DD229400A1 - METHOD FOR THE PRODUCTION OF N ', N'-DISUBSTITUTED BIS-N-ACYLTHINE OXYGEN AND THEIR INNERCHELATE METAL COMPLEXES II - 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 to provide a synthesis process in the course of which in a few reaction steps the desired end product is produced in good yield using readily available starting materials. The object is achieved by the reaction of aroyl isothiocyanates with secondary diamines in dry, aprotic solvents. The resulting N, N-disubstituted bis-N-acylthioureas can optionally be converted by the addition of metal salt to inner chelate metal complexes.

Description

Title of the invention :

Process for the preparation of NiH-disubstituted bis - acylthioureas and their internal chelate metal-metal complexes II

Field of application of the invention :

The invention relates to a process for the preparation of ϊθτ-disubstituted bis-N-acylthioureas, which are important as intermediates for organic synthesis and for the preparation of inner chelate metal complexes.

Characteristic of the known technical solutions ;

l ', lT-disubstituted bis-K-acylthioureas and their inner chelate metal complexes are not known. It is known that the N-monosubstatuierten mono-N-acylthioureas in their chemical behavior

mW2] 1) 047

of FjN-disubstituted mono-N-acylthioureas in many different ways. This relates in particular to the complexing behavior and is due to the additionally present HH ffasserst off in -CO-UH-CS-NH over -CO-NH-CS-UR- L.BEYER, E.HOYER, J.LIEBSCHER, H.EART] VIANN, Z. Chem., 21 (1981) 81). For the preparation of N-monosubstituted bis-N-acylthioureas, which have a bridge to the thiocarbamoyl function, there are some references: YAO TSElT CHEN et. al. (Co Hsueh Tung Pao 1963/10, 50-52, cf Chem.Abst.60: 12118 e) describes the preparation of compounds (R-CO-NH-CS-NH-) ₂ R'from 2 RONCS and R ' (NHg) ₂ with R = phenyl and R '= - (CH ₂ ) ^ - or -pr-CgH.-. A Soviet group of authors (TS ROMANSCHENKO et.al., USSR Patent 382615 Cl. C07 c, AT 23.5.73, Issue 9/7/1970) has a patent on compounds containing (R-CO-NH-CS-NH) ) _n R ¹ⁱ and R, R ^1t = aryl, arylene; η = 1,2 and R = aryl, alkyl, arylene (see Chem., Abstr. 79: P 66051 e). T. TAKAGI, H. TANAKA and M. YANO (Pharm. Bull. (Tokyo) 7 (1959), 206, cf Chem.Abst. 54: 22356 f) describe the synthesis of polymethylene bisthioureas R-HH- CS-HH- (OHg) _n -NH-CS-BH-R with R = benzoyl by reaction of benzoylisothiocyanate with primary

CH-G diamines H ₃ N- (CH ₃ ) _n- NH ₂ . By radicals X

bridged N-monosubstituted bis-N-acylthioureas of the type 1'glSlgilllZco ^ ^{with X} = ^W » ^CH

and R = phenyl are also from the primary

aromatic diamines hi ^ CNH ^{2 waa r1ccmcs}

Wuen (M.UHSR et al., Coll.Czech.Chem.Commun.48 / 6 (1983) I651i, Chem., Dept. 100: 6377 h). Y-, p-phenylenediamine, benzoyl chloride and NH.SCN in acetone were KC SATHPATHY, HPMISHRA, BNPATEL J. Indian. Soc. 5 ^ / 1 (1982) 40, cf. Chem.Abstr. 96: 227948 w, the N-monosubstituted bis-N-acylthiourea p, p-bis (benzoylthioureido) benzene C ₆ H ₅ -CO-NH-CS-HH-C ^^ § ^ C-NH-CS-NH-CO -C ₆ H ₅ ^ L and used it as ligands for the preparation of cationic complexes with neutral ligands, ie the ligand is not deprotonated in the complex. These are given the formula MLX ^ (X = Cl, Br, NO ^, ClO.), And their structure is unclear.

Similar N-monosubstituted bis (thioureido) benzene including their metal salts of copper, barium and calcium are described in DE DPK 1806123 (AT 30.10.68, Ausl. 5.4.1973) and DE DPK 1817879 (AT 30.10.1968, Ausl. 13.12.1973 ) by NOGUCHI et al. described and their use as fungicides. It deals

doing so, to compounds of the type

and Y = S, 0; R = CH-. inter alia ..

A method of making new diureid compounds of a similar type is disclosed by W. PBRKOW, DD No. 125567

IPK indicated:. .

^{2 2}

-WH-GO-IH-R ³ -IH-CO-NH-

Y. YASUO, S.SASAKI (Kobunshi Ronbunshu 36/2 (1979) 81, Chem., 90: 187379 d) represent N-monosubstituted polyacylthioureas by reacting iso-phthaloyldiisothiocyanate with aromatic and aliphatic primary diamines. More generally, such! Mono-substituted polyacylthioureas (R-iIH-CS-NH-GO-R-CO-NH-GS-HH-) _n , formed by reaction of bis (acyl isothiocyanates) with diamines, again describe YAO TSU CHEN et .al. (Ko Pen Tzu Hsun Tung £ / 3 (1964) '206, cf. Chem. Abstr. 64: 6778c) .-

Object of the invention :

The object of the invention is to provide a simple process for the preparation of representatives of novel N, N'-disubstituted bis-N-acylthioureas and their inner chelate complex compounds from readily available, inexpensive starting materials.

Explanation of the essence of the invention :

The preparation of N, N-disubstituted bis-N-acylthioureas occurs in accordance with the invention by linking two bidentate N, N-disubstituted N-acylthiourea molecules to their thiocarbamoyl function via bridges of the type

R ¹ R ¹ ' _R 3 ^

- W- R ² - N'- or - N '^ / ^, N-

R ⁴

With the addition of symmetrical disubstituted secondary

12 1 diamines R HN-R-NHR to Aroylisothiocyanaten, which are prepared by boiling acid monochloride and alkali metal thiocyanate in an aprotic solvent, such as acetone and the like., Form the. V _e rbindungen the general formula I

? ¹ R ¹

R - CO - NH - GS - N '- R ² - Ή - CS - NH - CO - R

I, where R = aryl, in particular phenyl, monosubstituted or polysubstituted, R is an alkyl group up to C.g or aryl

ρ can be; R may be arylene, preferably phenylene mono- or polysubstituted and linked in 1,4- or 1,3-position, furthermore aliphatic radicals - (CHp) - may be with η = 2-18. The N ^ N disubstitution which is crucial for the formation of the inner chelate can also be realized by

by the used secondary diamine of the kind

ΛΝΗ and R ^ and Ir are the same or different ⁴

and, for example, R 1 = R 1 each represent a - ₂ ^ p or - (GH = CH -) group, compounds of general formula Ia

R ³

R-CO-NH-CS-N ^ ΛN-CS-KH-CO-R Ia

to be obtained.

The solutions of I and Ia in solvents, such as DMF, are able to give solid, colored, internal-chelate-metal-polymer complexes with metal salts, preferably metal acetates (M = ITi, Cu and the like) in the same solvent with double deprotonation the molecular formula

jjRC (O)] iIC (S) l \ T ^ ^R ₄ "j: iC (S) liC (O) RJlvi? _n Ha

* · R

R suffice.

Exemplary embodiments t

I.Compounds of the general formula I, R = ρ-CgH.,

R ¹ = methyl (ethyl)

6.5 g of benzoyl isothiocyanate are removed by 2 hours

Heating of 4.0 g (0.04 mol) of potassium thiocyanate and 5.6 g (0.04 mol) of benzoyl chloride prepared in 80 ml of dry acetone and the resulting potassium chloride was filtered off with suction. The filtrate is added slowly to a solution of 2.6 g (0.019 mol) of N, I-dimethyl (diethyl) -p-phenylenediamine and 1.0 g (0.01 mol) of triethylamine in 30 ml of acetone and a further 1 hour at Room temperature stirred. The precipitated compound of general formula I is washed with acetone, recrystallized from a little DRIP with addition of activated carbon and washed again with acetone

White powder, soluble in DMSO and DMP Yield: 3.1 g (35% of theory) Melting point: 176-179 ⁰ C.

(R ¹ = methyl)

(25% of theory) Melting point: 185-187 ° C (R ¹ = ethyl)

2 2. Compound of the general formula I, R = ethylene,

R ¹ = ethyl

8.4 g (0.03 mol) of Ιί, Ν-diethyl-ethylenediamine dihydrobromide in 50 ml of acetone are mixed with 10.0 g (0.1 mol) of triethylamine and slowly with stirring, a solution of 9.8 g (0 , 06 mol) benzoylisothiocyanate in 50 ml of dry acetone was added dropwise.

After 2 hours, it is cooled to ⁰ ° C. and the resulting triethylammonium bromide is filtered off with suction, which is washed several times with a little warm acetone. The combined filtrates are concentrated to crystallization of the product of general formula I. It is recrystallized twice from acetonitrile.

Colorless, fine crystals Yield: 1.9 g (14% of theory) Melting point: 170-172 ⁰ C.

3. Preparation of the compound of general formula Ia, R ² = R ³ = ethylene

To a solution of 19 »4 g (0.1 mol) of piperazine hexahydrate and 110.0 g (0.1 mol) of triethylamine in 100 ml of acetone is added within. Two hours, a solution of 32.6 g (0.2 mol) of benzoyl isothiocyanate in 200 ml of dry acetone was added dropwise. After a further 2 hours, the reaction mixture is concentrated to 100 ml and then cooled to ⁰ ° C. The product of general formula Ia precipitates as a white powder and is recrystallized from acetonitrile. Yield: 8.6 g (21% of theory) Melting point: 184-186 ° C

4. Representation of the polymeric metal complexes of the general formulas II and Ha

1.25 g (5 mmol) of nickel (II) acetate tetrahydrate are dissolved in 150 ml DMF at 50 ⁰ C. With vigorous stirring, 5 mmol of one of the ligands of the general

ο ·? "

Formula I or Ia dissolved in 80 ml of warm DMF quickly added in one portion. The chelate polymer of the general formula II or Ha precipitates after a short time. If it comes to gelation, is added to the same volume of concentrated saline and stirred vigorously for 15 minutes. After filtration with suction, it is washed several times with water, ethanol and ether. The complexes are insoluble in water and in organic solvents.

Used metal salt R = C ₆ H ₅ colour Melting point (0 ^° C.) Yield (%) Ni (0ac) ₂ x4H ₂ 0 R ¹ = CH ₃ R ² = pC ₆ H ₄ violet powder 360 48 R = CpH ₁ - ^r2 = P ^g 6 ^H 4 violet powder 360 91 R ¹ = C ₂ H ₅ R ² -C ₂ H ₄ violet powder 345-352 80 R ³ = R ⁴ = ^C 2 ^H 4 violet powder 320-322 79 Cu (0ac) ₂ ^xH 2 ° R ¹ = CH ₃ R ² ^ pC ₆ H ₄ green powder 270 67 R ¹ = C ₂ H ₅ r! = Pc ₆ h ₄ green powder 209-213 82 R ¹ = C ₂ H ₅ R ² = C ₂ H ₄ green powder 218-223 79 R ^ = R * = ^G 2 ^H 4 brown powder 234-236 52

The elementary analyzes are in agreement.

Claims (4)

claims 1. A process for the preparation of .lOl-di sub constituted bis-N-acyl thioureas and their inner chelate metal complexes, characterized in that a secondary amine is reacted with an aroyl isothiocyanate in a dry aprotic solvent and the precipitating product is separated, whereupon it is optionally reacted in an aprotic solvent with a metal salt and the internal chelate metal complex precipitating on cooling or stripping off the solvent is separated. 2 · Method according to item 1, characterized in that as secondary amine a compound of the general R R 1 Formula ^ _ _R 2_ ^ _fi with R = alkyl group to G ₁₈ or Aryl; R = arylene or aliphatic radicals - (CHp) - with η = 2 - '18
is used. 3. The method according to item 1, characterized in that the secondary amine is a compound of the general formula with R ³ = - (CH ₂ ) j; - (CH = CH) - or the like. R
and R ⁴ = - (CH ₂ ) ₂ -, - (CH = CH) - or the like. can be. 4. The method according to item 1-3, characterized in that is used as solvent dry acetone,