03/15/2006 16:18 FAX 614 232 1685 Department of Chemist 1a004/005

REPORT DOCUMENTATION PAGE R06 0 0 8 8PvubliC r= njorting bUr•n tor Va oowectioo of hrfor'ma([tron7 arned a 0 av= ' 1 hour pe1 mapono ,ckJ Iha Irma t rIvg-i =dI• ngl~. Bn cm pl!rig retewn g nw mur CIh .llecticrl O led'Ctmaio.C. Sn oummuarwa rug ldag ma ci Q4Jr ~n ia~nQ or all OII •dais budn (W. Deauml O1a"5d laer 5e , Dn oeta rt lfor ml0i Otpatio n mid Repomia 70704-, - --. 1Z-41O0.. zondarft xhcijd 49 ww tham t 110 M1 noteUlandh any ~1f eo'ovidioi 6f law, no penman shan be 3utrjeda joany paflway or Qalii I omvalid OM8 control number. PLEASE DO NOT RErURN YOUR FORM TO THE ABOVE ADDRIES$. Or________ompy____a_____

1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To)March 8, 2006 Two Visual Summary Reports -Jan,1 2001 - June 30, 2005

4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER

Syntheses of 1,2,3,4-Tetrazines, 1,2,3,4-Tetrazine Di-N-oxides, Sb. GRANT NUMBERPentazole Derivatives, Pentazine Poly-N-oxides, and FA 9550-04-1-0410Nitroacetylenes Sc. PROGRAM ELEMENT NUMBER

6. AUTHOR(S) 5d. PROJECT NUMBER146566

H. Shechter, M. Venugopal, and D. Srinivasulu T. !ASK NUMBER

St. WORK UNIT NUMBER

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORTNUMBER

The Ohio State University Research Foundation1960 Kenny RoadColumbus, OH 43210

9. SPONSORING I MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORIMONITOR'S ACRONYM(S)

USAF, AFRL 1p. l4t 6 • "emtri/l./,.---. DARPA/AFOSRAPOSR MJ , 76 - -77kl 11. SPONSOR/MONITOR'S REPORT4015 Wilson Blvd., Room 317 NUMBER(S)Arlington, VA 22203-1954

12. DISTRIBUTION I AVAILABILITY STATEMENT

Publication by C. J. Woltermann and H. Shechter, He/v. Chim. Acta, 2005, 88, 354.

13- SUPPLEMENTARY NOTES

14. ABSTRACT

Study has been initiated of practical synthesis and the chemistry of 1) 1,2,3,4-tetrazines and theirproducts, 2) 5,6-disubstituted-!,2,3,4-tetrazine 1,3-di-N-oxides, 5,6-diketo-1,2,3,4-tetrazine 1,3-di-N-oxide andits derivatives, isomeric 1,2,3,4,5,6,7,8-octazanaphthalene tetroxides (DTTO and IsoDTIO), various substitutedbenzotetrazi ne 1,3-di -N-oxides and their transformations, isomeric furoxanotetrazine 1 ;3-di-N-oxides,furazanotetrazine 1,3-di-N-oxide, (FTDO), 5,6-(1,2,3-triazolo)-l,2,3,4-tetrazine 1,3-di-N-oxides, and various I-nitroacetylenes and dinitroacetylenes and their respective precursors and derivatives. The various syntheticroutes studied have been illustrated and discussed in part. Further studies of the above high-energy materialsare proposed.

IS. SUBJECT TERMS

16. SECURITY CLASSIFICATION OF: 17- UMITATION 18. NUMBER 19a. NAME OF RESPONSIBLE PERSONOF ABSTRACT OF PAGES 1-1. Shechter

a. REPORT b. ABSTRACT c. THIS PAGE 19b. TELEPHONE NUMBER (incrude areacode)

614-292-6300Standard Form 298 (Rev. 8-98)Prw.Aclbed by ANSI Std. Zns.1a

.01

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Stabilized N-Oxides

O" Very few chemistsknow that thismolecule, N60 3, will go

N*N through a massN ÷ N N ÷ N spectrometer! This11 1 + 1 + molecule is a trimer of

N N N. N nitrous oxide, N20!N -o= Ounstable life: < 1 sec

Many chemists in the Can N20 be polymerized1940s tried to prepare or copolymerized?N6, a benzene analog. 0M This tetrazine N-oxide

This molecule has melts at 72-74 °C andnot been genera- N can be "kept" for 6-7ted previously at N* N hours beforelow temperature. N decomposition toCan it be prepared benzofurazan uponand used? All prep dloss of N u!efforts at OSU toprepare thismolecule at temp- unstable preparableeratures as low as-112 TC have been This molecule undergoes rapidunsuccessful! loss of nitrogen to given benzyne!Physical chemists O M W The Zelinsky chemistsshould study this I have been studyingmolecule or its + this molecule, BTDO,bis-diazo isomer N N since 1984. Over 36in matrix. Is the Russians have beentetrazine ring open ' N N studying this molecule!or closed? 1+

1 0 Mstable,

unstable usableThis tetrazine dioxide loses N2 to This molecule is stable, is now readilyform o-dinitrosobenzene. No one prepared, and melts at 172-174 TC.has examined this molecule at low OSU has improved synthesis oftemperatures. BTDO! A practical molecule!

3

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Synthesis and determination of the utility of DTlO and IsoDTJO are of major interest at OSU (Dr. M. Venugopal)and in Moscow. This project at OSU will require additional funding. The structures of DTTO and IsoD7TO areillustrated and discussed below.

"0 0" 0 01+ +1I 1 1+1 /+ +IN I1+

NN N N +N .JJ""o - 0o

DTTO Note the alternating positive and negative(the more energetic isomer!) charges! DTTO and JsoDTTO will have

very high densities.

0" 0

1 + Q11+N N_

N 4 N "O N N"NO

I 0w 11 - 0-o 0IsoDTTO

This overhead illustrates the ultimate APNC characters of DTTO and IsoDTTO. Tartakovsky emphasized theMenkin concept in his West Coast seminar in 1995! Will these molecules ever be practical? We should makedetermined efforts to learn where the Russians and the Chinese are in syntheses of DTTO and IsoDTTO. Thisresearch effort at OSU will require further support and commitment. Foreign academic post-doctoralresearchers need long-term academic support in order to obtain visa stays in the US. It has not beenappreciated how emotionally difficult it is for a young researcher in the US to work in an area in which we areso far behind that in Russia.

6

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Compounds 1, 2, and 3 have been synthesized in Moscow. They are stable molecules. Preparation of 5 is

being attempted by Zelinsky chemists. As yet, no simple 1,2,3,4-tetrazine 1,3-di-N-oxide has been reported!

Such syntheses have been the main objectives of research by OSUIDARPA/Air Force investigators. 10

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