MXPA97010069A - Derivatives of aminofenil cetona and method for the preparation of the mis - Google Patents

Abstract

The present invention relates to: provides o-aminophenyl ketone derivatives which are intermediary-useful in the manufacture of sulfamoyl urea herbicidal compounds including the selective herbicidal culture 1-. { [§- (cyclopropylcarbonyl) phenyl] -sulfamoyl} -3- (4,6-Dimethoxy-2-pyrimidinyl) urea. A method for the preparation of said intermediary is also provided

Description

DERIVATIVES OF AMINOFENI CETONA AND METHOD FOR THE PREPARATION OF THE SAME The present invention provides Q-aminophenyl ketone derivatives of formula (I) wherein R, R, and X are as defined below. The compounds of formula I are useful as intermediates in the manufacture of a wide variety of sulfamoyl urea herbicidal derivatives, and in particular, the manufacture of the crop selective herbicidal agent 1-. { [g .- (cyclopropylcarbonyl) sulfamoyl} -3- (4,6-dimethoxy-2-pyrimidinyl) urea. A method for preparing said intermediate of formula I is also provided.

DESCRIPTION The invention provides a compound of formula wherein R is straight or branched chain C 1 Cg alkyl or phenyl optionally substituted with C 1 -C 4 alkyl, C 1 .C 3 alkoxy, chloro or bromo; R, is hydrogen, cyano, nitro halogen, formyl, CLC4 alkyl optionally REF: 26010 substituted with one or more of halogen, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C3. CrC4 alkoxy optionally substituted with one or more of halogen, groups 1 C, .C3 alkoxy; C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl or C 1 -C 3 alkylsulfonyl C 1 -C 4 alkylthio optionally substituted with one or more of halogen, C 1 C 3 alkoxy, C 1 .3 alkylthio, C 1 C 3 alkylsulfinyl or C 1 -C 3 alkylsulfonyl; alkylsulfinyl CpC4? optionally substituted with one or more of halogen, C, C, C3 alkoxy, C, C3, C, C3, C, C3, C, C3, C, C3, C, C3, C, C3, C, C3 alkyloxy; C.sub.4 -C.sub.12 alkylsulfonyl optionally substituted with one or more of halogen, C.sub.1, C.sub.3 alkylthio C.sub.C.sub.3, alkylsulfinyl C.sub.3, C.sub.3 or alkylsulfonyl C.sub.C.sub.3 alkylcarbonyl C.sub.1.C.sub.4 optionally substituted with one or more of halogen, C.sub.2 C.sub.2 alkoxy groups , .C3? alkyl C 1 -C 3, alkylsulfinyl C 1 C 3 or alkylsulfonyl C 1 C 3 C 4 C alkoxycarbonyl optionally substituted with one or more of halogen, or C 1, C 3 S alkoxy groups (CrC 4 alkyl) optionally substituted with one or more of halogen or C 1 .C 3 alkoxy groups (CrC4 alkyl) aminocarbonyl optionally substituted with one or more of halogen or C, .C3 alkoxy di (CrC4 alkyl) aminosulfonyl groups optionally substituted with one or more of halogen or C, .C3 alkoxy groups, or a heterocyclic ring having 2 to 6 carbon atoms and 1 to 3 nitrogen, oxygen or sulfur atoms and which is optionally substituted on the carbon atoms with one or more of halogen, C4 alkyl groups, or haloalkyl CT-C ^ X is - (CH2) 3 -A, cyclopropyl or tetrahydro-2-oxo-3-furoyl; and Y is chlorine, bromine or hydroxy; or the acid addition salt thereof. The invention also provides a process for preparing a compound of formula A wherein R is as defined in claim 1 comprising the following steps: i) reacting a compound of formula B s where R and Ri are as defined in claim 1 with a compound of formula C in the presence of a base and an organic solvent to form a mixture of compounds of formula D and formula EO ^ ^ H. Q E ii) isolate compound E by hydrolysis or crystallization; iii) reacting compound E with concentrated HCl in the presence of an organic solvent to form a compound of formula F; iv) treating compound F with an aqueous base at an elevated temperature; v) isolating a compound of formula G; vi) treating compound G with a strong acid; vii) isolating a compound of formula H; and H viii) reacting a compound H with HCl to form a compound of formula A. The compound A in which R is hydrogen, 1- (o-aminophenyl) -4-chloro-1-butanone hydrochloride, is used in the manufacture of the herbicidal intermediate or .- (aminophenyl) cyclopropyl ketone. A description of Q- (aminophenyl) cyclopropyl ketone and its use in the manufacture of the herbicide 1-. { [o- (cyclopropylcarbonyl) phenyl] -sulfamoyl} -3- (4,6-dimethoxy-2-pyrimidinyl) urea has been described in the prior art. The present invention also avoids the use of o-nitrobenzoium chloride, which is an explosive, as an intermediary. The base used in step 1 may be a magnesium CrC4 alkoxide, preferably an easily obtainable one such as magnesium methoxide or magnesium ethoxide. The organic solvent used in step 1 may be an aromatic ocarbon or a dialkyl ether such as toluene, xylene or tetraofuran. The organic solvent used in step 3 to prepare compound F can be an inert organic solvent such as toluene or xylene and the acid used in step 3 can be a mineral acid such as concentrated HCl. The base used in step 4 for preparing compound G can be an alkali metal oxide such as sodium oxide or potassium oxide. The elevated temperature in step 4 can be any temperature in excess of 25 ° C, preferably about 90 °-130 ° C. The strong acid used in step 6 to prepare compound H can be sulfuric acid. The acid used to prepare compound A in step 8 can be a mineral acid such as concentrated HCl. The compounds of the invention can be used to prepare sulfamoyl urea herbicidal compounds (K) using the process of the invention to prepare the compounds of formula A and convert said compounds of formula A to the corresponding g .- (aminophenyl) cyclopropyl ketones (J. ) using the conventional methods described in the prior art, and converting said phenyl ketones to the desired sulfamoylurea herbicide products, preferably to the cereals selective sulfamoyl urea herbicide, 1-. { [g _- (cyclopropylcarbonyl) phenyl] -sulfamoyl} -3- (4,6-dimethoxy-2-pyrimidinyl) urea. The conversion of the fenii ketone derivatives to sulfamoylurea herbicides can be carried out by known methods. The preparation is illustrated in flow diagram I.

FLOWCHART HCl -. According to the process of the invention, the compound of formula A is prepared as described below and converted to the compound of Q- (aminophenyl) cyclopropyl ketone of formula (J) by conventional dehydrohalogenation techniques and the compound of formula J can be reacted with a 2-aminoaryl compound of formula L and chlorosulfonyl isocyanate in the presence of triethylamine and a solvent to give the desired herbicidal sulfamoyl urea of formula K. The invention is further illustrated in the following examples but not JA. It is limited to them. The terms NMR and EM designate nuclear magnetic resonance and mass spectrometry, respectively.

Example 1 Preparation of 2 '- (Tetrahydro-2-oxo-3-furoin-D-toluensulfopanilide) fifteen 0 To a mixture of 40 ml of toluene and 2.03 g (178 mmol) of magnesium ethoxide in a flask under nitrogen at 5-10 ° C is charged 4.6 g (36 mmol) of 2-acetylbutyrolactone for 2 minutes. . The resulting suspension is stirred for 10 minutes at 5-10 ° C and for about 1.5 hours at 20 ° C. The reaction mixture is treated with a solution of 10.0 g. (32 mmol) of Np-tolylsulfonyl anthranoyl chloride in 20 ml of toluene is stirred several hours at room temperature and for about 2 hours at 45-50 ° C. Water (120 ml) is added and the gray suspension is stirred for about 4 hours at 65-70 ° C the pH is adjusted to 1 with concentrated sulfuric acid. The phases are separated and the organic layer is filtered to provide 7.6 g of 2 '- (tetrahydro-2-oxo-3-furo-l) -β-toluenesulfonanilide. The remaining product is isolated from the filtrate of the organic layer by concentration in vacuo to give 2.1 g. additional product for a total yield of 83% (p.p. 138-141 ° C). The product was identified by NMR and MS analysis.

Example 2 Preparation of 2'-cyclopropylcarbonyl-D-toluensulfopanilide NaOH r A mixture of a two phase suspension of 3.56 g (1.0 mmol) of the product of Example 1, 25 ml of toluene and 20 ml of 37% HCl is refluxed for approximately 12 hours, cooled and the resulting suspension filter to provide 1.98 g of 4-chloro-1- (2-N-tos? lam? nofen? l) -1-butanone. The phases of the filtrate are separated and the aqueous phase is extracted with toluene. The organic phases are combined and concentrated in vacuo to give the remaining product 4-chloro-1- (2-N-tosylaminophenyl) -1-butanone (1.15 g) for a total yield of 90% (mp 108-113). ° C). The product was identified by NMR and MS analysis. To a solution of 1.62 g (4.6 mmol) of 4-chloro-1- (2-N-tosylaminophenyl) -1- i butanone in 10 ml of toluene was charged 17.3 g (28.7 mmol). ) of 6.6% sodium hydroxide solution. The resulting two-phase mixture was refluxed for about 1 hour, cooled and adjusted to pH 1 with concentrated sulfuric acid. The organic layer was separated and concentrated in vacuo to give 1.50 g of 2 '- (cyclopropylcarbonyl) -β-toluenesulfonanilide in 100% yield (m.p.92-100 ° C). The product was identified by NMR and MS analysis. EXAMPLE 3 Preparation of 1- (0-Aminophenyl) -4-chloro-1-butanopa hydrochloride The product from Example 2 (1.5 g, 4.7 mmol) was treated with 96% sulfuric acid and heated at 90 ° C for 15 minutes. The solution was cooled, adjusted to pH 9 with ammonium hydroxide and extracted with methylene chloride. The combined extracts were concentrated in vacuo to provide 1- (o.-aminophenyl) -4-hydroxy-1-butanone (80% yield, m.p. 58-61 ° C). The product was identified by NMR and MS analysis. A mixture of 9.3 g (5.1 mmol) of 1- (o.-aminophenyl) -4-hydroxy-1-butanone, 26 mL of water and 90 mL of 37% HCl were refluxed for approximately 6.5 hours, cooled and filtered to provide 8.0 g. of 1- (a-aminophenyl) -4-chloro-1-butanone hydrochloride. Extraction of the aqueous mother liquor with methylene chloride gave an additional 1.10 g of the title product for a total yield of 73% (mp 142-145 ° C) The product was identified by NMR and MS analysis. EXAMPLE 4 Preparation of o-aminophenyl CYCODODGOOÍI ketone A solution of 0.30 g (1.3 mmol) of 1- (o.-aminophenyl) -4-chloro-1-butanone hydrochloride in 3 mL of methylene chloride and 3 mL of ethylene dichloride were treated with 1 , 2 g (3 mmol) of a 10% sodium hydroxide solution and 0.05 g (0.2 mmol) of 75% aqueous methyl tributylammonium chloride and heated at 50 ° C for about 5 hours. After cooling to room temperature, the phases were separated. The aqueous layer was extracted with methylene chloride. The combined organic extracts were washed with water and concentrated in vacuo to give 0.14 g (70% yield) of Q-aminophenyl cyclopropyl ketone (pp. 46-48 ° C). The product was identified by NMR and MS analysis. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (1)

1. A compound of the formula: (i) characterized in that R is straight or branched chain C 1 Cs alkyl or phenyl optionally substituted with C 1, C 4 alkyl, C 1 C 3 alkoxy, chlorine or bromine; R is hydrogen, cyano, nitro halogen, formyl, C, .C4 alkyl optionally substituted with one or more of halogen, CμC3 alkoxy groups, Cilt alkylthio, CμC3 alkylsulfinyl or CμC3 alkylsulfonyl; optionally substituted C 4 -alkoxy with one or more halogen, C 1 C 3 alkoxy groups; C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl or C 1 C 3 alkylsulphonyl C 4 alkylthio optionally substituted with one or more of halogen, C 1 C 3 alkoxy groups, C 3 C 3 alkylthio, C 1 C 3 alkylsulfinyl or C 1 C 3 alkylsulfonyl; alkylsulfinyl CrC 4 optionally substituted with one or more of halogen, C C 3 alkoxy groups, C 3 C 3 alkylthio, C C 3 alkylsulfinyl or C 1 C 3 alkylsulfonyl; alkylsulfonyl CrC 4 optionally substituted with one or more of halogen, C 1 C 3 alkyloxy C 3 C 3 alkoxy groups, C C 3 alkylsulfinyl or C C 3 alkylsulfonyl C 1 C 4 alkylcarbonyl optionally substituted with one or more of halogen, C 1 C 3 alkoxy groups? alkylthio C, .C3, alkylsulfinyl C, .C3 or alkylsulphonyl C C C3 alkoxycarbonyl C, -C4 optionally substituted with one or more of halogen, or C4, C3 alkoxy d? (alkyl CrC4) ammo groups opaquely substituted with one or more of halogen or C.sub.1 -C.sub.3.d alkoxy groups (C.sub.1 -C.sub.4 alkylo) aminocarbonyl optionally substituted with one or more halogen or C.sub.1 -C.sub.3 alkoxy groups (C.sub.4 C.alpha.-alkylsulfonyl) optionally substituted with one or more halogen or C C3 alkoxy groups, or a heterocyclic ring having 2 to 6 carbon atoms and 1 to 3 atoms of j * nitrogen, oxygen or sulfur and which is optionally substituted on the carbon atoms with one or more of halogen, alkyl groups C C4, or haloalkyl CpC4 > X is - (CH 2) 3-Y, cyclopropyl or tetrahydro-2-oxo-3-furole, and Y is chloro, bromo or hydroxy, or the acid addition salt thereof. which R is straight or branched chain C CS alkyl or optionally substituted phenyl With C 1 -C 4 alkyl C C 3 alkoxy, chloro or bromo, R is hydrogen, cyano, nitro halogen, foppyl, CLC 4 alkyl optionally substituted with one or more of halogen, C 1 C 3 alkoxy groups, C 1, C 3 alkyiocyl, C 1 C 3 alkylsulfinyl or C 1 -C 3 alkylsulfonyl, CrC 4 alkoxy opaquely substituted with one or more of halogen, C 0, C 3 alkoxy groups, C 3 C 3 alkylthio, C 1 -C 3 alkylsulfinyl or C 1 -C 4 alkylsulfonyl C 1 -C 4 alkylthio optionally substituted with one or more of halogen, alkoxy groups CμC3, Cι C 3 alkylthio, C 1 -C 3 alkylsulfinyl or CμC 3 alkylsulphonyl, C, -C 4 alkylsulfinyl opaquely substituted with one or more of halogen, C alco, CC alkoxy groups, CμC 3 alkylthio, CμC3 alkylsulfinyl or CμC3 alkylsulfonyl, C alquC alqu alkylsulfonyl optionally substituted with one or more of halogen, C 1 -C 3 alkyloxy C 1, C 3 alkyloxy, C 1 -C 3 alkylsulfinyl or C 1 C 3 alkylsulphonyl C 4 C alkylcarbonyl optionally substituted with one or more halogen, C 1 C 3 alkylthio C, C, alkoxy groups 3, C 1 -C 3 alkylsulfinyl or C 1 -C 4 alkylsulfonylate C 4 C alkoxycarbonyl optionally substituted with one or more of halogen, or C 1, C 3 alkylamino groups (C 1 -C 4 alkylamino) optionally substituted with one or more halogen or C C3 alkoxy groups d (CrC4 alkyl) aminocarbonyl optionally substituted with one or more of halogen or C, C3, C3 alkoxy groups (C12 alkyl) aminosulfonyl optionally substituted with one or more of halogen or C C3 alkoxy groups , or a heterocyclic ring having 2 to 6 carbon atoms and 1 to 3 nitrogen, oxygen or sulfur atoms and which is optionally substituted on the carbon atoms with one or more of halogen, C ^ C alkyl, or CrC4 haloalkyl groups , X is - (CH 2) 3-Y, cyclopropyl or tetrahydro-2-oxo-3-furole; and Y is chlorine, bromine or hydroxy; or the acid addition salt of the same 2 ELs has been added to the rsiviiEHcacicn 1, < and .jiur-itgrt- > pnj RJ. is hydrogen and optionally R is methyl or ß-tolyl 3 The water content of the water reVvird a? i 2, csa taza) GT * »xs cyclopropyl, - (CH2) 3-Y, or tetrahydro-2-oxo -3-furo? 4 A process for preparing a compound of formula A (GTW H it? Ft> pratpis R. It is such an event that the following steps i) react a compound of formula B (j? Fip h in reLviiii a ^ i ?? 1 qs ajq mJb) where R and R are as defined in claim 1 with a compound of formula C in the presence of a base and an organic solvent to form a mixture of compounds of formula D and formula E ü £ ii) isolating compound E by hydrolysis or crystallization; iii) reacting compound E with concentrated HCl in the presence of an organic solvent to form a compound of formula F; iv) treating compound F with an aqueous base at an elevated temperature; v) isolating a compound of formula G; vi) treating compound G with a strong acid; vii) isolating a compound of formula H; Y H viii) reacting a compound H with HCl to form a compound of formula A. 5. F3 pttp-finrippto < »Amwife mn the rt» ivitttiraH? N & l p * tr + pr¡tx? R > B, stage 1 is magnesium ethoxide and the organic solvent is toluene; the organic solvent in step 3 is toluene; the base in step 5 is NaOH; and the strong acid in step 6 is sulfuric acid. 6 EL [xx x Hl'iprifpeto s riimlj acn reivipdicacim 5, axacbeñzafe ["T * H« ¥ t VI compound of formula B in which R, is hydrogen 7. The prc acüp? ßptD of riiml) an reiviplicaci ? i 5, ptr »? -» Ha »n composed of formula B where R is ß-tolyl or methyl 8. The pmpRrtimimtp de aouaxfe with reivipdicacic 6, a_cactaza ± > penque nfn» * »addition reacting the compound of formula A with a base to prepare Q-aminophenyl cyclopropyl ketone 9. A process for preparing a compound of suifamoyl urea of formula K wherein Z is N or CR3; R2 is hydrogen, halogen, CpC4 alkoxy optionally substituted with one or more of halogen or C, C3 alkoxy groups; C 1 C 1 alkoxy optionally substituted with one or more of halogen, or C 1 C 3 alkoxy groups; alkylthio C, -C 4 optionally substituted with one or more of halogen or C C 3 alkoxy groups, C C 4 alkylsulfinyl optionally substituted with one or more of halogen, or C C 3 alkoxy groups, optionally substituted C 1 4 alkylsulfonyl with one or more halogen, or C, .C3 alkoxy or CrC4 alkylamino or di (CrC4 alkyl) amino groups wherein each alkyl group is optionally substituted with one or more of halogen or CrC3 alkoxy groups; R3 is hydrogen or halogen; and R 4 is hydrogen, C, -C 4 alkyl optionally substituted with one or more of halogen or CrC 3 alkoxy groups; CrC4 alkoxy optionally substituted with one or more of halogen or C? -C3 alkoxy groups, C? C4 alkylthio optionally substituted with one or more of halogen, or C? C3 alkylsulphs C, .C4 alkoxy groups optionally substituted with one or more of halogen, or alkoxy groups C C3 C44 alkylsulfonyl optionally substituted with one or more of halogen, or C9C3 alkylamino C9C4 alkoxy or di (CC) alkyl amino groups each optically substituted alkyl group having one or more of halogen or C, C3 alkoxy groups characterized in that it comprises: i) dehydrohalogenation of a compound of formula A wherein formula A is prepared by the process of claim 4 to form the o- (aminophenyl) cyclopropyl ketone of formula J J ii) reaction of said Q- (aminophenyl) cyclopropyl ketone with a 2-aminoaryl compound of formula L R • i L and chlorosulfonyl isocyanate, in the presence of triethylamine and a solvent to give the desired sulfamoyl urea compound of formula K. 10. The amount of aa-ecd cm the reL vipaicae? I 9, caracta? Zacb pesque pnßca i aapjThis trust is K cbpde Z is CR3; R, and R3 are each hydrogen; and R2 and R4 are each methoxy.