Synthesis of New Heterocycles by Halogenation of

Synthesis of New Heterocycles by Halogenation of Tetrasulfur Tetranitride S 4 N 4 * Y . MONTEIL a n d H .

VINCENT

Universite Claude Bernard, Lyon I, Laboratoire de Physico-Chimie minerale, Associe au C.N.R.S. N° 116, Service du Pr. Cueilleron, 43, Bd. du 11 novembre 1918, 69621 Villeurbanne, France (Z. Naturforsch. 31 b, 673-676 [1976]: received October 7, 1975)

Inorganic Heterocycles, Thiazyl Compounds, Tetrasulfur Tetranitride Reactions, P - S - N Compounds Bromine reacts with tetrasulfur tetranitride S4N4 in solution in different solvents to give thiodithiazyl dibromide S3N2Br2. Iodine reacts under the same conditions with S4N4 to give trithiazyl iodide (SN)3l. The addition of chlorine, bromine or iodine to a mixture of tetrasulfur tetranitride and white phosphorus leads to compounds with the general formula P2S3NsXw, with n — 1 or 3 depending on the nature of X . Introduction The thiazyl SN radical, the analogue of nitric oxide N O , polymerizes easily owing t o the sulfur d-orbitals. T h e better known o f these polymers, tetrasulfur tetranitride S4N4 can give S N radicals in the course o f reactions, but it is at present impossible t o predict h o w and where SN b o n d rupture occurs during a given reaction. The S4N4 structure is known 1 . This heterocycle can lead t o other cycles with very different shapes. E x a m p l e s are the structures o f the compounds 3 4 S 4 N 4 F 4 2 , S3N3CI3 , S3N2CI2 , S4N3NO3 5 , S 5 N 5 A1C1 4 e and S 6 N 4 X 2 7 . The large variety o f the c o m p o u n d s produced f r o m S4N4 shows that it is a g o o d starting material for the synthesis o f new combinations. T h e a c t i o n o f fluorine on S4N4 leads t o the c o m p o u n d S 4 N 4 F 4 8 . T h e chlorination reaction yields S3N3CI3 9 , via the intermediate step o f S4N4CI4 1 0 . W e studied the bromination and the iodination o f S4N4. While the bromination of S4N4 has been studied b y several workers 1 1 - 1 3 , it is the first time t h a t the iodination reaction is reported.

Moreover, we obtained also n e w combinations containing the pattern P2S3N3 b y reaction o f halogens o n a mixture o f white phosphorus with tetrasulfur tetranitride. A. Starting Compounds Very pure c o m p o u n d s are required t o study the reaction o f the halogens with tetrasulfur tetranitride. W e have been obliged t o synthetize some thiazyl chlorides which have been used either as reference or as starting materials f o r the bromination and iodination reactions. A.l.

Tetrasulfur

tetranitride

S4N4

N u m e r o u s authors studied the preparation o f S4N4. W e used the m e t h o d which has been perfected b y B E C K E - G O E H R I N G and revised b y V I L L E N A B L A N C O and J O L L Y 1 4 . I n this m e t h o d S4N4 is obtained b y ammonolysis o f disulfur dichloride according t o the overall reaction:

S2CI2 + 16 N H 3 S4N4 + 12 NH 4 C1 + 8 S. S4N4 is little sensitive t o moisture. Consequently, 6

it is easy t o r e m o v e a m m o n i u m chloride b y water treatment o f the p r o d u c t at 0 °C. On the other hand,

* Paper, presented at the 1. International Symposium on Inorganic Heterocycles, Besan^on (France), June 16-19, 1975. Requests for reprints should be sent to Prof. Dr. Y . MONTEIL, Universite Claude Bernard Lyon I, Lab. de Physico-Chimie Minerale I, Associe au C.N.R.S., Service du Pr. Cueilleron, 43, Boulevard du II Novembre 1918, F-69621 Villeurbanne, France.

the separation f r o m sulfur is m u c h more delicate because it is soluble in the same solvents as S4N4. After several recrystallisations o f the S-S4N4 m i x ture f r o m dioxane and benzene, it is possible t o obtain a p r o d u c t enriched in S 4 N 4 . This is then chromatographed on a column o f acid alumina t o exclude the residual sulfur 1 5 .

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674

Y. MONTEIL-H. VINCENT • SYNTHESIS OF NEW HETEROCYCLES

I R (KBr pellet) absorptions occurred (cm - 1 ) at: 925 s, 800 w, 768 w, 760 w, 728 s, 698 vs, 620 m, 550 vs, 528 m, 519 w. Powder diffraction data (copper radiation) at: 6.33 m, 6.04 m, 4.75 vs, 4.60 vs, 4.37 m, 3 . 1 1 m , 2.78 s Ä.

I R (CsBr pellet) absorptions occurred ( c m - 1 ) 1160 vs, 1125 m, 998 vs, 682 s, 608 m, 565 s, 465 450 s, 325 s. Powder diffraction data (copper radiation) 5.31 s, 4.56 m, 4.06 s, 3.21 m, 3.06 vs, 2.93 2.71 s, 2.56 m l .

A.2. Thiodithiazyl dichloride S3N2CI2

A 5. Thiotrithiazyl bromide SiN3Br

Thiazyl chlorides can be prepared from tetrasulfur tetranitride 9 . Ammonium chloride and disulfur dichloride are the preferred starting materials. They react easily according to the scheme 1 7 :

The ionic character of the thiotrithiazyl chloride and the stability of the S4N3+ ion enables the bromide to be obtained by methatesis with potassium bromide 1 7 :

2 NH4CI + 4 S2CI2 -> S3N2CI2 + 8 HCl + 5 S. The reaction is carried out in presence of sulfur to restrict the disproportionation of disulfur dichloride in sulfur dichloride SCI2. The compound S3N2CI2 segregates easily from the reaction mixture by sublimation. Since it is easily obtained, it is used as a starting material for the preparation of the thiazyl chlorides S4N3CI and S3N3CI3 instead of

S4N4 17.

I R (nujol mull) absorptions occurred (cm - 1 ) at: 1015 m, 940 s, 582 m, 548 w, 460 w, 398 w. Powder diffraction data (copper radiation) at: 4.57 vs, 4.28 m, 4.07 s, 3.73 m, 3.42 m, 3.34 m, 2.70 s, 2.68 vs, 2.60 s, 2.51 m, 2.27 m Ä. A.3. Trithiazyl trichloride

S3N3CI3

Trithiazyl trichloride is obtained by chlorination of thiodithiazyl dichloride:

3 S3N2CI2 + Cl2 -> 2 S3N3CI3 + 3 SC12. It can be separated from S3N2CI2 due to its solubility in carbon tetrachloride and benzene. The compound S3N3CI3 is very sensitive to moisture and must therefore be handled in a glove-box. I R (CS2 or CCI4 solution) absorption occurred (cm - 1 ) at: 1017 vs, 701s, 621 w, 514 s, 390 m, 260 w. Powder diffraction data (copper radiation) at: 5.56 s, 5.40 s, 4.08 s, 3.15 vs, 3.11 m, 3.06 m, 2.90 s, 2.64 vs, 1.90 m, 1.79 m, 1.61 m, 1.52 m Ä. A.4. Thiotrithiazyl chloride S4N3CI Thiotrithiazyl chloride is obtained by reaction between thiodithiazyl dichloride and disulfur dichloride :

3 S3N2CI2 + S2CI2 -> 2 S4N3CI + 3 SC12. The compound is ionic, S4N3+C1-, and the structure of the S4N3+ ion has been determined using a single crystal of thiotrithiazyl nitrate 5 . Further data are:

at: vs, at: m,

S 4 N 3 + C1 - + K+Br- - > S 4 N 3 Br + K+Cl - . The reaction has been carried out either in water at 0 °C or in formic acid. The thiotrithiazyl bromide precipitates from the solution: I R (CsBr pellet) absorptions occurred (cm - 1 ) a t : 1155 s, 992 vs, 670 m, 558 m, 462 vs, 315 s. Powder diffraction data (copper radiation) at: 5.41 s, 5.23 s, 4.79 s, 4.24 m, 4.08 s, 3.45 m, 3.17 m, 3.10 vs, 2.96 m, 2.75 s, 2.64 s, 2.60 m Ä. B. Study of the Bromination of S4N4 The first study 1 1 on the bromination of tetrasulfur tetranitride reported the formation of (SNBr)^. More recently, H E A L 1 2 and Z B O R I L O V A 1 3 concluded that a mixture of products is formed with a composition close to the formula S3N2Br2W e studied the reaction between S4N4 and bromine in carbon disulfide or carbon tetrachloride. It is very important to use moisture free conditions, i.e. strictly anhydrous solvents. Moreover, tetrasulfur tetranitride must be free from sulfur. All manipulations must be carried out in an inert atmosphere and the reaction products are therefore handled in a glove-box. The reaction between S4N4 and bromine has been studied at different temperatures. B.l.

Preparations of SsN^Brz

A solution of S4N4 and bromine in CS2 is refluxed for one hour. The precipitate found is thiodithiazyl dibromide. This new compound is a yellow-orange coloured crystalline product. S2N2Br2 has been obtained also by brominating S2N2CI2 with HBr. The solid-gas phase reaction proceeds according to the equation:

S3N2CI2 + 2 HBr -> S3N2Br2 + 2 HCl. The formation of HCl is evidenced b y I R absorption spectroscopy. Yet, the product is less pure than the SßNoBro obtained by bromination of S4N4.


675 Y. MONTEIL-H. VINCENT • SYNTHESIS OF NEW HETEROCYCLES Experimental A 250 ml flask was equipped a reflux condenser and the top of the condenser was fitted with a drying tube filled with calcium chloride. The reaction temperature was controlled with an electric heating mantle. The reaction flask was charged with 200 ml of CS2 or CCI4 dried with molecular sieves, and 1.84 g (0.01 mol) of S4N4 recrystallised in CßHe just prior

to use. After dissolution of S4N4, 3 ml of Br2 was

added. The reaction mixture was allowed to reflux for two hours. Then the SsN 2 Br 2 was collected by filtration in a glove-box, desiccated with P2O5, and subsenquently washed with dry CS2 • S 3 N 2 Br 2 was dried in vacuo. Analysis for S3N2.Br2, Calcd Found

S 33.80 S 34.1

N 9.86 N 9.94

Br 56.34, Br 56.4.

Bromine is titrated by potentiometry, nitrogen by the Kjeldahl's method and sulfur as barium mlfate. I R (CsBr pellet) absorptions occurred (cm - 1 ) at: 1160 s, 1010 vs, 1000 s, 675 m, 562 m, 470 vs, 320 s. Powder diffraction data (copper radiation) at: 5.14 m, 4.84 m, 4.52 m, 3.89 m, 3.48 vs, 3.30 s, 3.09 m, 2.85 m, 2.51 m, 2.42 w A. B.2. Study of the reaction of bromination of S4N4 W e will recall that chlorine and fluorine react vvith S4N4 to give S3N3CI3 and S4N4F4, and the compound S4N4CI4 is obtained as an intermediate. On an other hand, bromine does not lead to symnetrical compounds such as S4N4Br4 or SsNsBrs but yields SsN 2 Br 2 instead. In order to obtain information on the possible

existence of the compound S 3 N 3 Br3, S3N3CI3 was reated with HBr. The reaction takes place with EtCl and Br 2 evolution. The yellow S3N3Cl3 turns ed rapidly to finally give a yellow-orange coloured product. The X-ray diagram of this latter product s analogous to S3N2Br2. This result can be explained oy the formation of SsNsBrs as an intermediate compound with decomposes at once in SsN 2 Br 2 . In boiling CS2 (or CCI4) S 3 N 2 Br 2 is obtained in a Dure state; at room temperature, the bromination >f S4N4 leads to a mixture of products: SsN 2 Br 2 is >btained admixed with another compound, the iementary analysis of which corresponds to the ormula (SN^Br. S3N2Br2 is separated from (SN^Br )y dissolving the latter selectively in liquid S0 2 . The compound (SN^Br is orange coloured and •rystallized.

B.3. Transformation of SsN%Br2 into S^NsBr Thiotrithiazyl bromide S 4 N3Br has been found as an impurity in thiodithiazyl dibromide in the bromination of S4N4. It can result either from the hydrolysis of S3N2Br2 or from the presence of sulfur formed in the reaction of bromine on S4N4. The thermal decomposition of SsN 2 Br 2 leads likewise to the formation of S4N3Br. SsN 2 Br 2 is very sensible to moisture. It decomposes in the atmosphere giving mainly thiotrithiazyl bromide and ammonium bromide. The same thiotrithiazyl bromide has been found as an impurity in SsN 2 Br 2 when bromine reacts with a sulfur containing sample of S4N4. In this case, bromine reacts both with S4N4 and S, the latter forming disulfur dibromide. The formation of S4NsBr can then be explained by the reaction of S 2 Br 2 with S3N2Br2. In the same way, S2C12 transforms S3N2C12 into S4N3CI1«. S 4 N 3 Br and S 3 N 2 Br 2 are separated by selective dissolution of S4NsBr in liquid S 0 2 1 3 . At 90 °C and 10 - 1 torr, S 3 N 2 Br 2 decomposes according t o : 6 S 3 N 2 Br 2 - > 4 S 4 N 3 Br + S 2 Br 2 + 3 Br 2 .

C. Study of the Iodination of S4N4 The reaction between iodine and S4N4 has been studied in an inert solvent at different temperatures. In any case, a precipitate is formed which corresponds to the formula (SN)3l. The iodination of S4N4: 2 S4N4 + 2 I 2

4 (SN)sI

is slow at room temperature but is appreciably accelerated when carried out in boiling solvents. Experiments in progress show that hydrogen iodide displaces the chlorine atoms from the thiodithiazyl dichloride. The new compound (SN^I which is sensible to moisture is dark red. Its X-ray diagram is that of a nearly amorphous compound. Analysis for (SN Calcd S 36.22 Found S 35.5

N 15.85 N 15.9

147.92. 147.8.

I R (Csl pellet) absorptions occurred (cm - 1 ) at: 962 vs, 755 s, 665 w, 638 m, 590 w, 465 w, 425 m Ä. D. Study of the Halogenation of the Mixture S4N4-White Phosphorus The halogens (chlorine, bromine and iodine) react with a mixture of white phosphorus and tetrasulfur


Y . M O N T E I L - H . V I N C E N T • S Y N T H E S I S OF N E W H E T E R O C Y C L E S

676

tetranitride. T h e reactions are carried out in carbon disulfide which is a solvent o f both

S4N4 and

white

phosphorus. The reactions are rapid and can be represented as f o l l o w s :

3 S4N4 + 8 P + 6 Cl2 -> 4 P2S3N3CI3 3 S4N4 + 8 P + 6 Br 2 - > 4 PaSsNgBrg 3 S4N4 + 8 P + 2I2 4 P2S3N3I The

products

precipitate

from

medium. T h e y are characterized

the by

reaction

elementary

analysis and mass spectrometry. T h e y are amorphous t o X - r a y s . Their stability decreases when passing f r o m the iodinated t o the chlorinated c o m p o u n d . T h e y decompose below 100 °C. A p o l y m e r (PSN) n is obtained as residue in the d e c o m p o s i t i o n o f the iodinated derivate at 95 °C.

1

2 3

4

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4.96 g (0.16 mol) o f white phosphorus, 7.36 g (0.04 mol) o f finely ground tetrasulfur tetranitride and 300 ml o f inert solvent (CCI4, CS2) were p l a c e d in a 500 ml r o u n d - b o t t o m e d three necked flask. This flask was equipped with a mechanical stirrer, with a nitrogen inlet tube which was used t o prevent moisture during the reaction, and with a reflux condenser. T h e t o p of the condenser was connected with a drying tube containing calcium chloride, which was replaced with an inlet tube f o r the adding bromine and iodine solution in CCI4. T h e chlorine was passed directly through the solution. The mixture o f phosphorus and S4N4 was allowed t o reflux for 4 hours and cooled t o r o o m temperature. T h e solution was brown red. Soon after the start of the halogen adding, the colour turned into yellow. T h e halogens were added in excess. The c o m p o u n d s precipitated slowly. After 24 hours, the solid was collected b y filtration in a g l o v e - b o x , washed with ether and dried in vacuo.

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