DD293352A5 - PROCESS FOR PREPARING 2,2-DISUBSTITUTED 1-ACYL AND / OR 9-ACYL-2,3-DIHYDRO-IMIDAZO / 1,2-A / BENZIMIDAZOLE-3-ONEN - Google Patents

Abstract

The invention relates to a process for the preparation of novel 2,2-disubstituted 1-acyl and / or the invention by reacting 2,2-disubstituted * with an arylating / acylating agent such as acid chloride or cyanate in the presence of an acid-binding agent or in an aprotic solvent at temperatures of 100 to 200C. The new compounds are useful for biocides, especially herbicides, acaricides, insecticides, fungicides and anthelmintics. {Disubstituted * disubstituted * acylation; acid chloride; Carbonic acid ester chloride; Thiocarbonic acid O-ester chloride; cyanate ester; isocyanic; aprotic solvent; thermal isomerization}

Description

For this 1 page formulas

Field of application of the invention

The invention relates to a process for the selective preparation of novel 2,2-dlsubstltulerten 1-acyl and / or 9-acyl-2,3-dihydro-imidazol1,2-albenzimidazol-3-ones, which are used as active ingredients for biocidal agents, in particular as herbicides, acaricides, insecticides, fungicides and anthelmintics may be of interest.

Characteristic of the known state of the art

It is known that acyldorivatives of 1,3,5-triazino [1,2-a] -benzimidazoles are very good herbicides (D. MARTIN, H. GRAUBAUM, J.prakt.Chem.321,315 (1979), DD-PS 242340, DD-PS 227035, DE-OS 2144505, US-PS 4497650), fungicidal (DE-OS 2527677) and insecticidal (DD-PS 235019) properties. In addition, pharmacological properties of the triazino [1,2-albenzimidazoles against nematodes, clades and hookworms (DE-OS 2,452,365, GB-PS 1522076) are also known. Acyl derivatives of imidazo | 1,2-a] benzimidazoles have not yet been described. Only the 9-aryl-2,3-dihydro-imidazo [1,2-ajbenzimldazole are cited with pharmacological properties in the literature (GB-PS 1476949). Furthermore, the 2,2-diphenyl-2,3-dihydro-imidazol1,2-a] benzimidazol-3-one can be prepared by thermolysis of 1-aryl-2-cyano-3,3-diphenyl-diazetidin-4-one (CW.BIRD, MWKACZMAR, CKWONG: Tetrahedron 30, 2549 (19741).) The 2,2-disubstituted 2,3-dihydroimidazo [1,2-a] benzimidazol-3-ones required as starting materials were obtained from 2 -Amino-benzimidazole, chloroform and acetone or cyclohexanone and subsequent cyclization with thionyl chloride (H.GRAUBAUM, R.OZEGOWSKI: J.prakt. Chem: in preparation) prepared by known methods.

Object of the invention

It is the object of the invention to provide a selective process for the preparation of novel 2,2-disubstituted 1-acyl and / or 9-acyl-2,3-dihydroimidazo (1,2-a) benzimidazol-3-ones which does not require complicated process or separation steps and which makes a variety of compounds having different substituent patterns available.

Explanation of the essence of the invention

The object of the invention is to achieve the object of the invention by acylation of 2,2-disubstituted 1 (9) -H-2,3-dihydro-imidazol1,2-a] benzimidazol-3-ones.

This object is achieved by a process for the preparation of novel 2,2-disubstituted 1-acyl or 9-acyl-2,3-dihydroimidazo (1,2-a) benzimidazol-3-ones of the general formula 3 or 2,

7 »

in which mean: -

R, R ': in each case methyl or together pentamethylene,

Acyl: COR ', COOR ² , C (= NH) OR ² , CONHR ² or CI = S) OR ² , where R ^{2 is} alkyl or optionally

may be substituted aryl,

by according to the invention an acid chloride of the general formula R ² COCI, a carbonic acid ester chloride of the general formula R ² COOCI, a cyanic acid ester of the general formula R ² OCN, an isocyanic ester R ² NCO or a Thiokohlensäureester-Ö-ester chloride of the general Formula R ² OCSCI with a 2,2-disubstituted 2,3-dihydro-imidazo [1,2-a] benzimidazole 1 in which R and R ^{1 have} the abovementioned meanings, at temperatures from -10O ⁰ C to +200 ⁰ C converts.

Depending on the aryl radical and originate from the reaction temperature, thereby selectively 1-acylphenylalanine derivatives 3 or the isomeric 9-acyl derivatives 2. The compounds 2 formed at temperatures from -100 ⁰ C to 50 ° C can be thermally at temperatures of from 1O ⁰ C to 200 ⁰ C with and without solvent isomerize to 3, wherein as a solvent, for example, acetonitrile, dioxane, DMF, DMSO or pyridine can be used.

It can also be the compounds 3 directly from 1 and the corresponding acylating agent, without isolation of the isomeric compounds 2 (see Example 4). In the reaction of 1 with cyanic acid esters and isocyanic acid esters (Method A) is carried out according to the invention in an aprotic solvent, in the reaction with acid chlorides, carbonic acid ester chlorides or thiocarbonic O-ester chlorides is an acid-binding agent, eg. As triethylamine, Na ₂ CO ₃ or pyridine, advantageous (method B).

The process products are obtained, if appropriate after concentration of the solvent or precipitation with water, in good yields and are isolated by known methods (see Table 1 and 2). The structures of the resulting reaction products are derived from elemental analyzes, mass, ¹ H and ¹³ C NMR spectra.

embodiments

Method A

10 mmol of 2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-one are dissolved in 10 ml of acetone. These are added dropwise at -7O ⁰ C lOmmol phenyl isocyanate. After a few minutes, white crystals cut off, the product is filtered off with suction and dried. There are 80% of the S-phenyl-carbamoyl ^ dimethyl ^ S-dihydro-imidazololi ^ -albenzimidazol-S-one (2f) (mp. 178-180 ⁰ C) was isolated (see Table 1).

Method B

lOmmol of 2,2-dimethyl-2,3-dihydro-imidazo [1,2-albenzimidazol be on-3-introduced into 15 ml of THF at 10 to 15 ⁰ C. For this purpose, 10 mmol of carbonic acid ethyl ester chloride and then 10 mmol of triethylamine are added dropwise. After one hour of stirring at room temperature, 30 ml of water are added, the precipitate sucked off and dried. There are 70% 9-ethoxycarbonyl-2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazole-3-one (21) (mp. 144-145 ⁰ C) was isolated (see Table 1 ). 6somerizations 2 - *> 3

example 1

10 mmol of 9-phenoxycarbonyl-2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-one (2 ml) are stirred for 24 hours in 20 ml of acetone at room temperature, the product is filtered off with suction and dried. There can be obtained 84% i-phenoxycarbonyl-2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-one (3m) (see Table 2).

Example 2

1 g of 9-methylcarbamoyl-2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-one (2β) is briefly boiled in 5 ml of DMSO. Upon cooling, 89% of 1-methylcarbamoyl-2,2-dimethyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-one (3e) precipitate (see Table 2).

Example 3

1 g O-Acotyl ^^ - dlmothyl ^ .a-dlhydro-lmldazoII ^ -nlbonzlmldoiol-a-on (2 b) is heated for 1 hour at 200 ° C without solvent. After cooling, the product was 92% i-acetyl -dlmothyl-dihydro-imidazolium-alzolmidazol-S-one (3b) iso-norol (see Table 2).

Example 4

10 mmol of 4-chlorophenyl phthalocyanate was added dropwise to 20 ml of acetonitrile in 20 ml of acetonitrile at room temperature, then the solution was refluxed for 10 minutes 71% of 1- (4-chloroporonylcarbamoyl) -2,2-dlmothyl-2,3-dihydro-imidnzo [1,2-a] -benzylmkt-3-one (3l) nus (plohoTabollo2).

2 _{l of} 2-disubstituted 9-acyl-2,3-dihydro-imidazo [1,2-a] -bonzimidazol-3-oneo (2a-p) R ¹

acyl

Y. method

fp

( ⁰ C)

Total formula (molecular weight)

2a CH ₃ CH ₃ Ci = NH) OCH ₂ CCI ₃ 40 A 2 B CH ₃ CH ₃ COCHj 85 B 2c CH ₃ CH ₃ COCjH ₆ 84 B 2d CH ₃ CH ₃ COC ₆ H ₆ 92 B 2o CH ₃ CH ₃ CONHCH ₃ 93 A 2f CH ₃ CH ₃ CONHC ₆ H ₆ 80 A 2a CH ₃ CH ₃ CONHC _e H4-CH (CH ₃ ) 2-4 70 A 21 CH ₃ CH ₃ CONHC ₆ H ₄ -CM 71 A 2k CH ₃ CH ₃ COOCH ₃ 66 B 21 CH ₃ CH ₃ COOC ₂ H ₆ 70 B 2m CH ₃ CH ₃ COOC ₆ H ₆ 49 B 2n CH ₃ CH ₃ CI = S) OC ₈ H ₄ -OCHR ^ 82 B 2o -CH ₂ (CH ₂ I ₃ CH ₂ - CONHCH ₃ 80 B 2p -CH ₂ (CHj) ₃ CHr- CONHC ₆ H ₆ 89 B

176-178 ^b) C ₁₄ H ₁₃ CI ₃ N ₄ Oj (375.7 / 375) 188-190 ^bl C ₁₃ H ₁₃ N ₃ O ₂ (243.3 / 243) 166-167 ^b) C ₁₆ H ₁₆ N ₃ O ₂ (257.3) 147-148 ° ' C ₁₈ H ₁₆ N ₃ O, (305.3) 165-166 ^b) C ₁₃ H ₁₄ N ₄ O ₂ (258.3 / 258) 178-180 ^bli) C ₁₈ H ₁₆ N ₄ O ₂ (320.4 / 320) 143-144 ^blel C ₂₁ Hj ₂ N ₄ O ₂ (362.4) 235-236 "" " C ₁₈ H ₁₆ CIN ₄ O ₂ (354.8) 178-180 ^b) C ₁₃ H ₁₃ N ₃ O ₃ (259.3 / 259) 144-145 ' " C ₁₄ H ₁₆ N ₃ O ₃ (273.3) 178-179 ^bw C ₁₈ H ₁₆ N ₃ O ₃ (321.3) 127-128 ^b) C ₁₉ H ₁₇ N ₃ O ₃ S (367.4) 295-297 "" " C ₁₆ H ₁₈ N ₄ O ₂ (298.4) 185-186 ^bl " C ₂₁ H ₂₀ N ₄ O ₂ (360.4 / 360)

¹¹ MS-mole peak, ^bl out of CH ₃ CN, "from EtOH,"'from benzene / petroleum ether *' Recrystallization already leads to a partial isomerization to 3.

Tab. 2 2,2-Disubstituted 1-acyl-2,3-dihydro-imidazo [1,2-a] benzimidazol-3-ones (3a-q)

R ¹

R ²

acyl

Y. fp

( ⁰ o

Molecular formula

(Molecular weight " ¹

calc. [gef.])

3a CH ₃ CH ₃ CI = NH) OCHjCCI ₃ 3b CH ₃ CH ₃ COCH ₃ 3e CH ₃ CH ₃ CONHCH ₃ 3f CH ₃ CH ₃ CONHC ₆ H ₆ 3g CH ₃ CH ₃ CONHC ₆ H ₄ -CH (CH ₃ ) J- ^ 3h CH ₃ CH ₃ CONHNapth-1-yl 3! CH ₃ CH ₃ CONHC ₆ H ₄ -CM

91 176-178 ^bl 92 188-190 ^bl 89 165-166 " ¹ 75 178-180 ^bl 89 143-144 '' 82 188-189 ^bl 71 235-236 * '

C ₁₄ H ₁₃ Cl ₃ N ₄ O ₂

(375.7)

C ₁₃ H ₁₃ N ₃ O ₂

(243.3 / 243)

C ₁₃ H ₁₄ N ₄ O ₂

(258.3 / 258)

C ₁₈ H ₁₀ N ₄ O ₂

(320.4)

C ₂₁ H ₂₂ N ₄ O ₂

(362.4)

C ₂₂ H ₁₈ N ₄ O ₂

(370.4)

C ₁₈ H ₁₆ CIN ₄ O ₂

(354.8)

Continued Tob.2

R ¹

R ²

Acyl Ausb.

fp

⁽¹ C)

Surnmonformol

(Molmasso ''

) |. Bor |. Gof

3 | CH ₃ 3k CH ₃ 2 m CHj

CH ₃ CH ₃ CH ₃

COOCH ₃ COOC ₄ H ₆

2 ρ -CH ₂ (CHj) ₃ CH ₂ -CONHC ₆ H ₆ 3q -CH ₂ (CHj) ₃ CH ₂ -CONHC ₆ H ₄ -CH (CH ₃ ) j-4

68 216-216 " ' CeH ₁₄ Cl ₂ N ₄ O ₂ (389.3) 90 188-189 " ' CuHuNjO ₃ (259.3) 84 199-200 ^bl C ₁₆ H ₁₆ N ₃ O ₃ (321.3) 80 295-297 ^cl C ₂₁ H ₂₀ N ₄ O ₂ (360.4 / 360) 82 295-297 ° ' C ₂₄ H ₂₆ N ₄ O ₂ (402.6 / 402)

¹¹ MS mol peak '' from CH ₁ CN, ^{cl from} dioxane

Formula sheet

O R "

Claims (3)

1. A process for the preparation of 2,2-diazobenzlertone 1-acyl and / or 9-acyl-2,3-dlhydrolmldazo-1,2-a] -benzimidazol-3-one of general formula 3 or 2, in which: R, R ¹ : in each case methyl or together pentamothylene, Acyl: COR ² , C (= NH) OR ² , COOR ² , CONHR ² , C (= S) OR ² , where R ^{2 may be} alkyl or optionally substituted aryl, characterized in that 2,2-disubstituted 2,3-DlhydiO-imidazo [1,2-a] benzimidazol-3-one of the general formula 1 with a changing agent such as acid chloride, carbonic acid chloride or thiocarbonic O-ester chloride in In the presence of an acid-binding agent or with an acylating agent such as cyanic acid ester or isocyanic acid ester in the presence of an aprotic solvent at temperatures of -10O ⁰ C to +200 ⁰ C are reacted. 2. The method according to claim 1, characterized in that triethylamine, sodium carbonate or pyridine is used as the acid-binding agent. 3. The method according to claim 1, characterized in that the 2,2-disubstituted 9-acyl-2,3-dihydro-imidazo [1,2-albenzimidazol-3-one 2 thermally at temperatures of 10 to 200 ⁰ C to the 2,2-disubstituted 1-acyl-2,3-dihydro-imidazo (1,2-albenzimidazol-3-ones are isomerized.