DD144541A1 - METHOD FOR PRODUCING SUBSTITUTED 2-AMINO-3-ARYL-4- (3H) -PYRIMIDINONES AND THIONES - Google Patents

Abstract

The title compounds, which can be used as intermediates, are made accessible by a simple process according to the invention by the addition of enantiomers of isomers with isocyanates and isothiocyanafcene (substituted β-aminoacrylamides and -thioamides) I with cyanamide II to substituted 2-amino-3-aryl 4 (3H) -pyrimidiiionen and -thionen III be implemented.

Description

Title of the invention

Process for the preparation of substituted 2-amino-3-a-yl-4- (3H) -pyrimidinones and -thiones _:

\. '. Int. Cl. O 07 D, 239/32

Field of application of the invention

The invention relates to a process for the preparation of substituted 2-amino-3-aryl-4 (3H) -pyriéiidinones and -thiones. Such compounds may become important as intermediates, e.g. for the manufacture of pharmaceuticals, dyes or herbicides.

Charalctoristics of the known technical solutions'

2-A.mino-3-aryl-4 (3H) "Pyriiaidinones and thiones are not known but are the related 2-amino-3-aHvyl ~ 4 - (3H) -pyrimidinones." These are either as indicated, for example, in The Chemistry of Heterocyclic Compounds, VoI ₀ 16, Arppl * 1, by 'H-alkylation, or, for example, by Brit Pät _e 1.444.548, C _e A _e 86, s 55480 (ig ??) and Chem. Pharm. Bull. 2j ?, 215 (1977) prepared 2-amino-4-pyriniidinonen by rearrangement of the exocyclic N or 0-Aliiyi ~. For this purpose, first the corresponding ring systems must be ¹ synthesized in several steps.

Z-iel the! Invention ".

The aim of the invention is to produce substituted 2-amino-4-pyrimidinones and -thiones in a simple manner.

- · ^; '.-::. : -> -:. -. ' * Presentation of the essence of the invention

The object of the invention is to produce unknown 2-amino-3-aryl-4 (3H) -pyrimidinones and -tkenes by a simple process,... ; '''''''·..-.' ·. ' According to the invention, the object is achieved by reacting the addition compounds of amines and isocyanates and isothiocyanates, which are substituted .beta.-aminoacryic acid amides and thioamides of the general formula I,

R ₀ KO = CC-MI-R ³ I ^;

, , '. / :. , Rν Rf. Χ -'..- 'V'; , . ' ·.

where BRp is a! pyrrolidino, marpholino, piperidino or

  1 2 Dialkylamino, E and R is a water st off atom, an alkyl, aryl or cyclic linking alkyl group and R ^ is an aryl group and X is an oxygen or sulfur atom, with cyanamide II

'- cit. 11. ^; ...; _: '";. ... ^:

in a solvent at 60 - 120 ⁰ C reacted. This gives rise to the 2-amino-3-aryl-4 (3H) -pyrimidinones and -thiones of the general formula III

""^; V ' ^: ''

, , '. Λ ? * ί · '' · ''.

in which the radicals R, R, R ^ and X have the abovementioned meaning.

The starting materials are according to known, for example, in Fortschr. Chem. Forsch,! Ft, 235 O970).

 Exemplary embodiments.

Example 1: 2 _T A _ffl ino-5 ~ et! X7l-3-phenyl-A- (3H) -pyrimidinthione

A mixture of 0.01 Bio! ! 1 I yrrolidino-n-butene - (1) -thiocarbon-

      · - 3 - '' '' '

acid (2) ~ anilide, 0.012 mol of cyanamide and 10 ml of n-propanol are refluxed for 2 hrs. After standing for 10 hours is filtered off with suction and washed with water. Yield 82%, mp> 186-190 ⁰ G (from acetonitrile).

Example 2: 2-Amino-5,6-trimethylene-> phenyl-4 (3H) -pyri-quinidine

0.01 mol of S-morpholino-cyclopentene-CI) -thiocarbonsäureänilid together with 0.012 mol of gyanamide in 10 ml of n-propanol for 1.5 hours, heated to boiling. The product, which precipitates already in the heat, is filtered off with suction and recrystallised from glacial acetic acid, yield 64%, mp 285-290 ⁰ G ₉

Example 3ί 2-Amino-5,6-tetramethylene-3-ynyl-4 (3H) -pyrimidine:. ,; .. '. -. .. .-. thion .. · · .., '. \. '':. '.'"' . '. . ·

0.01 mol of S-morpholino-cyclohexene-Ci) -thiocarbonsäureanilid and 0.014 mol of gyanamide are heated in 10 ml of n-propanol for 1 hr. Reflux. After cooling, it is filtered off with suction and recrystallized from n-propaaol. Yield 70%, mp 283-285 ⁰ C.

Example 4: 2-amino-5,6-pentamethylene-3-phenyl-4 (3H) -pyrimidine

A solution of 0.01 mol of 2-morpholino-cyclohepten- (1) ™ thiocarbonsäureanilid and 0.014 mol of cyanamide in _: 15 ωΐ n-propanol is heated for 2 hrs. Reflux · .After cooling and crystallization terminated, possibly triggered by rubbing must be _s is filtered off with suction and recrystallized from ethanol. Yield 64 % _f mp. 208-210 ⁰ G. ^

Example 5: 2-Amino-3,6-dithenyl-4 (3H) -pyridinethione . ,

0.01 mol beta-morpholino-thiozimtsäureanilid and 0.012 mol Gyanamid be 2 h _e heated together in 40 ml n-propanol to boiling, "Thereafter, the solvent is distilled off in vacuo, stirred with 5 ml of ethanol and filtered off with suction _e Yield 54% , Schmp _e . 195-199 ⁰ C (from methanol), ',:.

Example 6 s 2 ~ Ajaino-5,6-tetramethylene-3-ip-toly3 -4 (3H) -pyria diathion

0.01 HLol 2-Morpliolino-c7Ciohexene ( ^/ i) thiocarboxylic acid p-toluidide (mp 112-117 ⁰ G) and 0.012 mol of cyanamide are abs. Dimetlaylformamide heated to boiling for 0.5 h. . If the iederschlag sucked * 67% yield, m.p., 223-224 ⁰ C (from ethanol) - after 12 hours is. -.

Example 7: 2-Aiaino-5,6-tetraniethylene-3- (cC-naphthyl) -3- (3H) -pyridinethione

0.01 mol of 2-morpholino ^ cyclohe2üej3- (1) ~ carbothioic acid (X ^ naphthylaEiid (m.p., 160-162 ⁰ G) for 0.5 h. In 5 ml of abs, DimetbyIformamid heated .-.! TACU standing over ITacht A second part of the product precipitates, which is filtered off with suction, and further dilution of the precipitate with water gives further iodine-thionione, yield 74 % of mp 29 ° -295 ° C (as nitromethane).

Example S: 2-Amino-5,6-trimethylene-3-phenyl-4 (3H) -pyriniidinone

A solution of 0.01 mol of 2-morpholino-cyclopenten- (1) -carboxylic acid ailide and 0.012 mol of cyanamide in 15 ml of n-propanol are refluxed for 2 hrs. After cooling, it is mixed with 50 starters and aspirated after standing for a very long time. Recrystallized from ethanol. Yield 56 ^, Schrap »252-255 ° 0.

Example $: 2-Aniino-5,6-tetrametti-1-yl-3-phenyl-4 (3H) -pyrimidi-... non _: /. - ^: ·. ' .- ":" ... "".

0.01 mol of 2-morpholino-cyclohexene- (1) -carboxanilide together with 0.014 mol of cyanamide in 8 ml of dimethylformamide for 20 min. Under gentle reflux. After cooling, it is stirred into 50 ml of water and filtered with suction. The product can be re-crystallized from acetonitrile. Yield 55%, mp 234-236 ⁰ C.

Example 10: 2-Amino-5,6-tetrame'tbyl-3- (3-naphthyl) -4- (3H) -pyrimidinone

To a solution of E, oil mol Morpholinocyc lohexen added dropwise with stirring and moisture terminal within 20 Min., 0.01 mol οι -Naphthylisocyanat in 10 ml of acetone, keeping the temperature zwischenΛ0 and 45 ⁰ C v / ill. After further standing for one hour at room temperature, the acetone i. Yak. The remaining light yellow syrup remaining in 5 ml absolute. After standing 2-3tägigem v heated under '''gentle .Rückfluß dimethylformamide and, after addition of 0,014- mol "Oyanamid 0.5 h;.... Ill be sucked from the failed ITiederschlag yield 51% i mp 269-273 ⁰ C ( from methanol),.

Claims (1)

Erf indungsansprucli. ./ ** for producing ¥ substituη substituted 2-Aiiiinc-3-aryl ~ ^/ ir- (3H) -pyrimidinones and -monen, characterized in that substituted ß ~ Äfflinoaerylsäure amides and thioamides of the general Eoriel I ,. R R X in which R0 is a morpholino-pyrrolidino, piperidino or dialkylamino group, R and R are an aryl or alkyl group, a cyclic linking alky group or a hydrogen atom, Rv is an aryl radical, and X is an oxygen radical or sulfur atom, in a solvent, preferably -. 'inν an alcohol or in Dimethylforiamid, at 60-120 ⁰ G with Gyananiid II - GN. - .. ./ II:::; ; ; ; ... ; , / be converted to the compounds of general formula III, , ·; ; '. '^> ϊ ^ ν; . ' .., ..; ^: -; .. ^ ^-y::; '\ \' ^-, -. '. ' -,· -in .' , / v: ·. , .- '^;:' in which R, R, R ^ and X dl © have the meaning given above.