NZ240320A - Diaminodiphenyl ether and diaminophenyl pyridyl ether intermediates - Google Patents

Diaminodiphenyl ether and diaminophenyl pyridyl ether intermediates

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NZ240320A
NZ240320A NZ24032089A NZ24032089A NZ240320A NZ 240320 A NZ240320 A NZ 240320A NZ 24032089 A NZ24032089 A NZ 24032089A NZ 24032089 A NZ24032089 A NZ 24032089A NZ 240320 A NZ240320 A NZ 240320A
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compound
formula
compounds
acid
water
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NZ24032089A
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John Edward Duncan Barton
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Ici Plc
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Priority claimed from GB888819660A external-priority patent/GB8819660D0/en
Priority claimed from GB898914041A external-priority patent/GB8914041D0/en
Application filed by Ici Plc filed Critical Ici Plc
Priority claimed from NZ230146A external-priority patent/NZ230146A/en
Publication of NZ240320A publication Critical patent/NZ240320A/en

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Description

New Zealand Paient Spedficaiion for Paient Number £40320 240 3 2 0 Priority Datefs):. i P Ci - <pi<P- • r-ri « Compfc»t* Specification Filed: ^ :.....L...^2ff..j. Class: (5) £Q102.l^i.CU.(. *26 MAR* 1992 Publication 5}ate: P.O. Journal, -No: 3. .■*??..^7.
H 4'*- -*■> yi Under the provisions of Regulation 23 (1) the .Nu,:.
Specification has been ante-dated to.
Date: .3.1. 19 ..a Initials NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION HETEROCYCLIC COMPOUNDS Divided out of No. 230146 Filed 31 July 1989 fJ.Z.P'iYF-'TCi-}-! C 23 OCT !3S: Rccr.'v ■-> I/'We, IMPERIAL CHEMICAL INDUSTRIES PLC, a British company of, Imperial Chemical House, Millbank, London SW1P 3JF, United Kingdom hereby declare the invention for which I / we pray that a patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by page 1A) 240 3 2 0 - 1A- HETEPQCYCLIC COMPOUNDS The present invention relates to intermediate canpounds useful 5 in the preparation of novel substituted benzotriazole derivatives.
European Patent No. 178,708 A describes certain benzheterocyclyl-phenyl ether derivatives which have herbicidal activity.
According to the invention of New Zealand Patent Specification No. 230146, there is provided a compound of formula (I) : 0 — R- (I in which R" is independently selected from H, CM, M02, halogen, lower alkyl, lower haloalkyl; m is an integer o: from 1 to 4; R2 is N or CR1 where R~ is as defined above; is a group of formula (a), (b) or (c): ( a) - 3'5 £40320 N ^ ^ \ N (b) ■M (c ) or N-oxide or quaternary salt derivatives thereof wnerein R* is a group -6 r\. r7-r8 6 where R , R are selected independently from H, lower alkyl, halogen or and R^ together form ~^2 or ^ and the carbon atom to which they are attached together form a C-_g cyclcalkyl r i ng ; F.9 0 l! R' is (CH,) . CH,CH, CH-CH, CCH,, CHOHCH- or CHORi0CH? a *■ n ^ iq where R is lower alkyl and R~ is Icwsr alkyl o: phenyl; and n is 0, 1 or 2; ,8 . ,11 ,10 O R II / / r 13 R is COOR , CH, OR" , OCN , CCN , COSR V2 V14 c CHO, CN, CH-NOR12, ?(0R12)7, OSO-.K, SO,H; vher, J R"^ is as defined hereinbefore; 11 2 4 0 3 2 0 R" is hydrogen, optionally substituted lever alkyl, optionally substituted lower alkenyl, optionally substituted lower alkvnvl, [(CH-,)-.0] (CK-,) OR"^, " " 2 2 p ^ q -N=C(R )-, optionally substituted phenyl, optionally substituted benzyl, optionally substituted cycloalkyl; p is 0, 1 or 2; a is an integer from 2 to 5 inclusive; 12 R is K or lower alkyl; 13 1 4 P. and R~ are selected independently from H, lower alkyl, lower cycloalkyl, alkenyl, alkynyl, / N(R-2)2» additionally R^ may be an optionally hydroxy- or phenyl-substituted alkyl radical cf 1 to 4 carbon atoms, a phenyl cr chlorophenyl radical, an alkoxy 1 5 radical cf 1 to 4 carbon atoms, or a group -MR R~ wherein R^ is hydrogen or alkyl of 1 to 4 carbon atoms 16 and R is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl, 13 14 or chlorophenyl, or the group -NR~ R" constitutes a 5 or 6-membered heterocyclic ring or alkyl quaternary g derivatives; and, in the case of compounds wherein R is a carboxyl group, salts thereof.
Scms of the compounds can exist in optical isomeric forms ana the present invention covers all these forms and mixtures thereof in all proportions including raceniic 2 5 mixtures.
Suitable optional substituents for the alkyl, alkenyl and alkynyl croup of R^ are one or rrore halogen atoms such as fluorine, chlorine, bromine cr iodine, hydroxy and C1-C4 alkoxy. Suitable optional substituents for the 30 phenyl, benzyl and cycloalkyl croups are one cr more halogen atoms such as fluorine, chlorine, bromine or iodine or methyl groups. 1 ^ £ Suitable halo croups R , R~ and ?." include fluorine, chlorine ana bromine.
Suitable halcalkvl groups ?.J", R^ and R° include alkyl groups substituted with up to 6 halogen atoms 24 0 3 2 0 - 4 selected from fluorine, chlorine and bromine. A particular haloalkyl group is trifiuoromethyi.
Suitable heterocyclic rir.cs formed from NR^ are pyrrolidine, piperidins ana morpholine.
Suitable salts of compounds of formula (I) are those formed with agriculturally acceptable cations, for example sodium, potassium or quaternary ammonium salts.
Examples of quaternary ammonium ions are ions of formula NR1"^18R19R20 where R17, R13, R19 and R20 are 10 independently selected from hydrogen or alkyl optionally substituted with for example hydroxy. Suitably 17 19 19 0 where any of R , R , R" and R^ are optionally substituted alkyl, they contain from 1 to 4 carbon atoms.
Particular examples of R~7, R'1"3, R^"9 and R2<^, are hydrogen, ethyl and 2-hydroxyethyl.
As used herein the term "lower alkyl" includes groups containing from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms. Similarly the terms "lower alkenyl" and "lower alkynyl"- includes groups containing from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms. rine , ,1 Preferably is selected from hydrogen, chlorine, 5 Preferably R and R are H, lower alkyl or halogen, fluorine or trifluoromethyl wherein at least one of the R groups is other than hydrogen and at least one of the R^ groups is trifiuoccmethyl. are H, 1 in pa r ti cular hydrogen, me thyl or fluoro.
A preferred example of the group R2 is C-Cl. Preferably is the group (b) as hereinbefore defined. 3 0 R3 Preferably R4 is CH-R/-R3. Preferably r' is (CH-)^ and n is 0 or 1, in particular 0. g Suitable groups R are alkcxycarbonyl groups wherein the alkoxy group is straight or branched and contains up 2 to 6 carbon atoms. In particular the group R is alkcxycarbonyl, preferably ethoxycarbonyl. 240 3 2 0 A suitable sub-grcup of compounds cf formula (I) ari compounds where (R~) is indeoendently selected from in - -1 hydrogen, halo, nitro, cyano cr haloalkyl, and m is an *2 1 1 integer of from i to 4 ; R is C-R where R is hvdrocen, halo, nitro, cyano or haloalkyl; R is a group cf formula (a), (b) or (c) as hereinbefore defined; R4 is CH-R7-R® wherein P.^ is H or C, , alkyl, R7 is is 1-4 n 3 (Ci^Jn where n is 0 cr 1, preferably 0 and R is a cyano group, a carbcxyl group, an alkoxycarbonyl group or 13 14 carboxamido group CONR R as hereinbefore defined.
A further sub-group of compounds of formula (I) are compounds where (R^)m is independently selected from hydrogen, halo, nitro, cyano or haloalkyl and m is an 2 1 1 integer of from 1 to 4 ; R is C-R where ?. is hydrogen, halo, nitre, cyano or haloalkyl; R^ is a group of formula 4 7 3 (a), (b) or (c) as hereinbefore defined; R" is CH-R -R ; wherein R^ is H, C1 alkyl or halo, ?.' is (C.^Jn where n is 0 or 1, preferably 0 and R^ is a group COOR"^" where R~x is as hereinbefore defined.
Another sub-group of suitable compounds of formula (I) are comoounds where (R^") is independently selected ** m from hydrogen, halo, nitro, cyano or haloalkyl and m is an 2 1 1 ' integer cf from 1 to 4; R is C-R where R is hydrogen, halo, nitro, cyano cr haloalkyl; R^ is a group of formula 4 (b) or (c) as hereinbefore defined; R is — Q C "7 CH-R'-R , R is H or C, , alkyl or halo, P. is O (CH-)n where n is 0, 1 cr 2, preferably 0; R is a grcup ^11 11 COOR ~ vhere R1" is as hereinbefore defined, and particularly alkyl, preferably ethyl.
Particular examples of compounds according to formula (I) are listed in Tables I, II and III. 240 320 - 6 TABLE I R' Compound No R R* f." Characterising Data (NMR unless othsrwise stated) Cl Cl Ci Cl Cl H 3 dHCooc^H- 2 3 Cl CH-COOC-, K-2 2D C?-, j r n ^HCOOC2H5 CDCl3 &7.51(ia)3H;7.26(m)2H; 6.96(d)1H; 5.6 6(q)1H; 4.21 (q)2H; 2.02(d)3H;1.23 (t)3H.
CDCl 67 . 49 (ra) 3H; 7.20-7.3S ( m) 2 H; 6 . 9 5 ( d ) 1H ; 5 . 4 0 ( s.) 2H; 4.2 8(q)2 H; 1.29(t)3K.
CDCl, o7.79(s)IK; 7.60(m) 2H; 7.46(d)1H; 7.2(dd) 1H? 7 . 0 0 ( d ) 1K ; 5 . 7 ( c ) 1H ; 4 . 2 4 ( a ) 2 H ; 2.01(d) 3?!; 1.24(t)3H.
C? f3 CHCOOC-H^ 2 D CDC13 67.62(s)l ; 7.54(c) 1H; 7.4 4(dd)IK; 7.35(dd) 1H; 7.2 9(s ) 1K; 5.63(c) 1H; 4 . 21(q)2 H; 2.00(d)3H; 1.21 (t) 3 H . 2403?0 TABLE I (Contd.) """N Compound Ra Rb n R.~ E4 Characterising Data No (NMR unless otherwise stated) 13 Cl CF3 F f'3 CHCOOK m.p248.5-249 °C 16 Cl CF3 F ch2cooc2 H5 CDC13 &7.62(s)1H; 7.35-7.5 (m)4K; 5.40(s)2H; 4.27(a) 2H; 1.30(b)3H. 19 Cl CF3 F F I CHCOOC2K CDC13 7.66(d)IH 67.63(s)lH; 5 7.4-7.5(m)2 H; 7.35(s)lH; 7.21+7.03(d)lH; 4.39(m)2H; 1. 3 0(t)3H . 2 0 22 Cl CF- J F CHCOOC „H 4 CDC13 7.66(d)IH 57 . 64(s)1H; g 7.44(m) 2H; 7.35(s)lH; 7 - 21 + 7.03(d)IH; 4 . 30(t)2K; 5 9(m)2 H; 1.23(m)2H; 0 .85(t)3H. 2 5 Cl CF3 F V 1 CHCCOH m.p 177-177.8 ° C 23 Cl CF3 V 1 f2H5 CHCOOC2K CDCl3 57.53(s)1K; 7.60(d) 5 1H;7 . 4 5(dd)1H; 7.35(dd)lH; 7.29(d) IK; 5.47(dd)IK; 4.22 ( q ) 2 H; 2 . 3 5 - 2 . 6 (;n ) 2 K ; 1.24 (t)3H; 0 . 91( u)3H. 240320 TABLE I (Contd . ) o 3-0 Compound Mo 31 34 43 44 H H K Cl R" CF, C F- cf Characterising Data (NKR unless otherwise stated) H P3 pHCOOC2H5 h r3 c-cqoc-, h„ 2 o tH-. :h. h :h(ch2)cooc2hs CDCl3 6 7 . 7 0(d)1K; 7.60(m) 3 H; 7•2 9(d)1K; 7.09(d)2H; 5.7 0(q)1H; 4.24(q)2H; 2.01 (d)3H; 1.2 4(t)3H.
CDC13 <5 7 . 5 9 ( a ) 1H ; 7.60(d) 2H; 7 . 4 4(d)1H; 7.22(dd)lH; 7. 0 7 ( d ) 2 H; 4.21(a)2K; 2.10 (s)6H; 1.16(t)3H.
CDC13 S7.69(d)lK;7.59(m) 3H; 7.2 5(dd)1H; 7. 05(d)2H; 5.0-5.15(m)lH; 4. 10(a)2H; 2.6-2.42(m)lH; 2 . 4-2 . 2S(m) IH; 2.1-2.3(m)2H; 1.77(d) 3H; 1 . 21(t)3H. ch2 ) 7cooc.,h5 CDC13 6 7 . 6 2(m)2 H; 7.43(dd) 13; 7.36(dd)IH; 7.24(d)1»; 4.8 9(t) 2 H; 4.11(t)2H; 3.09 (t)2H; 1 . 20(t)3H. 3-5 240 320 - 9 -TABLE I (Ccntd.) :20 3-5 Compound F.a Rb 1-1 Rw R4 Characterising Data No l (NMR unless ocherwise seated) sT h 3 45 Cl CF3 F ,hch2cooc 2H5 CDCl3 6 7 . 6 0(m)2 H; 7.43(dd) IH; 7.36(dd)IK; 7.25(d)IH; .31(m)1H ; 4.02(m)2H; 3.30(dd)IH; 3.01(dd)lH; 1.75(d)3H ; 1.12(t)3H . 9K3 46 Cl cf2 F :h0 chcooc-,h. 2 2 o CDC13 37 . 62(s)IH; 7.58(d) IH; 7.43(dd)IH; 7.35(dd)lH; 7.2 4(s)1H ; 4.87(dd)lK; 4.65 (dd)lH; 4 . 0 6(m)2 H; 3.26(ra) r> IH; 1.28(d)3H; 1.12(t > 3H. 47 Cl cf3 p fl 3 :H(CH2)2C :ooc_h,- 2 3 CDCl3 7 . 5 5(s)1K; 7.49(d)lH; 7.36(dd)IH; 7.26(dd)lK; 7 - 18 ( d ) 1H ; 4.90-5.01(m.)lH; 3.9 9(q)2 H; 2.00-2.50(m)4H; 1. 6 6 ( d ) 3 H ; 1.14 ( t) 3 H .
|H3 65 H cf3 NO CHCOOC- »H5 cdc1 3 68 . 29(d)1h; 67.74 (dd+d)2H; 57. 64(d) IK; 7.32 (dd)IH; 57.1(d)1H; 55 . 7 3 (q) i 1H ; 5 4.2 5(q)2 K; 5 2.0 7(d)3H; I i i ! i 51.2 5(t)3H. -10-TA5LE I ( Cor.td . ) Compound Mo R£ Rb „c r\ Characterising Data (NMR unless otherwise stated) CH, 56 Cl CF3 NO 2 1 CHCOOC2 H5 CDCl3 5 8 . 21(a)1H; 68.05(d) IH; 57.57(d)1H; 57.34(dd) IH; 6 7.2(d)1H; 65.68(q)IK; 54.22(q)2H; 52.0(d)3H; 51.23(t)3H. fr'3 67 p CF3 F CHCCCC2Kc CDCl3 67.5-7.62(m)lH; 57.3-7.4(m)4H; 65.68(q)lH; 4.2(q)2 H; 52.0(d)3K; 61.25(t)3 H. f3 68 cl cf3 Cl CHCOOCjI- i5 CDC13 6 7 . 7 2(s)2 H; 67.56 (d) IH; 57 . 3 4(dd)IH; 5 7.15(d) 1H,; 65.6 8(a)IK; 54.22(a)2H; 62.0(d)3H; Y1-22(t)3K. <FH3 2 5 75 H 3 CN C3COOC2Hs CDC13 58 .18(a)1H; 57.98(d) IH; 67 . 8 5(ad)IH; 67 . 44(d) IH;, 6 7 . 2 8 ( dd ) 1H ; 65.95(d) IH; 65.6 8(q)IH; S4.22(q)2H; 62.04(d)3H; S1.25(t)3H.
CH, 7 6 Cl CF, CN CHC00C2H5 CDC1 3 5 3 . 0 7(d)1H; 58.02(d) i I IK; 57.92(d)!H; 57.0(dd)lH; 56.9 4(d)IH; 55.5(a)IH; • i i i 64.15(q)2H; 51.9S(d)3K; 3'5 ! 1 ; 1 ■ 1 61.18(t)3H. < - 11 ?4 3 ta2lE TI \ 'N mi'K^ 2 0 Compound No 11 R Cl Cl Cl r T Cl Cl C.r C<3 R R Characterising Data (NMR unless otherwise stated) :h. in HCOOC2H5 H :h2COOC2H5 :h3 chcooc-h- 2 3 CHCOOC,Er 2 3 CDC13 67 . 87(d)1H; 7 . 50(s) IH; 7 . 4 3 ( m) 2 H; 7.12(s)lH; 7.01(d)1H; 5.63(a)IH; 4.23 (a)2 H; 2.03(d)3H; 1 . 2 4(t) 3H.
CDC13 67 . 78(d)1H; 7 . 40(s) IH; 7.12(m)2 H; 7.01(s)1K; 6.9 0(d)1H ; 5.3 9(s)2 H; 4.15 (q)2 H; 1.08(t)3K.
CDC13 67.9 2(d)1H; 7 78 ( s ) IH; 7.4 9(dd)IH; 7.3(s)IK; 7.21(dd)IH; 7.0 3(d)1H; 5.66 (q)lH; 4.2 4(q)2 H; 2.04(d) 3K; 1.2 5(t)3H.
CDC1 3 67. 91(d) IE; 7.61(s) IH; 7.4 5(dd)IH; 7. 30(ad) IH; 6.98(s ) 1H; 5. 64(a)IH; 4 . 2.2 ( q ) 2H ; 2.00(d)3H; 1.22 (t)3H. ^ ^0320 - 12 -TA3LS II (Contd. ) Compound No R3 Rb n R~ r4 Characterising Data NMR unless otherwise stated) 14 Cl C?3 F !H3 m.p. 168-169.3°C CHCOOH 17 Cl CF3 p CH-.CCOC-.H I 2 . CDC13 57.90(d)IH; 7.62(s) IH; 7.4 4(dd)1H; 7.31(dd)lK; 6.97(s)IH; 5.46(s)2H; 4.27 (q)2 H; 1.30(t)3H.
Cl CF3 F F 1 CDC13 67.95 (d) IK; 7.64(s) CHCOOC-H. 2 3 IH; 7 . 46(dd)IH; 7.40(dd)lK; 6.92(s ) IH; 6 .31 + 7.01(d)IK; 4.4 0(m)2 K; 1.33(t)3K. 23 Cl CF3 ? P 1 CDC13 67.9 3(d)1K; 7.o 3(s) CHCOOC,H0 4 9 IH; 7.46(dd)IH; '7.40(dd)IH; 7.01+6.32(d)lH; 6.91(s)lH; 4.35{t)2H; 1.65(m)2H; 1.3 (m)2 H; 0.33(t)3K.
Cl CF 3 F ? m.p. 135.3-137°C ! CHCOOH 29' Cl n Ul C-«Hc |i 5 CDC13 57 . 9 0(d)i H; 7 . S 2(s) CHCOOCjKe; IK; 7 . 4 4 ( dd ) IH ; 7,31(cd)lK;i 6.97(d) IK; 5.4 0(dd)1H; 4.21 (m)2K; 2 . 37-2.65(m)2K; 1.23 (t)3H; 0 . 9 4(t)3H. £40320 - 13 -TABLE II (Ccntd.) Compound No Ra Rb RC R4 Characterising Data NMR unless otherwise stated] 32 H CF3 H CH - 1 J CDC13 5 7 . 91 ( d ) 1H ; 7.60(d) CHCOOC2H, 2H; 7.4 0(s)1K; 7.19(dd)lH; 7.11(d)2H; 5 . 6 6(q)1H; 4.23 (q)2 H; 2.01(d)3H; 1.2 5(t) 3H.
H CF3 H 9H3 CDCl3 S7.90(d)IH; 7.60(d) C-COOC2CHc 2H; 7.39(d)lK; 7.18(dd)lH; CH3 7 .1(d)2 K; 4 . 2(a)2 H; 2.10(s) oH; 1. 20(t)3H. 42 Cl CF3 H CH -j DMSO 67.99(d)1H; 7.90 < s ) 1 CHCOOH IH; 7. 60(d) IK; 7.45(s)lH,; 7.21(dd)1H; 7 . 15(d)IH ; 5.7 5 (q)1H; 1.82(d)3H.
CH, i 3 48 K CF3 H CH(CH2)2COOC2H5 CDC13 67.89(d) IK; 7.51(d) 2H; 7.4 0{d)1H; 7.15(dd)lS; 7 . 09(d)2H ; 4 . 9-5 .15 (in) IH; 4.10(q)2H ; 2.22-2.58 (m)2H; I 2.19(d)2 H; 1.75(d)3H; I 1 . 21 ( t) 3 H . r* 9 L - ^ TABLE II (Contd■) Compound _ s n r R R4 Characterising Data No ( NMR unless otherwise stated) 49 Cl CF3 F (CH2)2COOC2H CDC13 7 . 6 6(d)1H; 7.61(s)lH; 7.4 4(dd)1H; 7.28(dd)lH; 6.9 5(s)1H; 5.96(t)2H; 4.15 (q)2K; 3 . 12(t)2H; 1.24 (t)3H.
CH, 50 Cl CF3 F 1 CHCH2COOC. >H5 CDC13 S7.87(d)lK; 7.61(s) IH; 7 . 4 2(dd)IH; 7.28(dd)lH; 6 . 94(s ) IH; 5.4 0(m)1H; 4.09 (q)2 H; 3 - 2 6(dd)1H; 2.92(da) IH; 1.70(d)3H; 1.16(t)3H.
C" r 3 51 Cl CF3 F CH2CKCOOC2H5 CDC13 57.8 5(d)1H; 7 . 61(s) IH; 7 . 4 2(dd)IK; 7.2o(dd)lH; 6.94(d) IK; 4.99(dd)lH; 4.70 (dd)lH; 4.15(q)2 H; 3.31(m) IH; 1.2 0(m)6 H. ch3 2 Cl CF3 F CH(CH2)2COOC2H5 CDC13 57.87(d)IH: 7.51(s) IH; 7 . 42(dd)IH; 7.27(dd)lH; 6 . 9 5 ( d ) 1H; 4 . 9 4 - 5 . 0 9 ( m) 11-i ; 4 . 07 ( q ) 2H; 2 . 1-2 . 5(m)4K; 1 . 6 9 ( d ) 3 H ; 1. 21 ( t) 3 H . 1 240 320 TABLE III Compound No Ra JQ RC R4 ( Characterising Data NMR unless otherwise stated) 3 Cl Cl K f3 CHCOOC , K,- 2 3 CDC13 67.9o(d)1H; 7.4 3{s) IH; 7 . 17(dd)IH; 7.00(dd)lH; 6.9 2(d)1H; 6.84(s)lH; 5.46 (q)1H; 4 .11(q)2H; 1.92(d) 3H; 1 .11(t ) 3H. 6 Cl Cl H CH-,COGC.,H-2 2 : CDC13 5 3 . 0 4(d)1H; 7.51(d) IH; 7.26(da)IH; 7.11(dd)lK; 7.01(d) IK; 6.32(d)IH; 5.31 (s)2H; 4 . 2 2(q)2H; 1.25(t) 3K. 9 Cl CF3 H CH3 CHCOOC-,H r- CDC1 3 58 . 0 S(d)1K; 7.79(s) IH; 7. 50(a)IK; 7. 0-7.15(m) 3 H; 5.59(q)IK; 4.20(q)2H; 2.0 0(d)3H; 1.20(t)3H. 3"0 12 Cl 1 CF3 i 57 k CB3 CHCOOC2Hg CDCl3 58. 03(a)IK; 7.62(s) IH; 7.45(dd)1H; 7.08(dc) IH; 6 . 9(s ) 1H; 5. 54(q)IK; 4.17(q)2 H; 1.99(d)3K; 1.15 3 5 { (t)2H.
TABLE III (Contd. ) c rompound No Rc rb rc R4 Characterising Data NMR unless otherwise stated) Cl CF3 f CH, i 6 CHCOOH m.p. 173-173.9°C 13 Cl CF3 f CH,COOC,H 2 2 - CDC13 S 8 . 0 5 ( a ) 1H; 7.6 3(s) IH; 7.4 5(dd)IH; 7.10(dd) IH; 6 . 8 0(s)1H; 5.31(s)2K; 4.2 3(q)2 H; 1.22(t)3H. 21 Cl CF3 f f i chcooc2h5 CDC13 6 8 .10(d)1H; 7.65(s) IH; 7.4 7(dd)IH; 7.19(d) 0.5 H ; 7 .15(s)1H; 6.96(s) 1.5H; 4 . 35(q)2H; 1.24(t ) 3 H. 24 Cl Cr3 f ihcooc4hg CDC13 5 3 .10(d)1H; 7.65(s) IH; 7.47(dd)IH; 7.15(dd) IK; 6.99(d)IH; 7.16+6.9 8 (a)1K; 4.27(t)2H; 1.57(m) 2H; 1.2 2(m)2 H; 0.35(t)3m. 27 Cl cf, f * " m.p. 150. 5-151.6 °C CHCOOH Cl CJ3 !* c,h5 | 2 _ CHCCOC-.H- 2 3 CDC13 6 9 . 0 4(d ) 1H; 7.62(s) IH; 7.44(cd)lH; 7.05(dd) IH; 6.9 4(d)1H; 5.36(dd)lH; 4.19(q)2 H; 2.3-2.51(m)2K; 1 .18 ( t) 3 K ; 0 . 9 0 ( t) 3 K . 240 320 TABLE III (Ccntd.) \ Compound No Ea Rb R C ,A Characesrising Data NMR unless otherwise stated) — 33 K cf3 H .ri3 CHCOOC2K5 CDCl3 S8.08(d)IH; 7.62(d) 2H? 7.10(m)4 K; 5.60(q)lH; 4.2 0(q)2 H; 1.99{d)3H; 1.2 0 (t)3H. 36 H cf.
H CH, 1 3 C-COOC-.H. 1.. 3 Cr" 3 CDCl3 &8.08(d)1K; 7.60(d) 2 H; 7.10(m)1H; 7.07(d)2H; 7.01(a)1H ; 4.16(a)2 H; 2.06 ( s ) 6 H ; 1. 13 (t) 3 H . 37 Cl CF3 f ch3 dlhcooc^hg CDC13 5 8 . 0 3(a)1H; 7.62(s) IH; 7 . 4 5(dd)1H; 7.06(ad) IH; 6 . 8 9(s)1H; 5.53(a) IH; 4.11(t)2 H; 2.0 0(d)3 H; 1.49 (m)2 H; 1.15(m)2K; 0.S1(t) 3H.
V • '' ' 38 Cl cf- J f CH , 1 mass soec. W+ 480 * 2 5 :kconhso2 CH3 39 Cl C?3 f f3 CHCHjOH CDC13 6 7 . 9 0(d)1H; 7,S5(s) IH; 7.45(dd)IH; 7.05(dd) IH; 6 . 89(s)1H; 4.79(m)lH; 4 . 2 2 ( m) 1H; 4 .10 ( m) 1H ; 2.79(t)lH; 1 . 6 3(t)3 H. 240 320 - la - TABLE III (Contd.) Compound Ra Mo Rb RC R4 ( Characterising Data NMR unless otherwise stated) 4 0 Cl CF3 F ch3 mass spec. M+ 445 chconhn(ch3 ) 2 41 Cl C?3 F 1 9K3 + I_ mass spec. M+ 460 CHCONHN(CH3 ) 3 fH3 I 53 K CF3 h CH(CH,)2COOC2H5 CDC13 6 3 . 0 3(d)1H; 7.61(d) 2H; 7.1(m)4H; 4.82-5.0(m) IH; 4 . 0 3(q)2 H; 2.4-2.6(m) IH; 2.20-2.39(m)lH; 2.20 | (dd)2H; 1.72(d)3H; 1. 20(t) 3H. fh3 54 Cl cf3 F CH-COOtBu CDC13 6 S . 0 2(d)1H; 7.61(s) v IE; 7 . 4 3(dd)IH; 7.08(dd) IS; 6 . 81(d)1H; 5.42(q)lH; . 1 .94(d)3K; 1.32(s)9H. fs 55 Cl cf3 p CHCONH2 m.p. 179 . 1-180 . 6 3 C.
CH, 5 Cl CF3 F 1 3 CHCON(C2K } 2 CDC13 57 .99(d)IH; 7.61(s) IK; 7.42(dd)lH; 7.19(d')lH; 7 . 05(dd)IH; 5.99(q)lH; 3 .15-3.5 0(m)4H; 1.75(d)3H; j i 1 1 1 . 0 0 ( t) 3 H ; 0 . 8 9 ( t) 3 H . 24 0 3 2,0 TABLE III (Contc.) Compound No Characterising Data (NMR unless otherwise stated 3 5 57 58 59 60 Cl Cl Cl Cl Cf CF. cf CH.
^KCONHC2H= CDC1, 5 3.0 5(a)1H; 7.54(s) ■3 IH; 7.4 5(dd)IH; 7.15(dd) IH; 6.81(d)1H; 6.0-6.15(s) IH; 5.2 9(q)1K; 3.10-3.35 (m)2 H; 1.95(d)3H; 1.0 4(t) 3H. (ch2)2cooc2h5 CDC13 5 8.0 0(a}1H; 7.65(s)IH; 7 . 46(dd) IH; 7.10(dd)1H ; 6.91(d)IH; 4.7 9(t)2 H; 4 . 09(a)2H; 3.0 5 ( t)2H; 1.19(t)3 H. f3 tHCH7COOC2H5 cf F CDC13 c8 . 0 0(d)1H; 7 . 64(s) IH; 7 . 4 6' ( dd ) 1K; 7.07(cdi)lH; 6.9 0(a)1H; 5.15(m)IH; 4.0 2(c)2 H; 3.26(dd)lH; 3.00 (dd)lK; 1 . 7 0(d)3H; l.ll(t) 3 H . f3 CK0 CHCOOC 2 2D CDCl 1" 57. 99(d) IK; 7.63(s) 45(dd)IK; 7.03(dc) 89(s)1H; 4 . 7 o(dd)IH; 4.5o(ad)lH; 4.02(m)2H; 3.22 (m)IH; 1.2 4(d)3 H; 1.12(t)3K 240 320 TAB LS III (Contd.) Compound No r3 p.w RC r4 Characterising Data (NMR unless otherwise stated) cn3 51 Cl CF3 F "CHCOOH m.p. 156.1-159.0 0 C.
*R Form f3 6 2 Cl CF3 F "CHCOOH m.p. 155.9-160.0°C. kS Form ch3 63 Cl CF3 F *CHCOOC-H- CDC13 58.04(d)IH; 7.63(s) R Form IH; 7 . 4 4(dd)IH; 7.06(dd) IK; 6 . 3 8(d)1H; 5.5 3(q)1H; 4.16(q)2 H; 1.98(d)3H; 1.16 ( t)3K.
CH, I ^ 54 Cl n Ul 7 *CHCOOC-,H,. CDCl, 88 . 03 (d) IK; 7.63(s) ZD j S Form 13; 7 . 4 4(dd)IH; 7.06(dd) IH; 6.88(d)lH; 5.53(q)lH; 4.16(q)2 H; 1.97(d)3H; 1.15 (t)3K; CH, ! 3 6 9 H CF3 NO ? cecooc2h5 CDC1 3 58 . 28 (d)1H; 58.13(d) IH; 57.77(dd)1H; 57.30(d) IK; 5 7.14(aa+d)2K; 5 5.65(a) IK; 54.2(a)2K; 52.02(d)3H; 51.2 5(t)3H.
TABLE III (Contd.) Compound Ra R° RC R4 Characterising Data Mo (NMR unless otherwise stated) i CH - 70 Cl cf3 NO 1 2 CHCOOC2 |H3 H r- 3 CDC13 5 8 . 2 0 ( d ) 1K ; 8.04(m) 2 H ; 7 . 0(dd)IH; 56.89(d)IH; 5 5 . 5 5(c)1H; 54.18(a)2H; 52.0(d)3H; 51.15(t)3H. 71 f CF3 f CHCOOC2Hc CDC1 3 58.0(d)1H; 57.36 (a) 2H; 7 .10(dd)1H; 56.97(d) IH; 55.5o(q)lH; 5 4.18(q) 2H; 52.0(d)3K; 51.13(t)3H. 72 Cl cf3 Cl CH , 1 J CHCOOC2H CDC1 , 53. 03(d) IK; 7.71(s) 2H; 57.03(dd)IK; 56.79(d) IH; 5 5.5 3 (q)1H; 54.18(q) 2K; 52.0(d)3K? 51.17(t)3H. 7 3 Cl cf3 f ch3 ch(ch2).
COOC-K, 2 3 CDC13 58 . 01(d) IK; 7.62(s) IK; 7 . 4 5 ( dd ) IH ; 7 . 0 7 ( dd ) 1H 6.91(d)IH ? 4.3Q-4.92(m)lH; | 4 . 0 5 (q) 2 K ; 2 . 01-2 . 5 4 (rr.) 4K ; j 1 . 7 1 ( d ) 3 H ; 1 .19 ( t) 3 K . 74 Cl cf. f CH, 0 1 3 II CH - CH CDC13 5 9 . 8 1 (s ) 1H; 8.09(d) IH; 7 . 64(s ) 1H; 7.4o(dd)IH; 7.11(dd)IK; 6. 73(d) IK; 5.3 2 ( q ) 1K; 1. 8 8 ( d ) 3 K . 240 32 TABLE III (Contd.) Compound Mo Ra Rb r R~ „ 4 n.
Characterising Data (NMR unless otherwise statsc) 77 H CF3 CN CH, 1 3 chcooc2:- I5 CDC13 57 . 9 4 (d)IK; 57.83(d) IH; 67 . 7 4 (dd)1H; 57.67(d) IH; 67.35(dd)lK; 56.95(d) IH; 5 5 . 7 5(q)IH; 54.25(q)2H; 5 2 . 07 (d)3H; 51.25(t)3K. 2 4 0 3 2 0 Further particular examples include Compound No. 78 CHCCCC-H- 2 D Characterising aata:- NMR: (CDC13) S7.57(d)lH; S7.5(d)lH; 57.37(dd)lH; S5.7(q) IH; 5 4.21(a)2 H; S2.0(d)3H; S1.23(t)3H.
Comnound No. 79 CHCOOC,H- I 2 3 CK , Characterisina data:- NMR: (CDC13) 53.06(dd)lH; 57.14(m)2H; 65.60(q)lH; 54.20 (q)2 H; 52.0(d)3H; S1.2(t)3H. 3 0 ComDcund No. 80 CHCOOC,H^ i 2 3 CH , 2 4 0 3 2 0 Characterising data:- NMR: (CDCi3) o3.37(d)iH; &8.12(d)IH; o3.02(d)lH; S7.4(d: IH: 87.2(dd)IH ; S5.S3(q)lH; 64.22(a)2H; S2.0(d)3H; Si.22(t)3H.
ComDOund No. 81 Characterising data:- NMR: (CDCl3): & 7.S7(d)lH; 7.64(s)lH; 7.06(dd) IH; 6 . 7 8 ( s)IH; 5.15(q)lH; 4.17(q)2H; 1.92(d) 3H; 1.17(t)3H.
Oomoound No. £2 3 0 C-, H- BF, 2o 4 COOEt 3 5 Characterising data:- M.P 13-0.1 - 131.6°C M+ 460 2 5 240320 NMR: (CDCl3): c 8.2(d)lH; 7.65{s)lK; 7.6(cd)lH; 7.49 (dd)lH; 7.18(d)1H; 5.85(q)IH; 4.99(q)2H; 4.24(q)2H, 2.1(d)3H, 1.7 5(t)3H, 1.24(t)3H.
Compound No. 83 Charaterising data:- NMR: (CDC13) 58.25(d)lH; 58.02(d)lH; 57.89(d)lH; 7.61 (d)lH; o7.3 5(da)IH; S5.71(q)lH; 4.23(q)2H; 52.05 ( d ) 3H ; 51. 2 4 ( t) 3H .
Compound No. 8 4 CH, I 3 CHCOOC2H5 CHCOOC0H, i ^ J CH Charaterisinc data:- NM.R: (CDC13 ) 58 . 40 (d)lH; 68 . 12 ( d) lrl; 57.95(dd)lH; 57,37 (d)lH; 87.18(cd)IK; 57.1{d)lH; 55.65(q)lH; o 4 . 2 0(q)2 H; 32.03(d)3H; 51.20(t)3H. ( ■r* 26 Compound No. 85 CF -N Characterising data:- NMR: (CDC13) 53.40(d)lH; 57.95(dd)lH; 87.85(d)lH; 57.6 '( d ) 1H ; 57 . 3 3 ( dd ) IH ; 57.1(d)lH; 55.7(q)lH; S4.23(q)2H; 5 2.0 2(d ) 3 H; S1.25(t)3H.
Compound No. 86 NMR: (CDC13 ) 5 8.0 2(d)1H ; 87.74(s)lH; S7.0(dd)lH; 56.76(d) IH; 5 5 . 5 2(q)1H; 54 .95(q)2H; 52.99(q)0.2H; 52.55(s) 2.7K; 52.0(d)3H; 51. 26(t)0.3H; 51.16(t)3H; and Characterising data:- 2 5 Compound No. 87 \ CH-CH-, I J CH-NOH Characterising cata:- m.p. 14 2 . 8 - 1 4 5.0 0 C Compounds of formula (I) can be prepared by reacting a compound of formula (II) ( II) 1 i wherein R~ and R" and m are as defined in relation to formula (I) with a compound of formula (III): r6 I 7 8 X— C — R — R (III) i5 6 7 8 wherein R , R , R and R are as defined in relation to formula (I) and X is a leaving group, optionally in the presence of a base, and thereafter if desired carrying cut one or more of the following steps: g i) when R is alkcxycarbonyl hydrclysing to the corresponding acid; 8 ii) when R is COOK esterifying or forming a salt, amide, sulchonamias, hydraside cr hydrazinium derivative; anc 8 iii) when R is an alcohol, oxidation to CCOH, CHC. Suitable leaving groups X include halogen, such as bromine and chlorine, and sulphcnates such as methanesuiphonate and £-toluenesulphonate.
Suitable bases for use in the reaction include alkali metal hydrides such as sodium hydride, and alkali mstal carbonates and hydroxides such as potassium carbonate or ? 4 0 3 2 0 sodium hydroxide.
The reaction is preferably carried cut in an suitable organic solvent such as dimethylformamide, toluene, dimethylsulphoxice, a lower alkanol such as methanol or ethanol, cr a lower alkyl ketone such as acetone.
Moderate temperatures, for example of from 15° to 30°C are suitably employed. Conveniently the reaction is carried cut at ambient temperature.
This reaction will produce a product consisting of a mixture cf compounds of formula (I) wherein R3 is each cf the sub-groups (a), (b).and (c). These three products can be separated by conventional techniques such as chromatography in particular flash chromatography.
One compound of formula (II), is a known compound (see EP-A-0173708).
However compounds of formula (II) other than the compound 5-[2-chloro-4-(trifIuoromethyl)phenoxv]-1H-benzotriazole are novel and these form a further aspect of the invention of NZ 230146. Processes for the preparation of these compounds are described hereinafter in Schemes A, B and C.
Compounds of formula (III) are known compounds or they can be prepared from known compounds by known methods .
Compounds cf formula (I) can also be prepared by reacting a compound of formula (II) with a compound of formula (IV) 7 3 CH » C-R ! ( IV) R21 R22 o i 2 2 wherein and R are independently H or'lower alkyl anc R23 is CN, CHO or COOK24 where R24 is lower alkyl optionally in the presence of a base and thereafter if desired carrying out cne cr more of the following seeps: -) 2 , i) when is alkcxycarbonyl or CN hydrolysing to tne /•—V 240 320 corresponding acid; 2 13 ii) when R is CHO, oxiaaticn to the correspcncing acid; and iii) from the acid formed in (i) cr (ii) forming a salt, amide, ester, sulphonamide, hydrazide or hydrazanium derivative.
This .Michael-type addition reaction produces 4 2 3 compounds of formula (I) wherein R is -CH - CH - R r21 A22 where R^, R22 and R2 ^ are as hereinbefore defined. 15 The reaction is carried out in the presence of a base such as Triton B, alkoxides, pyridine at 40 to 100°C as described by Wiley and Smith (JAC5 ( 1954 ), 7_6' 4933). Compounds (IV) are known compounds or they can be prepared from known compounds by known methods. This reaction also 20 produces a mixture of compounds cf formula (I) wherein is each of the subgroups (a), (b) and (c). These three products can be separated by conventional techniques such as chromatography and in particular flash chromatography.
In another embodiment compounds cf formula (I) 25' wherein R^ is represented by the subgroup (b) can be prepared by cyclisation of compounds of formula (V) (R1) m ^ \y-o-r )-n h2 (v) \-H2 R25 - b« - R26 0 II where ?,iJ is CK-,OH, COOK, CO O , COOR^ cr P(OC2H-)2 ,25 „„ rtrT __„_29 " .29 where M' is a cation for example sodium or potassium, R 2 6 is lower alkvl and R is K or lower alkyl anc thereafter 240 3 20 if desired carrying out one or more of the following steps: i) when is alkoxycarbonyl hydrclysing to ths corre spending acid; 2 5 i i) when R is COOH estenrying or forming a salt, amide, sulphonamide, hyaraziae or hydrazinium derivative; and 2 5 iii) when R is an alcohol, oxidation to COCH, CHO.
This reaction produces compounds of formula (I) 4 2 5 wherein R is R CH^ ^ /• ^ r ^ /• R" where R and R 0 are as hereinbefore defined.
The cyclisaticn of a compound of formula (V) is carried cut using a nitrite ion, provided for example by a nitrite salt such as sodium nitrite, in the presence of an acid such as a mineral acid, for example hydrochloric acid.
The reaction is suitably carried out in an aqueous solution at reduced temperature, for example of from -10 to +10°C. Conveniently the reaction may be carried out at 0SC to 5°C and then allowed to warm to ambient termperature .
Compounds of formula (V) are novel and these form the subject of the present invention. Processes fcr the preparation of thesa compounds are given hereafter (see Scheme D).
If chiral forms of compounds of formula (I) are desired, these can be produced by using chiral forms of compounds cf formula (XIX) as defined hereinafter in Scheme D as starting materials for the preparation cf compounds of formula (V) as described in Scheme D.
Further compounds cf formula (I) may be produced by 2 5 standard manipulation of the pendent R"°-CH-R^3 group.
, For example when R " is CH-OK, such manipulation includes ^ 2 6 oxidation to the aldehyde group R -CH-CHO, acid group 2 6 R -CH-COOK and then formation of escers, amides, salts and other derivatives or treatment with 1,1-dimethyl hydrazine to give the hydrazide R^-CH-CONHN( CH^) 2 which be further derivatised e.g. quaternised with methyl iodide 4- — to give R26-CH-CONHM(CH3)3I.
The esters produced may be further modified by standard techniques to give the corresponding acid which may be further modified to give esters, hydrazides, hydraziniums, sulphonaraides ana other well known acid de rivatives.
An alternative method for preparing compounds of formula (I) wherein R^ is represented by the subgroup (b) .27 R ,4 and R is represented by the group CHCOOH is by reacting a compound of formula (VI): (VI ) CHCOOH JL27 n where R~' is H or lower alkyl with a compound cf formula (VII): (VII) where R^", R~ and m are as defined for formula (I) and Y is a halo group in the presence of a base and thereafter if 2 A 0 3 2 0 - :z - desired converting the COOH group to an ester, amide, salt, sulphonamide, hydrazide or hydrazar.ium derivative.
The reaction is carried cut in a solvent such as DM?, DMSO, DMA and lower alkyl ketones such as acetone in the 5 presence of a base such as potassium carbonate or sodium hydroxide.
The reaction is carried out at temperatures of 25 to 120 0 C, preferably 100-120 9C.
Compounds cf formula (VII) are known compounds or 10 they can be prepared from known compounds by known methods .
A further method of preparing compounds of formula (I) wherein R^ is represented by subgroups (a) and (b) is by reacting a compound of formula (VIII): ^ 7T\ KO r- I! N (VIII) -N R 4 wherein R^", m, and R4 are as defined in formula (I) with a compound of formula (VII) as hereinbefore defined.
The reaction, is carried out in a solvent such as DM?, 25' DMSO, DMA end lover alkyl ketones e.g. acetone in tne presence of a base such as potassium carbonate or sodium hydroxide.
The reaction is carried cut at temperatures of 25 to 120°C, preferably 10O-i2O3C. 3'0 Certain compounds of formula (VIII) are novel and these form a further aspect of the invention of NZ 230146. particular the invention of NZ 230146 provides ccsripourds of formula (VIIIA).
I 240 320 (VIIIA) wherein R is as hereinbefore defined.
The compounds cf formula (VIII) are prepared for 10 example as set out in Scheme E hereinafter.
Compounds of formula (II) can be prepared as set cut in Scheme A. ' 240 320 Scheme A / ~ \ // \\ />~°i Vn02 H /?e i ^ '2 (R~)m —R ( R1 ) ^\— NH - ,2,0 2 5 (i: (X) ? 8 ( r co)20 HCOR 28 (XII) Dithionite ( Rx ) m 2B NHCOR KNO.
(XI) (i) HN02 ( ID (ii) Acid hydrolysis (XIII) 1 23 wherein R", R" and m are as defined hereinbefore; and R is a c1 — n o a9~cup.
As set out in this Scheme, the compounds cf formula (II) are prepared by cyclisation of a compound of formula (XIII) using a nitrite ion, provided for example by a nitrite salt such as sodium nitrite, in the presence of an 35 acid such as a mineral acid, for example hydrochloric acid. 240 3 20 .-""s The reaction is suitably carded cut in an aqueous solution at reduced temperature, fc: example of from -10 to -10°C. Conveniently the reaction may be carried cut at -3 to 0°C and then allowed to warm to ambient temperature. 5 Compounds of formula (XIII) are prepared by reduction of the corresponding nitro compound of formula (XII). A wide variety of reducing agents may be used and may be selected from the chemical literature by the skilled worker in the art. The reduction may be carried out for 10 example by using sodium aithionite or tin ana hydrochloric acid, iron and hydrochloric acid, or hydrogen with a palladium on charcoal catalyst. The reaction is preferably effected in an organic solvent such as a lower alcohol optionally mixed with water at temperatures of 15 from 20 0 C to 90°C.
Compounds of formula (XII) can be prepared by nitration of a compound of formula (XI) using a nitration agent such as concentrated nitric acid mixed with concentrated sulphuric acid or acetic anhydride. The 2.0 reaction is preferably carried cut in a suitable solvent such as acetic anhydride, ethylene dichloride or concentrated sulphuric acid. Moderate temperatures of from 0°C to 25°C are suitably employed.
Compounds of formula (XI) can be prepared by reacting 25 an amine of formula (X) with an appropriate anhydride in the presence of a base.
Suitable anhydrides include acetic anhyd.ride (where 2 3. . . -i > R is metnyl).
Suitable bases are bases such as tertiary amines for 30 example, triethylamine, pyridine, and 4-dimethylamino-pyridine.
The reaction is suitably carried out in an inert organic solvent. A wide variety of solvents may te used, including for example lower ketones such as acetone. The 35 reaction may be carried out for example at temperatures of from 20°C to 60°C.
The amine of fcrnula (X) can be prepared by reduction of the corresponding nitro compound of formula (IX). Reduction is suitably effected using a reducing agent such as iron or tin and hydrochloric acid. Temperatures of from 20°C to 90°C are suitably employed. The reaction can be effected in an organic solvent such as a lower alkanol, e.g. isopropanol optionally mixed with water.
Compounds of formula (IX) are known compounds or they can be prepared from known compounds by known methods.
A further method for preparing compounds cf formula (II) is set cut in Scheme (B).
L 1 7 ? fl Scheme 3 ( R~ )rrf Y ( VII ) NHCOR (XIV) R~ ) m ^V~0 - ft V-MHCOR^3 V Ac2° Cone. HNO- '2 5 28 di thionite NHCOR 28 (XII ) ( II (XV) 1 7 23 ~ whereir. R~ , R" , R anc m are as defined he r e ir.oe r o r a ; ana Y is a hale group.
As set out in this scheme, the compounds of formula (II) are prepared by acid hydrolysis of a compound o: f"s n 3 20 formula (XV) for example using concentrated hydrochloric acid and ethanol. The reaction is suitably carried out at temperatures from 20 to 80°C.
Compounds cf formula (xv) are prepared by cyclisation 5 of compound (XIII) using a nitrite ion, provided for example by a nitrite salt such as sodium nitrite, in the presence cf an acid such as a mineral acid, for example hydrochloric acid.
The reaction is suitably carried out in an aqueous 10 solution at reduced temperature, for example of from -10 to t100 C. Conveniently the reaction may be carried out at -3°C to 0°C and then allowed to warm to ambient tempe raturs.
Compounds of formula (XIII) are prepared from 15 compounds cf formula (XII) which are prepared from compounds of formula (xi). The preparations of compounds of formulae (xiii), (xii) and (xi) are described hereinbefore in relation to Scheme A.
Compounds of formula (xi) may also be prepared as 2 0 shown in this Scheme by the reaction cf a compound of formula (vii) with a compound of formula (xiv) in a ■ ' j solvent such as dmf, dmso, dma and lower alkyl ketones such as acetone in the presence of a base such as potassium carbonate or sodium hydroxide. 25 The reaction is carried out at temperatures cf 25 co 12 0 0 C, preferably 100-120 °C.
Compounds cf formulae (vii) and (xiv) are known compounds or they can be prepared from known compounds by known methods.
A third route to compounds of formula (II) is sat out in S.cherae C. 240 320 Scheme C f^s2 p (?.-)m (VII) DMSO KOH / NO.
Pd/C NaBK . 4 y \ acileOH \/ XVI conc^SO^ KN03 ClCH2CH2Cl o Ma NO. 2 5 c.HCl (XVIII) (XVII) (II) A set out in this Scheme, the compounds of formula 30- (II) are prepared by cyclisation of a compound cf formula (XVIII) using a nitrite ion, provided for example by a nitrite salt such as sodium nitrite, in the presence cf an acid such as mineral acid, for example hydrochloric acid.
The reaction is suitably carried out in an aqueous 3'5 solution at at reduced temperature, for example of from -10 to +10°C. Conveniently the reaction may be carried 240320 y out at O'C to 5SC and then allowed to warm to ambient temperature.
Compounds cf formula (XVIII) are prepared by reduction of the corresponding cinitro compound of formula 5 (XVII). A wide variety of reducing agents may be used and may be selected form the chemical literature by the skilled worker in the art. The reduction may be carried out for example by using sodium borohydride with a palladium on charcoal catalyst. The reaction is 10 preferably effected in an organic solvent such as a lower alcohol optionally mixed with water at temperatures of from -20°C to 10°C.
Compounds of formula (XVII) can be prepared by nitration of a compound of formula (XVI) using a nitrating 15 agent such as potassium nitrate mixed with concentrated sulphuric acid. The reaction is preferably carried out in a suitable solvent such as acetic anhydride, methylene dichloride, ethylene dichloride or concentrated sulphuric acid. Temperatures cf from -20°C to 25°C are suitably 20 employed.
Compounds of formula (XVI) are prepared by reacting m-nitrophenol with a compound of formula (VII) in an organic solvent, for example dimethylsulphoxide, lower alkyl ketones such as acetone, lower clymes e.g. 2;5 MeOCH^CI^OMe in the presence of a base e.g. alkaline metal hydroxides (KOH) or carbonates (K^CO^) at a temperature of 50 to 120 0 C.
The compounds of formula (V) can be prepared by the method shown in Scheme D. 3 5 240 3 20 2 0 Scheme D ( R" )m no.
\\ /)"°-C/"NT02 v_ Rz (XVII) K2N-CH (XIX) R . 2 o DMF K2C°3 R1) ra /X \ \ _ (XX) /- - 0 2 \ ■mo. nh- R25 i -CH 1 ? c R Pd/C me thanol aaNaBH ,, (RL)m V * mh. r25 nh — ch k25 2 5 (V) 3 5 Ik 0 3 20 As set out in this scheme, the compounds of formula (V) are prepared by reduction cf the corresponding nitro compound cf formula (XX). Comoounds of formula (XX) where 25" • 25 R is COOR are first hydrolysed to the compounds of 2 c _ formula (XX) where R is COO M"r. This hydrolysis reaction is carried out using alkaline metal hydroxides e.g. sodium cr potassium hydroxide in aqueous alcoholic or "•> THF solution at 20°C to 50°C. The reduction of compounds (XX) where R25 is COO~M~r can be carried out using aqueous 10 sodium borohydride with Pd/C at temperatures from -10 to -20 0 C . When 3 is CH2OH 0 or CH2^(OEt)2 a wide variety of reducing agents may be used and may be selected from the chemical literature by 15 ths skilled worker in the art. The reduction may be carried out for example by using sodium borohydride with Pd/C or tin and hydrochloric acid, iron and hydrochloric acid, or hydrogen with a palladium on charcoal catalyst. The reaction is preferably effected in an organic solvent 20 such as a lower alcohol optionally mixed with water at temperatures of from -5 to 903C.
Compounds of formula (XX) are prepared by reacting compounds of formula (XVII) with compounds of formula (XIX) in an organic solvent, for example dimethvlformamice 25 or a lower alkyl ketone or DMSO at 0 to 50CC in the presence of a base e.g. potassium carbonate. The preparation of compounds of formula (XVII) is described in relation to Scheme C. Compounds cf formula (XIX) are known compounds or they can be prepared from known 30 compounds by known methods.
A route tc compounds of formula (VIII) is set out in Scheme Z, 3 5 - 43 240320 Scheme E MaO i) EEr. ii ) Ethanol/ cH2S04 (VIII (XXI ) As set out in this scheme compounds of formula (VIII) are prepared by the reaction of compounds of formula (XXI) in an organic solvent for example dichloromethar.e using for example boron tribromide followed by ethanol/concentrated sulphuric acid. Compounds of formula (XXI) are prepared as described by Ecido et al, (Studi Sassararesi, Sezione 2, 1975, 57, 737 ) .
A routs for producing compounds cf formula (VI) is set out in Scheme ?.
Scheme F 240 3 20 (XXII) ch-coor aq.NaOH NO. ,27 NHCHCOCNa (XXI11) ONa V Pd/C aq/NaBH4 NH.
R OMa NaNO. conc. HCl 27 MHCHCOONa (XXIV) N N.
\ \\ // I OH ,27 CKCOOK (VI ) 7 7 ^ 0 where R is H cr lower alkyl and R is lower alkyl.
As set out in this scheme compounds of formula (VI) are prepared by the cyclisation of a compound cf formula (XXIV) using a nitrite ion provided for example by a 2 4 0 3 2 0 nitrite salt such as sodium nitrite, in the presence of an acid such as a mineral acid, for example hydrochloric acid.
The reaction is suitable carried out in an aqueous 5 solution at reduced temperature, for example cf from -10 to 4-10 °C. Conveniently the reaction may be carried out at C°C to 5°C and then allowed to warm to ambient tempe rature.
Compounds of formula (XXIV) are prepared by reduction 10 of the corresponding nicro compound of formula (XXIII). The reduction may be carried out for example by using aqueous sodium borohydride with Pd/C. The reaction is preferably effected in an organic solvent such as a lower alcohol optionally mixed with water at temperatures of 15 from -5 to 90°C.
Compounds of formula (XXIII) may be prepared by base hydrolysis of compounds of formula (XXII) using aqueous potassium or sodium hydroxide at temperature cf 30 to 120°C. 2:0 Compounds of formula (XXII) are known compounds or they can be prepared from known compounds by known methods, as described by Crcwther et al (JCS, 1949, 12 50 — 1271), Van Dusen and Schultz (J. Org Chen., 19 55. 2 1, 1326-29) and Fisher et al (J. Org. Chem, 1970, 35(7), 25 2240-2242).
The acids produced by the process may be modified if desired by esterifying cr forming a salt, amide, sulphonamide, hydrazide or hvdrasanium derivative.
The compounds of formula (I) are active as herbicidcs 20 and therefore, in a further aspect the invention of NZ 230146 provides a process for severely damaging or killing unwanted plants which process comprises applying to the plants, or to ths growth medium of the plants, an effective amount of a compound cf formula (I) as hereinbefore defined. 35 The compounds of formula (I) are active against a broad range of weed species including monocotyledsnous and ,4-m^ 240 320 dicotyledonous species. Some may show some selectivity towards certain species; they may be used as selective herbicides in rice and wheat crops.
The compounds of formula (I) may be applied directly 5 to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emeraence application). They are particularly useful when applied -—■% post-emergence.
The compounds of formula (I) may be used on their own 10 to inhibit the growth of, severely damage, or kill plants but are preferably used in the form of a composition comprising a compound in admixture with a carrier comprising a solid or liquid diluent.
Therefore, in yet a further aspect the invention of 15 NZ 230146 provides plant growth inhibiting, plant damaging, or plant killing compositions comprising a compound of formula (I) as hereinbefore defined and an inert carrier or diluent.
Compositions containing compounds of formula (I) include both dilute compositions, which are ready for 20 immediate use, and concentrated compositions, whlich require to be diluted before use, usually with water. Preferably tha compositions contain from 0.01% to 50% by weight of the active ingredient. Dilute compositions ready for use preferably contain from 0.C1 to 2% of active 25 ingredient, while concentrated compositions may contain from 20 to 50% cf active ingredient, although from 20 to . , 7 0% is usually preferred.
The solid compositions may be in the form of granules, or dusting powders wherein the active ingredient 30 is mixed with a finely divided solid diluent, e.g. kaolin, bentcnite, kieselguhr, dolomite, calcium carbcnacs, talc, powdered magnesia, Fuller's earth and gvpsum. They may also be in the form cf dispersible powders or grains, comprising a wetting agent to facilitate the dispersion cf 35 the powder or grains in liquid. Solid compositions in the fcrm cf a powder may be applied as foliar dusts. 240 320 - A Liquid compositions may comprise a solution or dispersion of an active ingredient in water optionally containing a surface-active agent, cr may comprise a solution or dispersion of an active ingredient in a 5 water-immiscible organic solvent which is dispersed as droplets in water.
Surface-active agents may be of the caticnic, anionic, or non-ionic type or mixtures thereof. The cationic agents are, for example, quaternary ammonium 10 compounds (e.g. cety1triImethylammonium bromide).
Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example scdium lauryl sulphate; and salts of sulphcnated aromatic compounds, for example sodium dcdecylbenzenesulphonate, sodium,calcium, 15 and ammonium 1ignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid. Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl 20 alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agral 90) or cctyl-cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurace; ths condensation products of the partial 25 ester with ethylene oxide; and the lecithins; silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77). A suitable mixture in mineral oil is Atplus 411F .
Ths aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent!s) and then, when organic solvents are used, adding the mixture so cbtained to water optionally containing 35 wetting cr dispersing acent(s). Suitable organic solvents include, for example, ethylene di-chloride, isopropyl 2 4 0 3 2 0 alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene .
The compositions for use in the form of aqueous 5 solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use. The concentrates are usually required to withstand storage for prolonged periods and 10 after such storage, to be capable of dilution with watsr to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active 15 ingredient!s) . Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.01% to 10.0% and preferably 0.01% to 2%, by weight of active ingredient(s) are normally used.
A preferred form of concentrated composition comprising the active ingredient which has been finely divided and which has been dispersed in water in the presence of a surface-active agent and a suspending agent. Suitable suspending agents are hydrophilic colloids and 25 include, for example, polyvinylpyrrolidone and sodiu.vi carboxymethylcellulcse, and the vegetable gums, for example gum acacia and cum tragacanth. Preferred suspending agents are those which impart thixotropic properties too, and increase the viscosity cf the 30 concentrate. Examples of preferred suspending agents include hvcrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorits, saponite, anc sauccrite. Bentonite is especially preferred. Other suspending agents include cellulose 35 derivatives and polyvinyl alcohol.
The rate of application cf the compounds cf the invention will depend on a number cf factors including, for example, the compound chosen for use, the identity of the plants whose crowth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage cr root uptake. As a general guide, hcwever, an application rate of from 0.001 to 20 kilograms per hectare is suitable while from 0.025 to 10 kilograms per hectare may be preferred.
The compositions of the invention of NZ 230146 may comprise, in addition to one or more compounds cf the invention, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention of-NZ 230146 provides a herbicidal catiposition comprising a mixture of at least one herbicidal compound of formula (I) as hereinbefore defined with at least one other herbicide.
The other herbicide may be any herbicide not having the formula (I). It will generally be a herbicide having a complementary action in the particular application.
Examples of useful complementary herbicides include: A. benzc-2,1,3-thiodiazin-4-one-2 , 2-dioxides such as 3-isopropylbenso-2,1,3-thiadiazin-4-one-2, 2-dioxide (bentazone); B. hormone herbicides, particularly the phenoxy alkanoic acids such as 4-chloro-2-methylphenoxy acetic acid (MC?A), S-ethyl 4-chloro-O-tolyloxy thio-acetate (MC?A-thicethyl), 2-(2,4- cichlorophenoxy) propionic acid (dichicrprop), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 4-(4-chlcro-2-methylphencxy)butyric acid (MC?E), 2,4-dichlorophenoxyacetic acid (2,4-D), 4-{2,4-dichlorophenoxy)butyric acid (2,4-D3), 2-(4-chlcro-2-methylphenoxy) propionic acid (mecoprop), 3,5,5-trichloro-2-pyridyloxyacetic acid (trichlopyr), 4-amino-3,5-dichloro-6- 240 320 fluoro-2-pyridyloxyacstic acid (fluroxypyr), 3,6-cichloropyricine-2-carboxylic acid (ciopvralid), and their derivatives (eg. salts, esters and amices); C. 1,3 dime thy1pyrazols derivatives such as 2-[4- (2 , 4-dichlorcbenzoyl) 1,3-dimethylpyrazol-5- ylcxy] acetcphenone (pyrazoxyfen), 4 —(2,4 — ^ dichlo robenzoy1)1,3-dimethylpyrazol-5-yltoluene suphonate (pvrasclate) and 2-[4-(2,4-dichloro-m -toluolv1)-1,3-dima thylpyrazol-5-yloxy]- 4'- raethylacetophenone (benzofenap); D. Dinitrophenols and their derivatives (eg. acetates such as 2-methvl-4,5-dinitrophencl (DNOC ) , 2-t-butyi-4,6-dinitrophenol (dinoterb), 2-sectutyl-4,5-dinitrophenol (dinoseb) and ics ester, dincseb acetate; E. dinitroani1ine herbicides such as N',N'-diethy1-2,6-dinitro-4-trifiuoromethy1- m-phenylenediamine (dinitramine) , • 2, 6-d.iniiro-H,N-dipropyl-4-tri£luoro-me-chylanilin3 (trifluralin), N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-tri f iuorcmethylar.il ine ( ethalflurclin) , 2S M-(l-ethylpropyl)-2,S-dinitro-3,4-xylidine 4 (pendimethalin); and 3,5-dinitro-N , 4 N -dipropylsulphani 1 amide (oryzalm); F. arylurea herbicides such as M'-(3,4- dichlorophenyl)-N,N-dimetnylurea (diuron), N , N-dime thyl-N' - [ 3- ( tr i f Iuo ro rue thyl) phenyl ] ur sa (flume turon), 3-(3-chlo ro-4-methoxyphenv1)-1, 1-dime thylurea(me toxuron) , 1-butyl-3-(3,4-cichlorophenyl)-l-methylurea(neburon), 3-(4-isoprcpylphenyl)-1, 1-dimethylurea (i sop rcturon), 3-(3-chloro-p-tolyl)-1,1-dime thylur ea t 240 320 (chicrotoluron), 3—[4—(4— chlorcphenoxy) phenyl]-i, 1-dimethylurea (chloroxuron), 3-(3,4-cichloropheny1)-l-methylurea (linuron), 3-(4-chlorophenyl)-1-methoxy-l-methylurea (mono 1inuron), 3-(4-bromo-4-5 chlorophenyl)-1-methoxy-l-methvlurea (chlorcbromuron), l-(1-methy1-1-phenyl ethyl)-3-£-tolylurea(daimuron), and l-benzothiazol-2-yl-l, 3-aimethylurea (methabenzthiazuron); G. phenvlcarbairioyloxyphenylcarbamates such as 3-[methoxyca rbony1amino]phenyl (3-methylphenyl)-carbamate (phenmedipham) and 3-[ ethoxycarbonylami.no ]-phenyl phenylcarbamate (desmedipham); H. 2-phenylpyridazin-3-ones such as 5-amino-4-chloro-2-phenylpyridazin-3-one (chloridazon), and 4-chloro-5-methylamino-2-(<=,«,«-trifluoro- m-tolyl) pyridazin-3(2H)-one (ncrflurazon); I. uracil herbicides such as 3-cyclchexyl-5,5-trimethvleneuracil (lenacil), 5-bromo-3-sec-buty 1-6-iuethyl-uraci 1 (bromacil) and 3-t-butyl- -chloro-o-methyl-uraci1 (terbaci1) ; J. triazins herbicides such as 2-chloro-4- 'ethylamino-6-( i-propylair.ino)-l,3,5-triazine (atrazine), 2-chlcro-4,S-di(ethylamino)-l,3,5- triazine (simazine), 2-azido-4-(i-propylamine)- 3-0 6-me thyl thio-1, 3 , 5-triazine ( azipr otryne ) , 2-(4-chloro-6-ethylamir.o-l,3/5-triazin-2- ylamino)-2-methylpropionitrile (cyanazine), N' , N'^-di-isop r cpy 1-6-methy 1 thio-1 , 3 , 5-triazine-2 , 4-diami 2 ne (prcmetryn), N -(1,2-dimethylpropvi) -N^-sthy1-6-mechy1thio-l,3,5-triazine-2,4 -diamine 2 4 ( dimethaiae t ryn ) , N ,N -diethyl-6- 240 320 methylthio-l,3,5-triazine-2,4-diamins ( sime t ryne) , 2 4 and M -tert-cutyl-M -ethy1-6- methylthio-l,3,5-triazine-2/4-ciainins (te rbu t ryn ) ; phosphcrcthioate herbicides such as S-2-me thylpipe ridinocarbonvl-methyl 0,0-dipropyl phosphorodithioata (piperophos), S-2-bensenesulphonamidoethyl 0,0-diisopropyl phosphonodithioate (bensulide), and O-ethyl C-6-nitro-m-tolyl sec-butylphosphoamidothicate (butamifcs); thiolcarbamate herbicides such a S-ethyl N-cyclchexyl-N-ethy1(thiocarbamate) (cycloate), S-propvl dipropyl-thiocarbamate (vernolate), S-ethyl-azepine-l-carbothioate (molinate), S-4-chlcrobensyl diethylthiocarbamate (thicbencarb), •k S-sthyl di-isobutyl- thiocarbamate (butylate) , * S-ethyl diisopropylthiocarbamate (EPTC) , -2,3,3-trichloroallyl ai-isopropyl (thiocarbamate) (tri-allate), S-2, 3-dichloroallvl di-isopropyl (thio-carbamate) (di-allate), S-benzyl 1,2-dimethylpropyl (ethyl) thiocarbamate (esprocarb), S_-benzyl di ( sec-butyl) thiocarbamate ( tioca r baz i 1) , 6-chlcro-3-phenylpyridazin 4-yl S-octyl thiocarbamate (pyridate), and S-l-raethy1-1- phenylethylpiperidine -1-carbothioate (dimepiperate); 1.2.4-triasin-5-one herbicides such as 4-amino-4 ,S-dihydrc-3-methyl-5-phenyi-l,2,4-triazine-5-cne(metamitron) and 4-araino-6-t-butyl-4,5-dihydro-3-methylthio-1,3,4 -1ciazin-5-cne (metribuzin); benzoic acid herbicides such as 2.3.5-trichloro-benzoic acid (2,3,6-TBA), 3,6-dichlcro-2-methoxy-benzoic acid (dicamba) and 3-amino-2, 5-dichloro benzoic acid (chloramben); anilide herbicides such as 2-chloro-2',6' -diethyl-N-(2-prcpoxyethyl)acetanilide (pretilachlor), N-butoxymathyl-chloro-2', 6'-diethylacetaniliae (butachlor), the correspcndin N-methoxy compound (alachlor), the corresponding N-i-propyl compound (propachlor), 3',4'-dichiorcpropionilide (propanil), 2-chloro-N-(pyrazol-l- ylmethyl]acet-2'-5' xy1idide(metasachlor), 2-chloro-o'-ethyl-N-(2-methoxy-1-methylethyl) acet-O-toluiaide (metolachlor), 2-chloro-N-ethoxymethyl-S'-ethylacet-O-toluidide (acetochlor), and 2-chlo ro-N-(2-me thoxye thyl)ace t-2',6'-xylidide (dimethachlor); dihalobenzonitrile herbicides such as 2,5-dichloro-benzcnitrile (dichlooeni1), 3,5-dibromo-4-hyd:oxy-benzonitrile (bromoxynil) and 3,5-diiodc-4-hydroxy-benzonicrile (ioxynil); haloalkanoic herbicides such as 2,2-di.chlcrcpropi onic acid (daiapon), trichloroacetic acid (TCA) and salts thereof; dip'nenylethe r herbicides such as ethyl 2 — [ 5 — ( 2-chloro-trifluoro-p-tolvloxy)-2- ni t robenzoylocxy propionate (lactofen), D—(5—(2— chlcro-*, «, c-trifl'Joro-p-tclyloxy)-2- ni trobenzcyl ] glycolic acid (flurcglycofen} or salts or ester thereof, 2,4-cichlorophenyl-4- nitrophenyl ether (nitrofen), methyl-(2,4- dichlorophenoxy)-2-nitrobenzoate (bifenox), 2-nitro-5-(2-chloro-4-trifluorcmethyl-phenoxy) benzoic acid (aciflurofen) and salts and esters thereof, 2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenvl ether (oxvfluorfen) and 5-(2-chloro-4-{triflucromethyl) phenoxy)-M-(me thylsulfonyl)-2-ni t robenzamide (fomesafen); 2,4,6-trichloropheny1 4-nitrophenyl ether ( chlorni trofen) and 5-( 2 , 4-dic'nlorophenoxy ) -2-nitroaniscle (chiomethoxyfen); phenoxyphenoxypropionata herbicides such as (RS)-2-[4-(2,4-dichlorc-phenoxv)phenoxy) propionic acid (diclofop) and esters thereof such as the methyl ester, 2-(4-(5-trifluoromethyl)-2-(pyridinyl)oxy) phenoxypropanoic acid (fluazifop) and esters thereof, 2-(4-(3-cnloro-5-triflucro-methy1)-2-pyridinyl)oxy)phenoxy)propanoic acid (haloxyfop) and esters thereof, 2-(4-((6-chloro-2-cuinoxalinvl)oxy) phenoxypropanoic acid (quizalofop) and esters thersoc and (+)-2—[4-(5-chlorobenzoxazol-2-yloxy)-phenoxyJpropionic acid (fencxaprop) and esters thereof such as the ethyl ester; cyciohexanecione herbicides such as 2,2-dime thvl-4,6-dioxo-5-(1-((2-propenyloxy)- imino)-Duty1) cyclohexane carboxylic acid (alloxydim) and salts thereof, 2-(1-ethoxyimino) butvl-5-(2-(e thylthio)-p ropyl)-3-hydroxy-2~ cyclohexan-1- one(sethoxydim), 2-(1-ethoxyiminc) 14 0 3 ?. 0 butyl)-3 -hydroxy-5-thian-3-ylcyclchex-2-encne (cycloxyaim)2-[1-(e thoxyimino)propyl]-3-hydroxy-5-mesityicyclohex-2-enone(tralkcxydim) , and ( + )-2-{ ( S ) — 1 — [ (E)-3-chloroallyloximir.o] propyl}-5-[2-(ethy1thio)propy1]-3-hydroxy-cyclc'nex-2-enone ( cletnodim) ; suifonyl urea herbicides such as 2-chioro-N (4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl) benzenesulphonamide (chlorcsulfurcn), methyl 2 — ((((4,6-dimethyl-2-pyrimidinyl)amino)-carbonyl)amino)-sulphonylbenzoic acid (sulfometurcn)( 2—(((3—(4-methoxy-6-methyl-l,3,5-triazin-2-yl)carbonyl) amino)-sulphonyl)benzoic acid (metsulfuron) and esters thereof; -(4,6-dime thoxypyrimidin-2-ylcarbamoylsuphamoy)-O-tci uic acid (benzsulfuron) and esters thereof such as the methyl3-[3-(4-methcxy-6methyl-l,3,5-triazin-2-yl)ureidosulphonyl]thiophene-2-carboxylate(DFX-M6313), 2-(4-chloro-6-methoxy pyrimiain-2-yl carbamoylsulphamoyl benzoic acid (chlorimuron) and esters such as the ethyl ester thereof 2-(4,6-dimethoxypyrimidin-2-ylcarbamoyl-sulpharaoyl )-N, N-dimethyl-nicotinamide, 2-[4,6-bis(ci fIuo romethoxy)pyr imidin-2-y lea rbanoy 1 sulphamovl) benzoic acid ( pi rimi sulfur or.) and esters such as the methyl ester thereof, 2-[3-(4-me thoxy-5-me thyl-1,3,5-triazin-zyl)-3-methylureidosulp'nonyl) benzoic acid estes such as the methyl ester thereof (DPX-LS300) and5-(4,6-dimethoxypyrimidin-2-ylea rbamoylsulphamovl)-1-methylpyrazole-4- carboxylic acid (pyrazosulfurcn); imidazolicinone herbicides such as 2 — (4,5 — dihydrc-4-isopropyl-4-methyl-5-oxoimidazcl-2- yl) quinoline-3-carbcxy1ic acid (imazaquin), methyl 6 - (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -m-toluate and p-tcluateisomer(imazamethabenz),2-(4 isoprcpyl-4-methyl- 5-oxc-2-imidazolin-2-yl) r.icocinic acid ( imazapyr ) and i sopr opvlammonium se thereof, (RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-o 2-imidasolin-2-yl)nicotinic acid (imazethapyr); arvianilide herbicides such as benzoy1-N-(3-chlo ro-4-f luo rophenyl)-L-alanir.e (flamprop) and esters thereof, ethyl N-benzoy1-N-(3,4-dichlorophenyl)-DL-alaninate (benzoylprop -ethyl) ■N-(2,4-diflucrophenyl)-2-{3- trifluoromethyl)phenoxy)-3-pyridinecarboxamide (diflufenican); amino acid harbicides such as N-(phosphonomethyl) glycine (glvphosate) and DL-homoalanin-4-yl (methyl)-phosphinic acid (glufosinate) and their salts and esters, trimethylsulfonium N'-( phosphonomechyl)-glycine { sulphosate ) , and bilanafos; orcanoarsanicai herbicides such as monosodium methanearsonate (MSMA); herbicidal amide derivative such as (E3)-N,N~ diethyl-2-(1-naohthyloxypropionamiae) (naprcpamid 3,5-di chlo ro-N-(1,1- dime thyIp rcpyny1)benzamide (prcpvzamide) , (?. )-l-(e thylca rtamoyl) e thyl carbanilate (carbetamide), N-benzyl-N- isopropylpivalamide (tebutam), ( RS ) -2-b r crac-N- ( = , <=—d i itie thyl benzyl) -3 , 3-dimethylbutyramide (brcmcbutide), N-[ 3-{1-ethy1-1-methylpropyl)-isoxazol-5-yl] 2 , 5-dine thcxyber.z amide , (isoxabsn), N-phenyl-2- (2-naphthyloxy) prcpionamide (naproanilide), 240 320 li, N-dime thy 1 -diphenyl ace tami de ( aiphenamid ) , ar.d H-(1-naphthyl)-phthalamic acid (napcaiara); miscellaneous herbicides including 2-ethoxy-2,3-dihyaro-3, 3-dimethylben2ofuran me thar.esul fona ts (ethofumesate ) , 7-oxabicyclo ( 2.2.l)heptar.e,1-me thy l-4-(l-nie thy lethyl)-2-(2-methylphenvlmethoxy)-exo (cinmethylin) , 1,2-dimethyl-3,5-aiphenylpyrazolium ion (difenzoquat) ana salts thereof such as the methyl sulphate salt, 2-(2-chlorcbenzyl)-4,4- dimethyl-1,2-cxazoldin -3-one (clomazone) , 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-l,3,4-oxadiazol-2(3H)-one (oxadiazon) , 3 , 5-cibronio-4-hycroxy benzaldahvda 2,4-dini t rophenyloxime (bromo fenoxim), 4-chlo robut-2-ynyl-3-chloroca rbanilate (ba rban ) , (RS)-2-(3,5-dichlorophenyl)-2-(2,2/ 2-trichloroechyl)oxirane (t ridiphane ) , (3?.S,4RS; 3RS,4SR)-3-chlo ro-4-chloromethyl-1-=, *,«-tri f lurc-m-totvl )-2-pyrrolidone (in the ratio 3:1) (flurochioridone), dichloroquinoline S-carbcxvlic acid (quincr.iorac) and 2-(l,3- benzothiazol-2-yl-oxy)-N-methvlacetaniliae (mefanacet); Examples of useful contact herbicides include: bipyridyiium herbicides such as thos in which tha active entity is the 1,1'-dimethyl-4,4' -dipyridylium ion (paraquat) and those in which the active entity is the 1,1'-ethylene-2,2' -dipvridylium ion (diquat); * These compounds are preferably employed in combination with a safener such as 2,2-dichloro -N,N'-di-2-propenylacetamide (dichlormid) Ths following Examples illustrate the invention.
EXAMPLE 1 Thi s Example illustrates the preparation cf compound 1 in Table I, compound 2 in Table II and compound 3 in Table III.
SteD A 4-(24'-dichlorophenoxy)nitrobenzene (1.7g) was dissolved in isopropanol (28 cm^ ) and reduced iron powder (3.73a) was added followed by water (6 cm^) and concentrated hydrochloric acid (0.23 cm^). The reaction mixture was stirred under reflux for 45 minutes and then filtererd through Hyflo while hot. The solvent was removed from the filtrate under reduced pressure. The residue was partitioned between ethyl acetate/water. The organic extract was washed with three further portions of water, then dried over MgSO^. The extract was filtered and the solvent removed from the filtrate under reduced pressure. The residue, a dark brown oil, was purified by flash chromatography using SiC>2 CHCl^ ^5:5 5S eluent of 4-(2',4'-dicnlcrophenoxv)benzamine (1.18g) was obtained as a straw coloured oil (75.4%).
Steo 3 - Che bensamine from Step (A) (31.8g) was dissolved i.r acetone (134 cm") and triethylamine (27 cm ) was added followed by acetic anhydride (20 cm^)with stirring. Ths reaction mixture was stirred under reflux for 14 hours. The solvent was removed under reduced pressure and the residue was partitioned between ethyl acetate/water. Th acueous phase was discarded and the organic extract was washed once more with water, once with saturated NaHCQ^ solution and then three times with water. The organic extract was dried over MgSO,,, filtered and the solvenc removed from the filtrate under reduced pressure. The residue was recrystallised from ethancl and air dried tc give 4-(24'-dichlorophenoxv)acetani1ide (31.4g); m.p. 143.7-144.5°C) .
Step C The acetanilide from Step (B) (23.2g) was suspended in acetic anhydride (83 cm^) acid and cooled in a salt/ice bath co -'8°C. Concentrated nitric acid (4.96 cm^ ) was dissolved in acetic anhydride (9.92 cm'3) at -5°C, and this solution was added dropwise with stirring and cooling to the reaction mixture, so that the final temperature was -5 °C.
The reaction mixture was allowed to warm to room temperature with stirring, and then allowed to stand at room temperature for 1 hour. Water (200 ca^) was added tc the reaction mixture with vigorous stirring. The bright yellow product was filtered off under reduced pressure and washed with three further portions cf water. The product was air dried then recrystallised from ethanol. The product was air dried to give 4-(2',4'-dichlorophenoxv)-2-nitroacetani1ide (21.23g); m.p. 129-133 . 3 9C.
Step D The nitroacetani1ide from Step (C) (21.23c) was dissolved in hot ethanol (750 cm^) and sodium dithionits (43.58g) was added portionwise (10 portions) ever ik hours, each portion being followed by water (20 c.u^) .
After the addition, the reaction mixture was stirred under reflux for 1* hours then left to stand overnight at room temperature. The solvent was removed under reduced pressure and mo re ethanol was added and removed also under reduced pressure. Ethyl acetate was added and the mixture stirred at 4C°C until all lumps had been broken up. The mixture was filtered to remove the inorganics and the solvent removed from the filtrate under reduced pressure. 4-(24'-cichicrophenoxv)-2-aminoacetani1ide was obtained as a sticky foam which became brittle on cooling.
Step £ The amine from step (D) (5g) was stirred with water (51 cm^) and concentrated hydrochloric acid (7.4 cm^) was added. The reaction was stirred at room temperature for 15 PAinutss after which more water (54 cm^) was added and the reaction cooled in a salt/ice bath to -38C. A solution of sodium nitrite (2.47g) in water (25 cm^) was added slowly wi th cons tan t st i r r ing and coding to -3 °C . After the addition, the reaction mixture was stirred below 0°C for 30 minutes, allowed to warm to room temperature and then stirred for 3 hours. The reaction mixture was extracted three times with ethyl acetate. The organic extracts were bulked and washed three times with water. The organic extract was dried over MgSO^, filtered, and the solvent removed from the filtrate under reduced pressure. The residue was a dark brown oil, which was purified by flash chromatography using SiC^, trichloromethane as eluent to give 1-acetyl-5-(2',4' -dichlorophenoxy)benzccriazole, as a straw coloured oil (yield « 2 . 35g).
Step F The amide from Step (E) (1.S5g) was dissolved in ethanol (5 craJ) and concentrated hydrochloric acid (3 cm"1) and stirred under reflux for hours. The reaction mixture was left to stand at room temperature overnight. The reaction was partitioned between water/ethyl acatate and the organic extract separated. The aqueous phasa wao extracted with three further portions of ethyl acetate. o / n 3 2 0 The organic extracts were bulked and washed four times with water. The organic extract was dried over MgSO^, filtered and the solvent removed from the filtrate under reduced pressure to cive 5-( 2 ' , 4 ' -dic'nloro-phenoxy)-benzotriatole, (1.65g) .
Step G The benzotriazole from Step (F) (1.62g) was dissolved in dry dimethylformamide (20 cm^l anc 50% NaH (0.28g) added slowly with stirring. The reaction mixture was stirred at room temperature for 20 minutes and then ethyl-2-brcmoprcpionate (1.04g) added. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with water (200 cmJ) and extracted four times with ethyl acetate. The organic extracts were bulked and washed with water. The organic extract was dried over MgSO^, filtered, and the solvent removed from the filtrate under reduced pressure. The residue was a straw coloured oil. The oil was purified by flash chromatography on SiC^ using trichloromethane: diethylether, 95:4 as eiuant . Three colourless oils were obtained which were shown by n.m.r. to be compound 1 Table I, compound 2 in Table II and compound 3 in Table III.
Compounds 4, 5, c, 31, 32, 33, 34, 35, 36 43, 47, 48, 52 and 53 were prepared by analogous methods using appropriate reactants.
EXAMPLE 2 This Example illustrates the preparation of compound 10 in Table I, compound 11 in Table II and compound 12 in Table III.
Step A 240 320 p-ace tarnidophencl (Ig) and 5-chlcro-3,4-difIuoro-benzotrifluoride (1.43g) were dissolved in dry DMF (4 crn^ ) . Dry potassium carbonate (1.37c) was added and ths mixture stirred anc heated at 110 to 120°C for 2 hours. 5 The reaction mixture wa5 cooled, poured into water "3 (40 cm"') and extracted three times with ethyl acetate.
The combined organic extracts were washed three times with water, dried (MgSO^) filtered and the solvent removed from the filtrate under vacuum. The residue was recrystal1ised from toluene to give 4-(2'-chloro-4'-trifluoromethy1-6'-flucrophenoxy) acetanilide, (135g, 59%) as a white solid.
Step B A cold solution of concentrated nitric acid (0.2 cm^) in acetic anhydride (1 cm^ ) was added dropwise to a stirred, cooled (-5°C) suspension of 4-(2'-chloro-4'-trifIuoromethy1-6'-flurophenoxy) acetanilide (1.12g) in acetic anhydride (4 coi"^) . After 10 minutes at -5°C, the 20 mixture was stirred at room temperature for 5 hours. The mixture was diluted with water and the solid removed by filtration, washed with water and air dried. Recrvstallisation from toluene gave 4-(2'-chloro-4'-tri fIuoromethy1-c' - fluo rophenoxy)-25 2-nitroacetanilide (0.54g, 43%), as a yellow solid, m.p. 152.5-153aC.
Step C 4-(2'-chlo r o-4'-1r i fluo rome thy1-6'-fluo rophenoxy)-2 - ni t roace tani 1 ide (35.33<g) was dissolved in stirred, hot ethanol (1L) and sodium aithionite (53.1c) added in 10 portions over 1* hours, each portion being followed by water (29 cm0). When addition was complete, the mixture 35 was stirred under reflux for 1.5 hours. The solvent was removed from the mixture under vacuum and the residua 1 <fe> uaxi extracted with ethyl acetate. Removal of the ethyl acetate after filtration cave crude 4-(2 '-chloro-4'-trifluorcmethyl-6'-fluarophencxy)-2-aminoacetanilide (22g, 67%) which was used without further purification.
Step D 4-(2'-chloro-4'-1r ifluo rome thy1-6'-fluo rophenoxy)-2-amino-acetani1ide (22g) was stirred in water ( 430 cm^) and 10 concentrated hydrochloric acid (28.25 cir^ ) added, and the mixture cooled to -2°C. Sodium nitrite (9.33g) in water (90 cm3) was added slowly with stirring and cooling to 0°C. When addition was complete, the mixture was stirred for a further 15 minutes at 0°C and then stirred to room 15 temperature over 3 hours. The mixture was extracted with ethyl acetate, the extracts washed with water, dried (MgSO^), filtered and the solvent removed under vacuum to give l-acetyl-5-(2'-chlcro-4'-trifluoromethy1-6'-fluorophenoxyjbenzctriasole (13.64a) as a brown oil. 2 5 2 A 0 3 2 0 te p E l-acetyl-5-(2'-chloro-4'-tri fluo romsthy1-6 ' -fluorophenoxy) benzotriazole (13.64g), concentrated 5 hydrochloric acid (48 cm^ ) and ethanol (80 cm^) were stirred and heated under reflux for 3 hours. The solvent was removed under vacuum and the residue partitioned between water ana ethyl acetate. The organic phase was washed with water, dried (MgSO^), filtered and the solvent 10 removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CHCl^EtOAc 4:1) to give 5-(2'-chloro-4'-trifluoromethy1-6fluorophenoxy) benzotriazole (9.6g) as a buff solid.
Step F £-(2'-chloro-4'-1 ri fluo romethy1-6'-fluorophenoxy) benzotriazole (8.91g) was dissolved in dry DMF (92 cm ) and 50% sodium hydride (1.2 S g ) added portionwise vich 20 stirring. After 10 minutes at room temperature, the mixture was cooled in a water bath and ethyl 2-bromcprcpionate (3.65 cm ) added. Stirring was continued for 1^ hours, when the mixture was poured into water ( 380 c:aJ ) and extracted four times with ethyl 2.5 acetate. The combined organic phase was washed with water, dried (MgSO^) filtered and the solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CHCl^:Ether, S5:4) to yield compounds: Compound No. 10 in Table I (l.S4g) Compound No. 11 in Taable II (2.34g) Compound No. 12 in Table III (2 . 4 2 g ) as oils.
Compounds 7, 8, 9, 13, 14, 15, 37 and 42 were 35 prepared by ar.lagous methods using appropriate reactanis.
EXAMPLE 3 This example illustrates the preparation cf compound 10 in Table I, compound II in Table II and compound 12 in Table III.
Step A M-nitrophencl (14.4g) was dissolved in DMSO (47 cm^) under nitrogen. The solution was stirred, heated to 80°C and pctassium hydroxide pellets (6.83g) added. After i'i hours at 80°C, 5-chloro-3 , 4-difluorobenzotrifluoride (21.9g) was added dropwise with constant stirring. When the addition was completed, the mixture was stirred and heated at 140°C fcr 18 hours. After cooling, most of the solvent was removed under vacuum, and the residue partitioned between water and diethylether. The organic phase was separated and the aqueous layer extracted with two further portions of ether. The ether extracts were combined, washed three times with water, dried (MgSO^, ) and filtered. Tha solvent was removed from the filtrate under vacuum to give 33g cf brown oil which was purified by flash chromatography (silica; CHCl^:hexane, 2:3) to give 25.5g of 3-(2'-chloro-4'-trifluoromethvl-5'-fluorophenoxy)nitrobenzene as a yellow oil.
Step B 3-(2'-chloro-4'-tri fiuoromethyl-6fiuo rophenoxv) nitrobenzene (25.5a) was dissolved in ethylene dichloride (51 cm^ ) stirred and cooled and in a salt/ice bath and concentrated sulphuric acid (91 cmJ) added. The mixture was cooled to -13C ana potassium nitrate (8.45g) added portionwise with vigorous stirring at -1 to 0°C. When addition was complete the reaction mixture was stirred cor 15 minutes at 00C and then allowed to warm to room 9 fi ■-< ■? 2 0 temperature whilst stirring fcr a further 18 hours. Thi mixture was pcured into ice/water (400 cm^) and extracted four times with dichlocome thane. Ths combined dichlocome thane extracts were dried (MgSO^), filtered and solvent removed from the filtrate under vacuum to give a pale brown oil which was purified by flash chromatography (silica, hexane: EtOAc:85:15) to give 4-(2'-chloro-4'-trifluoromethyl-o'-fluorophenoxy)-1,2- dinitrobenzene (2S.78g, 93%) as an oil.
Step C % palladium/carbon (0.28g) was suspended in methanol (38 cm^) through which nitrogen gas was being passed. A solution of sodium borohydride (0.56g) in water (15 cm ) was added with stirring and ice/salt bath cooling to -5°C. A solution cf 4-(2'-chloro-4'-trifluoromethyl-6'-f luo rophenoxy)-1, 2-dini trober.zene (0.934c) in methanol (20 cm^) was added, maintaining the stirred mixture at O'C. When addition was complete, the cooling bath was removed and the mixture stirred at room temperature for 45 minutes. The reaction mixture was filtered through 'hvfio' and solvents removed from the filtrate under vacuum. The residue was dissolved in chloroform, washed with water and the chloroform solution dried, (MgSG4) filtered and solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CKCl-j : EtOAc , 1:1) to give 4-(2'-chloro-4'-1 ri fluo rome thyl-6'-fluorophenoxy)-1,2-diam inobenzene (O.S8g, 85%) as a pale brcwn oil.
Step P 4-(2'-chloro-4'-trifluo rome thyl-5 '-fluorophenoxy)-l,2 -diaminobenzene (4.15g) was added to water (90 cm ) containing concentrated hydrochloric acid (6.1 ca^) with r*. - 67 2 4 0 3 2 0' stirring. The mixture was coded to 0°C. A solution of sodium nitrite (2.013c) in water (20 cmJ) was added cropwise with stirring and cooling between 0 and 5°C. During the course cf the addition more water (60 ca^) was added. The mixture was left to stir to room temperature overnight, extracted three times wih ethyl acetate and the combined organic phase washed with water, dried (MgSO^), filtered and the solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CHCl2 : EtOAc, 4:1) to give 5-(2'-chlorc-4'-trifluorcmethyl-6'-fluorophenoxy)-benzotriazole (3.87g, 90%) as a buff solid.
Step S -(2' - chloro-4'-trifluoromethy1-6'-fluerophenoxy) benzotriazole was converted to compound 10 or Table I, compound 11 of Table II and compound 12 of Table III by the process described in Example 2, Step F.
Compounds 16, 17, 13, 19, 20, 21, 22, 23, 24, 25, 25, 21, 28, 29, 30, 47, 52 and 73 were prepared by analagous methods using appropriate reactants.
EXAMPLE 4 2,5 This Example describes the preparation of compound 3-9 of Table III.
Step A DL 2-amino-l-prcpanol (5.01c) was dissolved in dry DMF (100ml) and dry potassium carbonate (13.7g) added. 4-( 2'-chloro-4'trif1uoromethy1-6'-fluorophenoxy)-1,2-ainit robenzene (25.05g) was added with stirring and the nurture 35 then stirred for 18 hours at room temperature. The reaction mixture was poured into water (450 ) and 2 4 0 3 2 0; extracted thrae tirr.es with ethyl acetate. Ths combined organic extracts were washed three times with water, dried (KcSO^), filtered arid the solvent removed from the filtrate under vacuum. The residue was purified by flash 5 chromatography (silica, 'nexane: EtOAc, 85:15) to give CL 2-[5-(2-chloro-4-trifluoromethy1-6-fluorophenoxy)-2-nitroani1ino ] propan-l-ol (21.4g, 75%) as a bright yellow oil .
Step S % pallaaium/C (O.llg) was added to methanol (13 cm3) which was stirred and purged with nitrogen. A solution of sodium borohydride(0.22g) in water (6.2 cm3) was added and 15 the mixture cooled in ice whilst a solution of DL 2 — [5 — ( 2-chlo ro-4-tri flue romethyl-6-flucrophenoxy)-2-nitroani1inc]propan-l-ol, ( 0.8g) in methanol (16 cm3) was added slowly. When addition was complete the reaction was stirred for a further 15 minutes with cooling followed by 20 30 minutes at room temperature. The mixture was filtered through 'hyflo' and the solvent removed from the filtrate under vacuum. The residue was dissolved in chloroform and the solution washed with water. The organic phase was dried and the solvent removed under vacuum tc give brown 25 oil (0.74g, 99%) which solidified on standing. The solid was racrystaiiised from toluene to give DL 2 -[ 5-(2-chlcro-4-trifluoromethy1-6-fluorophenoxy)-2-amino-anilino] propan-l-ol, (0.54a, 73%).
Step C DL 2-[5-(2-chloro-4-trifluoromethyi-6-fluorophencxy)-2-amincani1inc] propan-l-ol, (O.ElSg) was added to a 3 , stirred, cooled (0 to 50C) mixture of water (10 cm ) ana 35 concentrated hydrochloric acid (0.62 cm3). A solution of sodium nitrite (0.21a) in water (2.1 cm3) was added 240 320 dropwise, maintaining the temperature between 0 and 5 3 C, When the addition was completed, the reaction was kept ac 0 to 5°C for 10 minutes and then stirred to room temperature over 1.5 hours. The reaction mixture was extracted three times with ethyl acetate, the organic extracts combined and washed three times with water. The organic phase was cried (MgSO^), filtered and the solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CHCl^iEtOAc, 7:3) to give compound 39 of Table III, DL 2-(6-(2-chloro-4-triflucromethyl-6-fluorophenoxy)ber.zotriazol-l-yl] propanol (0.41g, 77%) as an oil.
EXAMPLE 5 This Example illustrates the preparation cf compound No 15 in Table III.
DL 2 - (6-(2-chloro-4-trifluoromethyl-6-fluorophenoxy) benzotriazol-l-yi]propanol (0 . 4g) was dissolved in aceton (15 cm^) and the solution cooled in an ice bath. 0.62 cm of 2.67M Jones reagent (made from 2.67g CrO, + 2.63 cm^ -> 3 concentrated K„ SO, + 4 cm"5 water diluted to 10 cm ) was z 4 added in six equal portions over 30 minutes, each portion being followed by acetone (5 ci^). When the additions were completed, the mixture was stirred and cooled for a further 15 minutes and then stirred at room temperature for 1 hour. Isopropanol (0.1 cm^) was added followed by stirring for 10 minutes. Water (15 ca^) was added and solvent removed under vacuum to leave about 20 ca^. The residue was extracted three times with ethyl acetate, thi organic extracts combined, washed with water, cried (MgSO^), filtered and the solvent removed from the filtrate under vacuum to give crude Compound No 15 in Table III, DL 2-i6-(2-chlorc-4-trifluorcmethyl-6-fluorophenoxy)benzotriazcl-l-yl]propionic acid (0.4g), n 240 320 - 70 -EXAMPLE 6 This Example illustrates the preparation of Compound No 12 in Table III. 5 DL 2-[6-(2-chloro-4-1rifluoromethy1- 6-fluorophenoxy)benzotriazol-l-yl]propionic acid (2.3g) was suspended in dry 1,2-dichloroethane (43 cm^ ) . Dry ethanol (0.37 cm^) and DMA? (0.07g) were added. The stirred mixture was cooled in ice and DCC ( 1.18g) added. 10 The reaction was stirred with cooling for 1 hour and then stirred to room temperature for 16 hours. The mixture was filtered and the solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography (silica, CHCl2:Et20, 96:4) to yield Compound 12 in Table 15 III, DL ethyl 2 —[6 —(2-chloro-4-trifluoromethy1-6-fluorophenoxy) benzotriazol-l-yl]propionate, (1.64g, 67%) as a colourless oil.
Compound 54 was prepared by an analagcus method using 20 appropriate reactants. ■->' EXAMPLE 7 This Example illustrates the preparation of Compound 25 Mo 40 in Table III.
Dl 2 —[£ —(2-chloro-4-trif1uoromethyl-6-flucrophenoxy)benzctriazol-l-yl] propionic acid, (0.5g), 1 , 1—dime thyl hydrazine, (0.094 cm"3) and DCC (0.256 g) were dissolved in dry, stirred, ice cooled dichloromethane (5 30 cm^ ) . The mixture was stirred at 0 to 5°C for 1 hour and then stirred to room temperature overnight. The mixture was filtered and solvent removed from the filtrate under vacuum. The residue was purified by flash chromatography, (silica, CKCl^sEtOH, 95:5) to give Compound 40 in Table 35 III, DL 2-[5-(2-chloro-4-trifluorcmethyl-6-fluorophenoxy)-benzotriazol-l-yl] propionyl dimethvlhydrazide (0.35c, o 2 4 0 3 2 01 63% ) EXAMPLE 8 Thi s Example illustrates the prepa ration of Compound 41 in Ta'ole III.
DL 2-[o-(2-chlo ro-4-1 r i fluoromethyl-6-fluorcphenoxy)benzotriazol-l-yl] propionyl dimethyl hydrazide (0.3 3 g ) was dissolved in methanol (12 ) and 10 methyl iodide (1 cm^) added. The mixture was kept in the dark at room temperature for 18 days, when the solvent was removed under vacuum. The residue was triturated with ether, the ether decanted and the residue dried under vacuum to civs Compound 41 in Table III, DL 2 —[6 —(2 — 15 chloro-4-trifluoromethyl-5-fluorophenoxy)benzotriazol-i-yj propionyl trimethyl hydrazinium iodide (0.245g).
EXAMPLE 9 This Example illustrates the preparation cf Compound 81.
Ethyl 2—[6 — (2-chlore-4-trifluoromethy1-6-fluorophenoxy) benzotriazol-l-yl]propionate (0.53a) was dissolved in 1,2-dichlorosthane (1.5 crri^ ) and stirred with 25 meta-chloro-per-benzoic acid (0 . 23g) at room temperature for 7 days. Ths solvent was removed under vacuum and ths residue purified by flash chromatography (silica, CHCl,:£tCH, 93:2) to give Compound 43, ethyl 2-[6-(2-chlorc-4-tri£luoromethyl-5- fiuorophenoxy) 30 benzotriazol-l-yl-3-M-oxide] propionate (0.37g, 67%).
NMR (CDC13): 3 7.37(d)iH; 7.54(s)lH; 7.47(dd)lH; 7.06(dd) iH; 5 . 7 8(s)1H; 5.15(c)lK; 4.17(q)2H; 1.92(d) 3 H ; 1.17 ( t) 3 H . 2 4 0 3 2 0) - 72 EXAMPLE 10 This Example illustrates the preparation of Compound 32 .
Ethyl 2-[6-(2-chlcro-4-1rifluoromethy1-6- fluorophenoxy) benzotriazol-l-yl]propionate (0.26g) was dissolved in dry dichloromethane (1 cm3) and triethylcxonium tetrafluoroborate (0.6 cm3 of IM solution in CH2CI2) added with stirring and left at room 10 temperature for 13 days. Ths solvent was removed under vacuum to give a white solid which was washed with ether and filtered to give Compound 44, ethyl 2-[6-(2-chloro-4-tri fluoromethyl- 6-fluorophenoxy)-3-ethyl-ber.zotr iazol-l-ylium] propionate tetraf luoroborate 15 (0.0S5g), m.p. 130 .1-131.6°C.
EXAMPLE 11 This Example illustrates the preparation of Compound 20 No 15 in table III.
Ethyl 2-(o-(2-chloro-4-triflucromethy1-6-fluorophenoxy) benzotriazol-l-yl] propionate (0.703c) in THF (2.2 c:r.3) and isopropanol (6.3 cm3) was stirred at room temperature with a solution of sodium hydroxide 25 (0.07g) in water (1 cm3) for 24 hours. The solvents were removed under vacuum and the residue dissolved in water (2'5 cm3) . 2M hydrochloric acid (0.86 cm3) was added with stirring. The precipitate was filtered, washed with water, air cried and recrystallised from toluene to give 30 Compound 15 in Table III, 2 - [ 6-(2-chlo ro-4-tr i fluo romethy1-6-fluorophenoxy) benzotriazol-l-yl ] propionic acid, (Q.5Sg, 90%) as a white solid, m.o. 173-173.9°C. - 73 EXAMPLE 12 240 320 Thi s Exair.pl e illustrates the preparation of Compound 35 in Table III.
DL 2-[6-(2-chloro-4-trif1uoromethy1-6-fluorophenoxy) benzotriazol-l-yl]propionic acid, (0.1S9g) in dry 1,2-dichloroethane (4.7 cm ) was stirred and refluxsd with thionyl chloride (0.06g) for 14 hours and left to cocl overnight. DMA? (0.0S6g) was added, the mixture stirred 10 at room temperature for 10 minutes, when methanesulphonamide (0.05g) was added and the mixture stirred at room temperature for 2 hours. The solvent was removed under vacuum and the residue purified by flash chromatography (silica, CHCl^:acetone:HOAc, 90:10:5) to 15 give DL 2-[6-(2-chloro-4-trifluoromethyl-6- fluorophenoxy)benzotriazol-l-yl]-N-(methylsulphonyl) propionaraide (0.138g, 58%) as a white solid.
Compounds 55, 56 and 57 were prepared by analagous methods using appropriate rectants.
EXAMPLE 13 This Example illustrates the preparation of compound No 15 in Table III.
S t e o A 4-(2-chloro-4-tri f luo rente thy 1-6- fluo rophenoxv) -1, 2-dinitcobenzene (8g) was dissolved in cry DM? (16 cm"^) and 30 DL alanine ethyl ester hydrochloride (3.24g) added followed by triethylamine (5.84 crn^). The mixture was stirred for 15 hours at room temperature, poured into water (80 cm^) and extracted four times with ethyl acetate. The compound extracts were washed with water, 35 dried (Mg.SQ,,!, filtered and the solvent removed from the t filtrate under vacuum. The residue was purified by flash 24 0 3 20i chromatography (siC^, CKCl^hexane 4:1, followed by CHCl^) to give DL ethyl 2-[5-(2-chiorc-4-trifiuoromethy 1-5-f luo r ophsnoxy )-2-r.i troar.il ino Jpropionate , (4.75g), as a bright yellow oil.
Steo B DL ethyl 2-[5-(2-chloro-4-trifluoromethyl-5-fluorophenoxy ) -2-ni trcanil ino ] propionate , (4.75g) was dissolved 3 in THF (18 cm )/isopropano1 (55 cm") and a solution of sodium hydroxide (Q.86g) in water (18 cm ) added slowly with stirring. The mixture was stirred at room temperature for 30 minutes and then the solvents were removed under vacuum. The residue was dissolved in water 15 (25 cm^) and added slcwly to a stirred, ice cooled mixture of 5% palladium/charcoal (O.lg) in water (30 cm^ ) and sodium borohydride (0.8g) in water (20 cm"^) under a nitrogen atmosphere. When addition was complete the mixture was stirred at room temperature for 2\ hcurs. The 20 reaction mixture was filtered through 'hvflo' and the filtrate cooled to 0°C when 2M hydrochloric acid (31.5 cni^) was added with stirring and cooling. A solution cf sodium nitrite (1.58c) in water (10 cm^) was added dropwise with stirring and cooling to 0°C. After the 25 addition, the mixture was stirred to room temperature foe 2 hours. The mixture was extracted three times with ethyl acetate and the combined extracts washed with water, dried (MgSO^), filtered and the solvent removed from the filtrate under vacuum. The residue was purified by flash 30 chromatography (Si02, CHCl-:acetone:glacial, acetic acid 85:10:5) tc give DL 2-{5-(2-chloro-4-trifluoromethyl-o-f iuo rophenoxy ) benzotr iasol-l-yl ] propionic acid, (1.63.g).
Compounds 61, 52, 6 3 and 5 4 were prepared by analagcus methods usir.c appropriate reactants. 3 5 2 4 0 3 2 ©1 EXAMPLE 14 This Example illustrates ths preparation of compound No 78 anc 79.
Ster> A A mixture of ethyl 2-(5- and 6-methoxybenzotriazc1-1 —y1) propionate (A Eiodo, I Vazzana, F Sparatore; Studi 10 Sassararesi, Sezicne 2, 787, 5_7, 1979 ), (3.8g), was dissolved in dry dichloromethane (150 cm^ ) , stirred and cooled to -703C. Boron tribromide (24 cm^), in dry dichloromethane (20 cm') was added dropwise over 30 minutes, the mixture maintained at -60°C for 30 minutes 15 and then stirred tc room temperature overnight. The mixture was cooled to 4*C, ethanol (80 cm^) added dropwise with stirring over 30 minutes, allowed to warm to room temperature, and the solvents removed under vacuum.
—* Ethanol (200 cm"3) and concentrated sulphuric acid (2 ml) 20 were added to the residue and the solution heated under reflux for 2 hours. The solvent was removed under vacuum and the residue dissolved in ethyl acetate, washed with water, dcied (MgSO^), filtered and ths ethyl acetate removed under vacuum. The crude product, 7.34g, was 25 purified by chromatography (SiO.,, Hexane:EtOAc, 2:3) to * u give 6.67a of a mixture of ethyl 2-(5- and 6-hydroxy-benzotriazol-l-yl) propionate as a pale yellow oil.
Characterising data: (CDC13) 5 1.2(t,3); o 2.0(t,3); S 4.2(q,2), o 5.5-5.7 (m,l); 6 5 . 85(broads); o 6 :13(breads); 6 6.89 (d); 6 6.S5(cd}; o 7.13(dd); h 7.40(m); 5 7.90(d); £4032 Seep 5 A mixture cf ethyl 2-(5- and 6-hycroxybenzotriazol-l-yl propionate (0.5g), anhydrous potassium carbonate (0.44g), dry methylethyl ketone (12 cm^) and octafluorotoluene (lg) were heated under reflux for 0.75 hour, filtered and the filtrate evaporated under reduced pressure tc give 0.93g of crude product as pale yellow oil. The crude product was purified by preparative plate chromatography (SiO^, hexane:t-butylmethylether , 7:3) to give ethyl 2-(6-heptafluorotolyloxybenzotriazol-1-yl }. propionate (0.4g) and ethyl 2-( 5-heptafluoro-tolyloxybenzotriazol-l-yl) propionate (0 . 22g) as colourless oils.
Compounds 65, 66, 67, 68, 69, 70, 71, 72, 75, 76, 77, 80, 83, 84, 85 and 86 were prepared by analogous method using appropriate reactants.
EXAMPLE 15 This Example illustrates the preparation of compound Mo 44 in Table I, compound Mo. 49 in Table II and compound Mo 58 in Table III. -(2'-chloro-4'-trifluoromethyl-6'-fluorophenoxy benzotriazole (as prepared in Example 1 Step F) (lg) was added to pyridine (1 cm"'). Ethyl acrylate ( 0 . 3 3 g) was added followed by sodium methoxide and the reaction mixture stirred at 50°C for 7 hours. The solvent was removed under vacuum and the residue partitioned between water and ethyl acetate. The organic extract was washed three times with water and dried (MgSO^). The solvent was removed under vacuum leaving a brown oil. The 'oil was purified by flash chromatography using SiC^ hexane : TBMZ 65:35 as eluent. Three products were obtained which were shown by NMR to be compound 44 in Table I, compound 4S in Table II and compound 53 in Table III. 240320 Compounds 45, 46, 50, 51, 59 and 60 were prepared by analagous methods using appropriate rsactants.
EXAMPLE 16 This Example illustrates the preparation of compound No. 7 4 in Table III.
Cxalyl chloride (0.49cm^) was dissolved in dry ■3 dichloromethane (12cmJ) and dry DMSO in cry dichloromethane (1.25cm^) was added dropwise with stirring and cooling to -50 to -6C°C. DL 2-[6-(2-chloro-4-1 ri fluoromethy1-6-fluo rophenoxy)benzotriazol-l-yl] propanol (lg) in dry DMSC (5cmJ) was added at -50°C and 15 stirred at -50°C for 30 minutes. Triethylamine (1.79cm^) was added at -50°C and the mixture a11owed to attain room temperature follwed by 30 minutes stirring at room temperature. /later (25citi^) was added, the organic phase separated and washed with water, dried and filtered and 20 the organic phase removed from the filtrate under vacuum. The residue was purified by flash chromatography (SiC7; hexane : 73MS, 1:1 increasing to 100% 73112) to give DL 2-[ 5-(2-chlcro-4-trifluc romethy1-6-fluorophenoxy)-benzotriazol-l-yl] prcpionalcehyde (O.lg) as an oil.
Biological Data The herbicidal activity of the compounds was tested as follows: Each compound in the appropriate concentration was incorporated into a 4% emulsion of methyl cyclohexane and a 0.4% blend of 2.5 parts Tween 20 and 1 part Span 30. Tvsen 20 is a Trade Mark for a surface active agent comprising a condensate of 20 molar proporticns cf 35 ethylene cxide with sorbitar. laurats. Span SO is a Trade Mark for a surface-active agent comprising sorbitan ^ 240 3 2 0 aonclaurate. Formulation was effected by dissolving the-compound in the requisite amount of solvent/surfactant blend. If necessary glass beds were added, the total liquid volume adjusted to 5 ml with water and the mixture 5 shaken to effect complete dissolution of the compound.
The formulation so prepared, after removal of beads where necessary, was then diluted to final spray volume (45 ml) with water.
The spray compositions so prepared were sprayed onto 10 young pot plants (post-emergence test) at a rate equivalent to 1000 litres per hectare. Damage to plants was assessed 13 days after spraying by comparison with untreated plants, on a scale of 0 to 5 where 0 is 0-101; damage, 1 is 11 to 25% damage, 2 is 26-50% damage, 3 is 15 51-30% damage, 4 is 81-55% damage and 5 is 96-100% damage.
In a test carried out to detect pre-eaergence herbicidal activity, seeds of the test species were placed on the surface of plastic trays of compost and sprayed with the compositions at the rate of 1000 litres per 20 hectare. The seeds were then covered with further compost. 20 days after spraying, the seedlings in the sprayed plastic trays were compared with the seedlings in unsprayed ccntrol trays, the damage being assessed on the same scale of 0 to 5.
The results of the tests are given in Table IV below: TABLE IV ,3 COMPOUND NO RATE OF APPLICATION kg/ha PRE- OR POST-EilER^ENCF. APPI.ICATIOM TEST PUNTS (see Table V) Sb Rp Ct Sy Hz Uu Rc Dd Ip Am Pi Ca Ga Xa Xs All Co Av Dg Al St Ec Sh Ag Cn 1 3 Post 345422153534 4- 54221120101 2 4 Pre Pos t 00113200100010-003433 4 1- 0 3 3 4 3 4 1 3 3 2 4 2 2 4 - 3 3 1 3 5 3 4 4 3 1 0 3 4 Pre Post 35453132 4 31143-301013 4 2-4 355 4 321555555-5522 4 2 4 331 3 4 3 Pre Po.s t 100020010000-0- 0 0000000-0 25 3 3102233033-13000011010 3.3 Pre Pos t 000000000000-0-00000000-1 2221120223003-03111122231 6 3 Pre Post 0210401 4 4300-3-00000100-0 354400 1 5 55355-5510003320 2 I vO po CD CM ro o TABLE IV (Contd.) 1 COMPOUND MO KATE OF APPLICATION kg/tia PNJ2- OR POST-EMERGENCE APPLICATION TEST PLANTS (see Table V) Sb Rp Ct Sy Hz L'u Rc fld Jp Am Pi Ca Ga Xa Xs Ab Co Av Dg Al St Ec Sli Ag Cn 7 3.5 Pre Post 03121014352330-22101402-2 '55444 3 3555555-55333 4 4 3 3 3 3 8 /.
Pre Pos t 1311013 4 151 4 20-31 122301 -0 35 4 35 4 2455545-453353555 4 2 9 3.5 Pre Post 55 4 55455555555-55555554-5 5555545555555-5555555555 4 1 Pre Po s t 0 0121001010000-00000201-1 55545335355-5-44133343421 1] 2. no 1 Pre Pos t 12012003340530-500202 10-0 4 554 A 225555-5-555242 4 55 3 2 12 i Pre Pos t 5 3 55555555555-55555555-4 55555555555-5-55555555553 3 TAOLE IV (Contd.) COMPOUND NO RATE OK APPLICATION kg/ha PRE- OR POST-EMERCEi'CE APPLICATION TEST PLANT'S (see Table V) Sb Rp Ct Sy Hz Uw Rc Bd Ip Ain Pi Ca Ga Xa Xs Ab Co Av Dg Al St Ec Sli Ag Ci: 13 1 Pre Post 00010000000000-00000000-0 1 3 3331013 4 3-1-221111112 0 0 14 1 Pre Pos t A 401001 A 4534 4 0-4 0 0303 0 3- 0 2553 4 11455 4- 5- 521504 4 4531 1 Pre Post 55555555555555-55555555-5 55555555555-5-55555555545 31 2.8 Pre Pos t 00000030000000-0003000---2222200243322-22002032200 32 3.57 Pre Post 0001335020 0 000-1015 4 5 4 ---2333 4 33143035-3 4 33 4 355 4 2 2 I OO fV 04 ro o ') TABLE IV (Contd.) COMPOUND NO RATE OF APPLICATION kg/!ia PRE- OR POST-EMERGENCE APPLICATION TEST PLANTS (see Table V) Sb Rp Ct Sy liz Vv Rc 3d Ip Am Pi Ca Ga Xa Xs Ab Co Av Dg Al St Ec Sh Ag Cn 33 2.2 Pre Pos t 3 5 3 344 4 04 3 3330-0225255--- 4 555 4 32555555-55 4 3 4 25552 3 37 0.25 Pre Post 5534 4 4 4555 4 555-5325 4 55 4 -1 5555554555555-55555555553 3fl 1 Pre Post 55 4 443555 5 5555-54253555-5 5555533555555-55535355533 3(J 1 Pre Pos t 5554 4 455555553-55555555-4 55555 4 3555555-555454555 4 3 O O* ro o TABLE V Abbreviations used fcr Test Plants Sb - Sugar beet Rp - Rape Ct - Cotton Sy - Soybean Mz - Maize Ww - Winter wheat Rc - Rice Bd - Bidens pilosa ip - Ipomcea purpurea Am - Amaranthus retroflexus Pi - Polygonum aviculare Ca - ChenoDodium album Ga - Galium aoarine Xa - Xanthium soinosun Xs - Santhium. struma riura Ab — Abutilon theochrasti Co - Cassia cbtusifolia Av - Avsna fatua Dg - Digitaria sanguinalis Al - Alocecurus myosuroides St - Setaria viridis Ec - Echinochloa crus-galli Sh - Sorchum haleoense Ag - Agropyron recens Cn - Cyperus rotundus 240 3 20 240 320 The herbicidal activity of some of the compounds was tested by an alternative method as follows: Each compound in the appropriate concentration was incorpcraced into a 4% emulsion of methyl cyclohsxanone 5 and 0.4% blend of 3.6 parts Tween 2.0 and 1 part Span 80. Tween 20 is a Trade Mark for a surface active agent comprising a condensate fo 20 molar proportions of e thylene oxide with sorbitan laurate. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan 10 monolaucate, Formulation was effected by dissolving the compound in the requisite amount of solvent/surfactant blend. If necessary glass beads we re added, the total liquid volume adjusted tc 5 ml with water and the mixture shaken to effect complete dissolution of the compound. 15 The formulation so prepared, after removal of beads where necessary, was then diluted to final spray volume (45 ml) with wate r.
The spray compositions so prepared were sprayed onto young pot plants (post-emergence test) at a rate 20 equivalent to 1000 litres per hactare. Damage to plants was assessed 13 days after spraying by comparison with untreated plants, cn a scale of 0 to 9 where 0 is 0% damage, 1 is 1-5% damage, 2 is 6-15% damage, 3 is 16—25% damage, 4 is 26-35% damage, 5 is 36-59% damage, o is 25 60-69% aamacs, 7 is 70-79% damage, 8 is 80-89% damage and 9 is 90-100% carnage.
In a test carried out to detect ore-emergence herbicidal activity, Crop seeds were sown at 2 cm depth (i.e. Sb, Ct, ?.p, Ww, Mz, Rc, Sy) and weed seeds at 1 cm 30 depth beneath compost and sprayed with the compositions ac the rate of 1000 litres per hectare. 20 days after spraying, the seedlings in the sprayed plastic trays were compared with the seedlings in unsporayed control trays, the damage being assessed on the same scale of 0 to 9. 35 The results of the tests are aiven in Table VI below.
TABLE VI COMPOUND NO RATE OF APPLICATION kg/ha PRE- OR POST-F.MERGEMCE APPLICATION TEST PLANTS (see Table VII) Sb Rp Ct Sy Hz Rc Uw Pi Ca Ga Am Bd Eh Ip Ab Xa Xs Av Al Ag Sh Sr Dg Ec Ce 16 1 0.25 Pre I'os t 0000000000000500-03-20 0 00 278 4 20059292899-500 1 7 6 650 17 1 Pie Pos t 8750000090908200-00-70001 099992299999999-915289 8 70 18 0.25 0.0625 1 0.25 Pre Post 9725000492929702-00-79682 999992999999999-95518 9 9 9 3 19 Pre Post 0000000090915520-03-00000 698661299999 9 9 9 - 910282- 0 1 1 Pre Post 00000 0 0000000000-00-6 0 000 59987128899 995-9101 6 6550 21 0.25 0.0625 Pre Pos t 923002059 A 927802-00-7 0 2 00 999892299999999- 9 34287881 1; ) TABLE VI (Contel.) JOHPOUHD 110 RATE OF APPLICATION kg/ha PRE- OR POST-EKHRGEMCii APPLICATION TEST PLANTS (see Table VII) Sb Rp Ct Sy Mz Rc Uu Pi Ca Ca Am Qii Eh Ip Ab Xa Xs Av Al Ag Sh St Dg Ec Ce 22 1 0.25 Pre Post 0003000090922 000-01 - 000 0 0 4 97680259897999-011 086701 23 1 Pie Pos t 0210000200010000-00-50022 4 99361156993095-90016 6 1 50 24 0.25 0.0625 P re Pos r 9113020091959002-00-2 9 4 30 099681379000999-9221909 (1 0 1 0.25 Pee Pos t 0000000000000300-02-000 0 0 110110028081 6 73-200021110 26 1 Pre Pos t 0033000232202 0 00-00-5 0 671 394572157195892-5110033 6 0 27 0.25 0.0625 Pre Post 2020300492955200-0 0 - 4 0 0 00 596581270 4 07999-01129 6 662 > J CO ON I rc o 04 ro o TABLE VI (Contd.) COMPOUND NO RATE OF APPLICATION kg/lia PRE- OR POS ['-EMERGENCE APPLICATION TEST PLANTS (see Table VII) Sb Rp Ct Sy Hz Rc Uw Pi Ca Ga Am Bd Eh Ip Ab Xa Xs Av Al Ag Sh St Dg Ec Ce 28 1 0.25 Pro Pos t 013300000-0 0 020--00-00 4 00 5239622 4 7572997-522112220 29 1 Pre Post 000019008-00202--00-00000 999853399999999-921203562 1 0.25 Pre Pos t 9955090-9-99999--75-79 9 93 999999999999999-999989990 1 Pre Post 0000000-0-000000-00-0005 -10028 0 000300200-005006 0 1 0 CO IV? -S^- OS ro TABLE VI (Contd.) ) COMPOUND NO RATE OF APPLICATION kg/ha PRE- OR POST-Eb'ERGENCE APPLICATION TEST PLANTS (see Table VII) Sb Rp Ct Sy Hz Rc Uu Pi Ca Ga Am Bd Eb Tp Ab Xa Xs Av Al Ag Sb Sr Dg Ec Cc 40 1 Pre Post 99 4 46-799-99999--07-9999 9 999995999999999-99967 9 99 9 41 1 Pre Pos t 99A36-599-99959--22- 9 9882 999993799999999-997 4 99907 42 0.4 Pre Post 0040000020022104-00-60000 385782167262903-501086750 43 1 Pre Post 9 9 52455-9-999995-01-99981 9 99997899999999-99 9 899997 44 1 Pre Pos c 50000 0 0- 0- 305000-00-0000 0 9999 9 56999999999-9569 4 9 94 I CO (X> I ro O CM ro o K.I K-: J ) TABLE VI (Contd.) rjOHPOUND RATE OF PRE - OR TEST PLANTS (see Table VII) MO APPLICATION POST -EMERGENCE Icg/lia APP LIGATION Sb Rp Ct Sy Hz Rc yv Pi Ca Ga Am Rd Eh Ip Ab Xa Y.s Av A] Ag Sh St Dg Ec Ce 45 1 Pre 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0 Post 7 0 2 a 1 1 0 0 9 7 9 1 3 8 9 - 4 3 2 0 1 2 2 0 0 1 cn vO 46 1 Pre 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0 1 Pos t - 4 2 7 6 0 3 7 0 3 9 0 6 2 9 - 5 0 0 2 0 1 2 0 0 4 a 1 Pre 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0 Pos t 2 3 0 0 0 0 0 2 0 0 0 1 0 0 - 0 0 0 0 0 0 0 0 0 40 1 Pre 1 0 0 0 0 0 - 2 0 0 0 0 - 0 0 - 0 0 0 0 0 Pos t 6 0 6 3 8 0 2 0 0 0 9 3 9 7 9 - 3 0 0 0 0 0 1 7 0 50 1 Pre 0 0 0 0 0 0 0 9 0 0 0 0 0 - 0 0 - 0 0 0 0 0 Pos t 9 9 6 6 3 I 0 9 9 9 9 6 9 9 9 - 7 0 0 0 0 0 0 0 0 ro 51 1 Pre 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0 Pos t 0 8 7 7 1 2 6 9 9 9 3 9 9 9 - 7 0 0 3 0 0 0 0 0 OS rsa ) > 3 TABLE VI COMPOUND NO RATE OF APPLICATION kg/ha ['RE- OR POST-EMERGENCE APPLICATION TEST PLANTS (see Table VIT) Sb Rp Ct Sy Hz Rc Uu Pi Ca Ga Am Bd Eh Ip Ab Xa Xs Av Al Ag Sh St Dg Ec Cc 53 I Pre Post 9 300000 - 4-00000 0 -00-000 0 0 59778 2 899099999-88059 7 770 -'. 1 Pre Pos I 9900090-9-999090-03-99986 997592 4 39997999-9 4 0 4 9 6 290 55 1 Pre Post 9 907338-9-999797-90-99992 099009000900090-000099 9 B9 56 1 Pre Pos t 050000 0 -9-999390-33-7 9 900 99090500 0 009009-98489997 9 57 1 Pre Pos t 90 0 0302-9-000270-00-7099 0 577604689796979- 9 33390 3 34 58 0.0625 Pre Post 0011001-0-000000-00-00000 00 4 372390997879-65509027 0 O ro CD Q4 ro <0 TABLE VI 1 ....
COMPOUND HO RATE OF APPLICATION kg/ha ■ ! PRE - OR POST-EMERGENCE APPLICATION TEST PLANTS (see Table VII) Sb Rp Ct Sy t'z Uc Uw Pi Ca Ga Am Bd Eh Ip Al) Xa Xs Av Al Ag Sli St Dg Ec Cc 61 1 0.03 Pre Post 9943297 -9-999997 - 3 0-9 9 992 99 4 096 9 - 9 099993-925885 4 92 62 1 0.03 Pre Post 9 9 0 2 2 9 6 - 9 - 9 9 9 0 9 7 - 5 0 - 9 9 9 9 1 49 2 8042-9193756-5121611 0 0 63 1 0.03 Pre Post 9970095-9-999997-01-99996 9989799-9 .9 99999-966 7 99Q96 6 A 1 0.03 Pre Pos t 9920090-9- 9 99495-00-99 4 90 4 937855-9997989-923 4 01221 65 1 Pre Pos t 0000000-0-000000-00-00 0 0 0 00000001607 0 000-2000-00 0 0 67 1 Pre Pos t 000000000-0-0000-00-0000 0 3 9 595 4 5 9 9893 9 98-763 4 65251 TABLE VI COMPOUND NO KATE OF APPLICATION kg/ha PRE- OK POST-EMERGENCE APPLICATION TEST PLANTS (see Table VII) Sb Rn Ct Sy Hz Rc Uw Pi Ca Ga Am Rd Eh Ip Ab Xa Xs Av Al Ag Sh St Dg Ec Ce 68 1 Pre Pos l 0000 0 0 000-0-0000-00-0000 0 3 4 1100300090229-610201 0 00 69 1 Pre Post 0000000-9 - 9 4 02 0 0- 04-37 0 80 595353 3 59697999-99 3 3097 9 5 80 1 Pre Pos t 5200097-8-879555-00-99800 999999999999999-996999995 81 1 Pre Post 9 952455-9-999995-01-99981 9999978999 9 9999-999899 9 97 82 0.0625 Pre Post OOOOOOOOOOOOOOO - -00-00000 795383597897997-902352391 i v£> ro I ro O CM ro 240320 TABLE VII Abbreviations used for Test Plants Sb - Sugar beet ?. p - Rape Ct - Cotton Sy - Soybean Mz - Maize Ww - Winter wheat Rc - Rice Bd - Bidens pilosa Ip - Iponioea lacunosa ( pre-emergencs ) Ipomoea hederacea (post-emergence Am - Amaranthus retroflexus Pi - Polygonum aviculare Ca - Chenopodium album Ga - Galium apar ine Xa - xanthium spinosum 2 0 Xs - Xanthium strumarjura Ab - AbutiIon thecphrasti \,J Eh - Euphorbia heterophylla Av - Avsna f atua Dg - Digitaria sanguinali s Al - Alopecurus myosuroides St - Setaria vi r idis Ec - Echinochloa crus-galli Sh - So rahum halecense Ag - Acropytor, repens Ce - Cyperus esculent.es 3-5 ?•? 3 4876 /AA JRW/VXM 1:8 July 1S89 240 3 20

Claims (3)

WHAT WE CLAIM IS:
1. A compound of formula (V): wherein each R* is independently selected from H, CN, NO2> halogen, Calkyl ancl ^1-10 haloalkyl; m is an integer of from 1 to 4; R2 is N or CR1 where R1 is as defined above; 0 R25 is CH20H, C00H, C00"M+, COOR29 or P(0C2H5)2 where M+ is a cation and R29 is C^.io alkyl; and R26 is H or C!_10 alkyl.
2. A compound of formula (V) as defined in claim 1 substantially as herein described with reference to any example thereof.
3. A compound of formula (V) as defined in claim 1 when prepared by a process as herein described. DATED THts25 DAY OF GC&QV A. J. PARK A SON PER AGENTS u k THE APPLICANTS
NZ24032089A 1988-08-18 1989-07-31 Diaminodiphenyl ether and diaminophenyl pyridyl ether intermediates NZ240320A (en)

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GB898914041A GB8914041D0 (en) 1989-06-19 1989-06-19 Heterocyclic compounds
NZ230146A NZ230146A (en) 1988-08-18 1989-07-31 Substituted 1,2,3-benzotriazoles, herbicidal compositions and intermediates

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