Synthesis of Ethyl 5-tetrazolyldinitroacetate as a Key ......tetrazole derivatives 100 200 300 400...

Synthesis of Ethyl 5Synthesis of Ethyl 5--tetrazolyldinitroacetate tetrazolyldinitroacetate as a Key Intermediate for as a Key Intermediate for 55--Dinitromethyltetrazole or Dinitromethyltetrazole or

55--DinitromethylideneDinitromethylidene--1,41,4--dihydrotetrazoledihydrotetrazole

Defense Acquisition Program Administration

Kyoo-Hyun Chung,* Choong Hwan Lim,* Jin Rai Cho†

* High Energy Material Research Center, Department of Chemistry, Inha

University† Agency for Defense Development

Agency for Defense Development

1

Agency for Defense DevelopmentAgency for Defense Development

High Energy Material High Energy Material

Some molecular explosivesSome molecular explosives

2

NNNN

N N NO2O2N

O2NO2N NO2NO2

HNIW

N

N N

NO2N

NO2

NO2

O2N

CH3O2N NO2

NO2

N N

NNO2

O2N NO2

TNT RDX HMX

N

NO2O2N

NO2

NH4+NNO2

NO2

ADN

N

N N

NO2N

NO2

NO2

O2N

bicyclo-HMX

NO2

NO2O2N

O2NO2N NO2

NO2

NO2

NO2O2N

O2NO2N NO2

NO2O2N

ONC

O2NOH2C CH2ONO2O2NOH2C CH2ONO2

TNAZ

. -

HpNC

PETN



50Pcj

(Gpa)15 20 25 30 35 40 45

10

100

HNS

TNT

RDXHMX

CI

-

20

NTO

TATB

10500Detonation velocity (

m

/sec)6500 7500 8500 9500

10

100

HNS

TNT

RDXHMX

CI

-

20

NTO

TATB

Impact sensitivity Impact sensitivity vsvs Detonation propertiesDetonation properties

3



Insensitive explosives Insensitive explosives

OOOO

N N NO2O2N

TOIW

N

NH

N

HN

O2N

NO2

O O

HN

NHN

O

NO2

NTO

NH2O2N NO2

NO2

NH2H2N

TATB

DINGU

CH3O2N NO2

NO2TNT

H2N

H2N NO2

NO2

FOX-7

4



Related compounds to FOXRelated compounds to FOX--77

H2N

H2N NO2

NO2

NH

HN NO2

NO2 NH

HN

O

O

NO2

NO2

H2N

H2NHN NO2

NO2

N

NNH

HN NO2

NO2

N

NN

N NO2

NO2

FOX-7

5



Synthesis of Synthesis of 55--dinitromethyltetrazole (I)dinitromethyltetrazole (I)

6

NN N

H

HN NO2

NO2

NN N

H

NNO2

H

NO2

+ NaN3NC NO2NO2

NO2

CH3CO2H

-35oCNN N

H

NNO2

NO2

NO2 NN N

NNO2

NO2

NO2

(n-Bu)4N

Shastin, A. V.; Godovikova, T. I.; Korsunshii, B. L. J. Heterocyclic Chem., 1998, 34, 383.

(n-Bu)4NBr

NC NO2NO2

Na+ NaN3

H2O NN N

H

NNO2

H

NO2

8~12%

Einberg, F. J. Org. Chem., 1964, 29, 2021-2024.

+ (CH3)3SiN3NN N

H

NNO2

NO2

NO2

quantitative

NC NO2NO2

NO2

CCl4

Grakauskas, V.; Albert, A. N. J. Heterocyclic Chem., 1981, 18, 1477-1479.



Synthesis of Synthesis of 55--dinitromethyltetrazole (Il)dinitromethyltetrazole (Il)

NN N

NNO2

NO2

NO2

NH4

NH2OH NN N

N

NO2

NO2

KK

Dipotassium salt

50% H2SO4 NN N

H

NNO2

H

NO2

86%

Terpigorev, A. N.; Tselinskii, I. V.; Makarevich, A. V.; Frolova, G. M.; Mel'nikov, A. A. J. Org. Chem., USSR, 1987, 23, 214-222.

NN N

H

NNO2

H

NO2

Einberg, F. J. Org. Chem., 1964, 29, 2021-2024.

NN N

N

NO2

NO2

Na

Na NN N

H

N

NO2

NO2

Na

NN N

H

N

NO2

NO2NH4

NN N

H

N

NO2

NO2

NaH2N

H2NHN

NO2

NO2 NaNO2AcOH, H2O

�Katritzky, A. R.; Sommen, G. L.; Gromova, A. V.; Witek, R. M.; Steel, P. J.; Damavarapu, R. Chem. Heterocycl. Comp. 2005, 41, 111.

+

KOH

H2N

H2N

NO2

NO2 H2NNH2

7



RetrosyntheticRetrosynthetic analysis of analysis of 55--dinitromethylidenedinitromethylidene--1,41,4--dihydrotetrazoledihydrotetrazole

8

NN N

H

HN NO2

NO2

NN N

H

NNO2

H

NO2

NN N

H

NNO2

CO2Et

NO2NC NO2

NO2

CO2Et

NN N

H

N

CO2Et

N OH NN N

H

N

CO2Et

NCCO2Et

NN N

H

N

CO2Et

NO2

NN N

H

NCH3



Latypov, N. V. ; Bergman, J.; Langlet, A.; Wellmar, U.; Bemm, U. Tetrahedron, 1998, 54, 11525.

Astrat'ev, A. A.; Dashko, D. V.; Mershin, A. Y.; Stepanov, A. I.; Urazgil'deev, N.Russian J. Org. Chem., 2001, 37(5), 729.

Synthesis of Synthesis of dinitromethylidenedinitromethylidene from methylfrom methyl

N

NNH

NN

NNH

HN NO2

NO2

HNO3H2SO4

9

NH

N

O

O

NH

NH

O

O

NO2

NO2O2N

O2N

HNO3H2SO4

FOX-7

NH

N

NH

HN

O

O

NO2

NO2

FOX-7HNO3H2SO4



Synthesis of Synthesis of oximeoxime 55-- dinitromethyltetrazolylacetatedinitromethyltetrazolylacetate

H2SO4

HNO3

NN N

H

N

CO2Et

NO2

NN N

H

N

CO2Et

N OH

NN N

H

N

CO2Et

HON CO2Et

CN

Terpigorev, A. N.; Tselinskii, I. V.;Malsarevich,A. V.; Frolova, G. M.; Mel'nikov, A. A. J. Org. Chem., USSR, 1987, 23, 214-222.

NaN3

H3PO4

NaNO2

Lunn, W. H. W.; Schoepp, D. D.; Calligaro, D. O.; Vasileff, R. T.; Heinz, L. J.; Salhoff, C. R.; O'malley, P. J. J. Med. Chem., 1992, 35, 4608-4612.

10



NN N

H

NNO2

CO2Et

NO2NN N

H

N

CO2Et

H2SO4

HNO3

NN N

N

NO2

NO2

KK

NN N

H

NNO2

H

NO2 NN N

H

N

NO2

NO2

K

KOH 1.1eqKOH

NN N

H

N

NO2

NO2

NH4

H2O aq.NH3

Synthesis of Synthesis of 55--dinitromethyltetrazole and its saltsdinitromethyltetrazole and its salts

NN N

H

N

CO2Et

NO2NN N

H

N

CO2Et

NO2NO2

oxidative

nitration

11



TautomerismTautomerism of of tetrazoletetrazole--tetrazolinetetrazoline

NN N

NOH

NN N

H

HN

O

=S

NN N

HN CN

CO2MePh

�Butler, R. N. Comp. Heterocycl. Chem., 1st edn 1984, 5, 791.

�Saalfrank, R. W.; Fischer, M.; Wirth, U.; Zimmermann, H. Angew. Chem., Int. Ed. Engl. 1987, 26, 1218.

HSH

NN N

H

HN NO2

NO2

NN N

H

NNO2

H

NO2?

12



NONO22 stretchingstretching

NN N

H

NNO2

CO2Et

NO2

NO2 NO2 NO2

NO2 NO2NO21558(asym)1368(sym)

1587(asym)1337(sym)

1595(asym)1304(sym)

1593

H2N

H2N NO2

NO2 NH

HN NO2

NO2

NN N

H

N

CO2Et1394

1524 15651500

NO2 15271353

13



IR of ETDNAIR of ETDNA

NN NH

NO2N NO2

O

O

ETDNA

14



IR of TDNMIR of TDNM

NN NH

NO2N NO2

TDNM

15



UV absorption in UV absorption in MeOHMeOH

16

Me2N

Me2N NO2

NO2 NH

HN NO2

NO2

264, 302, 340 280, 295, 330

NH

HN NO2

NO2240, 320, 335

NN N

N NO2

NO2--

2K+ 362 (in water)



UVUV--Vis of Vis of tetrazoletetrazole derivativesderivatives

100 200 300 400 500 600 700 800 900 1000-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0in

tens

ity

wavelength (nm)

ETA ETDNA DPS TDNM

17



1.4101.211

1.469

1.211

1.3141.410

1.3321.339

1.230

1.340

1.336

1.256

1.3171.329

1.288

1.486

1.5521.285

1.4871.337

1.247

1.3421.312

1.291

E=-701.43353 H E=-702.70106 H (0.0 kcal/

mol)

E=-702.69985 H(0.75 kcal/

mol) E=-702.57955 H (76.24 kcal/

mol)

RHF/6RHF/6--31G(d) calculations31G(d) calculations

18



1.3541.358

1.272

1.358

1.354 1.410

E=-705.24311 H E=-706.54601 H(0.00 kcal/

mol)

E=-706.53978 H(3.90 kcal/

mol)E=-706.44411 H(63.94 kcal/

mol)

B3LYP/6B3LYP/6--31G(d) calculations31G(d) calculations

1.477

1.3211.357

1.299

1.342

1.347

1.5971.286

1.361

1.286

1.3681.331

1.4831.321

1.222

1.4101.211

1.469

1.211

1.314

1.4261.222

1.693 1.426 1.340

1.222

19



Energy difference of Energy difference of tautomerstautomers

a) RHF/6-31G(d) calculation ΔE=0.75 kcal/molb) B3LYP/6-31G(d) calculation ΔE=3.90 kcal/mol

N

N N

N N

N

OO

OO

20

N

N N

N N

N

OO

OO

H

H

N

N N

N

H

H

N

NO

OO

O



DSC of ATDNMDSC of ATDNM

21



TGA of ATDNMTGA of ATDNM

22



55--Dinitrotetrazole was readily preparedDinitrotetrazole was readily prepared fromfrom ethyl 5ethyl 5-- tetrazolylacetate, via ethyl 5tetrazolylacetate, via ethyl 5--tetrazolyldinitroacetate. tetrazolyldinitroacetate.

55--Dinitroterazole exists in the mixture of Dinitroterazole exists in the mixture of tetrazoletetrazole and and tetrazolinetetrazoline, because of small energy difference., because of small energy difference.

ConclusionConclusion

23



High Energy Research CenterHigh Energy Research Center

Established in Inha University, Incheon, Korea Sponsored by Defense Acquisition Program Administration

& Agency for Defense Development Period : 2004. 3. 16 - 2012. 12. 31 (9 years)

25 Research topics1st period : 2004 - 2006 2nd period : 2007 - 20093rd period : 2010 - 2012

Participant : University Professor and Researcher of Private company

Three Research Divisions

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Division IDivision I

Design and Synthesis ResearchDesign and Synthesis ResearchDesign techniques of explosive moleculesDesign techniques of explosive moleculesSynthesis of polycyclic molecular explosives and oxidizers withSynthesis of polycyclic molecular explosives and oxidizers with high density high density and insensitivityand insensitivity

Design and synthesis of high energetic binder system containingDesign and synthesis of high energetic binder system containing molecular molecular explosivesexplosives

Crystallization and characterization of energetic materialsCrystallization and characterization of energetic materialsSynthetic method of high energetic and high dense cyclic hydrocSynthetic method of high energetic and high dense cyclic hydrocarbons arbons PolyphosphazenePolyphosphazene elastomerelastomer and its synthesisand its synthesisDesign and characterization of nitrogen cluster compounds Design and characterization of nitrogen cluster compounds Synthesis of Synthesis of nanocompositesnanocomposites of HEM with of HEM with nanostructurednanostructured materialsmaterials

25



Energy Conversion Phenomenon Analysis ResearchEnergy Conversion Phenomenon Analysis ResearchThree dimensional numerical study for shaped chargerThree dimensional numerical study for shaped chargerNumerical modeling of energy conversion processes in highNumerical modeling of energy conversion processes in high--temperature flowstemperature flowsNumerical analysis of interior ballisticsNumerical analysis of interior ballisticsMechanism analysis and power increasing methods for EMP generatMechanism analysis and power increasing methods for EMP generatorsorsAnalysis of the effects on the semiconductors by EMPAnalysis of the effects on the semiconductors by EMPMeasurement technique of solid propellant burning rates using uMeasurement technique of solid propellant burning rates using ultrasoundltrasound

RheologicalRheological Property ResearchProperty ResearchRheologicalRheological characteristics and characteristics and extrudabilityextrudability of highly viscous energetic materialsof highly viscous energetic materialsComposition research of silicone rubberComposition research of silicone rubberCharacteristics of Characteristics of nanonano aluminum slurry fuelaluminum slurry fuelSurface modification of high energy material using supercriticaSurface modification of high energy material using supercritical fluidl fluid

Division II & IIIDivision II & III

26



Defense AcquisitionDefense Acquisition Program AdministrationProgram Administration


AcknowledgementAcknowledgement

27

Slide Number 1Slide Number 2Slide Number 3Slide Number 4Slide Number 5Synthesis of � 5-dinitromethyltetrazole (I)Synthesis of � 5-dinitromethyltetrazole (Il)Retrosynthetic analysis of �5-dinitromethylidene-1,4-dihydrotetrazoleSlide Number 9Slide Number 10Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Slide Number 16Slide Number 17Slide Number 18Slide Number 19Slide Number 20DSC of ATDNMTGA of ATDNMSlide Number 23Slide Number 24Slide Number 25Slide Number 26Slide Number 27

Synthesis of Ethyl 5-tetrazolyldinitroacetate as a Key ......tetrazole derivatives 100 200 300 400...

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Transcript of Synthesis of Ethyl 5-tetrazolyldinitroacetate as a Key ......tetrazole derivatives 100 200 300 400...