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Phosphorus, Sulfur, and Siliconand the Related ElementsPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/gpss20

AMINOLYSIS, HYDROLYSISSTUDIES AND X-RAYSTRUCTURE OF 1,2,4-TRIAZOLEAND 1,2,4-OXADIAZOLE FROMTHE REACTION OF 1-AZA-2-AZONIAALLENE SALTS WITHISOTHIOCYANATEA. B. A. El-gazzar aa Photochemistry Department, National ResearchCenter, Dokki, Cairo, EgyptPublished online: 24 Sep 2006.

To cite this article: A. B. A. El-gazzar (1999): AMINOLYSIS, HYDROLYSIS STUDIES ANDX-RAY STRUCTURE OF 1,2,4-TRIAZOLE AND 1,2,4-OXADIAZOLE FROM THE REACTION OF1-AZA-2-AZONIAALLENE SALTS WITH ISOTHIOCYANATE, Phosphorus, Sulfur, and Siliconand the Related Elements, 152:1, 83-89

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Phosphorus. Sulfur ondSilicun, 1999, Val. 1.52, pp, 83-89 Reprints available directly from the publisher Photocopying permitted by I!cense only

0 1999 OPA (Overseas Publishers Association) Amsterdam N.V. Published by license under

the Gordon and Breach Science Publishers imprint. Printed in Malaysia

AMINOLYSIS, HYDROLYSIS STUDIES AND X-RAY STRUCTURE OF 1 ,2,4-TRIAZOLE

AND 1,2,4 -0XADIAZOLE FROM THE REACTION OF 1-AZA-2-AZONIAALLENE

SALTS WITH ISOTHIOCYANATE"

A. B. A. EL-GAZZAR~

Photochemistry Department, National Research Center, Dokki, Cairo, Egypt

(Received 20 October, 1998: In final form 19 November, 1998)

From the Hydrolysis of the 1,2,4-thiodiazolium salt of (1) in acetonitrile/sodium hydroxide solution the expected 1~,4-oxadiazole adducts 3 could be isolated, and in addition, the 1,2,4-triazole adduct 4 was obtained from the aminolysis process. This is evidenced by spec- troscopic and x-ray studies.

Keywords: Hydrolyses; X-ray structure; aminolysis; isothiocyanate

INTRODUCTION

Like many azo alkane derivatives"' 1 -hydroxyl/or 1 -amino 1,2-( l-ada- mantyl) diazine (1' or 1") has aroused some interest as a free radical source[241. Apart from the investigation of the thermal an attempt has been reported[31 to functionalize the hydroxyl and amino groups of 1' and 1". Water or ammonia solution were anticipated to add to the azo functions. Notably, from the reaction of 1 in acetonitrile/sodium hydroxide the expected adduct, namely the 1,2,4-thiodiazole 2 could be isolated, and conformed by spectroscopic evidence. Instead, merely the 1,2Poxadiazole or 1,2Ptriazole has been isolated when ace- tonitrile/water or ammonia solution were used for'hydrolysis or aminoly-

* Dedicated to Professor Ahmad Saleh Aly on the occasion of his 58th birhday. t Correspondence Author.

83

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84 A . B. A . EL-GAZZAR

sis. These compounds have been regarded to be the fragmentation products of the presumed intermediate diazenes 1'. However, no comple- menting fragments containing the isothiocyanate moiety or the azo nitro- gen atoms of the educt 1' have been found. This lack of stoichiometry led to the reinvestigation of this reaction.

As against the notoriously high reactivity of organic diazocompounds toward protic nuclophiles, the high reactivity of bis (hyhydoxyalky1)dia- zene 1' is striking. Compound 1 has been noted for its activeness toward water, thus not permitting the formation of 2 (and its homologues) in aque- ous solution. The hydrolysis of 1 with water or ammonia solution and pro- longed heating at elevated temperature is requried to convert 1 into several products (Schemes 1,2).

R R ~ - B ~ o H , ~ C' )=o + N H ~ H C O O C ~ H , - )=NNH.COOC,H, x R R R N=N-COOC,H,

I SbCI,

N-N

R 2

SCHEME 1

Adamantyl- and ethylhydrazone of adamantanone and hydrazinocarboxy- lic acid ethyl ester are transformed to the 1 -chloroadamantylazo-derivative compound with t-butyl hypochlorite. The latter compound reacts with methylisothiocyanate in presence of antimony (V) chloride in methylene chloride to give 1-aza-Zazoniaallene salts as reactive intermediates, which are intercepted as a mixture of 3H-1,2,3-thiadiazo-lium salts 1 with isothi- ~cyanate[~] (Scheme 1).

The solution of 1 (6.438, 10 mmol) in acetonitrile (50 ml) and water (5 ml) was boiled under reflux for 10 hrs. After cooling the adduct was extracted by chloroform (100 ml) followed by evaporation of the solvent under reduced pressure. The solid residue upon addition of diethyl ether furnished colorless crystals of 1,2,4-0xadiazole-3,3-5,5-bisadamantane (3) in a good yield 2.33 g, (71%), (Scheme 2).

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AMINOLY SIS STUDIES 85

1 CYCN N=N-CS NH.CH, ] - P E N , Heatmg HO N a O w O

N=NXR N E N Heating RXoH

"xo&r -N, R + R = R' N=>K . H e a w g ]

1' HO R -40 3

SCHEME 2

To a solution of 1 (6.438, 10 mmol) in acetonitrile (50 ml) and ammo- nium hydroxide solution (20 ml, 40%) was added and the reaction mixture boiled under reflux for 14 hrs. After cooling, the adduct was extracted by chloroform (100 ml), and the solvent was evaporated under reduced pres- sure. The solid residue upon addition of diethyl ether furnished colorless crystals of 1,2,4-triazole-3,3-5J-bisadamantane (4) (1.99 g, 64%), (Scheme 3) .

'H-, 13CNMR and IR spectra of the new compounds are collected in Tables 111 and IV. We found it difficult to decide the cofiguration of the substituents on the adamantyl moiety. Therefore, an x-ray diffraction analy- sis of adducts 3 and 4 was carried out confirming the substitution at C3 and C5. The structure was solved using programs SHELXS-86[331 and SHELX-76[341 by the Patterson method with subsequent difference-Fou-

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86 A. B. A. EL-GAZZAR

rier synthesis. The anisotropic refinement led to agreement factors R, = 9.0%, wR2= 13.8%. A molecular plot[61 for the adducts 3 and 4 is shown in figures 1 , 2 . Selected bond lenghts, bond angles and torsional angles are presented in Table I, 11.

TABLE I Selected Bond Lengths (pm), Bond angles and Torsional Angles (deq) of the aduct 3. (Monoclinic/p2l/c, temp. 244(2)K, Wave lenght 0.71073)

N 1 -N2 1.243 (2) N2-N1-CI 110.9 (2)

N2-C 11 1.489 (3) CI-0-CII 108.55 (14)

0-1 1 1 A28 (2) 0-C 1 -C8 110.8 (2)

CI-C2 1.532 (3) O-Cl-C2 11 1.4 (2)

c 1 1 x 1 8 1,533 (3) C8-Cl-C2 109.6 (2)

NI-CI 1.495(2) 0-Cll-C12 110.5 (2)

0-c 1 1.425 (2) 0-C ll-CI8 11 I .2 (2)

c 1 -C8 1.528 (3) C12-Cll-Cl8 109.8(2)

Cll-Cl2 I ,524 (3) N 1 -N2-C 1 1 11 1.2 (2)

0-C I-C8-C7 177.6 (2) NI-N2-Cll-C12 -121.2 (2)

0-CI 1-C18-C17 -60.9 (2) Nl-N2-CIl-O -2.4 (2)

TABLE I1 Selected Bond Lengths (pm), Bond angles and Torsional Angles (deq) of the aduct 4. (Monoclinic/p2l/c, temp. 236(2)K, Wave lenght 0.70089)

N1-N2 1.248 (2) N2-NI-CI 11 1.4 (2)

N2-C 1 1 1.483 (3) CI-N3-CIl 1 19.2 1( 14)

N3-C I 1.478 (2) N3-Cl-C8 109.8 (2)

CI-C2 1.542 (3) N3-Cl-C2 113.1 (2)

Cll-Cl8 1,521 (3) C8-CI-C2 109.4 (2)

NI-CI 1.473 (2) N3-C I 1 -C 12 11 1.2(2)

N3-Cl 1.485(2) N3-Cll-Cl8 111.3(2)

c 1 -C8 1.538 (3) C12-Cll-C18 109.9 (2)

CII-CI2 1.519(3) NI-N2-Cl 1 112.3(2)

N3-Cl-C8-C7 174.5 (2) NI-N2-Cll-C12 -122.2 (2)

N3-C1 I-CI 8 .~17 -58.9 (2) Nl-N2-Cll-N3 -2.2 (2)

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TABL

E I11

Phy

sica

l, an

alyt

ical

and

IR S

pect

ral d

ata

of c

ompo

unds

3 a

nd 4

Ana

l (C

alcd

/Fou

nd)

IR S

pect

ral d

ata

Cm-'

C H

N -N

H

-N=N

- C

omp

No.

Yi

eld

(9%

) m

.p. "C

M

ol. F

orm

(Mol

. wr)

~ 3 4

76.8

8 9.

03

8.97

...

71

155

C20

H28

N20

(3

12.

4)

76.6

1 8.

97

9.01

15

60

b

64

123

C2&

29N

3 (3

11.5

) 77

.12

9.38

13

.49

3180

I5

48

77.0

9 9.

44

13.5

7

Y E! E C

TA

BL

E IV

'H

-, "

C-N

MR

Spe

ctra

l dat

a of

com

poun

ds 3

and

4

Com

p.

No.

'H

-NM

R. (

6). pp

m (C

DC

I,)

I3C

-NM

R, (

6), pp

m (C

DC

13)

3 26

.87,

27.5

6.34

.43,

35.1

5,37

.39,

39.4

4, 12

3.29

for

20 sp

3 car

bon

atom

s

4 1.

53,1

.158

, 1.6

8,1.

81,1

.88,

2.08

,2.1

5,2.

17,2

.19,

2.27

,2,5

8,2.

67

26.8

1.27

.44,

34.3

8,35

.19,

37.4

8,39

.56,

124.

69fo

r20s

p3ca

rbon

1.56

, 1.6

6, 1

.71,

1.8

0, 1

.86,

2.04

,2.0

5,2.

07,2

.12.

2.17

,2.5

4 an

d 2

59

(as m

ultip

let s

igna

ls fo

r 28

pro

tons

)

(as

mul

tiple

t sig

nals

for

28 p

roto

ns) a

nd 4

.69

broa

d ba

nd fo

r N

H

atom

s

W

4

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88 A. B . A. EL-GAZZAR

FIGURE 1

FIGURE 2

CONCLUSION

The present study offers a new method for the preparation of 1,2,4-0xadia- zole and 1,2,4-triazole derivatives from triazolium salts. Also, the solving of the cofiguration around C3 and C5 by x-ray studies for the produced compounds.

Acknowledgements The author would like to thank Prof. Dr. J. C. Jochims, Facultat fur Chemie, Universitat Konstanz (Germany), for helpful discussion. Also my deep thanks to work group of Prof. Dr. Fischer, Facultat fur Chemie, Uni- versitat Konstanz (Germany), for this help in running and studying the x-ray analysis.

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AMINOLYSIS STUDIES 89

References [ l ] J .G. Schantl, H. Gastach, P. Hebeisen, and N. Lanznaster, Tetrahedron, 41, 5525

(1985). [2] H. C.Lang and R. E. Macleay, US Pat. 4,028,344 (1977); Chem. Abstr.. 87,103033~

(1978). [3] J. Akers, M. F. Dube, L. M. Trefonas, J. W. Timberlake, and R. Majeste, Tetrahedron

Left., 5083 (1978). [4] M. F. Dube, and, J . W. Timberlake, Tetrahedron, 1753 (1980). [5] A. B. El-Gazzar and J.C. Jochims, (Published results). [6] K.E. Schakal, a FORTRAN program for the grahpic representation of molecular models,

Freiburg, 1980.

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