DD229399A1 - PROCESS FOR THE PREPARATION OF N ', N'-DISUBSTITUTED BIS-N-ACYLTHIAROUS SUBSTANCES AND THEIR INNERCHELATE METAL COMPLEXES I - Google Patents

Abstract

The invention relates to a process for the preparation of N, N-disubstituted bis-N-acylthioureas. The goal is to provide the previously unknown compounds available. The object of the invention is seen in providing a synthesis process, in the course of which the desired final product is produced in good yield from easily accessible starting materials in a few reaction steps. The object is achieved by the reaction of dichlorides of aromatic dicarboxylic acids with alkali metal isothiocyanate and subsequent addition of secondary amine. The resulting N, N-disubstituted bis-N-acylthioureas may optionally be reacted by addition of a metal salt to inner chelate metal complexes.

Description

Title of the invention :

Process for the preparation of H ^ N-disubstituted bis-N-acylthioureas and their internal chelate metal complexes I

Field of application of the invention :

The invention relates to a process for the preparation of N'-N-disubstituted bis-N-acyl thioureas, which are important as intermediates for organic synthesis and for the preparation of internal chelating agents.

Characteristic of the known technical solutions :

ϊθϊ-disubstituted bis-N-acylthioureas are not yet known.

YAO TSU CHEN et.al. (Ko Hsueh Tung Pao 10 (1963) 50; see Chem.Abstr.60: 12118 f) indicate that bis-acyl

-6.0LZ.19S4-2IÜ54 6

thioureas of the type R-NH-GS-NH-CO-R-CO-NH-CS-NH-R 'with R' = phenyl, R = (CHg) ₄ , P-GgH ₄ of R (GOIIGS) ₂ and amines R-ITHp are representable, but only primary amines find application, as well as in the alternative variant of the preparation of bis-acyl thioureas (R-CO-NH-CS-NH ^ ₂ R'aus RONGS and RfNH ₂ ) ₂ . However, such N-monosubstituted N-acylthioureas are completely different in metal complex formation and organic compound formation than the Ν ', Ν-disubstituted species because of the presence of a second NH-hydrogen -NH-GS-NH (see L.BEYER E.HOYER, J.LIEBSGHER, H.HARTMANN, Z.Ghem 22 (1981) 81). The preparation of N-monosubstituted bis-N-acylthioureas is the subject of a patent by TSROMANSCHENKO, AISIEDVEDEV, VVMIKHAILOV and PI LEVIN (USSR Patent 382,615 CCOTc ν. 23.5.1973, see Chem.Abst.79: P 66051 e): ( R-CO-NH-GS-NH-) _n R ¹ and R (-GO-NH-GS-NH-R ¹ ) _n where η = 1.2; R, R ¹ = arylene, 'aryl, R = arylene, alkyl, aryl and published in Otkrytiya Isobret. Prom. Obraztsy Tovarnye Znaki 50 (23) (1973) 58.

In a manner similar to the N-monosubstituted bis-N-acylthioureas noted above, N-monosubstituted polyacylthioureas are also prepared by reacting bis (acyl isothiocyanates) with primary diamines

to give products of the type - (R-HH-CS -.]! TH-CO-R-CO-NH-CS-NH-) _n (YAO-TSU CHEN et al., in Ko Fen Tzu Tung Hsun β / 3 (1964) 2C6, see Chem.Abstr./64: 6778 c). Y. YASUO, S. SAZAKI (Kobunshi Ronbunshu 36/2 (1979) 81, cf Chem.Abst.90: 187379 d) obtained such N-monosubstituted polyacylthioureas from iso-phthaloyl diisothiocyanate with aromatic or aliphatic primary diamines or from Aminobenzoic acid, the latter of the type - (ITH-pC ₆ H ₄ -CO-in-CS-) _n (Y.SHIMONO, S.SASAKI, J. Polymer Sei.Polym. Chem., 21/5 (1983) 1331, See Chem.Abstistrasse 98: 2161O6 k). The same authors also described similar compounds of hydrazides - (R ¹ -CO-NH-CS-NH-KH-GO-R ² -C 0 -NH-NH-CS-NH-C0-) _n (Kobunshi Ronbunshu 37/2 1980) 131, see Chem.Abstract 92: 181719 j) · In all these cases neither metal chelates are described nor Ν ', Ν-disubstituted representatives are shown or indicated.

Object of the invention :

The invention has the goal of producing the hitherto unknown N ^ N-disubstituted bis-1-acylthioureas and their inner chelate metal complexes in a technically simple and economically advantageous manner

enable.

Explanation of the essence of the invention ;

The invention has for its object to provide a synthesis ^ process, in the course of easily accessible starting materials in a few reaction steps, the desired end product is formed, which can be easily separated from the reaction mixture and obtained in good yield.

The object is achieved in that two bidentate ÜT ^ N-disubstituted H-AcyIthiharnstoff molecules are linked via a bifunctional acyl radical -GO-R-GO, wherein the acyl radical is a bridge.

The bridging is realized according to the invention by the use of dichlorides of aromatic dicarboxylic acids, whereby on conversion of acid chloride Cl-GO-R-GO-Gl, alkali metal thiocyanate K (Ka) SCH and subsequent addition of

be of secondary amine HER R in an aprotic solvent such as acetone and the like in one. One-pot reaction of the IVT ^ I-disubstituted bis-H-acylthioharn-Stoffe.der general formula I.

R ¹ R ² Ii-GS-TIH-GO-R-CO-NH-GS-IiR ¹ R ² . I 'arise, which, depending on the reactants used in the form of their dialkyl (aryl) ammonium

salts of general formula II

[R ¹ R ² N-CS-KH-CO-RC = N-CS-NR ¹ R ² J "H ₂ NR ¹ R ^{2 +} II

1 2

may apply, where R and R, which may be identical or different, is an alkyl group up to C ^ "or cycloalkyl ring size C. to C "or an aryl mean. R may be arylene, preferably phenylene, which may be mono- or polysubstituted, with linkage in preferably before 1,4-, but also in 1,3- or 1,2-position, may be. The compounds of the type I or II formed in this way are converted according to the invention into their inner chelate metal complexes of the general formula III

η = 2.3 ....

M = Ni, Cu, Pd, Hg, Zn, Pb or the like .

in a solution of I or II in an aprotic solvent such as DMF or the like. A solution of the respective metal salt, preferably metal acetate (M = subgroup metals such as Ni, Cu, Pd, Hg, Zn, and main group metals such as Pb) in the ratio of 1 : 1 is added, wherein deprotonation of the ligand occurs and precipitates on cooling or partial subsequent removal of the solvent III in solid form. For example, for M = Ni, η = 3, R = P-CgH. the

'obtained the following structure:

-ti o 19

R "R% NR ¹ R ^

0-C ^/

R ¹ R ^ '^ ST \ ^N CRG / ^iU v7 "V ¹ R ²

due to the binuclear nature of the ligands and the resulting trimetallacyclic nature with their molecular cavities, e.g. as a host molecule for metal-specific interactions with guest molecules are suitable.

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

embodiments

1, compound of general formula I, R = p-CglL, R ¹ = R ² = n-propyl:

10.0 g (0.1 mol) of potassium thiocyanate are suspended in 100 ml of acetone dried over calcium chloride

and heated to boiling. 10.0 g (0.05 mol) of terephthaloyl dichloride (synthesized according to WRSOREESON, TWCAMPBELL "Preparative Methods of Polymer Chemistry", Verlag Chemie, Weinheim 1962, p.85) dissolved in 50 ml of dry, warm acetone become within 1.5 hours added dropwise, the reaction mixture assumes a bright yellow color. The mixture is stirred for 3 hours at 60 ° G water bath temperature, _r . then to O ⁰ C and sucks the resulting Kaliumv_ / chloride sharply. The PiItrat is added dropwise within one hour to 16.5 ml (0.12 mol) of di-n-propylamine in 50 ml of acetone with stirring. The reaction mixture is heated to about 35 ⁰ C. During the reaction, the product of general formula I begins to precipitate. 30 minutes after completion of the addition of Terephthaloyldiisothiocyanats the reaction mixture is cooled to 0 ⁰ C and the resulting product was suctioned off (colorless, fine crystals) ^{; :} , and dried in the air.

Yield: 4.2 g (1 9> 2 of theory) Melting point: 1 56-1 59 ⁰ C

2. Compound of general formula II, R = pC-HL, R ¹ = R ² = ethyl (η-butyl):

If the diethylamine (di-n-butylamine) is added to terephthaloyldiisothiocyanate after 1. instead of di-ri-propylamine, the resulting terphthaloyl bis-

Thiourea deprotonated by excess dialkylamine and is present as diethyl (di-n-t> utyl) ammonium salt

Yield: 33% of theory (R ¹ ', = R ² = Et)

21% of theory (R ¹ = R ² = n-Bu) Melting point: 162-163 ° C (Et); 109-113 ⁰ C (n-Bu)

3. Compound of the general formula IV, R = p-CgH. , R ¹ = R ² = ethyl, 1I = E:

7j5 g (moljNickelCUiacetat tetrahydrate v / ground dissolved 0.03 at 50 ⁰ C in 700 ml of dimethylformamide. Within 3 hours, a solution of 14.0 g (0.03 mol) of the compound of the general formula II (R = p -CgH; R ¹ⁱ = R ² = Et) is added dropwise in 300 ml of warm DMF, the crystallization of the chelate formed does not on cooling the reaction mixture to room temperature, allowed to stand overnight in the refrigerator ^ After aspirating ¹ with water, Ethanol and ether, and was recrystallized from methylene chloride / ethanol.

Yield: 10.3 g (76% of theory), brown leaves Melting point: 304 ° C. (dec.)

After the o.g. Process, the following complexes of general formula IV (R = P-CgH.) Synthesize:

inserted R ¹ = R ² = colour - colorless -Schmelz Yield(%) metal salt colorless point ( ⁰ C) Ni (Oac) ₂ χ 4H ₂ O Eth brown 304 76 , n-Prop brown 345 89 n-Bu brown 300-302 53 Cu (Oac) 2 ^xH 2 ° Eth green 219 66 n-Prop black- - green 258 78 n-Bu black green 216-218 49 Na ₂ PdCl ₄ ⁺ Eth orange 309 60. Zn (Oac) ₂ χ 2H ₂ O ⁺ Eth 264-266 76 Hg (0ac) ₂ ⁺ Eth 213-217 78

It was buffered with sodium acetate trihydrate

4. Compound of general formula III, R = m-CgH., R ¹ = R ² = ethyl, M = Hi:

In 400 ml of dry acetone, 25 g (0.1 mol) of iso-Phthaloyldiisothiocyanat (prepared from 20 g of iso-Phthaloyldichlorid and 20 g of potassium thiocyanate) with 31 ml (0.3 mol) of diethylamine implemented.,

After 3 hours, the acetone is removed by rotary evaporation and the oily residue is taken up in 200 ml of dimethylformamide. This solution is added with vigorous stirring to a solution of 25 g (0.1 mol) of Mckel (II) acetate tetrahydrate in 500 ml of DMF. The resulting nickel complex precipitates as a violet powder and is insoluble in organic solvents and in water

 Yield: 18 g (40% of theory) Melting point: 34 ° C. (dec.)

Claims (4)

claims 1. A process for the preparation of N-bis-disubstituted bis-N-acylthioureas and their internal chelate metal complexes, characterized in that Alkali metal thiocyanate is reacted with the dichloride of an aromatic dicarboxylic acid in an aprotic solvent in the heat, to the reaction mixture, a secondary amine is added gradually and the product separated by cooling is separated, whereupon it is optionally reacted in an aprotic solvent with a metal salt and the upon cooling or stripping of the solvent precipitating inside chelate metal complex is separated. 2. The method according to item 1, characterized in that the aprotic solvent acetone, DMF ο.dgl. be used. 3 »method according to item 1 and 2, characterized in that as a sec. Amines the following compounds used tferdenrfflTRVCR ¹ , R ² = alkyl, for example ethyl, n-propyl, n-butyl; Aryl). 4. The method according to item 1, characterized in that the reaction of the dicarboxylic acid dichloride is carried out with alkali metal allisothiocyanat in boiling acetone.