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Distribution authorized to U.S. Gov't.agencies and their contractors;Administrative/Operational Use; 16 MAY1962. Other requests shall be referred toU.S. Naval Ordnance Lab., White Oak, MD.

AUTHORITY31 May 1974, DoDD 5200.10; USNSWC ltr, 7Oct 1974

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NOTICE: When government or other drawings, speci-fications or other data are used for any purposeother than in connection with a definitely relatedgovernment procurement operation, the U. S.Government thereby incurs no responsibility, nor anyobligation whatsoever; and the fact that the Govern-ment may have formulated, furnished. or in any vaysupplied the said drawings, specifications, or otherdata is not to be regarded by implication or other-wise as in any manner licensing the holder or anyother person or corporation, or conveying any rightsor permission to manufacture, use or sell anypatented invention that may in any way be relatedthereto.

NOLTR 62-82

I HEAT RESISTANT EXPLOSIVES.XIII. PREPARATION AND PROPERTIESOF 3,3,-DIAMINO-2.2',4,4',b,1 '.HEXANITROBIPHENYL (DIPAM) (C)

7~7I, • ' .. '. :. " : : L .2-A O

..,,.', r a

16 May 1962

"VAL ORDNANCE LABORATORY, WHITE OAK, MARYLANDq

NOTICE: This material contains information affecting the nationaldefense of the United Statos within the meaning of the Espionage tows.Title 18, U.S.C. Sections 793 and 794, the tronsvissior or rtwelab., nof which in any manner to an unauthorized person is prohibitec by low.

Dlowngraded of J Year interval01Decloassfied offer 12 Yeoats 1D00 Die 32M.,10

C _NOLTh o•-QA

HEAT RESISTANT EXPLOSIVES. XIII. PRErARATION AND PROPERTIES OP5,i'-DIAMIN0-2,2', 4, 4',6,6'-HEXANITROBIPHENYL (DTPAM) (C)

Prepared by: Joseph C. DaconsHorst G. AdolphMuzL',intfl" j. Kamiet

Approved by: DARRELL V. SICKMAN, ChiefOrganic Chemistry Division

ABSTRACT: A new oxidative procedure wherein the methyl groupin substituted trInitrotoluene derivatives is replaced byhydroxyl has been applied to the prepz'ration of the title com-pound, a new thermally stable high explosive. The six-stepsynthesis involved the sequence: m-bromotoluene to bromotrini-trotoluene to dimethylhexanitrobiphenyl to dipicric acid todipyridinium dipicrate to dichlorohexanitrobiphenyl to DIPAM.The overall yield was 39.5%. DIPAM appears to have attractivepotentialities for high temperature mild detonating fuse andsimilar applications. (C)

CHEMISTRY RESEARCH DEPARTMENTU. S. Naval Ordnance Laboratory

White Oak, Silver Spring, Maryland

±A

NOLTR 6P-S 16 May 9q6?4/

This rbeport describes •be preparation of 600 grams of a newthermally stable high explosiv6 4fiIVI'T'ay be useful in milddetonating fuse for stage separation in advanced POLARISmissiles. lThe work was started under Task FR-W&, but as thepotential 1applications became apparent it was tranif'crrad toRUME 3E017. The newly-discovered reacLlon described inNOLTR 62-32 furnished -h). basis for this synthesis.

W. D. COLEMANCaptain, USNCommander

ALBERT LIGHTBODYBy directibn

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TAMJE OF CONTENTS

Page

INTRODUCTION ........................................... 1

DISCUSSION ............................................. 2

a) m-Bromotoluene to 3-Bromo-2, 14,6-trinitrotoluene ... 2

b) 3-Bromo-2, 14,6-trinitrotoluene to 3,3'-Dimethyl-2,2',4, 14',6, 6'-hexanitrobiphenyl . ....... .......... 5

c) 3,3'-Dimethyl-2,2',4,4',6,6'-hexanitrobiphenylto Dipicric Acid ............................ ...... 4

d) Dipicric Acid to Dipyridinium Dipicrate ........... 4

e) Dipyridinium Dipicrate to Dipicryl Chloride ....... 5

f) Dipicryl Chloride to Dipicramide .................. 6

PROPERTIES OF DIPAM .7..... ....................... 7

EXPERIMENTAL .......................... . ... .... ......... 8

3-Bromo-2,4,6-trinitrotoluene .... .......... 8

3,3'-Dimethyl-2,2',4,41', 6,6'-hexarnitrobiphenyl......... 8

Dipicric Acid (DIPA) ................................. 9Dipyridinium Dipicrate ............................... 10"5, 5 '-Dichloro-2, 2' ,4,41 ,6,6' -hexanitrobipheny]ýDIPICL) ............................... . ......... 10

5, .3 -Diamino-2, 2',4,4',6,6 '-hexanitrobiphenyl(DIPAM) ...................................... . .. 11

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INTRODUCTION

We have reported (1) that oxidations of TNT and 3-substi-tuted 2,4,6-trinitrotoluene derivatives with mixtures ordichromate, nitric acid and sulfuric acid generally effectedtheir conversion to the correspondingly 5ubstituted trinitro-phenols. In the case of 3,3'-dimethyl-2,2',4,4',6,6'-hexani-trobiphenyl (I), the main product was 3,3'-dihydroxy-P,9',4,o',o,ol-nexanitrobiphenyl (dipicric acid, DIPA, II) rather thanthe 3,3'-dicarboxylic acid as earlier workers had suggested (2).

C1:3 NO 2 NO2 CH3 HO NO2 N02 CH

0 2 N -~ / ~Na 2Cr 2 O70o2N -N02 HNC3,H 2 sO 4o 02 N- 02

NO2 NO2 NO2 NO2

I II, DIPA

Although DIPA has long been known, a number of investiga-tors having reported its preparation by the mixed-acid nitra-tion of 3, 3'-dihydroxybiphenyl (3), the novel dichromateoxidation provided for the first time a convenient method forits synthesis. With its availability in moderate quantities,DIPA merited consideration per se as a candidate for high-temperature booster explosive applications (1) but of greaterimmediate interest was its potential as an intermediate forfurther syathesis.

Treatment of the dipyridinium salt with phosphorusoxychloride, a procedure which has been reported to effect thehigh-yield tranformation of picric acid to picryl chloride (4)

-and styphnic acid to styphnyl chloride (5), afforded a conven-ient method for the conversion of II to 3,3'-dichloro-2,2',4,4 1 ',6,6'-hexanitrobiphenyl (dipicryl chloride, DIPICL, III).DIPICL, with ethanolic ammonia, was readily converted to 3,3'-diamino-2,V2,4,4',6, 6'-hexanitrobiphenyl (dipicramide, DIPAM,IV), the subject of the present report.

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%-__o,.• N_ Cl 12 1 P2 4HNO N9 "I_.?

DIV.A ... o2N -(, //--\ i" -oo--- O-, ;-~- \,;,', 2

O N2 NO2 1 O

iII, DIPICL IV, DIPAM

Shortly after the first preparation of DIPAM, there cameto our attention an urgent requirement for a thermally stablehigh explosive which was relatively non-volatile at advancedtemperatures and reduced pressures and which would propagatedetonation in relatively small diameters, this material to beused in mild detonating fuse (MDF) for stage separation inidvanced POLARIS missiles. Preliminary experiments in ourlaboratories, vide infra, indicated that our new product mightzatisfy the former requirement; from its chemical similarity topicramide-, we felt it might prove adequate .n the latterregard. For this reason we undertook the preparation of oversix hundred grams of DIPAM for evaluation both at NOL and inthe laboratories of Lockheed Aircraft Corporation.

DISCUSSION

From commercially available m-bromotoluene, the synthesisof DIPAM involves the six-step sequence: m-bromotoluene-(a)--!3-br omo.-2, 4,6-trinltrotoluene - (b)---• -I - (c)---> D1PA - (d)---

dipyridinium salt of DIPA -(e)-- DIPICL -(f)---)DIPAM.

a) m-Bromotoluene to 3-Brono-2,4, 6 -trinitrotoluene.-

3-Br-C 6 H4 -CH 3 HN03, H2 SOJ4 , 3-Br-2,4,6-(NO2 )3C6 H-C{ 3

For a chemically related series of aminonitrobenzenea thefollowing f•!l.ure diameters have been reported: TATB, 1.3 cm;DATB, 0.53 cm; picramide, 0.3 cm (6). This is the only Inves-tigation of which we are aware in which variation of anydetonation parampter with regularly changing chemical structurewas ever studied. We :annot overemphasize the value of the1'esults of such an approach to the synthetic chemist.

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m-Bromotoluene .may be made by reactions des&.;bed In"Organic Syntheses" (7): p-toluidine -,-p-acetotoluidi!e-*4-acetylamino-3-bromotoluene )-'-amino-3-bromotoluer.e- - m-bromo-toiu:ene. its iabcratory price. $11.00 per hundred •.-w (8).Js undoubtedly more a reflectioj, uf demand than of cost inmanufac ture.

The hest 1lterature method for, the prepnration of' •-h,.wo-2,4,6- Luene (9, 10) involved a two-step nitration withseparation of the intermediate 3-bromo-4,6-dinitrotoluene. Wehave found that the trinitration may conveniently be carried outin a single operation and in excellent yield by using an essen-tially arnhydrous nitric acid - sulfuric acid mixture and byholding the reaction mixture at about 550 for several hoursbefore heating to reflux for several hours. The product pre-cipitates directly on cooling the reaction mixture; the work-upinvolves simply drowning in excess ice.

Prior to the DIPAM program, prelimJnary trials on 0.04,0.1, 0.2 and 0.6 mole scales had re-sulted in yields of crudeproduct ranging from 92 to 96%. Acetone was a satisfactoryrecrystallization solvent; yields of recrystal-l.7,ed brontotrini-trotoluene were 84-88%.

In the present program tl-re preparations were carried outon a 1.2 mole scale and a final preparation using 3.5 moles.In the latter instance the total reactant volume was 3.7-3.8liters. From 1,238 g of m-bromotoluene, 1900 g (86%) of purebromotrinitrotoluene was carried over to the next step. Anadditional 50-100 g might have been recovered by further work-up of mother liquors.

b) Bromo-2,11,6-trlnitrotoluene to ,7,31-Dimethyl1-2,,21,1,41,-61 -Lp "n'" "-

3-Br-2 4, 6 (N02 ).C 6 H-CH, Cu, A3-CH 3 _2,4,6-(N02 )_C6 1_].

For init4al experiments in the Ullmann reaction the proce-dure of Phock, Moyer and Adams (2) was followed exactly. Thisinvolved reacting the bromotrinitrotoluene with activatedcopper in purified nitrobenzene at 175-1850. To obtain adecently crystalline product it was necessary to remove ths?TU-iJo:' proportion of the solvent ty steair di•tillation, thlzI,.-nr the most tedious and t~me-consurming part of the operitLon.

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In subzequent trials it was found that the relativequ~ntitLeZ; of nitrobenzene and copper could be reduced substan-ti.ily with consequent shortening of the steam distillation and

,U ?ppaIL ill t.ffCctc on yields. The product separated as aUlLck Serni-cryctalline solid in the pot-residue from the steamdistillation. For preliminary purification this material wastaket-r. in ht- i'rtone, decolorized with charcoal and theS..iý... o reAmoved A further recrystallization from acetone-icatic acid gave a product sU:iffciently pure for the next step.

One reaction was carried out on a 0.35 mole, four reac-tions on 0.7-0.8 mole and two reactions on 1.44 mole scales*.Yields of purified di.methylhexanitrobiphenyl ranged from 70 to81%. From 1,900'g of bromotrinitrotoluene, 1,077 g (77%) ofdimethylhexanitrobiphenyl was carried over- to the next step.

c) 3, 3'-Dimethyl-2,2 ',,4 ',6, 6'-hexanitrobiphenyl to DipicricAcid.-

Na2Cr207[3-CH,-2,4,6-( CO)36- .0,H20I: [3-H0-2,4I,6-(NO)C6-]

This reaction has been discussed in detail in reference 1.In the course of the present program five preparations werecarried out using essentially identical conditions. Improvementsin yield from 55 to 80% were achieved by varying dichromate con-centrations. Syntheses were carried out on 0.12, 0.27 and-. 55-0.61 mole scales. Reactant volumes In the larger-scaleexperiments were 4.0-4.2 liters and 12-15 liters of reactorcapacity were required for the drowning.

Although pure DIPA melts at 311-3120 (dec), materialwelting above 3000 was deemed satisfactory for subsequentoperations, vide infra. From 1,075 g of dimethylhexanitrobi-phenyl, 817 W-g-175,%)T dipicric acid was carried over to thenext ate;.

a) Dp.icric Acid to Dipyridinium Dipicrate.-

l3-HO-2,LL,6-(N0 2 I),C6HN.2 ~'[C5H5N 3-U-2,l4,6-(N02)3 C6R- 2

In' the largc-scale preparations total reactant volume was -I.:liters. A five liter flask was required for the steam,Aistillation.

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:',: :alt precipitated immediately o:i addition of pyridineto, a methanellc solution of DIPA. The reaction mixture waschlilezd and filtered and the product was washed with ether and

r When nure DIPA wa-s ,qed and the mothev i3.-1%Uzr wor-kedup, , h ieeld was close to quantitative. With DIPA preparedas in (c), however, a first crop of high-grade dipyridiniumdipicratr wias obtained in about 90% yield, but additionaliatetu-i- recovered from. mother liquors was of very much lower-,u-Ity. It was considered that losses in a;be'pting tofurther purify the dipicric acid would more than offset this 10%decrease in yield*.

Reactions were carried o"t on a 0.33 mole scale and thereactant volume was ca 1.7 liters. From 772.5 g of DIPA, 914 g(89%) of dipyridinium dipicrate was carried over to the next step.

e) Dipyridinium Dipicrate to Dipicryl Chloride.-

POCI3 L3-c ,,-N 2 ,6-I1[CHr NH 4 3-&-2, 4,6- (NO2 ) 3C6H-1 2 -. ;-Q-2,41,6-(NO2)3C6H

'1he dipyridinlum salt was converted to DIPICL in virtuallyquantitative yield by adding to an excess of phosphorus oxy-chloride, heating on the steam bath, allowing to cool anddrowning. The method of drowning Is critical and requiresextreme caution. If the reaction mixture is added to ice or anice-water mixture the reaction Is initially quite slow, but asthe ice melts it becomes more rapid and undergoes autoacceler-ation. This has, on one occasion, led to boiling and splatteringIn the mixture.

The preferred method was to aid the reaction mixture slowlyto water with vigorous agitation, adding ice as necessary tokccp the temperature at 300. For a typical reaction on a 0.25mole scale this required 3-4 liters of ice and water.

For purification the crude DIPICL was washed with water,then stirred with hot methanol in which It Is only very slightlysoluble and filtered. From 914 g dipyridinium salt there was

obtained 7-9 % (991) of DIPICL.

* The .aln '.miurlty :an the DIPA appears to be monohydroxy-hexanitroblphenyl (m-picrylpicric acid, PIPA).

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Sipl,• ,'hloride to Diplcramide.-

7H1 -I

rt•-- - .. al -,-o4,6-(%"..o 2 ),•c"#-- 2

Neither DIPICL nor DIPAM is soluble in cold ethanol. WhenDIPICL was added portionwise to saturated ammoniacal ethanol

1 "^0 }vwuv0, i dissolved completeLy to give a deep-redsolution. If this solution was slowly heated to the rfluxand the ammonia allowed to boll out, it lightened in color andDIPAM began to precipitate. Distilling off a portion of theethanol, chilling, filtering and washing with ethanol resultedin a 95-961 yleld of DIPAM, m. p. 296-80.

We interpret this behavior as being duo to immediate con-version of DIPICL to DIPAM whose amine hydrogens are suffi-ciently acidic that the material will form a soluble salt withexcess ammonia'. As the ammonia boils out the equilibrium isdrawn to the left and DIPAM precipitates.

NH2 -C1 2 H2 N601 2 -N{2 + 2NH3 01 NH4 + RR-C 1 0H2 N6 0 1 2 - H4 jl+

The reaction on a 0.45 mole scale involved 2.7-2.8 litersof reactant volume. From 729 g DIPICL there was obtained 643 g(95.7%) of DIPAM which may be sufficiently pure for the intend-ed application.

For evaluation purposes, however, it was deemed desirableto nupply the purest material obtainable. A variety ofsolvents were tried for recrystallization; an acetone-ethanolpair was found least inconvenient. To dissolve 200 g of crudeDIPAM, 7,500 ml of acetone was required and 4,000 ml of abso-lute alcohol was added durine the process of concentration. Atotal of 599 g (90%) of pure DIPAM, m. p 298-2990 (dec) wasobtained together with a further li.5 g(3%), m. p. 295-296O(dec).

The overall yield for the -lix steps from m-bromotoluen^ toT- T1 • . 0 .. .".. ..P c LjA.LL I1*1 W~.-lo. - 9. 5",

.or comparison, picramide has a pKa of 12.25 (11).

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Properties of rIPAMMolecular Formula: C1 2'yN 3 OI2 , ,ol. Wt. 2451.I

rleltin, Point: 298-290O (dec).Oxidant Balance (12). 0BI 0 0 -1.52 (balunced slightly

beIow CO level).Heat of Formation: The heat of formaiaion of picramide has

been~~ d.e1~e , ~ 15) 1&'P - -20. I AUUi/molie. ByAddiu ,ind subtracting appropriate bond'and standardizationeti-ges, DIPAM i.s computed to have ,Hf = -27.6 Kcal/mole. Inthe -omputation it; is assumed that, as seems reasonable, thereiS no interaction between the rings and that DIPAM has twicethe heat of sublination of picramide.

Heat of Detonatioa: Using the 1120, CO, C02 arbitrary incalculation, MIFAM i computed to nave a heat of detonation of384.4 Acali/mole or 845 cal/5. If the L2 CO - CO2 * Clequillb-rium .Ls taken into account, the values are somewhat higher.

crystal Denpi.y 1.79 g/cc.Imact Sensitivity: 132 cm, k,, 0.27. Determined on an

ERL machine as modlrled at NOL using type 12 tools. On thismachine TNT has a 50% imqact height of 1bO cm; Comp. A, 70 cm;Tetryl, 52 cm; RDX, 24 cn; PETN, 12 cm.

Vacuum Thermal Stability:

At 2500C. gas evolved - O.1 cc per g per hr 6 hr periodAt 2 ý°C. gas evolved w 0.3 cc per g per hr 2 hr period).At 260°C. gas evolved w -.5 cc per g per hr 2hr peI'od)

Voldtil4ty Studies: A weighed sample or tho Pxplosive washeld in an evacuaed- Aderhalden drying apparatus over boilingnitrobentene (ca. 2100) and the loss in weight due to sublima-tion or other causes was determined after a thirty minuteInterval. Results for DIPAM and other thermally stable explo-sives are as follows (compound, pressure, % weight loss): DIPAM.1.0 mu, nil; TNTACOT, 1.0 mms, 0.16; TATB, 1.0 too, 1.1%; DIPICL.1.0 mm, 23.%; DATB, 2.5 mm, 5,.. ; hexanitrostilbene, 0.9 mm,nil; KNN, 0.6 w.m, nil; nonanitrote';henvl. 0.8 mmn, 0.5%.;h..xanitrobipncnyl, 0.5 mm, b.4%. it should be appreciated thatthese were crude measurements and that pressure values reidfror! a McLoed gauge near the pump do not accurately describeprecotres above the sample.

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EXPERIMENTAL$..-Brorao-2. 4-O-Lr5n•'ii • otouene. -

To a well-stirred mixture of 1500 ml 30% oleum and 18OO ml(•C• nitric acid at 550 was added dropwise over 3 fifty minuteperiod 588 g 3.45 moles) m-bromotoluene (8). The resulting

Ii-.if-a, novinap .0oution wA stirred an additionsa seventy-fiveminutes at 550, then heated to the reflux. A mildly exothermicreaction which was self-sustaining for about fifteen minutesensued. The solution was held at the reflux for a total of twohcurc, then allowed to cool slowly with vigorous agitation*.

The cooled reaction mixture was drowned with stirring in5000 ml ice-water, filtered and the filter cake washed with8000 ml water and air-drled overnight to y~.eld 985 g (93%) crudebromotrinitrotoluene, m. p. 134-1370. A single recrystalliza-tion from 4000 ml acetone furnished three crops, totalling 808 g,m. p. 142-1440 and a further crop, 30 g, m. p. 141-143o. Theyield of recrystallized material was 88.

Materials: 440 g (1.44 mole) bromotrinitrotoluene280 g copper dust":*500 ml dry redistilled nitrobenzene

The bromotrinitrotoluene was dissolved in the nitrobenzenein a three-neck two-liter flask fitted with a mechanical stirrer,thermometer and powder funnel. The solution was heated to 1650on an oil bath and 10 g of copper was added with vigorousstirring. The temperature was slowly raised to 1850 and at some

-The prod, ct begins to precipitate at about 850. There appearsAto be considerable heat of crystallization and if the solutionis allowed to become too supersaturated the exotherm during theprecipitation mdy cause local splattering. The addition cf seed

r�y-ta'. cffcctve eldnminates th!ii puvsblbiilty.

**The copper used was electrolytic dust from Fisher ScientificComp.tny. It was activated by stirring with concentrated hydro-ohloric 'Acid, filtering, washing with water, methanol ;And zther

rind drying In the oven.

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point between the two temperatures reaction started. The2OPj4er was then added over a period of about thirty minutes inincrements of about 10 g. With each addition there was aslitght exother.. and a temperature of !84-186O was maintainedwith vcr-y little external heating until about three-fourths ofthe copper had been added, at which time external heating wasincreaso-d to maintaln this temperature. The mixture was heatedfor about ten minutes after the addition was complete, thorf1lcavud hot to remove the gray innr.g;nic saltsh. Thc precipl-tne :an! reaction flask were thoroughly washed with acctonc.

Steam distillation to remove the acetone and nitrobenzenefiom the reaction products required about three hours, afterwhich time the dark semi-crystalline residue was dissolved inhot acetone, treated with charcoal and filtered. The acetonewas then allowed to evaporate leaving as a residne 280 g (86%)of crude product.

This was taken up in the minimal amount of boiling acetone,an equal quantity of acetic acid was added and the mixtureheated to 05-970 on the steam bath to ,emove the acetone, thencooled to 50, filtered and the product washed with ether anderied in the oven at 70-800. There was obtained 260 g (80.30%of' pure dimthylhexanitrcbiphenyl, m. p. 240-24•0.

Diplcric Acid, DIPA.-

To 260 a (0.575 mole) dimethylhexanitrobiphenyl in a five-liter three-nee.. flask fitted with stirrer and thermometer wereadded with atirring P600 ml 90-100Q% nitric acid (no rise Intniparature) and sufficient of a total of 905 ml 30% oleum tGraise the temperatute to 500 and to hold the mixture at thistemperature un.il all or most of the dimethylhexanitrotiphanylhod cdssolved. The .emptniig oleum was then added While cool-ing the mixture with an iUe bath.

With cortinued cooling to maintain the temperature atabout 230 (not above 30C), 750 g of so'ium dichromati 4ihydratewas added portionwise over a severil hour period to the well-sttrred mixture which turned greeniseh-blh-1k Coolirn wasnereessary Vo an additirnal several hcura, after which time themixture iould be left unattended it room temperatuiv. Totalstirring time was about P5 hours.

M t is undestraLle :o allow the reaction mixture to rooi toambient temperatures and etand befire filtering. In one casewhere the mixture stood over-nlKnt before filtering, considerableof the product had to be recovered rrom the L-%'.-anic salt bywashing with hot acetone.

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Cr-ide dipicric acid was obtained as a yellow amorphousproduct by drowning the reaction mixture on about 10 liters ofcracked ice, allowing the precipitate to settles, filteringthm..h a coarsc sintered gi8ss funnel and washing the filtercake with 20% iydrochloric acid. For preliminary purif~oationthis material was digested with 500 ml ethanol, the solutionfiltered off through a sintered glass funnel, the residue

-•gteo•_ • n ... dltlci... 750-1000 ml ethanol and the mixtureagain filtered. Concentrated hydrochloric acid was then addedto the combined filtrates until the mixture appeared to bealmost colorless.

The mixture was then chilled, filtered and the productair-dried for several hours after which time it still retainedconsiderable water. Taking this material up in acetone andadding an equal volume of benzene caunei most of the water toseparate as a lower phase which was removed. The organic phasewas then dried over Drierite and concentrated to yield twosuccessive crops of' DIPA. The first crop, washed with benzeneand then with hexane and dried for 24 hrs. at 600 1 mm, weighed167 g and melted with decomposition at 3110. The second crop,treated similarly, amounted to 411 g. m. p. 3010 (dec). Thetotal yield of DIPA was t9% of theory.

Dipyridinium Dipicrate. -

A solution wan made by dissolving 150 9 or' diplcric acidin 1500 ml of warm absolute methanol then cooled to below 400.With vlgoivuu stirring 75 ml of pyridine was added in a -clowstream axid 64lrring was continued for one-half hour afteraddition was complete. The reaction mixture was then cooledin an ice-salt bath, filtered and the produ.'t washed with etherand dried. The yield was l8b 6 (90.6%) of bright yellow crys-talline solid, m. p. 256.-580 (dec).

.,3'-Dichloro-2,2',4,, 6,6'.-hexanitrobiphernyl1 (DIPICL).-

One hundred eighteen grams of the dipyridinium salt was,aded to u6 ml of phosphorus oxychloride and warmed on a

ztca~m Lath. Thm balt was nearly completely dissolved when thetemperature reached 600 at which time the product began toprecipitate. After heating for an additional half-hour the

•This material occasionally precipitates in a very fine formand passep quite slowly through the filter. When this occurnthe filtration is quite tedious and may be shortened appreciai-tly by allowing the material to settle and first passing thesupernatent liquor through the slntered glass funnel.

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reaction mixtur-e was cooled to below 400 and drowned slowly,starting with 500 ml water and adding the reaction mixture andice at a vate suffloient to keep the drowning mixt.irf. at. about.

t (AUm•TI, ~ d.4.6 c lon). chen drowning was complete thevolume was 2000-2500 ml. When the exotherm had ceased theproduct was recovered by filtration and washed with 2 liters ofcoliu w:)t&er. Tt wiR t~hen sulpended in a.0_' -' of mact-,,nol anýwaried almc6L, Lo Lhe boiilný noint with stirring, then filteredand dried. The yield was 94 g (99.5%), m. p. 27502(7o (dec).

ý,75'-Diamino-2,2',4,4',6,_6'-h.exanitrobiphenyl (DIPAM).-

To 2200 ml of absolute ethanol saturated with dry ammoniain a five-liter three-neck flask fitted with thexmovieter,stirrer and condenser was added porti.nwise over a one-hourperiod and at a temperature below 120 226 g of DIPICL. TheDIPICL dissolved as added to form a blood-red solution. Anhy-drous ammonia was then slowly bubbled in for an additional 15minutes after which time the solution was slowly heated to thereflux. At about 30-' °0 an orange solid began to precipitateand the solution lightened in color. The mixture was caused toreflux one-half hour after which time about 500 ml ethanol warboiled off, carrying with it the last of the excess ammonia.

The reaction mixture was cooled to 100, filtered and theproduct was wished with J% aqueous hydrochloric acid ethanoland ether and dried in the vacuum oven at 800 (30 mml. Therewas obtained 197.5 a (05%) of an orange-brown powder, m. p.2960 (dec).

For purification this materlal was taken up In 7500 ml hot

acetone tho solution lecolorized with charcoal and concentrated,addlr 11A50Cml of absolute ethanol during the course of the con-•entration. There was obtained as a f'irst crop 173.5 g of pureDIPAM. m. p. 2(1(0 (dee) In the form of' a nicely microcrystallineyellow p'wde.. A second crop, 11.,.4 p, m. p 29".0 (dec). wasagain recr'stalllzed to yleld 18.0 g,, m. p. 298o (dec). Theyl,'Id of pure VIIAM 1'rom PIPICI. w'.s 92%.

COa VP A DEf', IA. NL

'CONFIDENT'IAL.NOLTR 62-82

REFERENCES

i) H. G. Adolph, J. C. Dacons and M. J. Kamlet, NOLTR 62-32,"Heat Resistant Explosives. XI. An Unusual OxidationReaction Ledding to 3,3'-D~hydroxy-2,21 44,lI'6,6'-hcxanitrobipIeviyl1 (Dipicric Acid, D!kA);g 2b Feb. 1962.

2) L. H. Bock W. W. Moyer and R. Adams, J. Am. Chem. Soc., 52,205'4 (19305.

3) W. Borsche, Ber., 5o, 827 (1917); L. Mascarelli andB. Visintin, Gazz. chim. ital., 62, 358 (1931), (C. A., 26,4809 (1932).

4) R. Boyer, E. Y. Spencer and 0. F. Wright, Can. J. Research,2•4, 200 (1946).

,) M. Blais, M. Warman, V. I. Seile and H. J. Matsuguma,Picatinny Arsenal Technical Report 2524, "Preparation ofThermally Stable 2, 4, 6-Trlnitrobenzene Derivatives",June 195I.

6) N. L. Coleburn, NOLTR 61-79, "The Detonation Properties ofthe Amino Substituted Symmetrical Tri•itrobenzenes" Inpress.

7) L. A. Bigelow, J. R. Johnson and L. T. Sandborn inH. Oilman and A. H. Blatt, Editors, "Organic Syntheses"2nd. Ed.. Coll. Vol. 1, pp. 111, 133, John Wiley and Sons,New York, 1948.

8) Eastman Organic Chemicals, List No. 42, 6 Sept. 1960,Cat. No. 1142.

9) Orete, Ann, =7, 258 (1875).

10) Bentley and Warren, Am. Chem. J., 12, 4 (1890).

11) R. Schaal, J. chim. phys., ý,2, "79A (1955).

12) M. J. Kimlet and D. V. Sickman, NOLTR 62-73, "The Relation-ship of Sensitivity with Structure of Organic HighExplosiven. 1I. Polynitroaromatic Conmounds," In press.

1') Medinr Anrd Thonis, Mem. poudres, 21, l73 (194,9).

12C0?NVIDI*rIAL

Nuw'.Th 62-82

Di stribut ion

No.Conles

Chief, Bureau of Naval Weapons, Department of the Navy,Washington 25, D. C.^ -tv'. T\,.1 1Attn :g ý- ................... i oO.... . .. .....°.O.O ......

DLI-3 ......................................... 2RURF-5. ....................................... 1RUME-12 . ....................................... IRUME-323 ........................................ 1FMMP-21 ...................... 1..............1

Chief, Office or Naval Research, Washington 25, D. C.Attn: Power Branch (Code 429) ...................... 1

Dr. Ralph Roberts ........ ........ ... . 1Chief of Ordnance, Department of the Army, Wash. 25, D.C.

Attn: Technical Library ............................. 1ODTM ..................................... . ... 1

Chief of Engineers, Department of the Army, Wash. 25, D.C.Attn: Research and Development Division .............. 1

Commanding Officer, Naval Propellant Plant,Indian Head, MarylandAttn: TechnIcal Library ............................. 1

Chemistry Research Section .................... 1Commanding Officer, Engineer Research and Development

Laboratories, Fort Belvoir, VirginiaAttn: Technical Library ............................. 1

Commanding Officer, U. S. Army Ordnance Missile Command,Redstone Arsenal, AlabamaAttn: Technical Library ............................. 1

Roh. and Haas Division ...... . ................. 1Commanding Officer, U. S. Navl O•-inance Laboratory,

Corona, CaliforniaAttn: Technical Library ............................. I

Commanding Officer, Naval Weapons Station, Yorktown, Vm.Attn: Research and Development Laboratory ........... 1

Commanding General, Aberdeen Proving Ground, MarylandAttn; Ballistics Research Center .................... 1

Commanding Officer, Department of the Army, PantexOrdnance Plant, Amarillo, Texas ...................... 1

Commanding Officer, Lake City Arsenal, Ordnance Corph,Department or the Army, Independence, MissouriAttn: Technical Library•............................ 1

Commander, Eglin Air Force Base, FloridaAttn: POTHI, Technical Library ...................... i

Commanding Office:'r, Hostoha Ordnance Works, U. S. Army,Kingsport, TetinesseeAttn: Dr. 1tbert hobbins ............................ 1

"ImPMENTIAL

NOLLTR 62-82

D13tributJ oa(Cont.'d)

No.Copies

Commander, Navý.l Ordnance 'rest Station, China Lake, (Calif.Attn: Chemibtry Research Section ................... 1

Dr. Martin H. Kaufman (Code 4544) ............ 1Director, Navai hesearch laboratory, Washington 25, D. C.

Attn: C,,emistry Division ........................... 1Director, Advanced Research PRojects Agency, Pentagon,

Rm. 3D159, Washington 25, D. C.Attn: Advanced Propellant Chemistry Office ......... 1

Director, Special Projects Office, Department of the Navy,Washington 25, D. C.Attn: Technical Library ............................ 1

Solid Propellant Information Agency, Applied Physicslaboratory, Johns Hopkins University, Silver Spring,Md.Attn: Technical Library ............................ 2

Armed Forces Technical Information Agency,Arlington Hall Station, Arlington 12, VirginiaAttn: TIPDR ........................................ 10

Los Alamos Scientific Laboratory, P. 0. Box 1663,Los Alamios, New MexicoAttn: Reports Librarian for Dr. L. C. Smith ........ 2

U. S. Naval Ammunition Depot, Navy No. Six Six (66),c/o Fleet Post Office, San Francisco, CaliforniaAttn: Quality Evaluation laboratory ................ 1

University of California, Lawrence Radiation Laboratory,P. 0. Box 808, Livermore, CaliforniaAttn: Chemistry Division (Dr. Qua Dorough) ......... 1

Aerojet-General Corporation, Azusa, CaliforniaAttn: Dr. J. R. Fischer (Contract No•nr-2655(OO)) ... 1

Aerojet-General Corporation, P. 0. Box 1947,Sacramento, CaliforniaAttn: Dr. Marvin H. Gold . ...................... 1

American Cyanamid Company, P. 0. Box 270, NewCastles Pa.Attn: L. V. Clark, Director (Contract Now -60-0745-c)Explosives Research and Development ................. 1

Minnesota Kining and Manutacturing Company2301 Hudson Ka., St. Paul 19, Minn. kARPA Proj. 201-2)Attnt Dr. M. H. Friedman, Central Research Dept. ... 1

Thiokol Chemical Corporation, Reaction IMtors DivisionDenville, New Jersey (Contract Nonr 3664(00))Attn: Dr. 1%. D. Perry .............................. 1

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