DD291083A5 - PROCESS FOR PREPARING 1,2,3,4-TETRAHYDRO-2,4-DIOXO-CHINAZOLIN-3-YL-ALKANSAEUREESTERS - Google Patents

Abstract

The invention relates to a process for the preparation of * according to the invention a * is reacted with a Orthokohlensaeureester in an organic solvent or without solvents under Erwaermen over 150C to a * of the general formula II. Among the compounds of general formula II are fungicidal or plant growth regulatory substances. Formula II {* * Orthokohlensaeureester}

Description

For this 1 page formulas

Field of application of the invention

The invention relates to a sedimentation for the cleavage of I ^ .S ^ -Totrahydio ^ Adioxo-quinazolin-S-yl-alkonsäuroostorn dor general formula II. The invention is for the agriculture, Gorton- and forestry of Intorosso, where orfindungsgomäß prepared compounds, z. B. as fungicides or plant growth regulators, are emsotzbar.

Characteristic of the known state of the art

A large number of quinazolines with potential inhibition of phyto-effectors, fungicides, acaricides, insecticides or herbicides are known (M.Suess, S.Johno, Z. Chom. 21,431 (19811).

Of the compounds of general formula II are already known some representatives. Starting from the chlorazoline-2,4 (1H, 3H) .dione, after its salt formation, either 1,2,3,4-tetrahydro-2,4-dioxo-quinazolin-3-yl-acyl-ethylstyrene (II: n - O ₁ X = CH ₂₁ R ² = C ₂ H ₆ ) (M ₁ SuBe, S.Johne, B.Hillmonn, DDR PS 232269) odor with 4-bromobutyronitrile in a mixture in addition to other compounds, the corresponding Quinazolindionnitril prepared its hydrolysis the corresponding butanoic acid and by esterification 4- (1,2,3,4-tetrahydro-2,4-dloxo-3-chloro-3-yl) · butansäurehnestflhn = 0, X = CH ₂ CH ₂ CH ,, R ² = C ₂ H ₅ ) (LR Crook, ABA Jansen, KEV Spencer, DH Watson, British Patent 1036694).

Starting from 2-aminobenzonitrile and Isocyanatoossigsöureothylestor, 1,2,3,4-tetrahydro-2,4 · dioxo-quinazoline-Sylessipsäureothylesler (II: η = 0, X = CH ₂ , R ² = C ₂ H ₆ ) (EP Papadopoulos, J. Heterocycl.Chem.18, 515119811, EPPapadopoulos, CDTorres, J. Heterocycl.Chem.19,269 (1982)).

Some esters of the general formula II were prepared from anthranilic acid esters via the o-isocyanatobenzoic acid esters, their reaction with amino acid esters to give the corresponding o-ureidobenzoic acid ester or its derivatives and subsequent cyclization (E. Wolf, H. Kohl, J. Liebig, Ann Chem. 1975, . ^r .Kionzlo, A.Kaiser, Reminder, HoIv Chim Acta; |; 1245 N.Yamaya, N.Chau, Y.lwakura, Soikei Daigaku Kogaku Kogakubu Hokoku 33.223911982] Chom Abstr 97,72322g | 1,982th.. 66

However, these methods are not generally applicable.

Object of the invention

The aim of the invention is eSjbiologisch active 1,2,3,4-tetrahydro-2,4-dioxo-quinazoline ^'> vl-alkansäureester practice in the desired range, in sufficient quantity and using umwemreundlicheren and less dangerous agents available to put.

Explanation of the essence of the invention

The object of the invention is to develop a simple, generally applicable process for the preparation of compounds of general formula II which is characterized by industrially easy-to-handle starting materials. According to the invention, an N- (2-aminobenzoyl) -aminoalkanoic acid of the general formula I is reacted with an orthocarbonic acid ester in an inert organic solvent or without a solvent with heating to give a 1,2,3,4-tetrahydro-2,4-dioxochiazoline-3 -yl-alkanoic acid ester of the general formula II implemented.

In the general formulas I and II, R ² represents alkyl, X (straight chain C ₁ -C ₀₎ alkylene or branched, gogebenenfalls substituted), R ¹ is alkyl, alkoxy, halogen, CF _3, NO _2, CN, or N ( Alkyl) ₂ and η for 0 to 4, wherein in the cases η = 2,3 or 4, the R ^{1 are the} same or different.

Suitable solvents for the process according to the invention are, for example, DMF, DMSO or a Alkyl ethyl glycol acetate, which need not be specially purified or absolution. The reaction of the compounds of the general formula I with dimeric ortho-carbonate esters is carried out at temperatures above

15O ⁰ C performed. In general, the reaction mixture is heated to reflux. The Orthokohlonsäuroostor is in

Excess and / or sol used as solvent, Borreliaondorwoiso finds only under the angogobonon Bodingungon oino Cyclisiorung and olno gloichzoitigo pre-oror dor Carboxylgruppen to (lon compounds dor general formol Il instead. The compounds of allgomoinone of formula I are readily available from isatoic anhydride and aliphatic amino acids

(M.Süßo, S. Johno, HnIv. Chim. Acta 68, 892 (1985)) and can be used as Rohprodukto (including hydrous).

The orfirulungsgemo ancestor is nllgomoin admirable and goht of easily manageable and, in the Vorgloich to don

bokannton ancestors, all-friendly and non-hazardous raw materials that may have been traded on commercial products or bekannton ancestors. Thus, the compounds of general formula II are readily available

Diversity and in sufficient quantities. Dio compounds of allgomoinone formula II are biologically active. Untor them bofindon themselves those who have a fungiziclo odor

plant growth inhibitor effect zoigon.

The invention is described below by Ausführungsboisplolo otliiutort. embodiments example 1

1.94g2-Amino-hippuric acid (1: η = O ₁ X = CHj) -wordon was refluxed for 4 hours with 4.1 g of orthothocarbonic acid tetramethylamine. The excess of ortho-carbonic acid is distilled off in vacuo and the residue is separated by column chromatography (silica gel 60, elution with chloroform, increasing amounts of methanol are added) and recrystallized. R ₁ = 0.4 (benzene / Acoton = 20: 7), m.p .: 203-207 ⁰ C, yield: 1.4 g of I ^ .S ^ -tetrahydro ^ Adioxo-quinazolin-S-ylossigsäuromethylostor (II: η «= O, X» CH ₂ , R ² = CH ₃ ).

Example 2

2.1 g of N- (2-amino-benzoyl) aminopropanoic acid (1: η = O, X = CH ₂ CH ₂ ) and 4.5 g of orthotrene orthotrene are refluxed in 3 mol of methylene glycol acetate for 3 hours. The mixture is evaporated to dryness in a vacuum and analyzed by column chromatography (see Roissiol Dgotronnt.Ri = 0.4 (benzone / acetone = 20: 7), mp.: 179-181 ° C, yield: 1.1 g of SO 2 .AT-tetrahydro-adioxo-quinazoline -S-y-propanoic acid methyl ester (II: η = O, X = CH ₂ CH ₂ , R ₂ = CH ₁ ).

Example 3

1.63 g 2H-3.1-benzoxazin-2,4 -dione (1 H) are given to 50ml of an aqueous solution of 0.8 g of glycine and 1.1 g of triethylamine under stirring and at 30-5O ⁰ C until completion of the COj- Development (1 hour) stirred. The reaction solution is concentrated under reduced pressure and the residue is refluxed for 4 hours with 5.6 g orthotoluene of ortho-carbonic acid. Further as in Example 1.R ₍ = 0.4 (benzone / acetone = 20: 7), mp: 227-230 ⁰ C, yield: 990 mg of 1,2,3,4-toirahydro-2,4- dioxoquinazolin-3-yl-acetic acid ethyl ester (II: η = O, X = CH ₂ , R ₂ = C ₂ H ₆ ).

Example 4

1.63 g of 2H-3,1-benzoxazine-2,4 (1H) -dione are added with stirring to 70 ml of an aqueous solution of 1.1 g of 4-amino-butyric acid and 1.1 g of triethylamine and at 30-50 ⁰ C stirred until completion of CO ₂ evolution (2 hours). The reaction solution is concentrated under reduced pressure and the residue is reacted with 4.1 g of orthochloroserotetramethyl ester according to Example 1. R ₍₌ 0.35 (benzene / acetone = 20: 7), m.p .: 156-158 ⁰ C, yield: 930 mg of 4- (1,2,3,4-tetrahydro-2,4-dioxo-quinazoline 3-yl) -butanoic acid methyl ester (II: η = O, X = CH ₂ CH ₂ CH ₂ , R '= CH ₃ ).

134 of3

NH-X-COOH

-COOR ²

Claims (3)

1. ancestor for the preparation of 1,2,3,4-Totrahydro ^ A-dioxo-quinazolin-S-yl-alkansäureostorn the general formula II, characterized in that an N- (2-amino-benzoyl) -aminoalkansäuro dor general formol I with an orthoclomic acid ester in an inortonic organic solvent or without solvent under warming to give a 1,2,3,4-total tetrahydro-2,4-dioxo-quinazolin-3-yl-alkanoic acid ester of the general formula II; Formulas I and II R ² for alkyl, X for alkylene [straight-chain (C, -C ₎ O) or branched, where appropriate substituted), R 'for alkyl, alkoxy, halogen, CF ₃ , NO ₂ , CN or N (alkyl) ₂ and ,, are 0 to 4, wherein in the cases η - 2,3 or 4 dio R ^{1 are the} same or different. 2. The method according to claim 1, characterized in that one uses the Orthokohlensöuretotraalkyloster in excess and works at temperatures above 15O ⁰ C. 3. ancestors according to claim 1 and 2, characterized in that one uses the compounds of general formula I as crude products, including in hydrous form.