DD280759A1 - PROCESS FOR PREPARING 3-DIALKYL (ARYL) AMINO-5-PHENYL-1,2,4-DITHIAZOLIUM TETRACHLOROMETALLATE - Google Patents

Abstract

The invention relates to a process for the preparation of 3-dialkyl (aryl) amino-5-phenyl-1,2,4-dithiazolium tetrachlorometallates of the general formula. It is the object of making these compounds in a technically simple and economically auspicious manner. The object is achieved by the reaction of 1,1-dialkyl (aryl) -3-benzoyl thioureato-metallates with thionyl chloride in acetonitrile. The proof of their structure was provided by X-ray crystal structure analysis. formula

Description

i. ⁿ , i,

in nitriles with thionyl chloride, SOCl ₂ , to be reacted.

2. The method according to claim 1, characterized in that the solvent is preferably acetonitrile is used.

3. The method according to claim 1 and 2, characterized in that the reaction takes place at room temperature and the reaction is completed by stirring at temperatures between room temperature and the boiling point of the solvent.

Field of application of the invention

The invention relates to a process for the preparation of the title compounds, which have meaning as thermochroma substances.

Characteristic of known technical solutions

Methods for the preparation of S-DialkyKaryOamino-S-phenyl-I ^ adithiazolium tetrachlorometallatendl) are not yet known.

H. Hartmann, J. Liebscher and P. Czerney have described compounds (Tetrahedron 41 [1985] 5371) in which the title cations are combined with perchlorate anion. These salts are prepared from 1,1-dialkyl-3-aroyl-thioureas by oxidation with hydrogen peroxide in formic acid / perchloric acid or in glacial acetic acid / perchloric acid.

Analogous salts with perchlorate anion are also compatible with the 3,5-diaryl-1,2,4-dithiazolium cations, somewhat related to the title cations, similarly from the corresponding thioamides of aromatic carboxylic acids by oxidation in the above. Reaction medium according to J. Liebscher and H. Hartmann (Liebigs Annal. Chem. 1977, 1005) accessible.

In another way, the related 3,5-diamino-1,2,4-dithiazolium salt <3 was obtained with perchlorate as an anion (H. Prinzbach, E. Futterer: Adv. Herteocycl. Chem.7 ['966] 39. Structure: A.Hordvik, Quart. Rep. SuIf. Chem.5 [1970] 21) Also known are the title compounds CH-analogous compounds, "; e 3,5-disubstituted 1,2-dithiolium tetrahalometallates, which are obtained by oxidation of the corresponding 1, 3 - ""! Thioketones, mostly prepared only in situ, with the corresponding halogens, peroxides or atmospheric oxygen in the presence of the reacting metal halides, or with higher valency metal halides as the oxidant itself (VN Lockyer, RL Martin: Progr. Inorg.

Chem.27 [1980] 223; L. Menabue, G.C. Pellacani: J. Chem. Soc. Dalton Trans. 1976,155; A. Furuhashi, T.Takeuchi, A.Quchi:

Chem. Soc. Jap.41 [1968] 2049; K. Knauer, P. Hemerich, J.D.W. van Voorst: Ai gew. Chem. 79 [1967] 273; M.G.B. Drew, J. M. Kisenyi, G. R. Willey: J. Chem. Soc. Dalton Trans. 1984, 1727).

Object of the invention

The invention aims to provide a simple, technically feasible, cost-effective process for the preparation of S-dialkylkaryllamino-S-phenyl-1-adithiazolium tetrachlorometallatefll).

Explanation of the essence of the invention

The invention has the object, in a technically advantageous, simple way, the synthesis of 3-Oialkyl (ary lysinino-5-phenyl-1,2,4-dithiazolium tetrachlorometallate (II) of the general formula I.

- QAl _r

to enable.

The object is inventively achieved in that bis [1,1-dialkyl (aryl) -3-benzoyl-thioureato] metallates (II) of the general formula II are reacted with thionyl chloride in dried acetonitrile at room temperature with constant stirring, wherein Filter off and concentrate the Filfrats the compounds of general formula I, usually after addition of acetone, crystallize out and be obtained in good yield by filtration in sufficient purity.

R ¹ H ² I. -

.1 / ~ ^ vJ

i f

6 5

JOCl,

3 ". , 0

I-

(Acetonitrile,

3 \ :: τ) ι rat ur)

II

LGL

In compounds I and II, R ¹ and R ² , which may be the same or different, are an alkyl group to C ₁₈ or a cycloalkyl group of ring size C ₄ to C ₇ or a cycloheteroalkyl group or aryl group such as phenyl or substituted phenyl. M in the compounds of the general formulas I and II denotes a metal ion, preferably a divalent transition metal ion such as Ni (II), Cu (II) and others metal ions which are in principle capable of forming tetrachlorometalates. The compounds of general formula II can be prepared in a conventional manner in a one-pot reaction from the industrially available educts benzoyl chloride, potassium thiocyanate, secondary amine in acetone and reacting the crude mixture with corresponding metal salts simply in very good yield (see L. Beyer, E Hoyer, J. Liebs jher, H. Hartmann: Z. Chem.21 [1981] 81 and there cited literature).

The structure of the compounds of the general formula I which is of importance in view of the fields of application of the invention was elucidated by the example of the S-diethylamino-S-phenyl-1'-dithiazolium tetrachloro-conolate prepared according to Example 1 by means of an X-ray crystal structure analysis ,

Thereafter, the heteroaromatic dithiazolium cation is a planar five-membered ring in which all bonds are significantly shorter than single bonds, and they are also asymmetric due to the different substituents in the 3- and 5-positions, as well as the different CS bond lengths of the five-membered ring (1.756A or 1,735Ä). The tetrachloronic-claddD anions are tetrahedral with a mean Cl-Ni-Cl distance of 2.265Ä and an average Cl-Ni-Cl angle of 109.5Â °. Remarkable are zudom in the crystal structure of the o. G. Compound interionic S ... Cl contacts, which, at about 3.30Ä, fall short of the sum of the van der Waals radii of sulfur and chlorine (3.65A), with only two of the four chlorine atoms being S ... Cl interactions zeigon , This situation is significant with regard to structural changes at varied temperatures.

embodiments

The invention will be explained in more detail below with reference to exemplary embodiments:

Embodiment 1

Biso-diethylamino-S-phenyM ^^ - dithiazoliuml-tetrachloroniccolattll)

13.2 g (0.025 mol) of bis (1,1-diethyl-3-benzoylthioureato) nickel (II) are dissolved in 300 ml of dried acetonitrile. While stirring, 6.0 g (0.05 mol) of thionyl chloride are added dropwise at room temperature within 20 min and then further stirred for 90 min. The cyan reaction solution is then separated from the precipitated by-products, concentrated in a rotary decompressor to about 60 ml and treated with 200 ml of dried acetone. The compound precipitates, is filtered off and recrystallized twice from acetonitrile.

Yield: 3.7 g (42% of theory)

Mp .: 200-202 "C

Exemplary embodiment 2

BislS-diethylamino-ö-phenyl-i ^^ - dithiazoliumMetrachlorocupratdl)

13.5 g (0.025 mol) of bis (1,1-diethyl-3-benzoylthioureato) copper (II) are dissolved in 300 ml of dried acetonitrile. While stirring, 6.0 g (0.05 mol) of thionyl chloride are added dropwise at room temperature within 20 min and then stirred for a further 90 min. The red reaction solution is concentrated in a rotary evaporator to about 60 ml, separated from any by-products and mixed with 150 ml of dried acetone. Overnight the compound precipitates with cooling to 5 ° C. It is filtered off and recrystallized twice from acetonitrile.

Yield: 4.4 g (25% of theory)

Biso-morpholiro-B-phenyl-i ^ -dithiazoliuml-tetrachlorocupratdl)

Yield: 4.5 g (.. 24% of theory) of 14.1 g (0,025mol) of the corresponding copper (II) complex m.p .: 163-166 ⁰ C.

Embodiment 3

Bis (3-diethylamino-5-phenyl-1,2,4-dithiazolium) (l!) -Tetrachlorccobaltet

15.28 g (0.02 mol) TrisO.I-diethyl-S-benzoyl-thioureatol cobalt dll) are suspended in 50 ml of dried acetonitrile. While stirring, 6.0 g (0.05 mol) of thionyl chloride were added dropwise and then the blue solution was heated to just before boiling.

After removal of precipitated by-products, the product precipitates when cooled to about 5 ° C after one day. It is then filtered off with suction and recrystallized twice from acetonitrile.

Yield: 1.8 g (12% of theory)

Claims (1)

1. A process for the preparation of 3-dialkyl (aryl) amino-5-phenyl-1,2,4-dithiazolium tetrachlorometallates of the general formula I ¹ R ² I; - C ^ - ^ C - OAi ₁ - I Q I ° ⁵ in which R ¹ and R ^2, which may be identical or different, represent an alkyl group to C ₈ or cycloalkyl group of ring size C ₄ to C _7, or a cycloheteroalkyl group or an aryl group and M is a metal ion, preferably a divalent transition metal ion such as Ni (II ), Cu (II) and others, characterized in that 1,1-dialkyl (aryl) -3-benzoyl-thiourQato-metallated of the general formula II