TH68954A - Cyclic derivatives replaced with phenyl. - Google Patents

Abstract

DC60 (08/07/47) Novel phenyl-replaced cyclic derivatives exhibit unexpected insecticidal activity. These compounds are represented by formula I (chemical formula), where I, B, is a cyclic linking group containing at least one N or N oxide linkage, and a, A, b, B, c, d, D, L, M, R1 to R9 in total, and R13, R14, and R15 are fully described here. Furthermore, novel intermediates useful in the preparation of compounds of formula I, mixtures containing the insecticidal effect of at least one compound of formula I and possibly the selective effect of at least one second compound with at least one insecticidally compatible vector, are also revealed. Among the methods of insect control involving the application of such mixtures to insect locations or anticipated locations, the novel phenyl-replaced cyclic derivatives exhibit unexpected insecticidal activity. These compounds are represented by formula I (chemical formula), where I, B, is a cyclic linking group containing at least one N or N-oxide linkage, and a, A, b, B, c, d, D, L, M, R1 to R9 in total, and R13, R14, and R15 are fully described here. Furthermore, novel intermediates useful in the preparation of compounds of formula I, mixtures containing the insecticidal effect of at least one compound of formula I and possibly the selective effect of at least one second compound with at least one insecticidally compatible vector, are also revealed among methods of insect control involving the application of such mixtures to insect locations or anticipated locations.

Claims (18)

1. Compounds of formula I (chemical formula) I at -R and R4 are independently selected from hydrogen, halogen, hydroxyl, (C1-C6)alkyl, (C3-C6)cycloalkyl, (C2-C5)alkenyl, (C2-C5)alkinyl, halo(C1-C3)alkyl, (C1-C3)alxoxy, halo(C1-C3)alxoxy, (C1-C3)alkylthio, halo(C1-C3)alkylthio, (C1-C3)alkylsulfonyl, halo(C1-C3)alkylsulfonyl, cyano, nitro, amino, which may be selected as substitutes at the substitutes that are selected from (C1-C4)alkyl, (C1-C3)alkylcarbonyl and (C1-C3)alxoxycarbonyl, selective substitution imidazolyl, selective substitution imidazolinyl, selective substitution oxazolinyl, selective substitution oxazolil, selective substitution oxadiazolil, selective substitution thiazolil, selective substitution pyrazolil, selective substitution triazolil, selective substitution furanyl, selective substitution tetrahydrofuranyl, selective substitution dioxolanyl, selective substitution dioxanyl, -C(=E)-G, and -(R10)-J-R11, where the selective substitution is selected from (C1-C4)alkyl, halogen, halo(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxy(C1-C4)alkyl, (C3-C6)cycloalkyl, (C2-C5)alkinyl, (C2-C5)alkinyl, cyano, nitro and aryl where E is selected from O, S, NR12 and NOR12 where R12 is hydrogen, (C1-C4)alkyl, halo(C1-C4)alkyl, aryl and aryl(C1-C4)alkyl, G is selected from hydrogen, (C1-C3)alkyl, halo(C1-C3)alkyl, (C1-C3)alkoxy, (C1-C3)alkylamino and Di(C1-C3)alkylamino, J is selected from O, S, and NR12, where R12 is as described above. R10 and R11 are selected independently from hydrogen, (C1-C4)alkyl, and halo(C1-C4)alkyl, and R10 and R11 may be combined with -K(CHR12), where e is an integer 2 to 4, K is selected from O, S, and NR12, where R12 is as described above. -R1 and R3 are selected independently from hydrogen, halogen, and (C1-C3)alkyl, -L is selected from CH2, O, S, and NR16, where R16 is selected from hydrogen, (C1-C3)alkyl, and (C1-C3)alkoxy. (C1-C3)alkyl, aryl(C1-C3)alkyl, (C2-C4)alkenyl(C1-C3)alkyl, halo(C2-C4)alkenyl(C1-C3)alkyl, di(C1-C3)alkylphosphonate, (C1-C3)alkylcarbonyl, halo(C1-C3)alkylcarbonyl, (C1-C3)alxoxy(C1-C3)alkylcarbonyl, arylcarbonyl and (C1-C3)alkylsulfonyl, -M is chosen from O, S, *OCH2 and (CH2)f where asterisk indicates attachment to L and f is an integer from 1, 2 and 3 that determines that L and M are neither O nor S at the same time. -R13 is hydrogen. -R14 and R15 are chosen independently from halogens. -a is an integer chosen from 0 or 1, where a is 1; -A is O, CH2, OCH2, CH2O, OCH=CH, C(=O), S(O)g, -CH=CH-, -OC(=O)-; -OC(=O)NH-; -NHC(=O)-; -NHSO2- and -N=CH-, NR16 or N(oxide)R16, where R16 is as described above, and g is an integer chosen from 0, 1, or 2; -b is an integer chosen from 0, 1, 2, 3, or 4, and where b is 1 or greater; -R5 and R6 are chosen independently from hydrogen, halogen, (C1-C4)alkyl, cyclo(C3-C6)alkyl, halo(C1-C4)alkyl, or aryl; -B is the cyclic linking group of the structure (chemical formula), where Q and T are chosen independently from -CRa-, -N-, and -N(oxide)- is defined as at least one Q or T being -N- or -N(oxide)- and U being -(CRaRb)j- where Ra and Rb in Q, T, and U are chosen independently of hydrogen, hydroxya, (C1-C4) alkyl, halo(C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4) alkylcarbonyloxy, (C1-C4) alkylsulfonyl, (C1-C4) alkylphosphineto, and (C1-C4) alkylphosphoneto, and j is an integer chosen from 1 or 2, -c is an integer chosen from 0, 1, 2, 3, or 4, and c is 1 or greater, -R7 and R8 are chosen independently of hydrogen, (C1-C4) alkyl, halo(C1-C4) alkyl, or (C1-C4) alkoxy, or aryl -d is an integer chosen from 0 or 1, where d is 1. -D is chosen from O, CH=CH, S(O)g, HC=N, C(=O), OC(=O), C(=O)O, C(=O)NH, NR16, N(oxide) R16 and NR16 C(=O), where g and R16 are as described above. -R9 is chosen from (C1-C8)alkyl, halo (C1-C6)alkyl, (C1-C4)alkylthio, (C1-C4)alkoxy, aryl (C1-C3)alkyl, aryl(C1-C3)alkoxy, (C2-C6)alkenyl, halo(C2-C6)alkenyl, (C2-C6)alkinyl, (C3-C7)cycloalkyl. (C4-C10)cycloalkyl, (C1-C3)alkylamino, di(C1-C3)alkylamino, aryl(C1-C3)alkylamino, and phenylamino, where phenyl may be selectively substituted by one or more of cyano, halogen, (C1-C3)alkyl, (C1-C3)alkoxy, halo(C1-C3)alkyl, or halo(C1-C3)alkoxy, (C1-C3)alkyl-S(O)g, where g is described above. Pentahelothiol, tri(C1-C3)alkylsilyl, and NR16, where R16 is as described above and (chemical formula) where h is an integer chosen from 0 or 1, At is chosen from N, C, and C=, V, W, X, Y, and Z are chosen independently from O, S, N, N=, C, C=, or C(=O), given that when V, W, X, Y, and Z are chosen from N, C, or C=, then R17 to R21 in total are chosen independently from hydrogen, halogen, (C1-C6)alkyl, (C2-C4)alkinyl, (C2-C4)alkinyl, halo(C1-C6)alkyl, hydroxy(C1-C6)alkyl, cyclo(C3-C6)alkyl, halo(C2-C4)alkinyl. Halo(C2-C4)alkinil, (C1-C6)alkoxy, (C1-C6)alkoxy(C1-C6)alkyl, (C2-C4)alkiniloxy, (C2-C4)alkiniloxy, halo(C1-C6)alkoxy, halo(C2-C4)alkiniloxy, halo(C2-C4)alkiniloxy, (C1-C6)alkylthiothio, pentahalothio, (C1-C6)alkylsulfenil, (C1-C6)alkylsulfonil, halo(C1-C6)alkylthiothio, halo(C1-C6)alkylsulfonil, halo(C1-C6)alkylsulfonil, cyano, nitro, NRcRd, at Rc and Rd Independently selected from hydrogen, (C1-C6)alkyl, halo(C1-C6)alkyl, (C1-C6)alkoxy, (C1-C6)alkylcarbonyl, and (C1-C6)alkoxycarbonyl, where Rc and Rd may be combined to form saturated or unsaturated rings of 5 or 6 members containing carbon, O, N, or S, (C1-C6)alkylcarbonyl, (C1-C6)alkylcarbonyloxy, (C1-C6)alkoxycarbonyloxy, (C1-C6)alkylaminocarbonyl, (C1-C6)alkylaminocarbonyloxy, tri(C1-C6)alkylsilyl, di(C1-C6)alkylphosphinoyl, aryl, aryloxy. And eril(C1-C6)alcoxi, or where h is I and A1, W and Y are C= and V, X and Z are C, R17 and R18 or R18 and R19 may be combined with. -CR22=CR23CR24=CR25-, -OCR22R23CH2-, -CH2CR22R23O-, -OCR22R23O-, -OCR22R23CR24R25O-, -OCR22R23CH=CH-, -OCR22R23CH2CH2-, -OCR22=N-, -N=CR22O-, -ON=CR22-, -ONR22C(=O)-, -CH2NR22C(=O)-, -C3H6-, -C2H4(C=O), -SCR22=N-, -OCR22R23C(=O)-, -CR22=CR23NR24-, -CR22=NNR23-, -N=NNR22- and -N=CR22N=N- form fused rings at R22 to R25. Overall, it is independently selected from hydrogen, halogen, (C1-C3)alkyl, halo(C1-C3)alkyl, and aryl salts that are agriculturally acceptable. 2. Compounds of claim 1 where R and R4 are independently selected from halogens and (C1-C3) alkyls, L is O, M is (CH2)f where f is 1, R14 and R15 are independently selected from chlorine and bromine, a is an integer selected from 0 or 1 and where a is 1, A is selected from O, CH2, and OCH2, b is an integer selected from 0, 1, 2, 3, or 4 and when b is 1 or more, R5 and R6 are each hydrogen. B is the aforementioned cyclic linking group of the structure (chemical formula), where Q and T are independently selected from -CRa- and -N- where Ra is hydrogen or hydroxya- and U is -(CRaRb)j- where Ra and Rb are hydrogen and j is 2, c is an integer selected from 0, 1, 2, 3, or 4 and when c is 1 or more, R7 and R8 are hydrogen, d is an integer selected from... 0 or 1, and when d is 1, D is chosen from C(=O), C(=O)NH and S(O)g where g is 2, R9 is chosen from (C1-C8)alkyl and (chemical formula), where h is 1 and i) A1, W and Y are C= and V, X and Z are C or ii) A1, W and Y are C=, V is N and X and Z are C, R17 to R21 in combination are chosen independently from hydrogen, halogen, (C1-C6)alkyl and halo(C1-C3)alkyl, and when i) A1, W and Y are C= and V, X and Z are C, R17 and R18 or R18 and R19 may be combined with -OCR22R23CH2- or -CH2CR22R23O- to form a fused ring, where R22 and R23 each are hydrogen, fluorine, or (C1-C3) alkyl. 3. Compounds of claim 2 where each R and R4 is chlorine, each R1 and R3 is hydrogen, a is an integer chosen from 0 or 1, and where a is 1, A is O or OCH2, b is an integer chosen from 0 or 1, j is 2, Q is CRa or N where Ra is hydrogen and T is N, c is an integer chosen from 0 or 1, d is 0 or 1, and where d is 1, D is C(=O) or S(O)g, h is 1, and i) A1, W and Y are C= and V, X and Z are C, or ii) A1, W and Y are C=, V is N and X and Z are C. 4. Compounds of claim 3 where a is an integer chosen from 0 or 1 and when a is 1, A is OCH2, c is 0, d is an integer chosen from 0 or 1 and when d is 1, D is S(O)g, R21 is hydrogen and R17 through R20 inclusively are chosen independently from hydrogen, chlorine and trifluoromethyl. 5. A mixture containing the insecticidal quantities of the compounds of Claim 1 in the mixture with at least one agriculturally acceptable bulking agent or adjuvant. 6. The insecticidal mixture of claim 5 shall be further composed of one or more secondary compounds selected from a group comprising pesticides, plant growth regulators, fertilizers, and soil conditioners. 7. An insect control method consisting of applying an insecticidal dose of the mixture of claims 5 to locations where insects are present or expected to be present. 8. A method of insect control consisting of applying an insecticidal dose of the mixture of claim 6 to locations where insects are present or expected to be present. 9. Compounds of formula I (chemical formula) where -R and R4 are chosen independently from hydrogen, halogen, or (C1-C3)alkyl, -R1 and R3 are hydrogen, -L is O, -M is (CH2)f where f is 1, and -R14 and R15 are each chlorine, -a is an integer chosen from 0 or 1 and where a is 1 -A is chosen from O, CH2, or OCH2, -b is an integer chosen from 0, 1, 2, 3, or 4 and where b is 1 or greater, -R5 and R6 are each hydrogen, -B is the cyclic linking group of the structure (chemical formula), where Q and T are chosen independently from -CRa-, -N-, and -N(oxide)- given that at least one Q or T is -N- or -N(oxide)- where Ra is hydrogen or hydroxyl, U is -(CRaRb)j- where Ra and Rb are hydrogen and j is chlorine. -c is an integer chosen from 1 or 2, and where c is 1 or greater. -R7 and R8 are hydrogen, -d is an integer chosen from 0 or 1, and where d is 1. -D is chosen from O, C(=O), C(=O)NH, and S(O)g, where g is 2. -R9 is chosen from (C1-C8)alkyl and (chemical formula), where h is 1. A1 is chosen from N, C, and C=. V, W, X, Y, and Z are chosen independently from O, S, N, N=, C, C=O, or C(=O), given that when V, W, X, Y, and Z are chosen from N, C, or C=, then R17 to R21 in total are chosen independently from hydrogen, halogen, (C1-C6)alkyl, and halo(C1-C3)alkyl, or where A1, W, and Y are. C= and V, X and Z are C, R17 and R18 or R18 and R19 may be combined with -OCR22R23CH2- where R22 to R25 are chosen independently from hydrogen or (C1-C3) alkyl and its agriculturally acceptable salts. 10. Compounds of claim 9 where each R and R4 is chlorine, a is an integer chosen from 0 or 1, and when a is 1, A is O or OCH2, b is an integer chosen from 0 or 1, j is 2, Q is CRa or N where Ra is hydrogen and T is N, c is an integer chosen from 0 or 1, d is 0 or 1, and when d is 1, D is C(=O) or S(O)g, h is 1 and i) A1, W and Y are C= and V, X and Z are C or ii) A1, W and Y are C=, V is N and X and Z are C. 11. Compounds of claim 10 where a is an integer chosen from 0 or 1 and when a is 1, A is OCH2, c is 0, d is an integer chosen from 0 or 1 and when d is 1, D is S(O)a, R21 is hydrogen and R17 through R20 inclusively are chosen independently from hydrogen, chlorine and trifluoromethyl. 12. A mixture containing the insecticidal quantities of the compounds of claim 9 in the mixture with at least one agriculturally acceptable bulking agent or excipient. 13. The insecticidal mixture of claim 12 shall be further composed of one or more secondary compounds selected from a group comprising pesticides, plant growth regulators, fertilizers, and soil conditioners. 14. An insect control method consisting of applying an insecticidal dose of the mixture of claims 12 to locations where insects are present or expected to be present. 15. Methods of insect control consisting of the application of the officially prescribed insecticidal dosage of a mixture of substances under claim 13 to a location where or where they are expected to be present. 16. Compounds of formula II (chemical formula) II where -R is hydrogen, halogen, or (C1-C3)alkyl, -R2 is chosen from hydroxya, phenylmethoxy, and -L-M-C(R13)=C(R14)(R15) where L is O, M is (CH2)f where f is 1, R13 is hydrogen, and each R14 and R15 are chlorine. -R1 and R3 are chosen independently of hydrogen or halogen. -R4 is a halogen or (C1-C3)alkyl. -a is an integer chosen from 0 or 1, and when a is 1, A is OCH2. -b is an integer chosen from 0, 1, 2, 3, or 4, and when b is 1 or greater, each R5 and R6 are hydrogen. -Q is chosen from -N-, -N+H(X-)- where X- is the negative charge chosen from the halide. Sulfates, carbonates, bicarbonates, nitrates, perchlorates, formates, acetates, and trihaloacetates, and -CRa- where Ra is hydrogen, -T is chosen from -NRa where Ra is chosen from hydrogen, formil, acetyl, alkoxycarbonyl, alkenyl oxycarbonyl, benzoyl, benzyl oxycarbonyl, alkane sulfonyl, benzene sulfonyl, and toluene sulfonyl, -N+H(X-)- where X- is as described above, and -CRaRb where Ra and Rb are chosen independently from hydrogen, hydroxya and (C1-C6)alkoxy, and Ra and Rb may be combined with O to form carbonyl groups, or they may be combined with -O(C2-C3)alkoxy or -S(C2-C3)alkylthio. To form ketal or thioketal, respectively, given that at least one of Q or T is -N- or -N+H(X)- and U is -(CRaRb)j-, where Ra and Rb are hydrogen and j is 2. 17. Compounds of claim 16 where each R and R4 is chlorine, each R1 and R3 is hydrogen, R2 is -L-M-C(R13)=C(R14)(R15), b is an integer chosen from 0, 1, or 2, and T is -NRa where Ra is hydrogen or ter-butoxycarbonyl. 18. Compounds of claim 17 where i) a and b are 0, Q is N and T is -NRa where Ra is hydrogen, ii) a and b are 0, Q is -CRa and T is NRa where Ra is hydrogen, and iii) a is 1, b is 1 or 2 and Q is N and T is -NRa where Ra is hydrogen.