SYNTHESIS OF ENERGETIC MATERIALS IN IONIC LIQUIDS

Nina N. Makhova

and

Alexey B. Sheremetev

Workshop on Advances Energetic Materials Synthesis

University of Maryland

03-06.04.2011

N.D. Zelinsky Institute of

OrganicChemistry

Russian Academy of Sciences

IONIC LIQUIDS – PERSPECTIVE SOLVENTS AND CATALYSTS

FOR CHEMICAL REACTIONS

CATIONES

ANIONES

BF4, PF6, AlCl4, HSO4, CF3SO3, NTf2, N(CN)2, PF3(C2F5)2

2

N NBuMe

BF4 ([bmim][BF4])

CatalystAn

Kat

Kat Kat

An

An

An

Kat

An

Kat

Kat

KatKat

KatThe main advantages of ionic liquids (ILs)

(green chemistry)

• ILs are incombustible

• ILs have very low volatility

• ILs can be regenerated and reused again

• ILs display catalytic activity

N N R2

R1 N

R

NR1

R1 S N R N

R1

R4

R3

R2

S. G, Zlotin, N.N. Makhova, Mendeleev Commun., 2010, 20, 63-71

S. G. Zlotin, N. N. Makhova, Russ. Chem. Rev., 2010, 79, 543-583.

3

I.V.Seregin, L.V.Batog, N.N.Makhova: Mendeleev Commun., 2002, 83

SYNTHESIS OF 1-(FURAZANYL)-1,2,3-TRIAZOLES AND 5-

MONO- AND 1,5-DISUBSTITUTED TETRAZOLES IN ILs

NO

N

H2N N3

R1 R2i

ii NO CH CH NO2

NO

N

H2N NN

N

R1 R21

i. ILs = [bmim][BF4], 80 oC, 6.5-7.5 h (lit. 80 oC, 30h)

ii. ILs = [bmim][PF6], 70 oC, 12h (lit. 110 oC, 120h)a R1 = CH2OH, R2 =H

b R1 =H, R2 = CH2OH

a : b = 4.5 : 1 (71%)(lit. a : b = 2.5 : 1)

R1 = R2 = CH2OH (75%); R1 = H, R2 = NO2 (35%)

12

R Time, h yield, %

Ph 10 85

4-NO2C6H4 3.5 99

3-Py 9 96

Bn 5 80

R1 C N + N

NN

N

R1 R2

R2N3R C N + N

NN

N

R H

NaN3

[emim][HSO4]

95-100 oC

[emim][HSO4]

95-100 oC

3 3'a,b

R1 R2 Time, h yield, %

a

EtO2C Bn 18 74

b

PhCO Bu 50 72

N. N. Makhova, A. S. Kulikov, M. A. Epishina, N. V. Ignat’ev, M. Schulte, Russ. Patent, 2010

SYNTHESIS OF 3-ACYL-4-ACYLAMINOFURAZANS IN THE

REACTION OF 3,4-DIACYLFUROXANS WITH NITRILES IN ILs

4

I. V. Seregin, I. V. Ovchinnikov, N. N. Makhova, D. V. Lyubetsky, K. A. Lyssenko,

Mendeleev Commun., 2003, 230

NO

N

ROC COR

O

ROC

NC N

OCOR

O

RCOON

ROC N

NO R1

N

ON

O

N

H

R1

ROC

NO

N

ROC NHCOR1

5 (35-40%)

R = Me, cyclo-Pr; R1 = CCl3, EtCO2

R1CN

R1CN

4

6

H2O

-RCO2H

[bmim][BF4], 80 oC, 5.5h

7

NO

N

R NH2 1) CCl4/AlCl3 (3 mol)

2) CCl4/[emim][AlCl4] NO

N

R NCl

Cl

80 oC, 3-5h

R = Me, OMe, CO2Me, NO2, N=C(Cl)2

8 9 1) 48-80%2) 59-86%

SYNTHESIS OF DICHLOROIMINO- AND FLUOROFURAZANS IN ILs

A.B.Sheremetev, N.S.Alexandrova, D.E.Dmitriev, Mendeleev Commun., 2006, 163

A.B.Sheremetev, N.S.Alexandrova, I.L. Yudin, Mendeleev Commun., 2003, 31

5

NO

N

O2N NO2 Et3Nx3HF

NO

N

O2N F

NO

N

O2N

NO

N

NO2O

10 (50%)11

KF(NaF)

MeCN, 60-80 oC

12

[bmim][X], 50 oC, 4h

NO

N

O2N

NO

N

FN

ON

N N

NO

N

O2N F

On

X = BF4, PF6

10a (38%)

n = 0,1

10b (30-36%)

NO

N

H2N NH2 H2NSO3K+CH2ON N

N

SO3K

SO3KKO3S

HNO3/Ac2ORDX

N

N

NN

ON

SO3K

H

H

HNO3/Ac2O

N

N

NNO

NNO2

NO2

NO2

(36%)

NO

N

O2NHN NHNO2

[emim][HSO4]+

[bmpyrr][CF3SO3]

98% HNO3

0 20 oC

8hRO N OR

NO2

20 oC (75-85%)

17 (R = H, Ac)

DAF

14

1513

16

mp 150-151 oC (decomp)

X-ray = 1.959 g/cm3

ONE-POT SYNTHESIS OF FURAZANO[3,4-f]-1,3,5-TRIAZEPINE

AND BENZOFUROXANS IN ILs

A.B.Sheremetev, N.S.Alexandrova, K.Yu.Suponitsky, M.Yu.Antipin, V.A.Tartakovsky,

Mendeleev Commun., 2010, 20, 249.

6

Cl

NO2

NO2

NaN3, Bu4NBr

IL, 60 oC, 2h

N3

NO2

NO2

NO

NO

NO2

18a (93-95%)

N

ONN

O

N N

ONN

O

N

NO

N

O

O

O

O

O19 20

BDF

BTF (92%)IL = [empyrr][BF4]

№ IL Yield of TNE %

1 [bmim][BF4] 80

2 [bmim][PF6] 50

3 [emim][HSO4] 89 (1), 86 (2), 83(3), 94 (4)

HENRY REACTION OF POLYNITROALKANES IN ILs

Synthesis of TNE in ILs

M.A.Epishina, I.V.Ovchinnikov, A.S.Kulikov, N.N.Makhova, V.A.Tartakovsky,

Mendeleev Commun., 2011, 21, 21.

7

NaHC(NO2)2 + 2CH2O1-3 oC, acid

[bmim][BF4]

21 (40%)Acid = HCl, CF3COOH, AcOH

C

NO2

NO2

OHHO

HC(NO2)3 + CH2O20 oC, 24h

ILsTNE (89-94%) mp = 70-72 oC

HO C(NO2)3

IONIC LIQUID-ASSISTED SYNTHESIS OF

CARBOXYLIC ACIDS TRINITROETHYL ESTERS

A.B.Sheremetev, I.L.Yudin, K.Yu.Suponitsky: Mendeleev Commun., 2006, 264

8

HO C(NO2)3RCl

O+ R

O

O 23

ILs = [emim][X] X = BF4, PF6, AlCl4

R = Ph (93%), 4-ClC6H4 (95%),

N

N

ILs

(85%)O

(79%)

OO2N(92%)

NO

N

Me

, ,(95%) (74%)

,,

20 oC22 TNE

C(NO2)3

O

O

Cl

Cl

TNE

[emim][PF6], 20 oC

O

O

O

O

24 (95%)

C(NO2)3

C(NO2)3

N IL FeCl3 Yield, % N IL FeCl3 Yield, %

1 [emim][Cl] - 0 5 [emim][PF6] - 43

2 [emim][Cl] 5 mol % 41 6 [emim][PF6] 5 mol % 79

3 [emim][BF4] - 35 7 [emim][AlCl4] - 54

4 [emim][BF4] 5 mol % 72 8 [emim][AlCl4] 5 mol % 83

SYNTHESIS OF 2-R-2,2-DINITROETHANOL ORTHOESTERS IN ILs

Synthesis of compound 25a in different ILs

A.B.Sheremetev, I.L.Yudin, Mendeleev Commun., 2005, 204

*D.B. Lempert, G.B. Manelis, N.N. Makhova, Yu.M. Mikhailov, G.Nazin, G. Nechiporenko,

Proceeding of 10th NTREM, 2007, 25

9

O

O

O

O

C(NO2)2F

C(NO2)2F

F(O2N)2C

F(O2N)2C

CCl4

TNE

IL/FeCl3, 80 oC

HO C(NO2)2F

IL/FeCl3, 70-100 oC

O

O

O

O

C(NO2)3

C(NO2)3

(O2N)3C

(O2N)3C

25a (83%)25b (91%)

CHCl3

TNE

IL/FeCl3, 80 oC

HO C(NO2)2F

IL/FeCl3, 70-100 oCO

O

O

C(NO2)3

C(NO2)3

(O2N)3COO

O

C(NO2)2F

C(NO2)2F

F(O2N)2C

26a (76%)26b (88%) IL = [emim][AlCl4]

*K dec. at 110 oC = 2.9 x 10-8 s-1

*K dec. at 110 oC = 6.2 x 10-9 s-1

MANNICH REACTION OF UREA AND ACETAMIDE

WITH TRINITROETHANOL (or CH2O + TNM) IN ILs

10

M.A.Epishina, I.V.Ovchinnikov, A.S.Kulikov, N.N.Makhova, V.A.Tartakovsky,

Mendeleev Commun., 2011, 21, 21.

NH2CONH2

HC(NO2)3CH2O

HC(NO2)320 oC, 24h

(90%)BTNEU

MeCONH2

HC(NO2)3

28 TNE-acetamide (75-81%)

CH2O

[bmim][X]

K2CO3X = BF4, PF6

24 h, 20 oC

CH2O

IL

IL

ILIL,

IL = [emim][HSO4]

27

NH

NH

C(NO2)3(O2N)3C

O

MeOCHN C(NO2)3

NH

NH

OHHO

O

HO C(NO2)3

MeOCHN OH(pKa = -0.4)

(pKa = 0.1)

MANNICH REACTION OF AMINOFUROXANS

WITH TRINITROETHANOL (or CH2O + TNM) IN ILs11

M.A.Epishina, I.V.Ovchinnikov, A.S.Kulikov, N.N.Makhova, V.A.Tartakovsky, Russ. Chem. Bull. Int. Ed.,

2011, (in press)

*A.O.Finogenov, M.A. Epishina, A.S. Kulikov, N.N. Makhova, I.V. Anan’ev, V.A. Tartakovsky, Izv. AN; Ser.

Khim., 2010, 2054 (in Russian)

CH2O

NO

N

Me NH2

ON

ON

Me HN

O

HC(NO2)3

NO

N

Me HN

O[bmim][BF4]

29a 30b 31a (37%)K2CO3

24h, 20 oC

NO

N

R

O

HC(NO2)3, 20 oC

NO

N

R HN

O*32a-d

NO

N

R

O

31a-d (57-80%)

ILs = [bmim][HSO4], [bmpyrr][CF3SO3]

31a-d (57-63%)

NO

N

R NH2

O+ CH2O + HC(NO2)3 (or TNE)

20 oCN

ON

R HN

O

29a-d

a R =Me, b R = MeCO, c R = CO2Me, d R = Ph

HNO3/(CF3CO)2O

ILs, 0-5 oC 20 oC

33a,d (54-56%)

NO

N

R N

O

NO2

ILs

OH C(NO2)3

C(NO2)3

C(NO2)3C(NO2)3

HN HN

ILs = [bmim][HSO4], [bmpyrr][CF3SO3]

ILs

a R =Me, b R = MeCO, c R = CO2Me, d R = Ph

(pKa = -3.0)

IL, 0-5 oC 20 oC

(42%)

MeCOONH4HOCH2C(NO2)3

IL, 20 oC34

IL = [bmpyrr][CF3SO3]

HNO3 / (CF3CO)2

IL, 0-5 oC 20 oC

HOCH2C(NO2)3

IL, 20 oC

HNO3 / (CF3CO)2

37 (37%)

35

36

NN

NO2

C(NO2)3

NO2

(O2N)3C

N C(NO2)3

NO2

(O2N)3C

NH

C(NO2)3(O2N)3HC

HN

NH

C(NO2)3(O2N)3C

H2N NH2

ONE-POT SYNTHESIS OF N,N-BIS(2,2,2-TRINITROETHYL)NITRAMINE

AND N,N’-BIS(2,2,2-TRINITROETHYL)ETHYLENDINITRAMINE IN ILs

12

M.A.Epishina, I.V.Ovchinnikov, A.S.Kulikov, N.N.Makhova, V.A.Tartakovsky,

Russ. Chem. Bull. Int. Ed., 2011, (in press)

SUMMARY

ILs

NO

N

NN

NH2N

R1 R2

NH

NN

N

N

NN

N

R R1 R2

and

NO

N

ROC NHCOR1

NO

N

R N

NO

N

R FCl

Cland

N

N

N

NO

N

NO2

NO2

NO2

NO

N

NO2

OHO C(NO2)3

C

NO2

NO2

OHHO

and

NN

NO2

C(NO2)3

NO2

(O2N)3C

NH

NH

C(NO2)3(O2N)3C

N C(NO2)3

NO2

(O2N)3C

R C

O

O C(NO2)3

O O

O O

C(NO2)3

C(NO2)3

(O2N)3C

(O2N)3C

NO

N

R N

NO3

C(NO2)3

O

and BDF, BTF

O

O O

H O

C(NO2)3

C(NO2)3

(O2N)3C

and

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THANK YOU FOR YOUR ATTENTION !