presence of tetrahydrofuran (THF)and methanol (MeOH) as solvents (Shipp Process 6 ,7 ). It is assumedthat, under the alkaline conditions of the reaction, TNT formstrinitrobenzyl anion, which is chlorinated to yield trinitrobenzylchloride. Subsequent reaction of the chloride with alkali pro-duces a mixture of HNS and HNBiB as crystalline products in acombined yield of less than 50% with the remainder of the materialforming a red-tar fraction:

Shipp Process

TNT NaOCI (0-5°C) (HNS + HNBiB) + red-tarTHF, MeOH (-40%) (-60%)

1Kilmer, E. E., "Hexanitrostilbene Recrystallized from NitricAcid," NSWC/WOL TR 78-209, September 1979.

2Bement, L. J., "Application of Temperature Resistant Explosivesto NASA Missions," presented at the Symposium on Thermally StableExplosives at NSWC White Oak, Maryland, June 23-25, 1970.

3Rouch, L. L. and Maycock, J. N., NASA CR-2622, February 1976.4 Kilmer, E. E., J. Spacecraft, Vol. 1216, 1968, pp. 5, 10.5Kilmer, E. E., "Overview of HNS. Production/Properties/Applications," NSWC TR 79-181, July 1979.

6Shipp, K. G. and Kaplan, L. A., J. Org. Chem., Vol. 31, 1966,

p. 857.7 Shipp, K. G., J. Org. Chem., Vol. 29, 1964, p. 2620.

3

NSWC TR 80-111

The purpose of this study is two-fold: (1) to determinewhat products, other than HNS and HNBiB, are produced by the TNT-NaOCl reaction, and (2) to search for a way to reduce or eliminatethe concurrent side reactions which reduce the yield of HNS.An investigation of the composition of the red-tar fraction wasnecessary to determine the nature of the side reactions. Approxi-mately 90% of the compounds contained in the red-tar fractionwere isolated and characterized using thin layer chromatography(TLC) coupled with nuclear magnetic resonance spectroscopy (NMR),gas chromatography (GC), and/or high performance liquid chroma-tography (HPLC) r 10. Final product identification was achievedby comparison with known compounds. To facilitate the secondpart of this study, the HNS reaction (TNT - HNS) was separatedinto two steps:

(A) TNT NaOCl (0-5 C) > PiCH2C 1THF, MeOH (exothermic) 2

stableintermediate(-75%-85%)

NaOH(B) PiCH2C1 (non-exothermic)- N + HNBiB + red-tar

(-35%-40%) (-60%)

In Step A the stable intermediate, 2,4,6-trinitrobenzylchloride (PiCH2Cl), was obtained in a 75% - 85% yield by quenchingthe reaction mixture in dilute aqueous acid (HCl) approximatelyone minute after the NaOCl addition was complete. No evidenceof appreciable amounts of by-products, other than unreacted TNT,was found by short stopping the reaction at this step. Sincethe red tar products are formed in Step B of the HNS reaction,this step was studied independently by investigating the PiCH 2Clreaction with base in various solvents. In addition, severalby-products of the Shipp reaction, 1,3,5-trinitrobenzene (TNB),4,6-dinitro Zf,I7 benzisoxazole (Anil), 2,4,6-trinitrobenzyl alcohol(PiCH2OH) , 2,4,6-trinitrobenzaldehyde (PiCHO), and 2,4,6-trini-trobenzoic acid (PiCOOH),were also treated with base under differentconditions to observe the products formed.

8Kayser, E. G., "Analysis of 2,2',4,4',6,6'-Hexanitrostilbene (HNS)by High Performance Liquid Chromatography," NSWC/WOL TR 77-154,March 1975.

9Stull, T. W., "Synthesis of High Purity Hexanitrostilbene,"MHSMP-75-37, September 1975.10Schaffer, C. M., "HNS by Liquid Chromatography,"MHSMP-77-51, 1977.

4

NSWC TR 80-111

EXPERIMENTAL

Reaction Conditions and Work-Up Procedures

In order to determine the by-products which make up the red-tar fraction, a total of twenty TNT-NaOCl reactions were carriedout under the conditions reported to give a maximum yield ofHNS6 ,7 . The crystalline material (HNS-HNBiB) from each reactionwas filtered from the reaction mixture, washed with methanol,dried and weighed. Further by-product reactions in the remainingfiltrate were quenched by neutralization with aqueous HCl. Afteran initial extraction of the filtrate with benzene, both theextract and the remaining aqueous filtrate were evaporated todryness and assayed by TLC and NMR for identifiable products.The organic components of the red-tar material contained in thebenzene extract were separated using preparative TLC. After GCseparation, the compounds were characterized by NMR, GC, and HPLC.Structural confirmation was achieved by comparison with authenticcompounds.

Several of the TNT-NaOCl reactions were run in a closed systemto retain any volatile compounds formed. Although several volatilematerials were separated from both the benzene extract and theaqueous solution of the red-tar fraction, chloropicrin was theonly volatile product that could be characterized and identifiedwith GC and HPLC by comparison with the known compound.

A supplemental study of the reactions of TNT with severalof the isolated by-products of the Shipp process (TNB, Anil,PiCH 2OH, PiCH 2Cl, PiCHO, and PiCOOH) was carried out at roontemperature, with aqueous NaOH and NH4OH, to observe the productsformed. Reaction times were arbitraily set at 30 and 90 minutes.A 1:1 mole ratio of reactant to base was used in each case, andMeOH, THF and dioxane were used as solvents. The work-up procedurefor these reactions was identical to that used in the TNT-NaOCIreactions. The major reaction products were identified by NMRspectroscopy, and structural confirmation was achieved by com-parison with authentic compounds.

6 ' 7 See footnotes 6 and 7, page 3.

5

NSWC TR 80-111

Analysis Procedures

Components of the organic red-tar material contained in thebenzene extract were separated using preparative TIC. The plates(1/4" thickness) were prepared using Brinkman Silica gel HF 254as the absorbent with a calcium sulfate binder. As purchased,this material contains a fluorescent indicator which allows loca-tion of the developed spots with a 254 nm light. The TLC develop-ing solvents used were either benzene or a benzene:ether:ethanolmixture (50:30:20 by volume) depending on material polarity.

Estimated yields for HNS, HNBiB, unreacted TNT and nine by-products were obtained with a Varian HA-100 NMR spectrometer using2,3-dimethyl-2,3-dinitrobutane as an internal standard. The chemi-cal shift values (6) for the TNT and by-product protons weredetermined relative to the reference compound, tetramethylsilane(TMS). The NMR solvent used was dimethyl sulfoxide-d 6 (min.isotopic purity 99.5 atom % D), since it was the best generalsolvent found for the TNT-NaOCl reaction products.

High performance liquid chromatography (HPLC) was also usedto characterize the organic components from the benzene extractof the TNT-NaOCI reaction mixtures. A model ALC 202 liquid chroma-tograph equipped with a model 6000 solvent delivery system anda U6K high pressure loop injector (Waters Associates, Milford,Mass.) was used for the analyses and the eluent was continuouslymonitored with a 254nm UV detector. A Whatman HPLC guard columncontaining CO:PELL ODS pellicular material was used as a pre-column to the Whatman Partisil - 10 ODS-2 bonded octadecyl silane(C-18) reverse phase analytical column (25cm long, 4.6mm ID, 1/4"(6.350mm) OD). Typical efficiency of this analytical column,containing the (ODS) functionality, is 18,000 plates/meter. TheUV absorption signals were recorded on an Omniscribe strip chartrecorder set at 0.5cm/minute. The mobile phase consisted of MeOH(Baker - HPLC grade) and distilled water in a ratio of 2:3 byvolume. Pressure at the column head was approximately 2000 psiwith a flow rate of 2 ml/minute. The column temperature wasapproximately 25 C. All solvents and samples were filtered priorto use in the HPLC. Material concentration was determined bymanually integrating the area of the chromatographic peak. Di-methylsulfoxide (DMSO, Fisher Scientific, A.C.S. grade) was usedas the sample solvent. All the compounds, except PiCOOH at rela-tively low concentrations (<50 ppm), were found to be stable inthe sample solvent (DMSO). In dilute solutions, PiCOOH reactswith DMSO to form TNB (peak retention time, 6.9 minutes). However,a peak retention time of approximately 1.0 minute was obtainedwith more concentrated PiCOOH-DMSO solutions. This value agreeswith that obtained for PiCOOH in MeOH.

6

NSWC TR 80-111

Results and Discussion

To date twelve compounds (HNS, HNBiB, Anil, PiOH, PiCH OH,PiCH 2CI, chloropicrin, PiCOOH, PiCI, PiCHO, TNB, and TNT) eitractedfrom the HNS synthesis reaction (Shipp Process) have been identi-fied and characterized. Approximately 98% of the HNS is recoveredin the crystalline form; however, several by-products and soe^ 9,11unreacted TNT have been found trapped within the HNS crystal '",In addition, all twelve compounds were found in the red-tar fraction.NMR and TLC data from all the compounds studied (with the exceptionof chloropicrin) are summarized in Tables 1 and 2. HPLC dataare given in Table 3 and Figure 1.

Deuterium exchange experiments carried out earlier 12 indi-cated the formation of 2,4,6-trinitrobenzyl anion from 2,4,6-TNTin alkaline THF/MeOH solutions. The results of a recent photo-deuterium exchange study 13 of aqueous 2,4,6-TNT solutions alsoindicate the initial formation of 2,4,6-trinitrobenzyl anion.Previous work at this laboratory by Burlinson, Kaplan, Adams andSitzmann 14 ' 1 5 has shown that photolyzed aqueous solutions of TNT(using sunlight or a pyrex filtered HG-lamp) contain several ofthe compounds isolated from the TNT-NaOCI reaction (e.g., TNB,PiCHO, Anil, and PiCH 2OH).

Estimated weight percentages, based on NMR analysis, arereported for eleven of the organic components recovered from thered-tar fraction (Table 4). At least two other compounds formedin the reaction mixture but could not be identified due to theirvolatility at room temperature. The British (PERME Group atWaltham Abbey) have identified methyl nitrite as a volatile com-ponent of this reaction.

5See footnote 5, page 3.8 ' 9 See footnotes 8 and 9, page 4.11O'Keefe, D. M., "Digestion as a Process Aid for Hexanitrostilbee,"SAND 76-0330, February 1977.

12Shipp, K. G., Kaplan, L. A., and Sitzmann, M. E.,J. Org. Chem., Vol. 37, 1972, p. 1966.

13Burlinson, N. E., Sitzmann, M. E., Kaplan, L. A., andKayser, E. G., J. Org. Chem., Vol. 44, 1979, pp. 21,3695.

1 4Burlinson, N. E., Kaplan, L. A., and Adams, C. E., "Photochemistryof TNT: Investigation of the 'Pink Water' Problem," NSWC/WOLTR 73-172, October 1973.

15Kaplan, L. A., Burlinson, N. E.,and Sitzmann, M. E.,"Photochemistry of TNT: Investigation of the 'Pink Water'Problem," NSWC/WOL TR 75-152, November 1975.

7

NSWC TR 80-111

TABLE 1 NMR DATA FORCOMPOUNDS ISOLATED FROM THE TNT-NaOCI REACTION

Compound NMR Spectrum (a)

6

HNS 9.07 ( S, 4 Ar-H)7.11 ( s, CH=CH)

HNBIB 9.05 ( s, 4 Ar-H)3.39 ( s, CH2-CH2)

PiCH2 Ci 9.05 s, Ar-H)4.98 ( s, CH2 )

PiCH2OH 8.95 ( s, 2 Ar-H)4.82 ( s, CH2 )

PiCHO 9.14 ( s, 2 Ar-H)

10.51 ( s, CH)

PiCOOH 9.11 ( s, 2 Ar-H)

PiCi 9.20 ( s, 2 Ar-H)

TNB 9.14 ( s, 2 Ar-H)

PiOH 8.56 ( s, 2 Ar-H)

TNT 8.98 ( s, 2 Ar-H)2.53 ( s, CH 3 )

Anil 10.56 ( d, Ar-H)9.31 ( q, Ar-H)8.62 ( d, Ar-H)

(a)s=singlet, d=doublet, q=quartet, Ar=aromatic

protons. Chemical shifts are in 6 units down-

field from internal TMS with line multiplicityand relative intensity in parentheses. Spectrawere determined on a Varian HA-100 in DMSO-d6 .

8

NSWC TR 80-111

TABLE 2 TLC DATA a) OF

IDENTIFIED COMPOUNDS FROM THE HNS REACTION

Compound Rf (benzene)

TNT .86

PiCI .89

PiOH .17 (b)

PiCOOH 0.0 (origin)

PiCH 2Cl .83

TNB .74

PiCHO .56

An il .64

PiCH2OH .20

HNS .38

HNBiB .58

Red-Tar (unidentified) 0.0 (origin)

R f

(benzene :ether :ethanol)

Compound 50 30 20

PiOH .90

PiCOOH .73

Red-Tar (unidentified) 0.0 - 0.05

(a)Thin layer plates prepared with Brinkman Silica

gel - HF 254. Spot visualization by UV lamp.

Rf taken from leading edge of spot.

(b) Streaking from .17 to origin.

9

NSWC TR 80-111

TABLE 3 HPLC DATA OFCOMPOUNDS ISOLATED FROM THE TNT - NaOCI REACTION~a)

Peak Retention TimeCompound in Minutes

PiCOOH 1.0

PiOH 1.1

DMSO (b) 1.7

PiCH2OH 3.9

PiCHO 5.8

TNB 6.9

Anil 9.2

PiCI 12.0

TNT 12.8

Chloropicrin 18.5

PiCH2C1 19.8

HNS 38.5

HnBiB 58.6

(a)column: Partisil-01-ODS-2 (reverse phase)

Mobile Phase: 40% MeOH/60% HOH by volume.Flow Rate: 2 mis/minute.

(b) Sample Solvent: DMSO.

10

NSWC TR 80-111

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NSWC TR 80-111

TABLE 4 COMPOUNDS IDENTIFIED FROM THE TNT-NaOCI REACTION

ESTIMATEDCOMPOUND YIELD

NO NONOH

NO2 NO2

2, 2', 4, 4', 6, 6'- HEXANITROSTILBENE (HNS) 30-45

NO2 NO2HH

02 N / C / NO22 H H -2

NO2 NO 2

2, 2', 4,4', 6, 6' - HEXANITROBIBENZYL (HNBiB) 5-10DIPICRYLETHANE (DPE)

CH2CI

O 2N NO 2

NO2

2,4, 6 - TRINITOBENZYL CHLORIDE (PiCH 2CII 5-10

12

NSWC TR 80-111

TABLE 4 COMPOUNDS IDENTIFIED FROM THE TNT-NOi RATO CNIUD

ESTIMATEDCOMPOUND YIELD

CHO

O2N NO 2

NO2

2,4, 6 - TR INITROBENZALDE HYDE (PiCHO) - 5-10

COOH

02N NO 2

NO2

2,4, 6- TRINITROBENZOIC ACID (PiCOOH) 0-8

O N .~NO 2

NO2

PICRYL CHLORIDE (PiCI) 0-TRACE(a)

13

NSWC TR 80-111

TABLE 4 COMPOUNDS IDENTIFIED FROM THE TNT-NaOC1 REACTION (CONTINUED)

ESTIMATEDCOMPOUND YIELD

CH2 O

O2N NO 2

NO 2

2,4, 6 - TRINITROBENZYL AL~COHOL (PiCH 2 0H) 5-10

O N NO2

NO2

1, 3, 5 - TRINITROBENZENE (TNB) 5.10

OH

O2N INO 2

NO2

PICRIC ACID (PiOH) O-TRACE~a)

14

NSWC TR 80-111

TABLE 4 COMPOUNDS IDENTIFIED FROM THE TNT-NaOCI REACTION (CONTINUED)

ESTIMATED

COMPOUND YIELD

CH 3

02N N NO 2

NO 2

2,4,6 - TRINITROTOLUENE (TNT) 5-10

CI

Cl- C -NO 2

CI

TRICHLORONITROMETHANE (CHLOROPICRIN)(b) >1-?

HC - 0

0 2 N N

NO2

4,6 - DINITROO, I7bENZISOXAZOLE < 1-54, 6 - DINITROANTHRANIL (ANIL)

RED.TAR(cl 5-10

Pi 2,4,6 - TRINITROPHENYL

(a) TRACE - 1%(b) MATERIAL NOT ACCURATELY DETERMINED DUE TO VOLATILITY AT ROOM TEMPERATURE() UNIDENTIFIED MATERIAL - POSSIBLY HIGH MOLECULAR WEIGHT AND/OR POLAR MATERIAL

15

NSWC TR 80-111

Approximately 5-10% of the red-tar fraction that remainedin the aqueous filtrate after removal of the HNS/HNBiB crystalsand extraction with benzene could not be identified. This mate-rial probably contains high molecular weight and/or polar com-pounds, since most of the unidentifiable segment (>50%) remainedat the origin when chromatographed with the relatively polarsolvent mixture, benzene:ether:ethanol (50:30:20 by volume).

Results of investigations of (a) the non-exothermic basereactions with aqueous sodium hydroxide (NaOH) and aqueous ammoniumhydroxide (NHfOH) in various solvents, and (b) the reactions ofTNT with NAOCf in various solvents are summarized in Tables 5and 6. In general, the base study indicated a greater degreeof product reactivity in the aqueous NaOH system than in theaqueous NH40H system. As expected, the reactions of PiCH 2OH,PiCH2Cl, and TNT with NaOH formed highly colored species andresulted in the greatest number of reaction products. However,most of the products resulting from the reaction of TNT with NaOHcould not be separated or identified and remained at the originwhen chromatographed with the relatively polar solvent mixture,benzene:ether:ethanol (50:30:20 by volume). Approximately 5-15%HNBiB was isolated from the TNT-NaOH reaction mix. Both TNB andanil proved to be stable end products under these reaction condi-tions. Trinitrobenzoic acid (PiCOOH) decarboxylates to TNB inthe presence of base. This reaction also occurs quite rapidlyin DMSO (without added base) at PiCOOH concentrations of lessthan 50 ppm.

TNB is also the final roduct from trinitrobenzylaldehyde(PiCHO). This reaction1 6 ,17 proved to be quantitative in severalof the solvents investigated. As expected, the reaction of trini-trobenzyl chloride (PiCH2Cl) with NaOH produced the highest yieldof HNS (35-45%) in the THF-MeOH (2:1) and the THF solvent systems(Table 5). This is also true of the TNT-NaOCl reactions (Table6). None of the other solvents examined exhibited the apparentspecificity of THF for this reaction.

16Secareanu, S., Ber. Dtsch. Chem. Ges., Vol. 64, 1931, p. 837.17Secareanu, S., Bull. Soc. Chim., Vol. 51, 1931, p. 591.

16

NSWC TR 80-111

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NSWC TR 80-111

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NSWC TR 80-111

TABLE 6 TNT REACTIONS

% REACTION PRODUCTS

REACTION TIME TEMPERATURE IREACTANT NaOCI BASE SOLVENT SYSTEM IN MINUTES °C TNT TNB HNS HNBiB

TNT NaOH THF/MeOH (2:1) 30 22.50-250 53 <1 TRACE 6TN , NaOH M&OH 90 22.50-250 37 6

TNT NaOH DIOXANE 90 22,50-250 16 16TNT NaOH THF 90 22.50-250 29 18TNT NH 4 0H THF/MeOH (2:1) 90 22.50-250 74TNT NH 4OH DIOXANE 90 22.50-250 39TNT NH 40H MeOH 90 22.50-250 65

TNT NaOCI THF/MeOH (2.1) 2-3 <15020 22.50-250 43 8

TNT NaOCI THF/MeOH (2:1) 5 <15030 22.50 -250 38 10

TNT NaOCI THF/MeOH (2:1) 2-3 <15020 22.50-250 35 7

TNT NaOCI THF 2-3 <150

20 22.50-250 41 6

TNT NaOCI DIOXANE 2-3 <15020 22.50 -250 -12 <5

TNT NaOCI MeOH 2-3 < 15020 22.50 -250 -2

TNT NaOCI ACETONE 2-3 <15020 22.50 -250 <2 -2

TNT NaOCI ACETONITRILE 2-3 <15020 22.50-250 1-2

TNT/BASE REACTION MIXTURES:TO A SOLUTION OF 0.0042 MOLES OF TNT IN 16.92 ML THF AND 8.46 ML MeOH (AT AMBIENT TEMPERATURE) ISADDED 16.92 ML OF WATER CONTAINING 0.0042 MOLES OF EITHER NaOH OR NH 4OH.REACTION TIME: 30 AND/OR 90MINUTES

TNT/NaOCI REACTION MIXTURES:1.0 GM (0.0044 MOLES) OF TNT IN (10 ML THF AND 5 ML MeOH) IS CHILLED TO ABOUT 00C THEN ADDED QUICKLY,WITH THOROUGH MIXING, TO 10 ML OF "CHLOROX" (COMMERCIAL BLEACH - 5.25%) WHICH IS ALSO CHILLED TO0C. DURING THE INITIAL REACTION PERIOD OF ABOUT 2-3 MINUTES, THE TEMPERATURE OF THE MIXTURE IS HELDBELOW 150 C BY CHILLING IN AN ICE-SALT BATH. THE MIXTURE IS THEN ALLOWED TO STAND AT AMBIENTTEMPERATURE UNTIL PRECIPITATION OF THE HNS PRODUCT IS COMPLETE (APPROXIMATELY 20-30 MINUTES).

MAJOR IDENTIFIABLE REACTION PRODUCTS: DETERMINED BY NMR SPECTROSCOPYNMR SAMPLE SOLVENT: DMSO

19/20

NSWC TR 80-111

CONCLUS IONS

The by-products isolated from the Shipp Hexanitrostilbene(HNS) Process are: hexanitrobibenzyl (HNBiB), trinitrobenzene(TNB), trinitrobenzoic acid (PiCOOH), 4,6-dinitro 2,1 benzisoxa-zole (Anil), trinitrobenzaldehyde (PiCHO), trinitrobenzyl chloride(PiCH2Cl), picryl chloride (PiCl), picric acid (PiOH), trinitro-benzyl alcohol (PiCH2OH), and trichloronitromethane (chloropicrin).Some unreacted TNT (5-10%) was also isolated from the red-tarfraction of the reaction. The investigation of the reactionsof all of the above polynitroaromatic compounds with base furnishedsome additional information, but no method was found to eitherreduce the side reactions or increase the yield of HNS. Noneof the solvents investigated displayed the pronounced specificityof tetrahydrofuran (THF) for this reaction.

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REFERENCES

1. Kilmer, E. E., "Hexanitrostilbene Recrystallized fromNitric Acid," NSWC/WOL TR 78-209, September 1979.

2. Bement, L. J., "Application of Temperature Resistant Explosivesto NASA Missions," presented at the Symposium on Thermally StableExplosives at NSWC White Oak, Maryland, June 23-25, 1970.

3. Rouch, L. L. and Maycock, J. N., NASA CR-2622, February 1976.

4. Kilmer, E. E., J. Spacecraft, Vol. 1216, 1968, pp. 5, 10.

5. Kilmer, E. E., "Overviews of HNS. Production/Properties/Applications," NSWC TR 79-181, July 1979.

6. Shipp, K. G. and Kaplan, L. A., J. Org. Chem., Vol. 31,

1966, p. 857.

7. Shipp, K. G., J. Org. Chem., Vol. 29, 1964, p. 2620.

8. Kayser, E. G., "Aralysis of 2,2',4,4',6,6'-Hexanitrostilbene(HNS) by High Performance Liquid Chromatography,"NSWC TR 77-154, March 1975.

9. Stull, T. W., "Synthesis of High Purity Hexanitrostilbene,"MHSMP-75-37, September 1975.

10. Schaffer, C. M., "HNS by Liquid Chromatography,"MHSMP-77-51, 1977.

11. O'Keefe, D. M., "Digestion as a Process Aid forHexanitrostilbene," SAND 76-0330, February 1977.

12. Shipp, K. G., Kaplan, L. A., and Sitzmann, M. E.,J. Org. Chem., Vol. 37, 1972, p. 1966.

13. Burlinson, N. E., Sitzmann, M. E., Kaplan, L. A., andKayser, E. G., J. Org. Chem., Vol. 44, 1979, pp. 21, 2695.

14. Burlinson, N. E., Kaplan, L. A., and Adams, C. E.,"Photochemistry of TNT: Investigation of the 'Pink Water'Problem," NOLTR 73-172, October 1973.

23

NSWC TR 80-111

REFERENCES (continued)

15. Kaplan, L. A., Burlinson, N. E., and Sitzmann, M. E.,"Photochemistry of TNT: Investigation of the 'Pink Water'Problem," NSWC/WOL TR 75-152, November 1975.

16. Secareanu, S., Ber. Dtsch. Chem. Ges., Vol. 64, 1931,p. 837.

17. Secareanu, S., Bull. Soc. Chim., Vol. 51, 1932, p. 591.

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