.. . .... .

>-0... 0 c.,;)

'ECUI'IITY CLAISII'ICATION 01' THIS ~AGE (WII.., D.,o Ertloroll)

REPORT DOCUMENTATION PAGE READ UlSTRUCTIONS BEFORE COMPLETING FORM Z. OOVT ACCESSION NO. J. RECIPIENT'S CATALOG NUMBER

4. TITLE (Mil Sullllllo)

Nitrolysis of CN single bonds · and Chemistry of Nitro and Nitroso Groups.

7. AUTHOR(e)

Joseph H. Boyer

I . PEI"OIIIMING OIIIGANIZATION NAME AND ADDRESS

University of Illinois at Chicago Chicago, Illinois 60680 Box 4348

II. DIITRI8UTION STATEMENT (ollllfo ft ... )

I . TY~E 01' RE"'ORT I PERIOD COVERED

Feb. 1982 - Jan . . 1983 I . ~ERI'ORMING ORG. IIIEPORT N,UMBER

N00014-82-K-0210 NR 659-800

10. PROGRAM ELEMENT. PROJECT. T ASJ< AIIIEA I WORK UNIT NUMBERS

IZ. REPOIIIT DATE

March 1~83 II. NUMBEIII 01' PAGES

11. SECURITY C!.ASS. (ot IIIIo ,_,.orr)

Unclassified

lo. DECLASIII'ICATION DOWNGRADING I>:HEOULE

Reproduction in whOle pr in part is the United States Government.

permitted for any purpose of

Thb W..• aJPR)ftll for puWIIIII1 ... aM tale;· U. distriballoe II •ftpttzll.

17. DIITRI8UTION IT ATEMENT (ol lho ehllecl ottl-.4 In •lod JO, II •ttor_,l ,_ ltqort)

II. IU~~LEMENTARY NOTIEI

11. KEY 'IORt'l (Cor.l'-.., ,...., •• of• II rtocoeHIJ' -.4 '*""".,., ... ,_.or) Nitramines from tert-Amines. a-Substitution in Nitram~nes. Cyclic Nitronic-Carboxylic Acid Anhydrides. Nitroform and Isocyanides, Products !rom.

A

Nitro~yrroles, Peview o i . JO. A81TRACT (CMfl- M ,...., .. =-.. ~.-~~I;.;M:;,c~oo~o~_,~-.4~1::-::.,.~,::,~.,~.,~ ... ~~_..~~,:::-~----------------i A general procedure for the preparation of nitramines from ~amines was developed. The best procedure calls fvr an initial transformation of the tertiary amine into a nitrosamine followed by oxidation to the nitramine.

From tri-n-butyl amine and nitric and hydrochloric acids in acetic anhydride, di-n-butylnitrosamine was reproducibly obtained (60\). Other examples are discussed. Nitrosamines are routinely

DO~~=~~ 1Ql EDITION OP I NOV II II OMOL·T· SIN 0102-LF~I1._..01

MCU .. ITY CLAIIII'ICATION 01' THIS ~AGE,.,..., Dolo •"rorod.

•

UCW'SY CLAS"CAYIOW4 Of tMIS PAGE (Men Dase "94

20. Continued

oxidized to nitramines in nearly quanititative yields.

Conversion of a carboxyl into an amino group affordedl-nitro-2-aminopiperidine isolated as either its carbamate orurea derivative. This result has encouraged the exploration of'-e-aminonitramines (or selected derivatives) in synthesis of densefused ring systems (cage compounds).

2 Cyclic nitronic-carboxylic acid anhydrides is a thesis re-search area for a graduate student. A five membered and a six-membered (not confirmed) example have been prepared. An acylderivative of the former readily polymerized, as expected, byspontaneous ring opening. The work is continuing.

Sydnones are energetic compounds available from certainaryl isocyanides and nitroform- is new reaction was discoveredby an undergraduate research suen .A report for publicationis in preparation.

Arci' -,iiOt For

TAB F

Distribution1----f h,.i1Sblity codes

T. V CLA8IIPICAIIOW OF ?"IS PASGfW. 000 80#00

Nitrolys of CN Single Bo1ds and Chemistry

of Nitro and Nitroso Groups.

Progress gn ~ Projects.

I. Project Titles and Goals.

A. Nitramines from Tertiary Amines.

B. a-Substituents in Nitramines .

C. Cyclic Nitronic-Carboxylic Acid Anhydrides.

D. Products from Nitroform and Isocyanides.

E. Nitropyrroles.

II. Project Summaries (A-D).

III. Project Progress Reports.

A. Nitramines from Tertiary Amines.

B. a-Substituent& in Nitramines.

C. Cyclic-Nitronic-Carboxy1ic Acid Anhydrides.

· . D. Products from Nitroform and Isocyanides.

E. Nitropyrroles, a Review.

.. -

~

1

1

1

1

1

1

1

3

3

10

13

15

15

83 05 24 0 3 1

1

I. Project Titles and Goals.

A. Nitramines fro.m Tertian• Mines. Sparse information scat-

tered throughout the literature was to be organized and a general

procedure developed.

B. a-Substituents in Nitramines. An exploratory· survey of

functional group interchange at the a-position of nitramines was

undertaken.

c. Cyclic Nitronic-Carboxylic Acid Anhydrides. Nitro deri-.

vatives of five- and six-membered ring examples of these rarely

encountered molecules were sought for evaluation as monomers for

polymeric binders.

D. Products from Nitroform and Isocyanides. Further inves-

tigation on a recently discovered reaction was proposed to evalu-

ate the potential preparation of energetic materials, e.g.,

nitromesoionic heterocycles.

E. Nitrogyrroles. A thorough revi ew of the literature on

nitropyrroles was undertaken.

II. Project Summaries.

A. Nitramines from Tertiary Amines. The nitronium cation

converted tertiary amines ~ to nitrosamine& ~ which were oxidized

to nitramines ~. Certain exceptional examples directly gave

nitramines ~ rather than nitrosamine& i• these correlated with

the dissociation of a stable carbonium ion, e.g., R3t, rather . than an elimination of nitrous acid from an intermediate quater-

nary nitrammonium ion ~. The reactions are discussed and

examples given.

8 3 0 ~ 2 - 0 ~~

2

N02+ + - HNO2 +R2NCH2 R , R2NCH2R - R2 N-CHR

2A

HONO- [013 RHO R2NNO - R2NNO2- RCH

4. 5.

R2N-CR3 - R2NNO2 + R3C+

NO22J2

B. a-Substituents in Nitramines. a-Pipecolinic acid a was

converted to 1-nitro-2-piperideine 2. via the isolated intermedi-

ates: 1-nitropiperidine-2-carboxylic acid ib, azide fi, 1-nitro-

piperidine-2-isocyanate d, and methyl 1-nitropiperidine-2-car-

bamate.

A B

La C02H H

A 12 C02H N0

a CON3 N02

d NCO NO2 NO2

a a NHCO2CH3 NO2 I

C. Cyclic Nitronic-Carboxylic Acid Anhydrides. The anhy-

drides I and I have been prepared. The latter and its easily

obtained polymer 10, a liquid, have the calculated density of

1.9.

.i

3

O:.N/ O 0 2,7 N0 0 N NO0.

CH O): =0 O- CO- "O'N NO2 j x

D. Products from Nitroform and Isocyanides. From aryl iso-

cyanides U1 and nitroform 12 sydnones 11, related aromatic

amines, and unknown products were obtained.

ArN -CHARNC HC(N02)3 / \N ,C-0O

11

III. Project Progress Report-.

A. Nitramines from tertiary amman.

1. Introduction. An efficient conversion of a tertiary

aliphatic amine I to a dialkylnitrosamine J by treatment with

nitric acid has been elucidated and developed. When followed by

4 any of the several known oxidations of nitrosamines an additional

route to nitramines I became available.

R2NCH2R R2NNO R2NNO2I 1. 5.2. lkgr.IUl4. Prior to this work there were scattered

reports of tertiary amine conversions to nitramines with nitroly-

sis of hexamethylene tetramine to RDX and HMX being the best

______________Mt r, i

4

known example.1-3 In the generally accepted explanation for this

reaction of a gza-diamine jj a combination with a nitronium

cation to give initially an N-nitroammonium cation 15 was

proposed.4 A dissociation then afforded a nitramine I and an

a-aminocarbenium cation ii. Stability of the cation 1i favored

this dissociation over other conceivable fates of the cation 15.

* ii ~2NCH2NR 2 + o Rs2H2

+15. R2NCH2 + A

Attempts to extend the nitrolysis reaction to other tertiary

amines met with minimal success2 except for certain isolated

examples,3 each of which depended on the breakdown of a nitrammo-

nium cation into a stable carbenium cation. This was recently

demonstrated in the nitrolysis of dimethyl tzert-butyl amine 12 to

dimethyl nitramine 5. (R - C93 ).5 The simultaneous formation of a

trace amount of tkzl-butylmethylnitrosamine 11 furnished a clue

for an important alternative breakdown of the nitrammonium cation

15. This competitive reaction has afforded a general method for

the conversion of a tertiary aliphatic amine to a dialkylnitros-

amine.

0 - 4 I CR- CH3) + (CH3)3C+

(CH3)2NC(CH3)3 C S3C

)2 0 L5 %C 3 13

ltrace

A proposed elimination of nitrous acid from a nitramsonium

JJ

.. .

U- -

~5

cation 2a is analogous to the similar elimination of nitroxyl

from nitrosamnonium cation intermediates 19 in the conversion of

tertiary aliphatic amines to dialkylnitrosamines by nitrous

acid . 6

N 2 + +R2 NCH2R - 2N-CHR + HN02

' 2AN00

-- R2NCH2R - 31+ NOHI

NO

There is also a similarity with an elimination of nitrous

acid from an o-nitrosohydroxylammonium cation intermediate 2& in

the conversion of a tertiary amine oxide 21 to a nitrosamine £ by

treatment with a nitrosating agent.7

+ N+0+2NC 2R - R2 NCH2 R - 1 + ONO

I I0- ONO

21 2A

In each of these last three reactions the intermediate immo-

nium cation I combined with nitrous acid (or other nitrosating

agent, if present) to produce a nitrosamine IL and a carbonyl com-

pound via a proposed nitrite ester 21.

- 3+I+ B030 0--- R29-CER +44 RCHO

03-0~21

*Pi7 ~ ~ - ~~c-

6

3. Results. Initial development of this preparative

method for nitrosamines was brought about by investigating

N,N-dimethylbenzyl amine 2,8 NN-dimethyldibenzyl amine 24,8

triethyl amine 2,8 and tri-n-butylamine 21.8

C6H5CH2N(CH3 )2 C6HsCH2CH2N(CH3)2 (C6H5CH2)2NCH3

23 2A

(C2u5 )3N (CH3CH2CH2CH2)3N

21 Z

Nitronium tetrafluoroborate either in various organic sol-

vents or in concentrated sulfuric acid efficiently nitrated the

aromatic rings in amines 22 and 21.10 From the reaction of 23 in

sulfolane a trace of dimethylnitramine 5 (R = CH3) was also

detected. As expected, ring nitration was also brought about by

a mixture of concentrated nitric and sulfuric acids and by a mix-

ture of nitric and perchloric acids.

A mixture of the amine 22, nitric and hydrochloric acids in

acetic anhydridell brought about the formation of benzylmethylni-

trosamine 22 and benzaldehyde 21. It was presumed that unde-

tected formaldehyde accompanied the formation of product 22 and

that undetected dimethylnitrosamine j (R - CH3) accompanied the

formation of product 2A. A redox reaction between nitric and

hydrochloric acids 12 produced dinitrogen trioxide, a nitrosating

agent for the intermediate formation of the nitrite ester 21.

Acetyl nitrate13 and nitrite1 4 were probably presentp however,

their contribution to product formations was not determined.

- 777

7700 HNO 3 (2 ms1)70 3 (2o) C6 SCB2NCB 3 + [CB 201 + 2£

SCI (3 -ol) 1(CB3CO)20 (10 nol) NO 36%15 m at 500 , 16 h at 250 2

100% BN0l3 (2 ms1)e00ess d O l ) 2 + + [CH20 + (CH3 )2NNO]excess dry Dcl gas(CH3CO)20 (10 Mol) 26% 2&16 h at 250 69%

2 HCi + 2 DNO3 + 3 (C 3C0)2 O 2 CH3COC1 + N203 + 4 CH3CO2H

CD3COCl + H203 .- CH3CO2NO + NOC1A similar treatment converted dibenzyl methyl amine 2. to

the nitrosamine 22 and benzaldehyde 28. Diethyl nitrosamine I. (R

- C2R5) was obtained from triethyl amine 25.

90% HNO 3 (2 mol)24 ..... ... 21+21CI (3 mol)(CH3CO)20 (10 mol) 64% 34%50 h at 250

70% HU 3 (2 mol)z 25 ... . A (R- C2 H5 )iHC1 (3 mol)(CH3CO)20 (10 mol) 32%0.5 h at 500, 16 h at 250

* Tri-n-butylamine 2i was converted to di-n-butylnitrosamime I

(R - CH3CH2CH2CH2 ) in 62% yield by similar treatment with nitric

and hydrochloric acids in acetic anhydride. On repeating thereaction without hydrochloric acid the yield was 47%. In the

latter example the presence of the nitrosating agent depended on

the breakdown of the intermediate nitraumonium cation 2a.

8

70% NO3 (2 m)21 . . .... 0 (nt-C4H9)2NNOSCI (3 m)(CB3CO)2 (10 m) 62%

0.5 h at 500, 16 h at 250

100% HNO 3 (3 m)2A " (n-C49I9)2NNO

(CH3 CO)2 0 (10 a) 47%

A-i. G.F. Wright, "Methods of Formation of the Nitramino Group

and its Properties and Reactions," in "The Chemistry of the

Nitro and Nitroso Groups," ed. H. Feuer, in "The Chemistry

of Functional Groups," series ed. S. Patai, J. Wiley, New

York, 1969, pp 613-684.

A-2. W.P. Norris, J. Org. Chem., 1960, 21, 1244.

A-3. O.A. Luk'yanov, N.M. Seregina, and V.A. Tartakovskii, Izv.

Akad. Nauk SSSR, Ser. Khim., 1976, 2251 Chem. Abstr., 1976,

84, 135574w.

A-4. Ref 1, pp 653, 654.

A-5. D.A. Cichra and H.G. Adolph, J. Org. Chem., 1982, 4l 2474.

From the amine Z hydrochloride the nitramine a (R - CH 3 )

(55%) was obtained.

A-6. W. Lijinsky, L.Keefer, E. Conrad, and R. Van de Bogart, J.

Nat. Cancer Inst., 1972, A9, 1239.

A-7. P.A.8. Smith and R.N. Loeppky, J. Amer. Chem. Soc., 1967,

.t7....__H__...... ..___________"_____________________"___.......______

9

llr 1147.

A-8. Aldrich Chem. Co.

A-9. Organic Syntheses, III, 723.

A-10. J.H. Boyer, V.T. Ramakrishnan, T.P. Pillai and c.-B. Huang,

Final Report April 1, 1979 to March 31, 1982 on Contract

No. 0014-79-C-0353 to ONR.

. A-11 . Triethyl and· tri-n-butylamines were converted to corres-

ponding dialkylni trosamines by this mixture of nitric and

hydrochloric acids in ac~tic anhydride (Y. Ogata, Y.

Sawaki, andY. Kuriyama, Tetrahedron, 1968, 1425).

A-12. Ref. 1, p 634.

A-13. Acetyl nitrate was produced in aitY from acetic anhydride

and nittic acid as reported by F.G. Bordwell and E.W. Gar-

bisch, J . Am. Chem. Soc., 1960, 11, 3588.

A- 4. Ace~yl nitrite from silver aceta te and nitrosyl chloride

was recently reported (A.B. Kyte, R. Jones-Parry, and D.

Whitt&ker, J. Chem. Soc. Chem. Commun., 1982, 74). Nitrite

was detected in a preparation of acetyl nitrate from dini-

trogen pentoxide and acetic anhydride (A.R. Cooksey, K.J.

Morgan, and D.P. Morrey, Tetrahedron, 1970, 1i, 5101 •

•

10

B. a-substituent in Nitraminea. Except for aam>dinitramines

11,1 the chemnistry of a-functional groups in nitramines is

underdeveloped. A few examples e.g. ~,1 described a nitramine . . with a t&xt-amino group attached to a primary a-carbon atom, how-

ever, with a ~-amino group an example was unstable on libera-

tion from its nitrate salt ll,l and an a-primary aminonitramine

l1 has not been reported.

+---CB-N I I

CB3NCB2N(CB2CB2)2NCB2NCH3 I I

R N02 x

11 ~

02NN NN02

lN) I ·HN03 H ll

~2 ~2

~

R-N---CBR' I I N02 NH2

l1

There are a few examples of nitramines with a-functions.

a-Bydroxynitramines (unstable) and a-alkoxynitramines have been

interconverted,l a-cyano,l a-chloro,2,3 a-fluoro,3 a-azido,3

a-pyrazolo,3 and a-nitraminoacids4 have been reported.

When it ?ecame desirable to extend amine-carbonyl condensa-

tion to a-aminonitramines the initial problem of their prepara-

tion had to be solved. We have investigated a standard sequence

of converting a carboxyl group to an amino group as is shown for

the conversion of 1-nitropiperidine-2-carboxylic acid 6h to 1-ni-, tro-2-aminopiperidine if isolated as the methyl carbamate deriva-

tive i& (R • CB3). Yields are shown for each conversion • .

11

1. NSo + N C0H Cl0.2H

C 1 CO2H I 2 NiCONs.2. [0] NO 2 2. NaN3 I70% 75% N02

60% 75%

80CH 3OH(:: -NNO2 ' - N

1N2 65%100%

Compounds fic~d. represent the first examples of nitramines

with a-azidocarbonyl, a-isocyanato, and a-alkoxycarbonylamino

functions.

An initial attempt to liberate the free amine if from its

carbamate fi (R - CH3 ) under anhydrous conditions5 gave instead

the olefin 2 apparently by a spontaneous deamination of the amine

fil. NH2

(CH3 )3Si I iOC3fi .__ - , ) NNO2

R - CH3 - CH3I R - (CH3 )3Si - (CH3 )3 SiOCH3

ii4

-NH 3 ,,6f -. * 2

Investigations are continuing.Attempts to achieve a-functionalization in a secondary

4nitramine ((RCH 2 )2 NN02 ) by metal interchange reactions failedwhen a-metallation could not be brought about.6

. .. . , , _ . . .. ., • . ." .

12

References

B-1. Ref A-1.

B-2. I.J. Shishkov, N.L Sadova, L.V. V~lkov, and V.P. Ivshin, Zh.

Strukt. Khim., 1982, 11, 73t Cl.em. Abstr. 1982, 11, 215453p.

B-3. B. Unterhalt and F. Lieblein, Arch. Pharm., 1979, 112, 159.

B-4. B.T. Nagasawa, W.P. Muldoon, and F.N. Shirota, J. Med.

Chem., 1977, ~' 1588.

B-5. Th~s two step procedure with trimethylsilyl iodide followed

by methanolysis has been reported: H.-J. Altenbach, B.

Blech, J.A. Marco, and E. Vogel, Angew. Chern. Int. Ed.

Engl., 1982, 21, 778.

B-6. D. Siebach and D. ENders, Angew. Chern •• Internat. Edit.

Engl., 1975, 1!, 15.

13

C. Cyclic Nitronic-Carboxylic Acid Anhydrides. Ring-opening

polymerization has many practical applications, e.g., the conver-

sion of caprolactam to nylon. A facile ring-opening polymeriza-

tion of an isoxazolone-N-oxide was first encountered by Russian

workers in attempts to transform derivatives of 2-nitro-3-hydrox-

ybenzoic acid U3 into actinomycin analogs.1 Dehydration con-

verted the acid U3 to an isoxazolone-N-oxide U5 which thermally.

polymerized readily at ambient temperatures. Our investigations

on similar converstions of 2t4#6-trinitro-3-hydroxybenzoic acid

3A to I are continuing.

R R" R R.R'

RN=C-NRHO C=O

NO2 -----(RNH)2C--O

33 R - CH3 , R' - H R = CH3, R' =HU R - R' N02

At0 C

L No, j

A review of the dehydration of 1-nitronaphthyl-2-acetic acid

31 is underway. A product U was reported in 1918.2 We antici-

pate the collection of data to permit reassignment of the com-

pound as an ozazinone-N-oxide A.

7

14

N02 <~Q1 J~fCH2CO2H 6f~C 2H

C-1. 3.V. Toukermang E.N. Glibin, and O.P. Ginzburg, Zhi. Org.

Khim., 1982, lA 1721.

C-2. F. Mayer and T, Oppenheimer, Ber., 1918, .1,510.

15

D'. Producta from Nitroforn and Isocyanides. The project

initiated by an undergraduate has been investigated further by

Dr. Pillai.

In addition to the sydnone 11 '(Ar - -P-02NC6 85) the reaction

between p-nitrophenyl isocyanide and nitroform also produced

P-nitroaniline ..

AriLC HC(N02)3 pON 6 1 H

Ar - -P-02NC6 H4 A

The similar reaction with p-tolyl isocyanide gave,-the syd-

none U (Ar - P-li3CC6H5) (needs to be confirmed) and 2-ni-

tro-4-methylanil inc.NH

HAE C(N02)3 _ +O

Ar - pR-H3CC6H5CH3

E. Nitropyrroles. A draft of the review will be published

by Verlag Chemie International by arrangement with Professor

Henry Feuer# ed., Purdue University. A copy is available on

request.

. ..

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Mr. B. Sobers 1. Mr. John Boyle INaval Air Systems Command Materials BranchCode 350 Naval Ship Engineering CenterWashington, DC 20360 Philadelphia, PA 19112

Dr. L. R. Rothstein 1 Mr. J. MurrlnAssistant Director Naval Sea Systems CommandNaval Explosives Dev. Code 62R2Engineering Dept. Washington, DC 20362Naval Weapons StationYorktown, VA 23691 Dr. D. R. Derr

Naval Weapons CenterDr. Lionel Dickinson 1 Code 388Naval Explosive Ordnance China Lake, CA 93555Disposal Tech. CenterCode D Mr. Lee N. GilbertIndian Head, MD 20640 Naval Weapons Center

Code 3205Mr. C. L. Adams 1 China Lake, CA 93555Naval Ordnance StationCode Pt44 Dr. E. MartinIndian Head, MD 20640 Naval Weapons Center

Code 3858Mr. S. Mitchell I China Lake, CA 93555Naval Ordnance StationCode 5253 Mr. R. McCartenIndian Head, MD 20640 Naval Weapons Center

Code 3272Dr. William Tolles I China Lake, CA 93555Dean of ResearchNaval Postgraduate School Dr. A. NielsenMonterey, CA 93940 Naval Weapons Center

Code 385Naval Research Laboratory 1 China Lake, CA 93555Code 6100Washington, DC 20375 Dr. R. Reed, Jr.

Naval Weapons CenterDr. J. Schnur 1 Code 388Naval Research Laboratory China Lake, CA 93555Code 6510Washington, DC 20375 Dr. L. Smith

Naval Weapons CenterMr. R. Beauregard 1 Code 3205Naval Sea Systems Command China Lake, CA 93555SEA 64EWashington, DC 20362 Dr. B. Douda

Naval Weapons Support CenterMr. G. Edwards I Code 5042Naval Sea Systems Command Crane, Indiana 47522

4 Code 62R3Washington, DC 20362

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No. Cogies No. CopiesDr. T. Sinden 1 Professor J. C. ChienMunitions Directorate University of MassachusettsPropellants and Explosives Department of ChemistryDefence Equipment Staff Amherst, MA 03003British Embassy3100 Massachusetts Ave. Professor Richard A. Reinhardt IWashington, DC 20008 Naval Postgraduate School

Physics and Chemistry DepartmentCaptain S. Shackelford 1 Monterey, CA 93940AFRPL/LKLREdwards AFB, CA 93523 Dr. J. Karle

Naval Research LaboratoryDr. Merrill K. King 1 Code 6030Atlantic Research Corporation Washington, DC 203755390 Cherokee AvenueAlexandria, VA 22314 Dr. R. Atkins

Naval Weapons CenterDr. W. Wharton 1 Code 3852Army Missile Command China Lake, CA 93555DRSMI-RKRedstone Arsenal, AL 35898 Dr. May L. Chan

Naval Weapons CenterDr. David C. Sayles 1 Code 3244Ballistic Missile Defense China Lake, CA 93555

Advanced Technology CenterP.O. Box 1500 Dr. T. B. JoynerHuntsville, AL 35807 Naval Weapons Center

Code 3264Dr. Kurt Baum 1 China Lake, CA 93555Fluorochem, Inc.680 South Ayon Avenue Dr. R. A. RheinAzusa, CA 91702 Naval Weapons Center

Code 3244Professor J. H. Boyer 1 China Lake, CA 93555University of IllinoisDepartment of Chemistry Dr. B. David HalpernBox 4348 Polysciences, Inc.Chicago, IL 60680 Paul Valley Industrial Park~Warnington, PA 18976Dr. Joyce J. Kaufman

1

The Johns Hopkins University Dr. Karl 0. ChristeDepartment of Chemistry Rockwell InternationalBaltimore, MD 21218 6633 Canoga Avenue

, Canoga Park, CA 91304SDr. C. Coon1

Lawrence Livermore Laboratory Dr. M. B. FrankelUniversity of California Rockwell InternationalP.O. Box 808 Rocketdyne DivisionLivermore, CA 94550 6633 Canoga Avenue

Canoga Park, CA 91304

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No. Copies No. CopiesMr. M. Baron

Dr. 0. L. Ross SP 27314SRI International333 Ravenswood Avenue •Strategic Systems Project OfficeMenlo Park, CA 94025 Department of the Navy

Washington, DC 20376

Mr. Ed van Rlbbink 1Space Ordnance Systems25977 San Canyon RoadCanyon Country, CA 91351

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