REPORT No. (O-Ti tr.

SPERIOD COVERED. I January 19e2 Through 31 Dec~mbec 1982

RESEARCH IN ENERGETIC COMFPOUNDS

A Report on Work Sponsored byTHE OFFICE OF NAVAL RESEARCH

Contract N00014-78-C-01i7NR 6dr.-796/10-22-81 410

January 1983

REPRODUCTION IN WHOLE OR IN PART IS FERMITTED FOR ANYPURPOSE OF THE UNITED STATES GOVERNMENT

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C-

•:" ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ -,. - ----- ,-_._. -...-. • -.-

2-,"

Ja•nuarV 1983 Report No. ONR-2-5 (Interim)

RESEARCH IN ENERGETIC COMPOUNDS

S~By

K. Baus and T. G. Archibald

A Report on Vork Sponsored by

THE OFFICE OF NAVAL RESEARCH

Controct H00014-78-C-0147

Si I-

Fluoroohon. I n

680 lSouth Ayon Ave.Azusa, Caitfornia 91702

SECURITY CLASSIFICATION OF TH!S PAGE (wh.n Do'so Et"•• dj'•"KtUWI [I•'UUMFTATIOki 'A~.L |n z"

- ..... 337C C'OU.5 ,,RT'fl4 FO.RM1. RIEPORT NUM GOVT ACCESSION NO. I. ACIFIENT'S CATALOG NUER

4. TITLE (and Subtitle) 7TYPE OF REPORT & PERIOD COVERE;•- Interim Surmary

Research in Energetic Compounds 1 Jan 19W- 31 Dee 19826 PERFORMING ORO. REPORT NUMBER

7. AUTHOR(#) 3. CONTRACT OR GRANT NUMBER(9)

Kurt Baum and Thomas G. Archibald NOO01-4-78-C-O1o 7

S. PERFORMING ORGANIZATION NAME ADL) •DUF'55 10. PROG.,RAM ELEMENT, PROJECT. TASK

FJluorochem, Inc. Af•tA & WORK UNIT NUMBERS

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11. CONTROLLING OFItLNAt4E A10 ,ADonRfSS 12. REPORT OAT SDeprme e aV January 193Office of Naval Research, Code 432 I MEo- PAGEsArlington, VA 22217

I-•. MONITORING AGK N CY NAME & AODHL5SS(tg dIillt-lnt from Co ,ollu ('l'hr..) IS. SECuRITY CLASS. (of (ite report)

Unclassifisd•4!• ~I-. O-ECL ASSIFcA"rIo,,/ ooNOR-OINO

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"7. OISTRIBUTION STATEMENT (of tri obeffact entered In ffnlo, .0, If diff*lont from Report)

III. SUPPLEMENTARY NOTES

is. KEY WORDS (Contanu, an ,erover aid*e if necpavery And Ide•,lify ty bbirk Inimbe,)

Nitroadamntanes Nuclear magnetic resonance spectra3-Azidooxetane Infrared spectraPolymerization Chromatography3, 3-Dinitrooxetane

S!20, ABSTRACT (Camtinue on to-e*,* side if .* end Idenrity by blo-k nurb..)

(over)

I

DD , 1473 EoDTIoN OF I NCV 65 15 o0o3LETC

Sf CuRITy CLAý.SIFIC t

TION OF TIlS PAGE (•e•n Date Ernleqed)4

* LE~OCtPtTY CLASPPICAYI14OF 0,TwigPo~r'n l

Reaction parameters for the polymerization of `--azidooxetarne.catalyzed by boron triftuoride, were investigated Hlo significantimprovements over the previously attained yields (about 50%/,) resultedfrom variations of temperature, catalyst levcl, water content or 'heuse of 1,4-butanediol as a cocatalyst. Increasing the monomerconcentration from 20% to. 50%, however. aave 80--0% yields ofpolymer.

2-Aminoadamantane, prepared from 2- adamant anone and sodiumcyanoborohydride. was oxidized to give 2-nitroadamantane. Thereaction of q-bromo-2,z-dinitroadamantane with sodium azide gave4-azido-2-adamantanone. Nitration of 2,4-adamantanedione diorime gavethe internal nitroso dimer of 2.4-dlnitro-2,4-dinitrosoadamantane.Reaction of 2,6-adamantanedione dioxime with NBS gave 2.6-di-bromo-2,6-dinitroadamantane. Debrominstion with sodium borohydride.followed by nitration with tetranitromethane, gave 2,2.6,6-tetranitro-adamantane. The reaction of bicyclo[3.3.1lnona-2,6-dione dioximewith hypochlorous acid gave a chlorohydrocarbon, but reaction of thedioxime with chlorine gave 2,6-dichloro-2.6-dinitrosobicyclo[3.3.1)-non&ne. This nitroso compound reacted with hypochIorous acid to give2.6-dichloro-2,6-dinitrobicyclo[3.3.llnonane. 2,6-Diaminoblcvolo-f3.3,1]nonane, obtained from bicyclo[3.3.l1nona-2.6-dione and sodiumcyanoborohydride was oxidized to the 2,6-dinitro derivative. *.

Synthesis work related to 3-azidooxetane and 3.3-dinitiooxetaneis summarized as a journal manuscript.

UNCLASlil F'1LLU' ,. ;tW -

CONTENTS

I . In t r o d u c t ion . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . .. 1

11. Oxetane Chem istry . ... ............ ... . .... ..... 1

A . D i s c u s s i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1

React ion Temperature............ ................ 2

C a ta lys t Leve l .. ....... ........ ..... ... ........ 2

1,4-Butanedial Cocatalyst ..... ................. 4

Fractional Precipitation .......... ............ 6

Effect of W ater ................................ a

Nitrogen Formation ............................. 8

C onc lus ions ................................... 10

B . Exper im enta l ......... ................. ..... .. 1 O

Polymerization of 3-Azidoozetane

(-30 to *40*C). ................ ...... ..... .... ... 10

Polymerization ot 3-Asidoozetane

-,1 303 C) ....................... .... .... . .. . 11

Folymerization of 3-Asidooxetane

(-309C, 1,4-Butantediol) .......... 12

Nitrogen Evouution Studies ..................... 13

4 2-Azido-1.3-propanedtol ....................... 13

Hydrolytic Stability of Poly-3-azldoosetane...13

III. Polycyclic Nitro Compounds ........................... 14

gA. Discussion .......................... ............... 14

Monofunctional Adamantanes .. . .......... .15

2,4-Derivatives of Adamantane ........ ........ 16

,!

Z,6-Derivatives of Adamantane.. .. 17

BicycloL3.3..l nozna-2 .'-dione Derivatives ...... 19

B . Exper im en ta l .... ............ ....... . . ...... . 21

Peracad Oxidation of 2-Adamantanone Oime ..... 21

Z-Aminoadamantane ......... ..... . ... .. .. .. 21

Peracid Oxidation of 2--Aminoadamantane . 22

Reaction of 4-Bromo-2,2-dinitroadamantane

with Sodium Azide ... .......... ............. 2Z

2,6-Adamantanedione Dioxime .... ... ........... 23

2-.6-Dibromo-2,6-dinitroadamantane .............. 23

2 ,6, 6-Tot ranit r oadamant ane and

6,,6-Dinitro-2-adamantanone ..... ............. 24

Reaction of 4-Eromo-2 6-adamantanedione

with Hydroxyv amine .. ........... ............ 25

2,6-Dibromo-2, 6-dinitrobicyclo[a.3.llnonane. .. 25

Reaction of BicycloC3.3.1]nonane

with Hypochlorous Acid......... ........... 26

2,6-Dichloro-2,6-dinitrobicycloL3.3. t)nonane..27

6 2,6-Diamino-bicyclo(3.3.1 Jnonane ..... . 28

Oxidation of Z,6-Diamino-bicyclo(33.I3nonane.2S

IV. R e fe ren ce s .. .... . . .. ... .... . ... .. .. . ... . .9

6 Appendix A. Synthesis of Electron-Def icient Oxetnares.

3-Azidooxetane, 3-Nitrooxetane and

3,3-Dinitro oxetans ... ...... ...... .. ..... .. . 31

Distribution List.... .. 4

6

-------------

S~TABLES

1. Effect of Temperature on Yield........ . ...... .2

II. Effect of Catalyst Concentration on Yield . .3

III. Effect of Monomer Concentration on Yield... 4

IV. Boron Trifluoride and I.q-Butanedzol Catalysis. o

V . Parallel Runs ............. .... . . .... 6

VI. Fractional Precipitation of Polymers .. ............ 7

- VII . Effect of Water ......... ..................... 8

VIII. Nitrogen Formation .................. ..... .......... 9

- --

0•

C.

C

Report No. ONR-2-5

I. INTRODUCTION

This report summarizes the reoearcn under Contract

N00014-78-C-0147 during the period i January 159827 throui i

31 December 1,8z. Additional work was carried out in the

area of energetic oxetanes, with emphasis on a study ot

reaction parameters for the poivmerization ct

3-azidoosetane. Work was continued on the synthesis ot

polycyclic compounds, with the objective 0i developing

procedures for the introduction of multiple energetic

groups. A journal manuscript summarizing work olt the

synthesis of 3-azidooxetane and 3.3-dinitrooxetane

comprises Appendix A of this report.

It. OXETANE CHEMISTRY

A. DISCUSSION

In the previous report t . a streamlined procedure tor

, the preparation multi-pound quantities of 3o-azidooxetane

was described. Hydroxy-terminated polymers were obtained

from 3-azidooxetane with catalysis by boron trifluoride•4

etherate. A problem with this polymerization was that

yields were generally in the 50% range- Also. the

polymerization reaction is highly exothermic, maktng

scale-up difficult. Typically. quantities of 10 grams in

20% solutions of methylene chloride would show 20 to 300 C

aeotharms even with external cooling. Yhase pronlems w-ere

addressed by a systematic study of ,.hlnges in reaction

variables.

, I,

Report 4ac. ONR-2--

kaact IoIna T~aanax&atuza . The *eftect of tamperatusa& on thea

course of the polymerization is summarized in fable I. 'Tie

r reaction was essentially complete in about 20 minutes at

0-20t whereas at -300C the reaction took 24 to 36 hours.

At -62'C no siglntficant polymeriztion occurred although

monomer was slowly consumed. In refluxing methylene

chloride, the reaction was very rapid and gave a largety

insoluble high molecular weight polymer. At a reaction

temperature of -300C the exotherm wAs readily controlled.

but at the monomer concentration used for this series of

experiments, 20%, yields were generally in the 50-60%

range.

C Effect of Temperature on Yield

Temp. % Oxetane % Yield Mol. Wt. PhysicalDeg.C reacted polymer (VPO) state

-62 40 0 - -

-30 80-90 50 Z400 Oil

-10 80+ 50-60 2400* Gum40+ 90+ 50-60 3400+ Insol. gum

0 0. INo1 3-azidoosetane, 20% solution in methylene chloride6 mole % SF I-Et 0 catalysta

Catalyst Level. The effects of varying concentrations

"of boron trifluoride etherate catalyst under the same

Sreoaction temperature and monomer concentration are

summarised in Table 11. As one would expect, increasing

the boron trifluorid* catalyst concentration has the effect

* Iof speeding up the rate of reaction of the 3-azidooxetane.

It was found that when 6 mole % of the catalyst used, 6U to

2

'I

-t Report No ONR-2-5

80% -of the monomer was consumed in ZD mni.tes, whazeas with

11 mole % catalyst, 100% oa the monomer wai consumed Ln the

same period. However the conversion to polymer was the

same in both cases. When more than i1 mole ¾ of the

catalyst was used, the polymer formed was insoluble.

TABLE II

Effeot of Catalyst Concentration on Yield

Mole % % Osetane % Yield Mol Appearancecatalyst reacted polymer wt.

5-6 60-80 50 2400+ oil9-10 85+ so 2400+ Qum12 100 50-60 2400+ gum15 100 70+ 3400L+ 1n0ol guxi

0.1 Moi 3-azidooxetane. 20% solution in methylene chloride

at 0-10C, boron trifluoride etherate catalyst

The reaction parameter that was tound to have tht

greatest effeot on polymer yield was the concentration ot

the monomer in the reaction solvent (Table III). Thus.

Increasing the concentration of 3-atidooxetane in methylene

chloride from 20 wt % to 50 wt % improved the polymer yield

from 50 to 50% without loss of polymer quality. In order

to prevent the formation of high rwolocular weight Solubic

polymer, the temperature must be kept below 25 C 1o

maintain this temperature limit with jj.. 0.1 mole batch

reactions, it was necessary to start the reaction at -20C:

the reaction was complete in less than a minute. Under

these reaction conditions it was found that very little low

molecular weight polymer was produced. Thus the usual

fractionation with methylene chloride and hexane rcsulted

3

IIP I PIIM ...

Report No. ONR-2-5

in almost no weight loss, suggesting a relatively narrow

molecrlar weight distribution. In larqer scale work, a flow

C system might be used for temperature control. fna

functionality of the polymer was found to te two

Effect of Monomer Conoentration on Yield

% Monomer Solvent % iielo 4ol

by weight polymer wt

10 1 50 2400+20 1 50-60 Z400+

50 1 80-90 2400+12 2 24 (160025 2 75 )2000

Solvent: 1. methylene chloride; 2, diethyl etherCatalyst: d mol % boron trifluoride etherate

1J4-Butanediol C•oasllty . It has been reported that

ocetanes are polymerized with a Z I complex of boron

trifluoride and 1.4-butanediol by stepwise addition of the

hyirozy groups to the oxetane rings; polymer yieids are

almost quantitative, and molecular weights are determanci

by the amount of initiator. W'e have applied these

conditions to the polymerization of 3-azidooxetane; results*1 are summarized in Table IV. The results are aeneraiv

similar to those we obtained without 1,4-4utaneodio. InI. Table V, parallel experiments at three temperatures are

described in which identical conditions were used with ana

without 1,4-butanedlol. It is particularly noteworthy thAt

"i4

Roepr, No. OIIR-Z-!

in almost all cases no incorpoffed w .s-butanediol wŽ

detected in the polymers by NNR: zr only onE case a trace

n waS found.

The generally3 accepted r-eznanism for tni

polymerisation of an ozetane by . Lewis acid-alcohol

Complex Is based on the liberation of protons from the

complex. Protonation of the ring cxvaen Olves an

oxetanonium ion which undergles a en-3 .n rmoction with ctr-er

I oxetane molecules:

l4-

H+ + N - ]Nt -4 cj fOHCHO )4 CM]6 3

Insertion of the alcohol into the oxetane ring in the

initiation rep would not be expectel It is generally

thought that the incorporation of alcohols into oxetane

: ep4polymers takes place in the termination step Expertmentc

were therefore conducted in which k-,e polymeritation

reactions were quenched with 1.4-butanediol and with

methanol. in these reactions there also was no

Incorporation of the alcohol izwc the polymers. This

;result suggests that terminatlcn of polymer growth takes

place before quenching by some type of elimination or chain

transftr mechanism-

6

6-

I

Rep~ort No. OHR.-2-5

SBoror Trifluoride and 1,4-13utantdiol (BDL*) CatalygiF

Run Temp 1ol % Mol % M1oles Yield Mol DODeg C BF 8DO Oxetano Wt [lncor p

(aý (a)

A -30 6 3 0 .4 30(b) 1300 A'ioB -30 6 3 0.4 30(b) 1600 NoC -30 6 3 J .4 5(b, 2100 NoD -30 6 3 0.4 51(b) -- NoE -30 6 3 0.4 52(b) 1550 NoF -30 6 3 0.4 52(b) 2100 NoG -30 6 3 0 4 48(C) 2400 Ho

- H -15 12 4 0.05 44(c) 2400 No1 -15 12 5 0.05 12(ce -- Noj -15 9 4 0V05 J1c) 2350 TraceK 1 6 3 0.05 40(c) 2350 No"L 2 9 3 0.05 60(c) 300 No1M 2 12 3 0.05 50(c) 3000+ No

25% Solution of 3-azidooxetane In methvlene chloride.(a) Based on moles 3-asidooxetane. (b) Precipitated from1:1 methanol-wate*. (o) Precipitated from 1;1hoxane-methyIene ohtorldo.

Parallel Runs

Run Temp Mol % Mol % Moles Yield MCl BoDeg C BF BDO Oxetane Wt Incorp

A -30 6 3 0.4 37 2400 No"B -30 6 0 0.4 48 2400 NoC -15 6 3 0.5 4 -- I0D -15 6 0 0.5 36 -- NoE -2 6 3 0 .5 40 2350 14oF -2 6 0 0.5 55 3000 No

25% Solution of 3-asidooxetane in methylene chloride uted;product precipitated from 1:1 hexane-methylene chloride.(a) Based on moles 3-azidoozetanf

F otI onal Precipitation. In our earlier work', we

used traotionai precipitation irom 1"1 hexane-methyiena

chloride to remove low molecular waight materials trom tha

:6

.j •,.• •;_:• _

~~~~~~~N P~d~~ o~-po1~.---Pnir I SMM

been used is 1:1 metihenoL-waterl Thexe methods are

compared in Table VI, using two polymer mixtures preparzd

with the butanediol-boron trifluoride catalyst. It is seen

that the methanol-water method provides substantially

greater yields but the product is of lower molecular weight

than the hexane-methylene chloride rroduct Resuits sivilar

to those of the methanol-water precipitetion were obtained

by simple water washing. The physical appearance of the

polymer was influenced by small amounts of diluents.

Untreated or methanol-water precipitated polymer was a

mobile oil, whereas material with a molecular weiqht of

2,400-3,000 that was Precipitated from hexane-methyieno

chloride and dried thoroughly was a gum Small amounts of

remaining solvent, as little as 5% methylone chloride or

monomer, provided fluidity.

Fractlonational Precipitation of Polymers

Methanol-water Hetane-met hyl ne

Run % Yield MoI % Yield MolWt wt

A 30 1300 le 2400B 52 1550 37 Z400

0.4 mol 3-atidoouetane; Catalvst: .02l mol borontrifluoride etherate, 0.012 mol 1.4-butanediol.

-." .-'---Wat_ Although pzoau"•'o.s wege always

observed to eaclude water from the system, the possibility

was considered tnat trace amounts at water would have a

detrimental effect on ,he course of the reaction. It was

found, however (Table VII) that reactions tun with

scrupulously dried equipment and solvents gave the same

Sresults as those run in open flasks with u..tro.:ted

industrial grade methylene chloride. Even in the presence

of stoichlometric amounts of water, the overall conversion

to polymer remained about the same with only a reduotion in

-molecular weight. Even when the reaction was done in equal

volumes of msthylene chloride and water, some polymer

Sformed.

Effect of Water

Solvent % Yield hol- treatment polymer wt

Dried/ mol sieve 50-60 2400+

None, 0.2% water 55 240U+1 moldmanomer added 16 2000+

761 800+

* 0.1 Mole 3-asidooxetane, 20% solution in jnathylone onlortde6% mol % boron trifluoride etherate catalyst, 0-I0C

Nitroaen Formation. It was noted that the

polymerluat:nn reaction was not improved by incremental

additions of catilyst. In general, a catalyst level of 6Imole % was sufficient to Consume only zbout So% of the

"monomer. If more catalyst was then added, the remainder of

II.

- a- - - - . . . . .---. - -i-. . - - -

Report No, ONR-2-5

the xoncaa: dissapea&ae4 but u po u.i iyma waa L sai

and in fact, nitrogen aas began to evolve Ihe condLtions

causing the gas formation were investigated ('able V111)

It war found that in reactions kep.t at 50C and below, ine

gas evolution was never more thar, 3 mol % based on monomui.

However, if additional catalyst Was added, a mole ot

nitrogen was liberated for each additionNI mole oi

catalyst. In reactions conducted at room temp.trature, no

9-aL was observed during the course of the polymerization.

but when the polymerization was complete, gas evolution

began. In reactions containing only boron trifiuoride

etherate catalyst, II mole % nitrogen was observed, whereas

when 1.4-butanedlol was present, 22 mole % nitrogen was

observed. Samples of the polymer yielded no observabie gas

under the polymerization conditions. WJhen 3--atidoometane

was treated with aqueous sulfuric acid, 22 mole % nitrogen

was observed.

•---:Tabl.•. vu r

Nitrooen FormationE

Catalyst Time (Hrs) Mol% 1itrooavn

A 1 3A 24 i

4 I IB 24 14C 24 22D 24 21

A a6 Maol% boron trifluoride *thoratc

i3 a 12 Mol% boron trifluoride etherateC = 6 Mol% boron trifluoride etherate

+ 3 mOl% 1.4-butanedlolD - 50% Aqueous sulfurtc acid

?9

Report No. CNh-;-j

Conclusions. The 2ffects of temporntture.

concentration, catalyst levels, water contamination anti

alcohol cocatalysts on the polymerization ot 3-azioooxotane

were studied with the obiective of imcoiv~ng polymer yieldo

and controlling the reaction exotherm. The only

significant improvement in yield waS attairnc by usin,'

higher monomer concentrations than those that we.re useua

previously. Under these condition -. batch operation

results in a more severe exothetrm probiem. howsver. tne

reaction is so rapid that a continuous flow system would Le

feasible, and the exotherm could be ýontrolted by

regulating the introduction of reagents

B. EXPERIMENTAL

21 PI &e•L&t jion ci 3-Aztidooxet ane (-30 to +40DC) A !0

aL magnetically stirred round bottom flask, fitted with a

condenser and drying tube. was loaded with 20 g of a 12'/ by

weight solution of 3-azidoouetane in methylene chloride

( (0.085 moil. The solution was cooled to -30 C anid 0 6u mi.

(0.0052 mol) of freshly distiilled ooron tritluoride

etherate was added rapidly by syringe After aibu- 30

seconds the reaction temperature increased to the reilu,.

temperature and a gelatinou5 polymer faormrt Tne Materi.L

was allowed to stand for 5 minutes at rocm temperature and

0 then 5 mL of water was added and the mi•ture was asltated

to disperse the gel. Ethyl acetate 36 ml, was added and

01o

I%_ to_ L a ti a w - re- c,- -f o-r--- -4-h...-Th ---, ,-,,,,t rr- -

scparated and dried over magnesium sulfate. $olveiit was

removed with a rotary evaporator (70 0 C zt 20 mm Hg) to give

a brown oil: NMR (CDCI1) & 3.58 (s); IR (CH1C1 2 ) 3000. 2900

(CH), 2150 tN), 1l35 cm! 'C-O-C); molecu ar wcight (varor

pressure osmometry, ethyl acetate) 2200; equivalent weight

(silylation) 1200.

The polymer was dissolved n 20 mL of methylene

chloride and this solution was poured into 20 mL of hexane

with vioarous stirring After 20 mIn the solvent was

decanted from the precipitated oil, and the product was

dried at 700 C under vacuum to give 7.4 q of material

essentially identical with the unfractionated polymer.

Polymerization of_ 3-.Aidooxetane (-30C). A solution

of 1.0 g (0.009 mol) of boron trifluoride etherata in 50 ml

dry methylene chloride was cooled to -301C and a solution

of 9.9 g (0,1 mol) of 3-a:±dooxetane In 50 ml of methylene

chloride was added dropwise. The solution was stirred at

-30. GLC analysis after 6 hours showed that approximately

half of the monomer was consumed. The solution was stirred

for an additional 48 h period. GLC analysis showed that

monomer consumption was 95% complete and essentially no

additional monomer monemer was consumed after this time.

S Saturated sodium chloride solution (5 ml.) w;s added and the

mixture was stirred for 30 min. The organic layer was

allowed to come to ambient temperiture and wAs wasned with

100 mL of 5% potassium carbonate solution anC 100 mL water.

The methylene chloride solution w.as dried crer mranesium

a. atwas evaporated under vacuum. e sidu, was

redissolved in 30 mL of methylene chloride and the volution

was filtered into 30 mL of rapidly stirring hexane.

After 30 min the solvent was decanted and tne remtaining

oil was washed with 3' mL of hexane The product was dri•i

at 700C under vacuum to yield 4.8 q (49%) cf a very viscous

oil with molecular weight 2350 (VPO, ethyl acetate).

PoIymerization of 3--Azidoonetzne (-J40°C, -4.3ut ine.

diol). Boron trifluoride etherate .3.83 g, 0.02? Yrol) wcs

added to a solution of 1.25 g (0.0135 mol) cf freshly

distilled l,4-butanedxol in 50 nL of methyline chloride.

This solution was stirred at 25 1C fior 1 hour and was

cooled to -25C. Then 3-asidooxotare (40.0 q, 0.404 moI)

in 150 mL of methylene chloride was added dropwise and the

solution was stirred at -300C for 48 h. The reacticn

mixture was worked up as above to yield 21.0 g (52%) of

viscous oil with molecular weight of 1650 (VPO. ethyl

acetate). NKR (DCCI) showed no proton absorption betw4een

& 1.5 and & 2.0 (the central methylene of i,4-butanediol

and its ethers appears at S 1.6)

In multiple parallel 0.05 mol runs, afte.- 48 hours at

-3 0, the polymerization was quenched with 5 mL U1I0, with

5 ml of 1.4-butanediol, with 5 ml of methanol and iinally

warmed to 25 OC for 15 minutes before quenching wztn

saturated sodium chloride solution. In none of these cases

could 1,4-butanediol or methanol be detected in tne final

polymer.

iZ

Report No. ONR-2-5

Hitroustn Evolution Studiesl A dry o'ne n~ack xlask

fitted with a gas burette and pressure equalzzino bulb, was

loaded with a solution of 5.0 v (0 05 mol) of

"3-ahldoowetane in 20 mL of methylene chloride, and was

cooled to 26C. Then boron trifluoride etherate, (0.3 mL,

0.0026 mol) was added and the evolved gas was measured

every 5 min for the first hour and every 1I' min thereafter.

The concentration of monomer was fol)v'aed ,v CLC, using

- methylene chloride as the internal reference.

Z-Aslgo-¶.oro-o~anedioi. To a solution of I00 mf. of

10% aqueous hydrochloric acid was addd 20 g (0.2 mol) of

3-asidooxetane and the mixture was stirred for 1 h at ZtOC.

The solution became homogeneous. The pwosct wa xtracted

with two 50 mL por'ionj of methylene chloride and the

organic layer was dried over magnesium chloride Removal

of the methylens chloride under vacuum gave 14.0 q (t8%i)

of a liquid identified as 2-azido-1,3-propanediol: IR

(neat) 3400 (0-H), 2950, 2900 (C4H), 2140 on"1 (); NNRH

3.65 (s). Sylation gave an 18:5 ratio for trimethyl%:ilyl

to methylene protons. This material was unstable above

4 110IC under 0.1 m1. Hg Retreating 3.0 g of this material

with 10 mL of 10% aqueous hydrochloric acid for 1 hr gave

no methylene chloride extractable materials.

4 Hvdrolyt ig Stability of .Yo v-3-aaIdo tan•o.

Poly-3-asidoozetane (0.912 g, equivalent weight 1550) was

dissolved in 20 mL of methylene chloride and 20 mL ci twater

4 added. The Iniatuie was stirred rapxdiv for o h.

Satuarated sodium chloride solution was added End tne

:; I13

q

Report No. ONR-2--5

phases were allowed to separate overnjiht The oroanir

layer was separated, dried over anhydrous magnesium sulfate

and evaporated to yield polv-3-azidoo;etane (0.902 (1,

equivalent weight 1500).

In a parallel run, 20 mL of 10% aqueous hydrothloric

acid was substituted for water. The recovery of

poly-3-azidooretane was 90% (equivalent weight 1200).

III. POLYCYCLIC NITRO COMPOUNDS

A. DISCUSSION

A study of the synthesis of polycyclic nitro compound;

wes initiated in the preceding yearl with the objeotive of

producing useful high density explosives. Monosubstituted

adaimantanes were used as model compounds for developing

methods to introduce ges-dinitro groups into cage

molecules. One method used for the preparation of

gem-dinitro adamantanes was the direct nitration of the

corresponding oximes. In another approach, 2--adamantarano

oxime was treated with H-bromosucvinimide or with 5odium

hypochlorite to give 2-bromo-2-nrtroadamantane and

2-ohloro-2-nitroadamantane respectively. The bromo

derivative was dehaligenated with soditm borohydride0 and

the resulting 2-nitroadamantane was converted to

2,2-dinitroadamantane by oxidative nitrat on or by reactzon

with tetranltromethane.

!4

Man-of-unctio'nal Adawar.ýntanes. U11 a continuod with

monofunctional model compounds 1n nrder to increase the

available options for applicakion. to more energetic

systems. The direct oxidation of 2-oximinoadamantano to

2-nitroadamaittane was attempted with a wide variety of

oxidizing agents including mangnasa dioxide, chromic

acid-pyridine, and peracids. The inorganic reagents did

not produce 2-nitroadamantan,. It was found, however. ttat

relatively strong aromatiu peracids gave low yieldn of the

desired product. Thus, p-chloroperbenzoic acid in

re~fluing dichloroethane gave yields below 10% and tne use

of buffers was ineffective. The maior prod'zct In this

reaction was the ring expanded lactene resulting from the

Bayer Villiger oxidation of 2-adimantanono. Attempts to

extend this reaction to difunctinnal oximes wore

unsuccessful.

z ~?NOH rOR NO2

The oxidation of aminosdamantanes is another potential

route to nitroadamantanes. i-asmuch as there are severalii

,-jspar No. oN- -:

av-4-ab-I.--nt------ the aine -- " :-va cr--

ketones to useondary amines with sodium cyanoboronvdrzde

has been reported 5 We obtained 2-aminc&damantane in 50%

yield by the reaction of 2-adamantanone with sodium

cyanoborohydride. Conversion of 2-aminoadamantane to tro

Z-nitro deriviative took place i:r 66"% vzeid with

p-nitroperbenzoic acid in refluxing l,2-C2c'loroethanc

-!e

.L.L..DRtQjvattves of Akduaantan.. Tha ready availablity

of 4-bromo-2-adamantanone by the treatment of adamantanone

.oime with hydrobromic acidi, ±ed us to ±nvcstioate its use

as an intermediate to nitroadamantanes Previously't

4-bromo-2,2-dinltroadamantane was obtainad xrom

4-bromo-Z-adamantcnonc by nitration of the oxime. However,

attempts to displace the bromine of 4-bromo-2,2-dinitroadam--

antane with sodium azide at the relati.vely hign

temperatures needed for reaction to take place resulted in

loss of the nitro groups. 4-Azido-? adamantanone was

isolated.

BrN3

Previously 1 -te reported that the nitrAtion of 2,6-•di •--

),t

I

Report No. ONR-Z2-5

antanedione dioxime 'prepared accordinc to fiqrat ar-

Raszatb) aave a compound e-at gave elementat inzlvs•I dat:.

consistent with a dlnitrodinitroso derivattvo.

Subsequently, we obtained this same product fr-,, 2,t-admmxn.-

tanedione dioxime0 but not from 2.6-adamantandei•ne dzoxamn

obtained by a different route 6 . it is conciudeU tnat tne

original starting material was the 2,4 derivative, which

yields on nitration, 2,Q-dinztro--,l--du-ttrosoadarntane

This compound gives a geometricaliv r avored internri•

nitroso dimer which is not possible for for the 2.6 isomer.

Attempts to convert the nitroso m3.terlat to

2,2. 44 4-tetranitroadamantaiie under more forcing conditions

were unsuccessful. No nitro cempounds or nitroso diamers

were formed in the reaction of N-bromosuccinimide with

2,4-adamantanedione diosime_

NON 0

S•N 0

.,6 Cer IxYa tv psA oAdamant-%ne. T1her e are tArec

reports of 2.6-adamantandione irn the Itterature. One

involves an i1apractical multi-step synthets, 9 the sc=nd '7

very low yield enamane reactioni and the third proved to

have an incorrect product assingmentl It was reportei

that 2,6 -adamantane diacne was obtained in 30% yield by the

direct chromic acid oxidation of 2-adamantanone

Relnvestgation showed that this reaction gives

17

Report tNo ONR-2-5

5-acetoxy-2-adamantane and 2.4 d am antTnidirne with L.Q

detectable 2,6-isomer by GLC analysis

The mOst reasonable route to 2.6-adamantanedione

involved a critical dienamine reaction wita nerhvlene

iodide which proved to be unreliable and gave poor yields

at best. However, sufficient 2,6--adamantanedzonc dioximo

was prepared by this route fnr a preliminary investigation

of its conversion to nitro derzvativek. Reaction witn

N-bromosuccinimlde gave 2,6-dibromo-2,6-dinitroadamintant.

Subsequently, reduction with sodium borohydride gave

2,6-dlnitroadamantane, an Intermediate that was net

isolated. The crude material Was treated with sodium

carbonate and tetranitromethane to give a low yiCld of

i2,A6,6-tetranitroadamantanc. The material was identified

by elemental analysis, NMR and IR. Its density was a.Ui.

Br

,r >NO2

NOO

go2(C 2 )2i•

Cirect oxidation of 2,6-adamantanodione dioxime witn

peracids failed to y i!d nitro co upounds D5r2Ct

n nitration of the oxime gave some convervzon to gem--dinltro

material, but considerable amounts :f ketone woie

regenezated. However, treating the mixture with

I- hydrosylamine to recycle the carbonyl-ccntaninip materials

destroyed the nitro compounds present

i18

a a

accessible than the unsubstituted diont. 41owe-0

treatment of the material with hyvcrcrv;.ininc cave An e.n

yield of 3-carboxy-9-oximinobicyclot3.3. lnonene-6.

- IHON-. •

S0 Br

The readily available 1 1 ,3,5.7-(tetracarbomethlxv,-

adamantan-2,6-dione was converted to its cioxime Nitration

or bromination of this material gave no nitro,-containing

4 compounds, but rather, ring closure to the isoxazoiine took

place. This material was observed previously -vhen tnt

oxime was heated with refluxing ethanoll-

153 5%,

WeOCCOMeC

cfloG~e

9;cclo3.3ijoyi-2,-direDerivaiives beCcause of

the difficulty in preparing large quantitles 01

2,6-adainantanedione, a model s,1stem with structuuai

Similaritiesu was sought for the devopmz~nI o1 rcact~o'Ir

procedures. Hicyclocr2I 3.linona-2.6-dicne, knew.n 1

Neerwein's ketoneO was11 selected since- it has tftn s~r 1 Ž

4 geometry and ring structure with the excr-ptzcn t~hat one of

the rings is open.

)J > /

- I

Report No ONR -Z2 5

A general method has recent IV been rOpOL tej for J

conversion o f ketoaimes t~ chlIor on it rr c OMPoUn d 1 e:

benzene solution of the o'ilue is Simpiv treated with

neutralized hypochlcrous aCid in th prfsenc a

tetrabutylammonium bisulfate. The dioxime of Merwean's

ketone reacted under these mild conditions to give a high

yield of a chlorohydrocarbon; no nitrogen or onen

remained. Further work is needed to 4rsion the stiuctur-e.

The appearance of a transient blue coioration suggested

that a nitroso intermediate was involved. Subsequently,

the oxime was treated wtth elemental chlorine in mathvione

chloride. Under these conditions, the nitroso compound wAs

formed as evidenced by a persistent blue color of the

solution. Removal ot the methylene chloride and addition

of the materixi to the benzene-hypochlorous acid rnac ernt

then gave a 59% yield of the expected chU'ronitro

deriva tve of Morwein's ketono, Z.6--dichloro..,6-ci.-Snltrobicye1oc3 .3 1lJnonane.

Direct reduction of the diouime to the diamine witn

lithium aluminum hydride failed, but the dia'utne war,

prepared directly from Meerwein's ketone with sodiun

cya•noborohydride. Oxidation of this diamine with

p-nitroperbenzoic acid gave the 2,6-dinitro derivative, and

conversion of this compound to the tetranitro derivative is

being studied.

20

-- a

C1012

CU

OClOON

OH0 W1 "2

NO t 4 -

g 0 NBH 3 D

I B EXPERIMENTAL

EP er aoci d Oxidat ion o f...tgAAn. C', Ma

refluxing solution of 10.0 g of 45A p-chl-roperbenzoic acid

in 50 %mL of 1,2-dlchloroethane was added, portionwise, 1.65

g (0,010 aol) of 2-adamantanone oxime. A slight grcon

color was observed. After a 3 h reflux period, the

solution was cooled, filtered, wished with 20 mL at 5%

sodium carbonate and evaporated to yield 1.5 g of a wanv

solid. IR and NIR analysis showed (.15 . (8.3%) at

* 2-nitroadamantaane and I .3 (81%) of 3-ozahomo--

adamantan-1-one. Attemps to improve thzs rdaio by runniln

the reaction in the presence of discidium hvydrogcn phosphate

S•In aoetonltrile reduced the yield of 2-nttroadAmantant' tn a

L-AatnoasArantane. A mri:ture of j00 ME. of aiihvdro'i

* methanol , 215 g of ammonium acetate ,ind ̀ 0 .a (0 033 nol ) -)

2-adamantanor,e was utirzed for I h at room temperaturo.

=2

- -Th__n . - " • a 0_a a01) of_ sod ium z _n: bor_ I h S Jr I do w_ _ .

added and the solution was stirred for 21 h The soiution

was acidified with concentrated hydrochloric aoid to pH ?2

and was extracted twice with 50 mL of ether. EvaporaLion

of the ether yielded 2.1 g ( 42%) of 2-hyroxyadamantane.

The water solution was then made alkaline witn soJid

potassium hydroxide to pH >10. Yater was addod t, prevent

crystallization of potassium chLoride. The •olutionwa

W extracted with methylene chloride (2x5O ml.). Fhe orgimni

%,Ayer was dried over maganesium sulfate tnd the solvknt was

removed to yield 2.52 g (50%) of I-aminoadamantsne, m.p.

S1S0-1850C, identified by comparison with an .;uthentic

s amp It.

£L& Qi ogiasin of 2-AMiýnodamantzane. To a solution

U of 5.0 g (0.025 mol, 96% assay) of p-nitr'perbcnzoic acid

in 100 aL of refluwing 1,2-diohloroethane was added,

dropwise, a solution of 1 0 g (0.006? m•ol)

"2-aminoadamantane in 25 mL 1,2-dichloroethane. The

*olutlon was refluxed for 30 min, cooled and filtered. The

solution was extracted with a pH 5.0 phosphate buftor (2;r50

0 mI), dried over maganesium sulfate and evipozated to yield

1.15 g of a semi-solid which upon rec.rvstallization iror

ethanol-water gave 0.80 g. (66%) ot 2-nitroadmntr.no,

identified by IR and NMR comparison with authentic

mateorialI,

S.Li_ on _f 4=krm- =, 2-dinit toqad mýi ntane wi th 5o I q r

A ki d. Sodium azide (0.5 g), activate] by recrys t ;:-

liszation from water-acetone, was added to , solutzon oi 0 1

2Z

dimethyl formamide. The solution was kept at 00 to 1.2 0 0C

C for 12 hrs, cooled, and added to 100 inL or water. The

organic material was extracted with methylene chloride (2 x

50 mL) and the resulting solution was dried over maonei•irn

sulfate. Evaporation of solvents and aublimation of the

residual oil yielded 0.015 a (25% of qo-az do--

adamantan-2-one, identiiied by IR comprrx3ion wita

authentic material.

2-6-Adamantan•d•one Diowime. To a ratluxing solution

of 1.05 g (0.006 mol) of 2,6-adamantandiozie in 50 mL of

ethanol was added a solution of 1 0 g (0.005 mol) ot

hydrosylamin* hydroohoride and 2.0 a of sodium carbonate in

20 ml of water. The solution was allowed to stand for 48 11

and was then concentrated to one third ot its original

volume, The precipitate was filtered to yield 1.00 g (99%)

of 1,6-adamantandlone dioxime, mp 279-2800,.

Anal. CaIcd for C0 H 14N O: C. dl1 83; H, 7.26; N,

14,41. Found; C, 61.8q, H, 7.40, N. 14.1,

Z.6-Dibromo•6-d4Jj .• • !'_.LP To P solution of

0.50 g (0.00Z5 mol) of 2,6--adamantAndLone diomjimc? in SO ml

of I:1 dioxans-water was added 3.0 q <0.OI0 mo)) of

N-bromosucoinimz de, and 1.5 g (0.017 Mol; of sodium

bicarbonate, and the mixture was stirred at ambient

tempera~ure for 48 h The color initally turned light

green then slowly faded. The dioxane was evnpotatced under

Ivacuum and 50 mL of water added The solid product was

reorystallized from ethanol-water to give 0 23 q (Z4%) of

!2

Report No. ObR-2-5

2.6-dtbromo-2,6-dinitroadamantane, mp 16;'-.165(," IR

(CHI Ci) 3000 (C-H), 1540 1460 cm 1 (N--C)O; NMIR (D[.C CI &

A 1.8 - 2.8 complex.

Anal. Calod for C H, N 2 D-11r : C. 31 27; H. 3. 3 U; N,

7.29; Br, 41.6. Found: C, 31.33: H, i.14; N, 7 45; BE,

41. 44,

2.tn r 2 , 6 a ant ane _ýadn c t S in2 tr. _.-,.

tLanone. To a solution of 0 31 g (Q. o00 mnl o t

U 2,6-dibromo-2,6-dinltroadam~natana in 2O mL of ethanol ,r.•

added 0.1 g of sodium borohi; ride and I'6 niL -f water. T'he

solution was stirred at 250C for 30 mIn. Thu e~hanol was

- evaporated under vacuum and the aqueous solution W45

extracted with ether (2 x 50 mL) , The ether eolut ion wai

dried over magnerium sulfate and evaporated to vicld crude

2,6-dinitroadamantane a waxy solid, mp i100-150 0 C (Nt1R & 4..4

"2 protons, & 1.8-2.7 12 protons). The nitro compound was

dissolved in A solution of this material in 10 mL ot

methanol was stirred with a solution of 0.2 g os 5odium

carbonate in 10 mL of water for 15 min at 20°C

Totranitiomethane (1.0 mL) was added and the raixture was

stirred for 1 h. The methanol. was ev'porated, 20 nL of

water was added, and the product was c-tiractod with ether

(2 u 50 mL>. The ether layer was washed with t-0 mt. of 5%

sodium carbonate solution ar.d 50 mL o1 10% potassi•um

hydroxide solution, dried with magnesium sAliate and

evaporated to yield 0 16 Q of crudc slid, 501 IS

0 TLC of this material on silica gal with chloroform y:ieided

0.040 g, (20%) of, ,6-dlnttro-2-adamant.nono: IH (CUi C)

2.4

0y

......

Report No. ONK-2-5

3o W~ H . 177.U (CTY m _ __ __ _ _

(DCC1 3.7 (2 H), 2.7 (2H) 2n 2. ppm tP H

CAnal. Calcd for C to H 11NIO C. 5 031.H 0, >3; N.

11.60. Found: C, 50.26; H, 5.07; N, 10.7.1

A second TLC band with slightly less rotent ion timu.

provided 0.010 9 (2.4%) of 2,.6,6-tetranitroadi.mintenc.

The mate r ialI sublIimed wit h o ut me Lt in-i above 280 cC 1ý

(CH ICl I) 3000 (C-H) , 1580 and 1'l60 cm-1 (N-O0) ; NqME( (tICCI

6 3.4 (4 H) and 2.0 ppm (8 H); density, 1.75

Ana.l. C aIo d f or C H NO C. 37.98. 14, 1.82. N,It 12 4 1

17.72. Found: C, 39.93; 8., 4 13; N, 16.80.

RIA2 t i n o f S-IrM02-2,4-a~dA~mant~Argdio]e Wi th.

Fydirosv][pMine. A solution of 1.0 g (0.0041 Mot) of

4-brorbo-2,6-adamantanedilon, 1 0 fa' 014 Moi) ot

hydroxylazine hydrochloride and 1,O m'l, of pyridine irk 35

mL of absolute ethanol was refluxed for 2 h. The solvent

was then evaporated, 50 niL of water was added and th~e

Mixture was stirred for 30 min. The water was riacanted and

the oil was recrystallized from cthanol to give' 0.65 g

(80%) of 3-carboxy-9-oxmjnobicyclo(3..31.ilznan--6..ene, MP

2858C ( dec) . Thir product was identis>a1 vmth materzia

obtained by oximation of 4-bromo-2 6-&Jiamantanedi-nna in

ethanol-water or oiiimaticn of 2c~rtoxy-9-.oitoflx.

cycloC3.3.13nonan-6-*ne directly NO dioxime could be

detected.

N-Bromosuccinimide (10 0 g' 0.056 mIno) was added. v'itn

9 t ir r ing a t 5'c, to0 a s o IUt i on o f 1 50 a ý0.008 n'o1 of

spor-t a -d 0 di-- .... i+ v cl €io[ 5.3. 12•nv-nr-trt-dt---r-r- ---- Ji-o•i~ ( s up 2 l•-2-7--Ct--t-1}• -

.L of water and 150 mL of dioxane. Then S.0 a oa socid

sodium bicarbonate was added over & 20 min eriod The

solution became green and then blue and the cior taoed in

30 in. The mixture was stirred 30 min a?: 5C and 2 his at

ambient temperature. The reaction mixturQ was concentrattd

to kne third of its oricxnal volume with - rotrry ev;..ar-, r

under reduced pressure and was e.tracted witn two 100 mL

14 portions of methylene chloridc. The organic 1a,-r ,,Yas

separated and dried over magnesium sulfate. Flazh column

chromatography of the resulting oil (silica gel, methylene

chloride) yielded a nitro containing traction -IHD and

several fractions containing only carbonyl compounds.

Recrystallization of tha nitro containing oil trrm

ethanol-water yielded 0.20 g (6.5%) of pure

Z.6-dibromo-2,6-dinitro bicyclot3.3 .lnonane. -p 4041(:

IR (K~r) 2950 (C-H), 1540, 1i50 on-I. (N-O); NMR (DCCI 6

2.0-3.0 (complex).

I.aI CaIod f0orC N rI: C. 29.06, H, 3.75: N,

7.53; Br, 42.96. Found: C, 29.20; H, 3.33;U. "," s-' : 13r,

43.12.

Reaction21 of --Ei-cvcl9C 3 3.lnona-2j6±-dicone d i o'!xmoe-i tfn

, c lo a Ac d A pH meter was used tc neutralizo 2.00

=L of commercial pool bleach (5% sodiur hypochlor-ie' to pM

5.0 at 0-2'C with 10% sulfuric acid. Benzone (100 mL[ and

5.0 g (0.027 mtol) of bicyclot3 3 1:lnona-2.6-dionc2 _ dioxime

were added. As the diozimo dissolved, the solution becrmc

deap blue and then the color slowly fadad. Aiter I h. 100

=L- .-.- " at 1Isa tr a At lx ed . leOaCh an4 0.5 ot__ __

tetra-n-butylammonium bisulfate were added and the mixture

was stirred :or an additional 2 hours. The organic layer

was separattd, washed with 5% sodium thiosultafe solution

and dried with magnesium sultate. T'ha benzene was

evaporated and the residual oil wac dissoved in hxeane ano

filtered thru 5 g of silica gel. Evaporation of the heuane

gave an oil which solidified to give 4.Z g of a waxy -. lid,

mq p 18-22t: IR (CH CI ) 3000 (C-H), 1440, 1460 cm*! (C-Cl)

NKR (DCCI ) & 2.0-2.8.I

Ana.l. Found: C, 43.09; H. 5.86; CI, 51.15.

' ~2,_6.-Dichloro-2,6-dinitro-bicvlcoC33,.,1 none.

Chlorine gas was bubbled into a solution oi 2.0 g (0.011

Sol) of bicylcoo3.3.13nona-Z,6-dione dioxime in 50 mL ot

methylene chloride. The dioxime zlowly dissolved awid the

solution became dark blue and then green. This solution was

stirred for 4 h and the methylene chloride was removed.

Then, 50 mL of benzene 0.2 g of tetra-n-butylammonfum

bisulfate and 30 mL of 5% sodium hypochlortte were added

and the solution was stirred for 48 h. The organic layer

(now colorless) was separated, washed with 5% sodium

thiosulfate and dried over magnesium sulfate. The banzann

was evaporated and the residual oil was dissolved in !J0 mL

of methylene chloride and was filtered through t a of

silica gel. The methylene chloride w .s ev.porattd ano tie

risidual semi-solid was recrystallized trom ethanol to

yield 1 .84 q (59%) of 2,S*dichloro-Z.6-di-.

nitro-ticyloo[3.3.13nonane, mp 111--1130- Il (LH C1) 1,000

L7

Report No. ONR-2-5

(CH), 1,580 and 1,460 ca"I (N-0); YMR (DCCI & 2.0-3-0.

Anil, Cald for C IH CINHO C, 38.18; H, 4.2?; N,

9.89; CI, 25.04. Found; C, 38.2S;H, 4.21; N, ,.79; Cl,

26.31,

2.6-Diam no-bjo csip[.3.31nonane A mixture of I00 mL.

of anhydrous methanol, 30 g of ammonium acetate and 10.0 q

(0.066 mCI) of bicylco[3.3.l3nona-2.,6-dione was stirred it

zo0C for 2 h. Then 6.0 a (0.1 M01) of sodium

i cyanoborohydride was added slowly eve' ! h. A. vater bath

was used to keep the temperature of the exothomic reaction

a t 201C. The mixture was stirred 24 h,. the methanol w&s

evaporated under vacuum and the pH was adjusted to below 2

with concentrated hydrochloric acid. The solution was

extracted with ether (Z X 50 mL.. The aqueous layer was

then made basic (pH 13) with solid potasslum hydioxide;

water was added as necessary to prevent salt precipation.

The solution was cooled and was extracted with =ethylene

chloride (2 X 50 mL). The organic layer was dried over

magnesium sulfate and the solvent was ronoved to yzelc; 6.2

g, (61%) of 2,6-dIamino-bicy clot3 3S l1nonane as a oil-.4

IR (CHXCI) 3400-3300 (N-H), Z900 (C-H). 1450, 1320. 1270.

1110. 960 cm4'; NHR (DCCI ) & 2.0-3 5; P--nitroben-oato, np.

19 0-1,2 C. Elemental analys.s results are pending.

OxidLtUIf_ 2, 6-a O n o bsyj v 1Ic__ 3. - I In on a Ve_. A

solution of 5.0 g (0.032 mol) of 2,6-diamino-

bzoylcoC3.3.1]nonane in 100 mL of i,2-dichloroethanu wis

heated to reflux. Then 25 g (80% purity, 0.1 mol) of

p-nitropurbenzoic acid was added slowly over i; 30 min

Report No. ONR-2-5

• period. Thei aiitii was rei id -r , c-of le- a--

filtered. The solution was washed with pH 5.0 buffer (2 X

30 mL), dried over magnesium sulfate and stripped of

solvent to yield 1.50 g (21%) of crude

2.6-diflitrobieyclo(3.3.l)flnonan as an oil: IR (C~H IC1 2 3000

(C-H), 1550 and 1460 ca"I (H-O)i NMR (DCCI3) & 4.2 (2 H)

and 1.8-3.0 (12 H). Upon attempted distillition this

material decomposed. On passing the material through

silioa gel, all nitro functions were lost.

IV. REUERENCES

1. Fluorochem, Inc., report No. ONR-2-4, Researoh in

&nergatic Cotneounds, January 1982.

2. SRI International. Final Report, 5ynthesi2 21 _A*_02ti2

LPoljye.s, September 1982.

3. Ledwith, A., North, A.M., "Holeculer Dehavior and

Development of Polymeric Materials". J. Wiley Pi sons, New

York, 1978, p.41ff.

4. Saegusa, T; Fulii, H; Kobayalu, S; Ando, H. and Kawase,

ii. liiogj 193 _k2.' 26..

5. Borch, R. F.; Bernstein, K. D.; Durst, i. D. J. A.

Chenj~. fij 1?1 22, 2897.

6. Trlska, J. Vodicka, L; Hlavatyr J r-.LL..LI.. 52. C Lf -

£maLJ. 1279, AA, 1448.

7. Stetter, H.; Thomas, H. G. .k 1., 1966, 99, 920-

29

135 375.

9. Morat, C.; Rassat, A.-, Ttrahedroz Lutters. tg7ý, ,15.

4409.

10. Stutter, H.; Dorsch. U. P. Ann.. _1976, ieUo.

•-•11. Bottger, 0. ; I--,-3-. 1 .7 , 3 1 4

12. Moi seev. 1. K . L_ al . Zh 2_L2_ Khxm l'7 , tV.

2341.

13. Schaefer, J. P.; Honig, L J Org. Ch4tm. , 968, 33,

2658.

14. Coreya E. 3.; Estreicher, Ti Te t r.hedron LetLr.xs.

Ltij. 1117

.70

0.

Apendix A

C Synthesis of Electron-DeficLent Ozetanes.

3-Asidoozetane 3-Ntitroowetans and

3-3,3-Dinitroozetane1

Kurt BaumA, Phillip T Berkowitz,

Vytautas Grakauskas and Thomas C. Archibald

Fluorochem, Inc., Azusa, California 91702

2

ABSTRACT

A facile synthesis of 3-hydroxyoxatane is described,

based on the addition of acetic acid to epichiorohydrin.

protection of the resulting primary alcohol as an acetal,

basic acetate hydrolysis and ring closure, and removal ot

the protecting group. 3-Asidoexetane was prepared trom

3-tosyloxyoxetane and sodiuxo aside. Redurtion of the aride

with triphenylphosphine or hydrogen gave 3-aminooxutana.

and oxidation of the amine with m-chloroperbenzcic a&td

gave 3-nitrocxetane. Oxidative nitrat ion cr reaction wich

tetranitromethane gave 3.3-dinitrooxetane. 3-Azidooxetane

and 3,3-dinltrooxetane were polymerized with Lewis acids

31

I .|dt.,Ja& s I ~ ~ '...

- .- - - - 'rgP ~ .' - t ~ s - ~ r r r - ~ s . 4 ~ - t v ' ~ ,

Apendix A

Recently we reported the svntnests CtI

3-fluoro-3-nitrooxetane by the bh _,--cat.ivzed ring ciosure

of the sonotriflate derived from 2--fluoro-Z-nztro--±,5--ro.-

panediol 2 . The "fluorine effect", or the destabilization

of a nitronate salt by an adiacent fluorine, enables this

ring closure to take place desoite the cenerai tendency of

2-nitro alcohols to split off form3ldehvde (raverse nenr,

reaction). The use of a less potent leaving group, suCn as

tosylate, gave adducts of 1-fluoro-l-nitroethylene rathec

than the oxetane 3. and even trlflates from nontluorinated

nitroaloohols such as Z.Z-dinitro-l.3-propanedioi and

2-(hydroxymethyl).-Z-nitro-l,3-propancdioL gave no

~owe tines!

An alternative to tnis ring closure is tne

introduction of nitro groups by operating on oxetanes which

contain other reactive functional groups The conversion

in high yield of 3-hydroxyozetane to the tosytate has bien

reported, and the tcsylate group has been displaced by

halidedos The 3-hydroxyowetane eas ebtained by t'le

* hydrolysis of 3-propenoxyoxetane, which. in turn. was

prepared by the base-catalvzed rearrangment of

3-ailyloxyozetane The latter compound. however, was

* obtained only in low yield by the cyclization o± Z--allyl-

osy-3-chtorapropanoi 5 , a low-conversion cnlorinatioon

product of allyl alcohol"6.

6 We have developed a procedLre suitabie tor tue

preparation of latge quantities c-t 3 nudroxyoxetane jforn

32

Apendit A

epichiorohydrin using the route ouiined in Scnome n r-,

hydroxyl group of the acetlc acid adruct .-t epichioronyd ri•:

was blocked with a base-resistant protecting group. £star

hydrolysis and ring closure with ague'us baese was foliotw'ed

by deblocking with acid

HC- CHCHCI + HOAc A AcQCXCCH(C H'Ck-{HCL

0

AcOCHKCH(OH)CHICI + CHI=CHOEt • AcOCHIC H CH ICI iM te'C'Zt t

AcOCHKCH(CHICI)OCHMe(OEt) + NaOH

HOCH CH(CH H C)OCHMeMOEt) t - OCHM.CtOF F

-- OCHMe(OEt) + H*--

Scheme I

The reaction of epichiorohydrin with acetic acid.

catalyzed by ferric chloride, has been rep-rted to nive

3-chloro-Z-hydroxy-l-propyi acetate 1n high yield 7 Thi-t

procedure was modified by elimin .rting the use of sol-vnts

and minimizing the amount of cat-.lvst The l.ow Iron 2.i,,ol

did not prevent monitoring the r..:t t n b-t NMR.• nd td-e

product was used wsth-vut taorkur (,:r 'the following sten

The hydroxyl gr oup p ,,a then -:cr L • w ttn a vi.v .!c

ethet. Dihydropyran Ind ethy: v,,zr-iI her 've szIroi r

results, and p-toIuene. ,1Uton c ac, i I ' s ts used as a L.a _•..,s

No solvent W"s used se ;II to thi_ hr.n . - hv . o ne E r

•3

e •Apendix A

process. Next, aqueous sodium hydroxide hydroivzed the

ester and also closed the oxetzne rino. ihe resultinc

orude 3-(1-ethoxyethoxyloxetane was then treated with

methanol and a catalytic amount of p-toluenesultonic acid

to give 3-hydroxyoxetane. Flash distillation Mave

3-hydrozyoxelane of ab.*Tt 80% purity, and the pure airhoi

could be isolated by tractionation. The impure materiai,

however, was suitable for conversion to the tosylate with

aqueous sco dium hydroxide And tosyl chloride 4 . The overall

yield of 3-tosyloxyoxetanoe based on epichlorohydriri was 2"0%

Attempts to prepare 3-nitrooxetane from

3-tosylosyox*etane, 3-bromooxetene or 3-iodooxtane by

ditplacement reactions with silver nitrite o0 sodium

nitrite were unsuccessful, Decomposition took place when

reaction temperatures were high enouqh for the consumption

of starting materials. It has been re&iorted that

displacements of 3-tosyloxyometane with netal ha'lides

require temperatures of about 170'C and that tho reaction ot

3-iodooxetane with diethylamine takes place at 2000C.

Aside salts, however, were found to react with

3-tosyloxyoxetane under relatively mild conditions to give

.- azidooxetane. A 50% yield was cbtainec with potassium

aside at 871C in hexamethylphosphoramide and a 28% yieid

was obtained in ref luxi ng ac.ton t r i le in the pr-sncL of

18-crown-6. Polyethylene glycols were also reported to lave

crown-ether type complexing abi i , ( , and these me.ter taiI

were investigated as solvents for the displacement. Souium

04

Apendiw A

naeid and the tosylate gave an 86% yield of ,-azidooxet.ne

at i20-130 C at 7-10 mm Hg; under these conditionis. the

product was distilled from the reaction mixture as it was

forimed. ?he solvent did not codistill with the product

when tetraethylsne glycol or higher homoloas ware used.

The azide was handled SafelvU by dittilling the materiai

directly into methylene chloride ani usini tho solution tor

subsequent reactions.

*~ NaN3 N.

3-Aminooxetane was obtained in low yi*id from tne

reaction of 3-tosyloxyoxetant with liquid ammonia. A more

satisfaotory method. however, was the reduction or

3-azidoosetane. Azides have been convarted to amines by a

reaction with triphenylphosphi:e folowed by ammonolysis

and by this procedure. 3-azidooxetane gave a 96% yield of

3-aminoosetane. This reduction wasi also carrird out by

hydrogenation at atmospheric pressure in mothanol over lU"

palladium on carbon, but the reaction was not rce-lzably

reproducible. The synthesis of 3-amznoonetane by the high

pressure hydrogenation of $-oxetincne oxime Wat, been

reported in the patent literatureiz

jN: PhP NH NHz

3 5

I:

Apendix A

3-Aminooxetane was used as a staiting materiai to

. prepare 3-nitrooxatane and 3,3-dinitrooxetane. "fhe

"oxidation of cyclohexylamine witll m-chloroperbenzoic acid

to give nitrocyclohexcnre har recently been reported1)

This reaction was found to give R 75% yield of

3-nitroozetane from 3-aminooxetane. The most generally

used method for converting a mononitro aliphatic compound

. - to a gem-dinitro compound is the oxidative nitration

reaction 11 , using base, sodium nitrite and silver nitrate.

3.3-Dinttrooxetane was obtained in this way from

3-nitroosetane but only in 22% yield. Nitronate saltF have

recently been nitrated wiih tetranitromethane , Addition

of this reagent to a solutiun of the salt of 3-nitrooxetane

in aqueous methanol gave a 60% yield of 3,3--dinitrooxetane.

r]NO OH', AgNO N&102-(10

The polymerization of 3-Lluoro-3-.nitrooxetane W.S

Previously shown to be catalyzed by the strong Lewis acid

catalyst, phosphorus pentafluoride, but not by boron

trifluorlde. 3,3-Dinitrooxetane was iound to be even more

* resistant to cationic polymerization, requiring prolonged

exposure to an atmosphere of phoEphorus pantafluoride. A

36

Apendix A

polymer was obtained with a melt in' pnint of 200- 202c

Tie polymer was insoluble in methyiene chloride or ethyl

acetate, but was soluble in &cetone. The molecuiar weight

by vapor pressure osmometry was 2870

r (NOI) PF HOtCH 1 C (NO C) 1CH 10H

3-Azidooxetane, which is not so highly deactivated by

electon-withdrawing groups, was polymerized readily by

boron trifluorid. etherate, at temperatures as iow as

-306C. Details are described in the Experimental Section.

N HBF XOCCH CH(N )CHO 0H1

Determination of the hydroxyl equivalent weight Of

polymers has generally provided difficulties 16 . Je havo

used a simple procedure consisting of trimethylsilylation,

removal of volatales. and determzni.tion of silyl hydrooens,4

by quantitative NMR

Lay1er MentiA kkcSectP

NNMR and IR spectra were recorded %w th a Vtripit T.-60

spectrometer and a Perkin-timer ?00 spectrometer,

respectively A Varian 920 gas chromatoaraph was used for

37

Apex ix A

-.G ..t . ....s . Tr I- " t i as I I IaInd ...... ...

osmometer was used for molecular weight determinations.

3-Tosvloxvoetane. Epichlorohydrin (925 9. 10.0 moe)

- was added with stirring, over a 10 min period, to a

solution of 1,5 g of ferric chloride in 612 g (JO 02 mol)

of glacial acetic acid. The mixture was heated at 65-70C

for 24 h to give crude 3-chloro-2-hydroxy-1-propyl acetata;

NAR (CDCl 3 2.10 ~s 3 H. COC.H 3, 3 0 (xc 6 ki,

CH CXH (OH)CH ) ; IR (film) 3500 (OH), 1735 cm"1 (COC 33 3 3

After 10 g of p-toluenesulfonic acid monohydrate was

added to this crude material 815 g (11 3 moI) of ethyl

vinyl other was added dropwise, with stirring. over a

period of 2 h. The flask was cooled to maintain a reaction

temperature of 35-37kC After the addition was completed,

- the mixture was heated at 35-408C for 16 h to give crude

3-chloro-2-(l-ethoxyethozy)-I-propyl acetate.

This Intermediate was added over a 1.5 h pevrod with

stirring to a solution of 1.1 kg (27.5 mol) of sodium

hydroxide in 1. I L of water at 1050C. and the reaction

mixture was refluxed for an additional 4 h period The

mixture was cooled and was warhed with I.7 L of water. Tne

aqueous layer was washed with 1.5 L of methylene chloride,

and the combined organic phases were stripped of solvent to

give 1.2 kg of crude 3-(l-ethozyuthoxy)oxetana.

M.ethanol (400 q) was added and the mixture was cooled

to IS-IeC. p-Toluenesulfonto acid monohvdrato (10 a) was

added with stirring. The reaction temperaturD increased

38

Apendix A

over a 5 sin period to 349 and then decreased to 2.AC in

30 min. The mixture was stirred for in additional 45 min

period and then 5 g of solid sodium bicarbonate was added.

Distillation gave 280 g of 3-hydroxyonotane. bp 'i5.50 0 C

(0.3 mm), of 80% purity (NMR).

This 3-hydroxyoxetane (3.07 mol) wAs stirred witri 660

g (3.46 mol) of technical p-toiuenesulfon,r l chloride in 530

mLr of water, and a solution of 194 g (4 84 mol) of godiun,

hydroxide in 200 mL of water was added over a period of 2,

min. Ice bath cooling was used to keep the reaction

temperature below 701C. When the exothermic rezctton

subsided, the bath was removed and the mixt,,re was allowed

to cool to 40 0 C over a I hr period The otoduct was

isolated by filtration, washed with four IBO mL of warm

S(500C) water, and air dried to give 649 9 (93%) of

3-tosyloxyoxetane, mp 86-88t (reported4 88 5-890C).

S3-Azidoozetanp. A stirred solution of 92 g (0.40 mol)

of 3-tosyloxyoxetane and 40 g (0.48 mol) of sodium axido in

Z05 mL of polyethylene oxide (Carbowax 300) was heated to

120-1306C over 30 min at 7-10 mm lig The product distilled

as it was formed, over a 1.5 h period, and was collzcted in

a stirred receiver containing 200 mL of me.thyvlfne chloride

at -78eC. The re*sulting methylenc cnloride solution

contained 34 g (86%) of 3-azidooxetanL., 7.nd an analytical

sample was isolated by CC (9% OF-I on Chromasorb V. IU0O ":

IH NMR (CDCl) &4 70 (m, 4 H, CH ) 4 4 76 'zn, I H, CH,3 ) . IR

(CH CIl) 3l 00, 2930 kCH), 2150 (N ) , "0 cm" 80xevane,

2139

39

* Apendix A

A•a.l. Calcd for C HN0. C. 36 36, H. k0; N 42.41.'53

Foumd: C, 36.29; H, 4.82; N, 43.06.

The product was handled safely as a methylene chloride

solution (see discussion)

-3-Aminooxetaneo Trtphenylphosphine (132. 5 a 0 .50

Mol) was added to a solution of 50 o (0.50 mol) ot

3-azLdooxz tane in 800 mL of methvlene cnioride it 0. O 'C

The solution was allowed to stand for 0.5 h at 0-50C andU"for 3.5 h at room temperature The zoivnnt was rcmovej

under vacuum, aad an ice-cooled solution of 80C myl of

methsnol saturated with ammonia was added to the residue.

The resulting orange solution was stirred for 40 h at

0 -St. Distillattnn gave 32 g of 3-aminoometane, bp 50-82C

(60-70 am: Hg) - repojrted 1 1 80-82*C (100 mm Hg) - ano

.etraotion of the distillation residue with ether followed

by distillation gave an additional 3.29 (96% total): IM

1NMR (CDCl £2. 03 (s, 2 H, NH 1 ), 4.0-4.S (m, 5 H); IR

(fil ) 3350 (NH ) , 3000, 2900 (CH) , 1605 (NH , 970 citk"

(ozetane); n" 1.4500. Elemental analysis wAs cArried out

on the p-nitrrobenzamide, mp 189-191 '..0

An&l. CaIcd for C ItHt N O1 C. 54 03: Hi. 4 50; N.

12.60. Found: C, 54.02; H, 4.51; NM 12 32

3 -Mi 1 o22 1 .a.ft- A solution of 7 •. g (0.10 mol, Uf

3-aminriooetan. in 100 mL of 1,2-dichloictethane was a-Ided

over 1 hr to a refluming solution ot 71 a '0.31, mol) of 8,%

-- chloroperbenzoic acid in 600 mL of 1,2-dichloroethane.

The reaction mixture was heated at reflux for an additionai

40

bt

Apendix A

3 h period and was aliowed to stand ii arr.bint temperatuit!

for 16 h. The precipitated ff-.hl orob-nzoic , w.as

filtered and was washed with 1 1-dict*lore'hane 'The

combined solutions were stripped of .;,1vent under vi.cuum

and the residue was distilled in ?, Kuoelrohr apparatus to

give 6.35 g '62'k) of 3-nitrooxetane at 'e70C (0.5-. 1 .0 mi

Hg), An analyt Ical sample was iso ?.t ed by GC (9,Ys OF--i on

Chromosorb W, IZO0 C)- NMR (CDCI 4 8? 1(0, 4 H, CHi,

5.5.23 (a, I H, CHNO ) IR (CH C 1 3000. 91940 (CH). 15 0

1370 (NO ) 980 cm"1 (oxetane); n 1 4618, d 1.33.

&.,LL. Calcd for C H NO I C, 34 96; H. 4 89. 1 ,urid

C, 34.77; H, 4.87.

""3,23-Dtnitropxetane (Oxidative Nitratton) A solution

of 3.38 g (0 033 mol) of 3-nitrooxetane. . q5 a (0 036 mol)

of sodium hydroxide and 2 .56 g (0 03,6 mol) of Soiiu7,1

.nitrite In 72 mL of water at 0-5 0 C w;-s added to a stiLred

solution of 12.2 g (0 072 mcO ) of silver nitrate in 25 mL

of water at 0-50C An immediate 'lack suspension formed.

After the reaction mixture was stirred at 0-56C for 2 h. 2,j

mL of saturated sodium chloride solutfj'n was added and

stirring was continued for 30 min The mixture wits

filtered through celite and the filter cake was washed with

4 10 mL of water and 100 mL of ether Tho a•-qeous Coiutioin

was washed with two 100 mL portions of ether and the

combined ether solutions were dried arid the solvent w,-..

removed. Column chromatography of the residue (siiici cgel,

methylene chloride-hexane) gave 1 07 a (21 9%) of

41

e

* Apeindi A

3,3-dinitrooxettane, mp 70---0 Osub1 700°Z- NHi (CCi.) &

5.27 (s); IR (CH Cl 1) 3000, 2940 (CH), 1560. 1325 NO22 2

1000 cu 4 l (ozetane) d, 1 65,

Anal. Caled for C3H4NO05 : C. 24 34; H, 2.72. Found-

C. 34.54; H, 2.80,

m3-Pinitrogget ( Tetranitr t ape).

solution of 1.03 g (C.010 mol) of 3--nitrooRetane aid 2.0 a

(0.010 mol) Of tetranitromethane in S mnL of methanol was

addeed dropwise, with stirring over a 21) min period, to z

"solution •f 0.42 g (0.010 mol of sodium hydroxide in I 1 L

of water and 2 mL of methanol at 0CC. Stirrino was

continued for 30 min and 10 mL of water was then •ddad.

The pH was adiusted to 9-10 with sodium hydroxide, ;nd thf

mixture was extracted with ether (3 x 25 mL). The atnei

solution was washed with water and dried. Removal of the

solvent gave 0.89 q (60%) of 3.3-dinitrooxetane identical

with that above.

P-. lvmerirAtion of 3,3-Dinitrooxetane. A dry 100 mL

flask, fitted with a syringe valve, W.5 loaded with a

solution of 0.113 g (0.76 mmol) of 3,3-dinitrooxekanu in

0.5 mL of dry methylene chloride, and was flushed witn Zlk)

of a white solid: MW (VPO, ethyl acotate) 484; IR 35.O

(OH), 1575, 132 of phosphorus pentafluoride was added.

After 30 h. solvent and catalyst were removed under vacuum.

Extraction of the residue with 15 mL of methylerie gave

0.018 g (16%) of recovered 3,3-dinitrooxetane ihe

material insoluble in methylene chloride was extr~ctu-d with

qz

I

e - .. .. f . -IpW t-a

solid: HMW (VPO, ethyl acetate) 484; IR 3S5C (OH), t?,75, 1420

Sca" (NO). The material insoluble in ethyl acetate was

extracted with 15 aL of acetone to give 0.071 g (63%) of

whjIte solid, up iQ-02G MR (D 3CCOCD) 6 '1.67 (br s)'; ZR

(acetone) 3600 (OH), 1565, 1320 cm"1 (140 ); moleculat

weight (vapor pressure osmometry, acetone) 2670. density

.Povaerisation of 3-Azudowe f,.l. A 50 nL

magnetically stirred round bottom flask, fitted with a

condenser and a drying tube, was loaded with 20 g of a 42%

by weight solution of 3-azldoxetaiie in methylene chloride

(0.085 aol), and was cooled to -30'CC treshly dzstiiled

boron trifluoride etherate (0.60 mL., 0.0052 mol) was added

rapidly by syringe. After about 30 •ec the reaction

temperature incrcased to the reflux temperature and i

gelatenoug polymer iormed. The material was alilowoc to

stand for 5 min at room temperature and then 5 aL of water

was added and the mixture was agitated to disperse tne gel.

Ethyl acetate (30 mL) was added and the minttire was stirred

for I h. The organic layer was separated and was dried

over magnesium sulfate. Solv2nt was removed with a rotary

evaporator (700C at 20 mm Hg) to give a brown oil: NMML

(CDCI 1 ) & 3.58 Cs); IR (CH 2CI1 3,000. 2900 (CH). 21S0

(N) 3 1135 cm- 1 (C-O-C); molecular weight (vapot pressure

osmometry, ethyl acetate) 2200. eauivalent weiQht

(silylation) 1200.

43

4. . . . " . .. . . .. •

Apendix A

The polymer dissolved in 20 mL of methylene chiorzde

was poured into 20 mL of hexane with vicorous stirrinc.

After 30 mmn the solvent was decanted from the pretziitated

lol, and the latter was dried at 700 C under vacuum to acve

7.4 g of material essentially identical with the

unfratilonated polymer.

The polymerization was also carried out at submbient

tempeaatures with more dilute solutions. A solution of 1.0

g (0.0071 iol) of boron trifluoride etherate in 50 mL of

methylene chloride was cooled to -301C and a solution ot

9.9 g (0.10 mol) of 3-asoxyoxetane in 100 mL of methylene

chloride was added dropwise. The solution was stirred Pt

-301C for 48 h. GLC analysis showed that less than 0.5% of

the oxatane rem.ined. Saturated sodium chloride solittion (5

mL) was added and the mixture was stirred for 30 min. The

organic layer was allowed to come to ambient temp, :atre and

was washed with 100 mL of 5% potassium carbonate solution

and with 100 mL of water. The methylene chloride solution

wis dried over magnesium sulfate and was evaporated undar

* vaCuuM. The residue was dissolved in 30 mL of methylene

chloride and the solution was filtered into 30 mL of

rapidly stirred hexane. After 30 min the solvent wAs

decanted and the remaining oil was washed with 30 mL of

hexane. The product was dried at 700C under vacuum to

yield 4.8 g (49%) of very viscous oil with molecular weight

2350 (VPO, ethyl acetate).

A similar reaction using 0.1 mol of 3-azidooxetaie

44

Apendix A

and 0.0052 aol of boron trifluoride ethorate in 50 mT. of

aethyle ne chl or ideo ma inta4ined at 0-56C ciave a 54.5% y ie id

of product with a molecular weight of 2400

£sat.L1 AIonJ 2ttWeigh Determ&ak3tion. A 50 ML round but toia

flask wquiped with a magnetic stirrer. a condenser and a

drying tube was loaded with approximately Q 2 U ot

3-asidoosetano polymer, 5 mL of 1.2-dichloroethane. 2 mL of

l1,l.,3.3.3-hezamethyl~disilatane and D.S mL of

chiorotrimethylslane. Volatile materials were removed at

704C under vacuum. The residue was dissolved in I mL. 0 1

4 ~deuterochloroform and the proton NIIR spectrum was recorded.

The hydroxyl equivalent weight was calculated on the basis

of the &teas of the 83.3 signal (5 protons per monomer

unit) and the & 0 signal (9 protons per silozy group. The

same method was used for polymers with more* complex 14MM

spectra by using weighed mixtures of the stlylated polymer

* and a reference such as p-dichlorobenzene. The equivalent

weight was caloulated on the basis of the areas of the

reference and siloxy signals.

1. Thi, work was supported by the Office Of Naval

Researcoh.

2. Berkowitz, P. T.; Baum. K. 4 QLg. jýbn 1980. 4_ý

6 4853.

3. Berkowitz, P. T.; Baum, K. 4..LQ IQ~*.&k..4

45

- Apendis A

S~3826.

4. Woitowics, J.A.; Polak, R.J- J. Or . p973 38,

•- 2061.

S. Vojtowicz. J.A.; Polak, R.J.. Zavslowlcky, J.A. . _. QL.s.

VLtk-a It,•-. 3, 2232. Processing of 145 kg of allyl

&lcohol gave 435 g of 3-allylowyozetane

6. Emling, B.L.; Vogt, R.R.; Henion. C.F. J. frm. Ch..,

.-- .... •- . ,. •t1941, Al, 1624.

7. Knoevenagel, E. Ann &he. 1914, 402, 136

8. For a review see "Reagents for Organic Synthesis",

Yeser, L. F.; Fieser, M., John Wiley and Sons. Inc.: New

York, 1967; Vol 1, pp 256, 386.

9. Kluuura, Y.; Regmn, S.L. gJ Qtg.. g .. 19.. . 4_7. 2494,

and references therein.

10. Adiabatic compression tests performed by R. Reed and

fM.L. Chan (Naval Weapons Center, China Lake, CA) indicate

that the material tIs a sensitive explosive.

It. tungall, W.-S,; Greene, G.L.; Heavner. G.A.; Letsznoli.

R. L. 97. j.j.9..G 3. . . 4f, 1659

12. Berestn, G.M., U.S. Patent 3.449,369, 10 Jume. 1969;

Chem. katr .L. 1969. ._L, 38792.

13. Gilbert, K.E.; Borden, .T 3 QJ. £Js.a 1-9-7•?. qj.

14. Kaplan, R.B.; Scheoc ter, H. Am.. he. .Cihs 1961, V._,

3535.

15. Bedford, C.D.; Nielson. A T _j "r -a.-- - iv7 . !i,

2460.

46

Apeu•stz A

_... ----- t ---t t rltr,-ru- t. t r ---••n----- ------

,.-.

44

i4"

° -

-i ... . . . . OiSi.U... ...BUTIO. -tST_

No. Copies , C...

Or. L.V. Schmidt 1 Dr. F. Roberto 1

Assistant Secretary of the Navy Code AFRPL MKPA(RE, and S) Room SE 731 Edwards AFB, CA 93523

• PentagonPWshington, D.C. 20350 Dr. L.H. Caveny_ahn. Air Force Office of ScientificDr. .A.L. Slafkosky ResearchScientific Advisor Directorate of Aerospace SciencesCommandant of the Marine Corps Boiling Air Force BaseCode RD-i Washington, D.C. 20332Washington, D.C. 20380

Mr. Donald L. Ball IDr. Richard S. Miller 10 Air Force Office of ScientificOffice of Naval Research ResearchCode 473 Directorate of Chemical SciencesArlington, VA 22217 Bolling Air Force Base

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