CA1262725A - Nitromethylene derivatives, intermediates thereof, processes for production thereof, and insecticides - Google Patents

Nitromethylene derivatives, intermediates thereof, processes for production thereof, and insecticides

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Publication number
CA1262725A
CA1262725A CA000478814A CA478814A CA1262725A CA 1262725 A CA1262725 A CA 1262725A CA 000478814 A CA000478814 A CA 000478814A CA 478814 A CA478814 A CA 478814A CA 1262725 A CA1262725 A CA 1262725A
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Canada
Prior art keywords
pyridylmethyl
group
nitromethylene
compound
chloro
Prior art date
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Expired
Application number
CA000478814A
Other languages
French (fr)
Inventor
Kozo Shiokawa
Shinichi Tsuboi
Shinzo Kagabu
Koichi Moriya
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Bayer CropScience KK
Original Assignee
Nihon Tokushu Noyaku Seizo KK
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Priority claimed from JP7296684A external-priority patent/JPS60218386A/en
Priority claimed from JP59132943A external-priority patent/JPS6112682A/en
Application filed by Nihon Tokushu Noyaku Seizo KK filed Critical Nihon Tokushu Noyaku Seizo KK
Application granted granted Critical
Publication of CA1262725A publication Critical patent/CA1262725A/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

NITROMETHYLENE DERIVATIVES, INTERMEDIATES
THEREOF, PROCESSES FOR PRODUCTION THEREOF, AND INSECTICIDES
Abstract This invention relates to novel nitromethylene derivatives, intermediates thereof, processes for production thereof, and insecticides containing said novel nitromethylene derivatives as active ingredients.
More specifically this invention relates to novel nitromethylone derivatives represented by the following general formula (I

Description

- 2 ~ 7~ 23189-5964 This invention relates to novel ni-tromethylene derivatives, intermediates thereof, processes for production thereof, and insecticides.con~ainig said novel nitromethylene derivatives as active ingredients.
More speciEically~ this invention relates to novel nitromethylene derivatives represented by the Eollowing general formula (I)J ~ s~lts -~e~~
H

~ N
(C~ )m ~ HN02 (CH2)n-CH t~ ~ X~
.

wherein R represents a hydrogen atom or a lower alkyl group, X represents a halogen a-tom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfon~l group, a lo~er alkenyl group, a lower alkynyl group, an aryl group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group which may be optionally substituted by a halogen atom, or an aralkyl group, Q represents 1, 2, 3 or 4, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3~

It has to be stated that in case ~ the radicals X may be the same or different from each other.
The nitromethylene derivatives of formula (I) in accordance with this invention can ~e produced by the follow-ing process i) to which the invention also pertains.

Process i A process ~or producing the nitromethylene deri-vatives of general formula ~I~, which comprises reacting a compound represented by the general formula ~ Sa )~s there~-~

X~ ~ CH-(cH2)n-NH-(cH2)m-NH2 (II) wherein R, X, Q, m and n are as defined above, with a compound represented by the general formula R'-S
~C=CHN02 (III) R'-S~

wherein each R' represents a lower alkyl group, a benzyl group or the two R' groups together represent a lower alkylene group having ~t least 2 carbon atoms and may form a ring together with the sulfur atoms adjacent thereto.
This invention also rela~es to insecticides comprising the nitromethylene derivative of general formula (I) as an active ingredient.
In the production of the novel nitromethylene derivatives of general formula (I) in accordance with this invention, the compound of general formula ~II), an intermediate, is ~ novel compound which is not described in any known publication, and ~he present invention also relates to said compounds (intermediates).
The novel compound of general formula (II) can be produced by the following process (ii) to which the invention also pertains~

. -- 4 --Process i~) A process for producing the compound of general formula (II), which comprises reacting a compound rep~esented by the general formula XQ ~ C~-(CH2)n~Y (IV) wherein R, X, Q, and n are as defined above, and Y represents a halogen atom or the group -0502R" in which R" represents a lower alkyl or an aryl group, with a compound represented by the general formula H2N-(CH2)m NH2 (V) wherein m is as defined above.
Compounds of general formula ~IV) are either known or can be produced by known preparation methods.

2~:~5 German Offenlegungsschr~t Ng. 2,514,402 known before the filing date o the present application atates that 2-nitro-methylene-imidazolidine derivatives and 2-nitromethylene-hexahydropyrimidine derivatives of the following general formula (CH2)n 2 RlNJ~CHNO

have insecticidal activity. The above general formula includes cases of n=2, Rl=phenyl-(Cl-C2)alkyl group and R2=R3=hydrogen and the specification of the abo~e German patent document describes a compound of the following formula HN ~ N-CH2 ~ (A-l) German Offenlegungsschrif~ No- 2,732,660 states to the effect that l-substituted benzyl-2-nitromethylene-imidazQlidine derivatives represented by the following general formula ~ , NH

~, CH2~

have insecticidal activity. The specification of this GP~n~n OEfen-l~gsschrift describes a compound represented by the following formula.
I NH
CHNO2 (B-l) CH2~Cl ,, .. .

- 6 ~

It has been found that the compounds oE this invention in low dosages have quite outstanding controlling activity over the compounds of formulae (A-1) and (B-1) which are described in the above cited German Offenlegungsschriften and are most similar to the compounds of this inven-tion, and tha-t the compounds of this invention exhibit a marked controlling effect a~ainst noxious .2~
~ 7 insects which have acquired resistance to organic phosphate and carbamate type insecticides through long-term use, particularly sucking insects typified by hemipterous insects such as aphides, planthoppers and leafhoppers.
- It is an object of this invention to provide novel nitromethylene derivatives of ~eneral formula (I), intermediates thereof, processes for production thereof t and the use thereof as insecticides.

Th~ active compounds of this invention exhibit an accurate controlling effect against noxious insects, without causing any phytotoxicity to cultivated plants. Furthermore, the compounds of this invention can be used for control and eradication of a wide ranye of pests, including sucking insects, biting insects and other plant parasites, pests on stored grains and pests causing health hazards.
Examples of the pests are shown below.
Coleopterous insects Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneus, Epilachna vigitoctomaculata, Agriotes fuscicollis, Anomala rufocuprea f I,eptinotarsa decemkineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus~ and Lyctus brunneus.
Lepidopterous insects ~ymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, and Phyllocnistis citrella.
Hemipterous_in_ects Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus cometocki, Unaspis yanonensis, Myzus persicae~ ~ ¦
Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, ~6~
_ 9 _ Trialeurodes vaporariorum, and Psyll~ spp.
Ortho~terous insects Blatella germanica, - Periplaneta americana, Cryllotalpa africana, and Locusta migratoria migratoriodes.
Isopterous insects Deucotermes speratus, and Coptotermes formosanus.
Dipterous i~sects Musca domestica~
Aedes aegypti, ~ylemia platura, Culex pipens, Anopheles sinensis, and Culex tritaeniorhynchus.
In the field of veterinary medicine, the novel compounds of this invention are Pffecti~e against various noxious animal parasites (endo- and ecto-parasites) such as insects and worms. Examples of such animal parasites are shown below.
Insects Gastrophilus spp., Stomoxys spp., ; Trichodectes spp., Rhodnius spp., and Ctenocephalides canis.
Substances having pesticidal activity against all of these pests may sometimes be referred to in this application simply as insecticides.

_ __ _ .
.. . .

--10 ~

The nitromethylene derivative of general formula (I) in accordance with this invention can be easily produced, for example, by the following process i).
Process i) R
XQ ~ H~(CH2)n~N~I~(CH2)m NH2 (II) R'-S \
~ C=CHN02 R -S
(III) N
(CH~_ ~=CHN02 (CH2)n~CH ~ XQ

(I~

(In the formulae, R, X, Q, m, n and R' are as defined hereinabove.) In the above reaction scheme, R represents a hydrogen atom or a lower alkyl group, and specific examples of a lower alkyl group may include methyl, ethyl, propyl, isopropyl and _ n-(iso-, sec- or tert-)butylO
X represents halogen atom, a lower alkyl group with preferably 1 to 6 car on atoms, a lower alkoxy group, a lower alkylthio group with preferably 1 to 6 carbon atoms, a lower alkylsulfinyl group with preferably 1 to 6 car~on atoms, a lower alkylsulfonyl group with preferably 1 to 6 carbon atoms, a lower al kenyl group with preferably 2 to 6 carkon atoms, a lower aLkynylgroup with preferably 2 to 4 carban atoms, an aryl gro~p with preferably 6 or 12 ring carkon ~toms, an aryloxy group which may ke optionally sukstituted by a halogen atom~ an arylthio group which may be optionally su~stituted by a halogen atcm, or an aralkyl group, and specific examples of a halogen atom may includP
fluoro, chloro, bromo and iodo, specific examples of a lower alkyl are the same as those exemplified above, specific examples of a lower alkoxy group, a lower alkylthio group, a lower alkylsufinyl group and a lower alkylsulfonyl group may be respectively those having the same a lower alkyl group as exemplified above, specific examples of a lower alkenyl may include vinyl, allyl, l-propenyl or 1-(2- or 3-)butenyl, specific examples of a lower alkynyl may include ethynyl, l-propynyl or propargyl, specific examples of a aryl group may include phenyl or ~-tor ~-) naphthy~, specific examples of an aryloxy group and an arylthio group which may be optionally substituted by a halogen atom may be respectively those having the same an aryl group as exemplified above which may be substituted by one or two halogen atom(s) such as exemplified above, and specific examples of an aralXyl group may include benzyl, phenethyl or ~-naphthylmethyl.
Q represents 1, 2, 3 or 4.
m represents 2, 3 or 4~
n represents 0, 1, 2 or 3.
R' represents a 1~ alkyl group with preferably 1 to 6 car~on at~, a ~ zyl group, or the tw~ R' groups together represent a lower alkylene group having at least 2 carbon atoms. Specific examples oE the lower alkyl group are the same as those exemplified above for ~. The two R' groups together represent a lower alkylene group having at least 2 carbon atoms and may form a ring together with the sulfur atoms adjacent thereto. An ethylene group may be cited as an example of such an alkylene group.

- 12 - ~ 2~

In the process ~or producing the compounds of general formula (I) of this inven~ion represented ~y the reaction scheme, specific examples of the starting compound of general formula (II) lnclude.

II- 1. N-t5-methyl-2-pyridylmethyl)ethylenediamine, II- 2. N-(5-methyl-2-pyridylmethyl)trimethylenediamine,' II- 3. N-(6 methyl-2-pyridylmethyl)ethylenediamine, II- 4. N-(6-methyl 2-pyridylmethyl)trimethylenediamine, II- 5. N-(4-methyl-2-pyridylmethyl)ethylenediamine, II- 6. N-(4-methyl-2-pyridylmethyl)trimethylenediamine, II- 7. N-(5-ethyl-2.pyridylmethyl)ethylenediamine, II~ 8. N-(5-buthyl-2-pyridylmethyl)ethylenediamine, II- 9. N-(4,6 dimethyl-2 pyridylmethyl)ethylenediamine, II-10. N-(3-chloro-2-pyridylmethyl)ethylenediamine, II-ll. N-(5-chloro-2-pyridylmethyl)ethylenediamine, II-12. N-(5-chloro-2-pyridylmethyl)trimethylenediamine, II-13. N-(3,5-dichloro-2-pyridylmethyl)ethylenediamine, II-14. N-(5-fl~oro-2-pyridylmethyl)trimethyldiamine, II 15. N-(6-bromo-2-pyridylmethyl)Pthyl2nediamine, II-16. N-[2-(5-ethyl-2-pyridyl)ethyl~trimethylenediamine, II-17. N-(6-chloro-4-methyl-2-pyridylmethyl)ethylenediamine, II-18. N-(5-rnethyl-3-pyridylmethyl)ethylenediamine, II-19. N-(2-methyl-5-pyridylmethyl)ethylenediamine, II-20. N-(2~methyl-5-pyridylmethyl)trimethylenediamine, 21. N-(2-phenyl-5-pyridylmethyl)ethylenediamine, II-22. N-(2-phenyl-5-pyridylmethyl)trimethylenediamine, II-23. N-(2-benzyl-5-pyridylmethyl)ethylenediamine, II-24. N-(2-chloro-3-pyridylmethyl)ethylenediamine, II-25. N-(2-chloro-3-pyridylmethyl)trimethylenediamine, -~L~6~æ72~;

II-26. N-l5-chloro-3-pyridylmethyl)ethylenediamine, II-27. N-(S-chloro-3-pyridylme~hyl)trimethylenediamine, II-28. N-(5-bromo-3-pyridylmethyl)ethylenediamine, II 29. N-(5-bromo-3-pyridylmethyl)trimethylenediamine, II-30. N-(2-bromo-5-pyridylmethyl)ethylenediamine, II-31. N-~2-bromo-5-pyridylmethyl)trimethylenediamine, II-32. N-(5-fluoro-3-pyridylmethyl)ethylenediamine, II-33. N-(2-fluoro-5~pyridylmethyl)ethylenediamine, II-34. N-(2-fluoro-5-pyridylmethyl)trimethylenediamine, II-35. N-(1-(2-fluoro-5-pyridyl)ethyl~ethylenediamine, II-36. N-~2-methyl-1-(2-fluoro-5-pyridyl)propyl~ethylenediamine, II-37. N-[2-(2-fluoro-5-pyridyl)ethyl~ethylenediamine, II-38 N-(3-(2-bromo-S-pyridyl)propyl~trimethylenedimine, II-39. N-(2-bromo-5 pyridylmethyl)tetramethylenediamine, II-40. N-~4-(2-bromo-5-pyridyl)butyl)trimethylenediamine, II-41. N-(2-chloro-6-methyl-3-pyridylmethyl)ethylenediamine, II-42. N-(2,4-dichloro-5-pyridylmethyl)trimethylenediamine, II-43. N-(2,6-dichloro-3-pyridylmethyl)ethylenediamine, II-44. N-(2,4-dibromo-5-pyridylmethyl)ethylenediamine, II-45. N-t2,4-difluoro-5-pyridylmethyl)ethylenediamine, II-46. N-(2,4,5,6-tetrafluoro-3-pyridylmethyl)ethylenediamine, II-47. N-(2,4,5,6-tetrachloro-3-pyridylmethyl)ethylenediamine, II-48. N-(2-methoxy-3-pyridylmethyl)trimethylenediamine, II-49. N-(2-methoxy-5-pyridylmethyl)ethylenediamine, II-S0. M-(2-methoxy-5-pyridylmethyl)trimethylenediamine, II-51. N-(2-ethoxy-5-pyridylmethyl)ethylenediamine, II-52. N-(2-ethoxy-S-pyridylmethyl)trimethylenediamine, II-53. ~-(2-iso-propoxy-5-pyridylmethyl)ethylenediamine, II-54. N-~2-phenoxy-5-pyridylmethyl)ethylenediamine, .

1 4 ~ 3L 2~ ~7.~
r II-55. N-~2-phenoxy-5-pyridylmethyl)trimethylenediamine, II-56. N-~2-~2,4-dichlorophenoxy~-5-pyridylmethyl~ethylene-diamine, II-57. N-(2-methylthio-3-pyridylmethyl)ethylenediamine, II-58. N-(2-methylthio-5-pyridylmethyl)ethylenediamine, II-59. N-(2-methylthio-5-pyridylmethyl)trimethylenediamine, II-60. N-t4-methyl-2-methylthio-5-pyridylmethyl)ethylene-diamine, II-61. N-(2-phenylthio-5-pyridylmethyl)ethylenediamine, II-62. N-~2-(4-chlorophenylthio)-5-pyridylmethyl~ethylenediamine, II-63. N- (2~ethylthio 5-pyridylmethyl)ethylenediamine, II-64. N-( 2-methylsulfinyl-5-pyridylmethyl)e hylenediamine, II-65. N- ( 2-methylsulfonyl-S-pyridylmethyl~trimethylenediamine~
II-66. N-(4-chloro-2-fluoro-5-pyridylmethyl)~rimethylenediamine, II-67. N-(6-chloro-2-methyl-3-pyridylmethyl)ethylenediamine, II-68. N-(2-chloro-4-methyl-5-pyridylrne~hyl)ethylenediamine, II-69. N-~2-allyl-5-pyridylmethyl)ethylenediamine, II-70. N-(2~propargyl-5-pyridylmethyl)ethylenediamine, II-71. N-(2,3-dichloro-5-pyridylmethyl)ethylenediamine, II-72. N-~2-(1-propenyl)-5-pyridylmethyl~ethylenediamine, II-73. N-(2-chloro-4-pyridylmethyl)ethylenediamine, II-74. N-(2-chloro-4-pyridylmethyl)trimethylenediamine, II-75. N-(2-Eluoro-4-pyridylmethyl)ethylenediamine, II-76. N-(2-fluoro-4-pyridylmethyl)trimethylenediamine, II-77. N-(2,6-dichloro-4-pyridylmethyl)ethylenediamine, II-78. N-(2,6-difluoro-4-pyxidylmethyl)trimethylenediamine, II-79. N-(Z-methyl-4-pyridylmethyljethylenediamine, II-80. N-(2-methyl-4-pyridylmethyl)trimethylenediamine~
II-81~ N~ (2-chloro-4-pyridyl)ethyl~ethylenediamine, II-82. N-(2-chloro 6-methyl-4-pyridylmethyl)ethylenediamine, II-83. N-(2-chloro~6-methyl-4-pyridylmethyl~trimethylenediamine, II-84. N-(2,6-dimethyl-4-pyridylmethyl~ethylenediamine, II-85. N-(2~bromo-4-pyridylmethyl)ethylenediamine, II-85. N-(2,6-dibromo-4-pyridylmethyl)ethylenediamine, II-87. N-(2,3,5,6-tetrafluoro-4-pyridylmethyl)ethylenediamine, II-88. N-(2,3,5,6-tetrafluoro-4-pyridyl)trimethylenediamine~
II 89. N-(2,6 dichloro-4-pyridylmethyl)trimethylenediamine, II-90. N-(3-chloro-2-fluoro-5-pyridylmethyl)ethylenediamine, II-91. N-(3-bromo-2-~luoro-5-pyridylmethyl)ethylendiamine, II-92. N-(2-chloro- -fluoro-5-pyridylmethyl)ethylenediamine, II-93. N-(2,3,4-trichloro-5-pyridylmethyl)ethylenediamine, II-94. N-(3-chloro-2-methylthio-5-pyxidylmethyl)ethylenediamine, II-9S. N-(2-chloro-5-pyridylmethyl)ethylenediamine, II-96. N-~2-(2-chloro-5-pyridyl)ethyl)ethylenediamine~
II-97. N-(2-chloro-S-pyridylmethyl)trimethylenediamine, II-98. N-~2-(2-chloro-5-pyridyl)ethyl~trimethylenediamine, II-99. N-~1-(2-chloro-5-pyridyl)ethyl~trimethylenediamine, II-100. N-~3-(2-chloro-5-pyridyl)propyl~trimethylenediamine, II-101. N-(1-(2-chloro-5-pyridyl)ethyl~ethylenediamine, II-102. N-2-chloro-5-pydylmethyl)tetramethylenediamine, II-103. N-~4-(2-chloro-5-pyridyl)butyl~trimethylenediamine, II-104. N-~1-(2-chloro-5-pyridyl)propyl)trimethylenediamine, and II-105. N-~2-methyl-1-(2-chloro-5-pyridyl)propyl)ethylenediamine.
Speci~ic examples of the compound of general formula (III) which is likewise a starting material include l-nitro-2,2-bis(methylthio)ethylene, l-nitro-2,2-bis(ethylthiojethylene, l-nitro-2,2-bis(benzylthio)ethylene, and ~ - 16 - ~26~7~
2-nitromethylene-1,3-dithiolane.
By citing thP followin~ typical example, the above process will be specifically described.

Cl ~ CH2-NH-(CH2)3 NH2 (CH3S)2C=CH~02 ~ CHN02 CH2 ~ Cl Desirably,-the above process for producing the compound of this invention can be carried out using a solvent or a diluent. For this purpose, any inert solvents and ~iluents can be used.
Examples of such solvents or diluents include ~ater;
. aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene, chloride, chloroform, car~on tetrachloride, ethylene chloride, trichloro-ethylene and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone;
nitriles such as acetonitrile, propionitril.e and acrylonitrile;
- alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters such as e-thyl acetate and amyl acetate;
acid amides such as dimethylformamide and dimethylacetamide;
sulones and sulfoxides such as dimethyl sulfoxide and sulfolane;
and bases such as pyridine.

The above process can be carried out over a wide temperature range. Generally, it can be carried out at a temperature between about -20C and the boiling point of the mixture, preferably between about 0C and about 1004C.
Desirably, the reaction is carried out under normal atomospheric pressure, but it is also possible to operate under elevated or reduced pressures.
The compound of general formula (I) in accordance with this invention may also be produced by an alternative process schematically shown below.

Alternative process 1 R
CH-tCH ) -Y -~ H ~ ~ ~\NH >

(IV) (VI) N

N ~
(CH2)n-cH ~ Q

(I) (In the above formulae, R, X, Q, m, n and y are as defined hereinabove)~
The compound of general formula (II) in accordance with this invention can be produced for example, by the following process ii).

, _ .

~Le~3 ~ 7.~5 ~}CH-(cH2)n-y ~ H2N-(CH2)~ NH2 (I~J) (V) - ~ X~ _ ~ CH-(cH2)n-NH-(cH2)m-NH2 (II) (In the formulae, R, X, Q, m, n and ~ are as defined hereinabove.) In the above reaction scheme, R, X~ Q, m and n may be the same as those given above for the process i). Y represents halogen atom such as fluoro J chloro, bromo and iodo, or the group -OS02R", in which R" represents the same lower alkyl as exemplified above for the process i), or aryl groups such as phenyl and p-tolyl.
In the process for producing the compound of general formula (II) of this invention represented by the reaction scheme, specific examples of the starti~g compound of general formula (IV) include IV- l. 5-methyl-2-pyridylmethyl chloride, `
IV- 2. 6-methyl~2-pyridylmethyl chloride, IV- 3. 4-methyl-2-pyridylmethyl chloride, IV- 4. 5-ethyl-2 pyridylmethyl chloride, IV- 5. 5-butyl-2-pyridylmethyl chloride, IV- 6. 4,6-dimethyl-2-pyridylmethyl chloride, IV- 7. 3-chloro-2-pyridylmethyl chloride, IV- 8. S-chloro-2-pyridylmethyl chloride, IV- 9. 3,5-dichloro-2-pyridylmethyl chloride, - lg IV-10. 5-fluoro-2-pyridylmethyl chloride~
IV-ll. 6-bro~o-2-pyridylmethyl shloride, IV-12. 2-(5-ethyl-2-pyridyl)ethyl chloride, IV-13. 6-chloro-4-methyl-2-pyridylmethyl chloride~
IV-14~ 5-methyl-3-pyridylmethyl chloride, IV-lS. 2-methyl-5-pyridylmethyl chloride, IV-16. 2-phenyl-5-pyridylmethyl chloride, IV-17. 2-benzyl-5-pyridylmethyl chloxide, IV-18. 2-chloro-3-pyridylmethyl chloride, IV-l9. 5-chloro-3-pyridylmethyl chloride, -.
IV-20. 5-bromo-3-pyridylmethyl ~hloride, IV-21. 2-bromo-5-pyridylmethyl chloride, IV-22. 5-fluoro-3-pyridylmethyl chloride, IV-23. 2-fluoro~5-pyridylmethyl chloride, IV-24. 1-(2-fluoro-5-pyridyl)ethyl chloride, IV-25. 2-methyl-1-(2-fluoro-5-pyridyl)propyl~chloride, IV-26. 2-~2-fluoro-5-pyridyl)ethyl chloride, IV-27~ 3-(2-bromo-5-pyridyl)propyl chloride, IV-28. 2-bromo-5-pyridylmethyl chloride, IV-29. 4-(2-bromo-5-pyridyl)butyl chloride, IV-30. 2-chloro-6-methyl-3-pyridylmethyl chloride, IV-31. 2,4-dichloro-5-pyridylmethyl chloride, IV-32. 2,6-dichloro-5-pyridylmethyl chloride, IV-33. 2,4-dibromo-5-pyridylmethyl chloride, IV-34. 2,4-difluoro-5-pyridylmethyl chloride, IV-`35. 2,4,5,6-tetrafluoro-3-pyridylmethyl chloride, IV~36. 2,4,5,6-tetrachloro-3-pyridylmethyl chloride, IV-37. 2-methoxy-3-pyridylmethyl chloride, IV-38. 2-methoxy-5-pyridylmethyl chloride, - 20 - ~2~
IV-39. 2-ethoxy-5-pyridylmethyl chloride, IV-40. ~-isopropoxy-5-pyridylme~hyl chloride, IV-41. 2-phenoxy-5-pyrldylmethyl chlorlde, IV-42. 2-(2,4-dichlorophenoxy)-5-pyridylmethyl chloride, IV-43. 2-methylthio-3-pyridylmethyl chloride, IV-44. 2-methylthio-5-pyridylmethyl chloride, IV-45. 4-methyl-2-methylthio-5-pyridylmethyl chloride, IV-46. 2-phenylthio-5-pyridylmethyl chloride IV-47. 2-(4-chlorophenylthio)-5-pyridylmethyl chloride, IV-48. 2-ethylthio-5-pyridylmethyl chloride, IV-49. 2-methylsufinyl-5-pyridylmethyl chloride, IV-50. 2-methylsufonyl-5-pyridylmethyl chloride, IV-Sl. 4-chloro-2-fluoro-5-pyridylmethyl chloride, IV-52. 6-chloro-2-methyl-3-pyridylmethyl chloride, IV-53. 2-chloro-4-methyl-5 pyridylmethyl chloride, IV-54. 2-allyl-5-pyridylmethyl chloride, IV-5S. 2-propargyl-5~pyridylmethyl chloridel IV-56. 2,3-dichloro-5-pyridylmethyl chloride, IV-57. 2-(1-propenyl)-5-pyridylmethyl chloride, IV-58. 2-chloro-4-pyridylmethyl chloride, IV-59. 2-fluoro-4-pyridylmethyl chloridP, IV-60. 2,6-dichloro-4-pyridylmethyl chloride, IV-61. 2,6-difluoro-4-pyridylmethyl chloride, IV-62. 2-methyl 4 pyridylmethyl chloride, IV-63. 1-(2-chloro-4-pyridyl)ethyl chloride, IV-64. 2-chloro-6-methyl-4-pyridylmethyl chloride, IV-65. 2,6-dimethyl-4-pyridylmethyl chloride, IV-66. 2-bromo-4-pyridylmethyl chloride, IV 67. 2,6-dibromo-4-pyridylmethyl chloride, .

IV-6~. 2,3,5,~-tetrafluoro-4~pyridylmethyl chloride~
IV-69. 3-chloro-2-fluoro-5-pyridylmethyl chloride, IV-70. 3-bromo-2-fluoro-5-pyridylmethyl chloride, IV-71. 2-chloro-3-fluoro-5-pyridylmethyl chloride, IV-72. 2,3,4-trichloro-5-pyridylmethyl chloride, IV-73. 3-chloro-2-methylthio-5-pyridylmethyl chloride IV-74. 2-chloro-5-pyridylmethyl chloride, IV-75. 2-(2-chloro-5-pyridyl)ethyl chloride, IV-76. 1 (2-chloro-5-pyridyl)ethyl chloride, and IV-77. 3-(2-chloro-5-pyridyl)propyl chloride.
The corres~onding bromides and p-toluenesulEonates can also be cited instead of the above chlorides.
Specific examples of the compound of gen~ral formula (V) which is likewise a starting material include ethylenediamine, trimethylenediamine, and tetramethylenediamine.
By citing the following typical example, the above process will be specifically described.

Cl ~ 2 Cl H2N-(CH2)3 NH2 > Cl- ~ CH2-NH-(cH2)3 NH2 The above process can be carried out by using the same inert solvents or diluents as exemplified for the process i).
The above reaction may be carried out ln the presence of an acid binder. Examples of the acid binder are the hydroxi~esS carbona~es, bicarbonates and alcohola~es of alkali _ _ . _ _ ,, 7~

metals, and tertiary amines such as triethylamine, diethyl-anil~ne and pyridine, which are generally used.
As is the case with the process i), the above process can be carried out over a wide temperature range~ The reaction is carried out desirably ~nder normal atmospheric pressure, but it is also possible to operate under elevated or reduced pressure.
The compound of general formula (II)~ provided that n represents 0, may also be produced by a process schematically shown below as an alternative process 1n addition to the above process ii).
Alternative process 2 X~ ~ C-R + 2 (C~2)m NH2 ~VII) . (V) XQ ~ ( 2)m NH2 ~H~ .
XQ ~ H-NH-(cH2)m-NH2 (II') (In the formulae, X, R, Q, and m are as defined hereinabove.) As shown by the above reaction scheme, the compound of general formula (II') can be produced by reacting a reducing agent such as sodium boron hydride ~NaBH4) and so on with the imines which is produced by reacting the pyridine aldehyde derivative or ~he pyridylalkylketone derivative of general . ~ .

formula (VII~ with ~hP compound of general formula (V).

Moreover, the compound of general formula (II), provided that R represents a hydrogen atom and n represents O, may also be produced by a process schematically shown below as an alternative process.

Alternative proc ss 3 XQ ~ COCl + H2N~(CH2)m~NH2 (VIII) . (V) ~ XQ ~ ( 2)m H2 + ~
XQ ~ ~ CH2-NH-(cH2)m-NH2 5II"~

(In the formulae~ X, Q, and m are as defined hereinabove.) As shown by the above reaction scheme,-the compound of general formula (II') can be produced by reacting a reducing agent such as lithium alminium hydride (LiAlH4) and so on with the nicotinic amide derivative or the picolinic amide derivative which is produced by reacting -the pyridyl-carbonyl chloride derivative of general ~ormula (YIII) with the compound of general formula (V).
The compound of general formura (II), provided that R represents a hydrogen Atom, n represents 0 and m represents
3, may also be produced by a process schematically shown below as an altPrnative processO
Alterna ive process 4 XQ ~ -C~2N~2 ~ CH2-CH-CN

(IX~

~ XQ ~ CH2-NH-(CH2~2-C

+ ~H3 ~
> x t ~ CH2-NH-(CH2)3 N 2 (II"') .

(In the formulae, X and ~, are as defined hereinabove.) As shown by the above reaction scheme, the compound of general formula (IIt'') an be produced by reducing, in accordance with the same as aforesaid alternative process 2, the adduct which is produced by reacting acrylonitrile with the compound of general formula (IX).
For example, N (2-chloro-5-pyridylmethyl)trimethylene diamine which is compound No. II-97 mentioned later can also be produced by the above alternative process 4.
The compound of general formula (II), provided that m represents 2, may also be produced by a process schematically shown below as an alternative processO
Alternative process 5 Q ~ (X) A

R
- > XQ ~ CH-(cH2)n-NH-(cH2)2 NH2 III"" ) ~2$~

(In the fo.rmulae, R, X, Q and n are as defined hPreinabove. ) As shown by the above reaction scheme, the compound of general formula (IInn) can also be produced by reacting the pyridylalkylamine derivative of general formula (X) with ethyleneimine.
The compounds of this invention may be present in the form of salts. The salts may, for example, be inorganic salts, sulfonates, organic acid salts, and rnetal salts. Specific examples of the compounds of this invention in the form of salts include ' 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene) tetrahydropyrimidine hydrochloride, 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene3 tetrahydropyrimidine P-toluenesulfonate~
1-(2-chloro-5-pyridylmethyl)-2-~nitromethylene~
imidazolidine hydrochloride, and 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene) imidazolidine cupric acetate.
1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene) tetrahydropyrimidine hydrochloride, 1-~2-methoxy-5-pyridylmethyl)-2-(nitromethylene) imidazolidine-hydrochloride, 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene) imidazolidine-P-tOluenesulfOnate, 1-(2-bromo-5-pyridylmethyl)-2-(nitrornethylene) tetrahydropyrimidine-cupric acetate, 1-(3-bromo-5-pyridylmethyl)-2-(nitromethylene) imidazolidine-succinate.

As insecticides, theao~x~nds of this invention may be used directly upon dilution with water, or in various formulations obtained by methods generally practiced in the production of agricultural chemicals using a~riculturally acceptable adjuvants. In actual use, these various formulations may be applied directly or after diluting them with water to the desired concentrations.
The agriculturally acceptable adjuvants as referred to herin include, for example, diluents (solvents, extenders, carriers)~ surface-active agents (solubilizing a~ents, emulsifiers, dispersing agents, wetting agents, stabilizers, stickers, aerosol propellants and synergists.
Examples of the solvents are waterl and organic solvents, for example hydrocarbons ~such as n-hexane, petroleum ether, petroleum fractions (e.g. paraffin waxes, kerosene, light oils, middle oils, and heavy oils)~ benzenet toluene, and xylene~, halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, ethylene chloride~ ethylene dibromide t chlorobenzene and chloroform), alcohols (such as methanol, ethanol, propanol and ethylene glycol), ethers (such as diethyl ether, ethylene oxide and dioxane), alcohol ethers (such as ethylene glycol monomethyl ether), ketones (such as acetone and isophorone), esters (such as ethyl acetate and amyl acetate), amides (such as dimethylformamide and dimethylacetamide) and sulfoxides (such as dimethyl sulfoxide).
Examples of the extenders or carriers include inorganic powders, for example slaked lime, magnesium lime, gypsum, calcium carbonate, silisa, perlite, pumice, calcite, diatomaceous earth, amorphous silica, alumina, zeolites, and clay minerals (such as .

_ .

- 27 - ~2~
pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite and mica); vegetable powders such as cereal powders 9 starches, processed starches, sugar, glucose and crushed stalks of plants; and powders of synthetic resins such as phenolic resins, urea resins, and vinyl chloride resins.
Examples of the surface-active agents include anionic surface-active agents such as alkylsulfonic acid esters (such as sodium laurylsulfate), arylsulfonic acids (such as alkylaryl-sulfonic acid salts and sodium alkylnaphthalenesulfonates), succinic acid salts, and salts of sulfuric acid esters of polyethylene glycol alkylaryl ethers; cationic surface-active agents such as alkylamines (e.g~, laurylamine, stearyl trimethyl ammonium chloride and alkyl dimethylbenzyl ammonium chlorides) and polyoxyethylene alkylamines; nonionic surface-active agents such as polyoxyethylene glycol ethers (e.g., polyoxyethylene alkylaryl ethers and the condensation products thereof), polyoxy-ethylene glycol esters (e.g., polyoxyethylene fatty ~cid esters), and polyhydric alcohol esters ~e.g., polyoxyethylene sorbitan monolaurate~; and amphoteric surface-active agents.
Examples of other adjuvants include stabilizers;
stickers (such as agricultural soaps, casein lime, sodium alginate, polyvinyl alcohol, vinyl acetate-type adhesives and acrylic adhesives); aerosol propellants (such as trichloro-fluoromethane, dichlorofluoromethane, 1,2,2-trichloro-1,1,2-trifluoroethane, chlorobenzene, LNG, and lower ethers); combustion controlling agents for fumigants (such as nitrites, zinc power, and dicyandiamide); oxygen-yielding agents (such as chlorates);
effect-prolonging agents; dispersion stabilizers ~such as casein, tragacanth, carboxymethyl cellulose (CMC), and polyvinyl alcohol (PVA) ) ; and synergist.

The compounds of this invention can be formulatsd into various forms by methods generally practiced in the production of agricultural chemicals. Illustrative of such forms are emulsifiable concentrates, oil preparations, wettable powders, soluble powders, suspensions, dusts, granules, pulverulent preparations, fumigants, tablets, aerosols, pastes and capsules.
The insecticides of this invention may contain about 0.1 to about 95% by weight, preferably about 0.5 to about 90%
by weight, of the aforesaid active ingredient.
In actual use, the suitable amount of the active compound in the aforesaid various formulations and ready to-use preparations is generally about 0.0001 to about 20~ by weight, preferably about 0.005 to about 10% by weight.
The content of the active ingredient can ~e properly varied depending upon the type of the formulation t the method, purpose, time and locus of its application, the state of occurrence of noxious insects.
If required, the compounds of this invention may be used in combination with other agricultural chemicals, for example other insecticides, fungicides, other miticides, other nematocides, antiviral agents, herbicides, plant growth regulators and attractants (such as organophosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organosulfur or organometallic compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, and tria~ine compounds)~ and/or fertilizers.
Various formulations and ready-to-use preparations _ -29 - ~2~

containing the aforesaid active ingredient of the invention can be applied by various methods generally practiced in the field of agricultural chemical application, for example spraying (liquid spraying, misting, atomizing, du~ting, granule scattering, water surface application, pouring, etc.); fumigation; soil application ~mixing, sprinkling, vaporing, pouring, etc.);
surface application (coating, banding, powder coating, covering, etc.); dipping; and baiting. It can also be used by the so~called ultralow volume spraying method. According to this method, the active ingredient may be included in an amount of 100%.
The rate of application per unit area is, for example, about 0.03 to about 10 Kg, preferably about 0.3 to about 6 Xg, per hectare. In special cases, however, it may, and sometimes should, be outside the specified range.
According to this invention, there can be provided an insecticidal composition comprising the compound of general formula (I) as an active ingredient and a diluent (a solvent and/or an extPnder and/or a carrier) andfor a surface-active agent9 and if further required, a stabilizer, a sticker, a synergist, etc.
This invention also provides a method for controlling noxious insect, which comprises applying to a noxious insect and/or its habitat or the locus of its occurrence the compound of general formula (I) alone or in admixture with a diluent (a solvent and/or an extender and/or a carrier) and~or a surface-active agent and if further re~uired, a stabilizer, a sticker, a synergist, etc.
The following examples ilIustrate the present invention specifically. It should be noted however that the invention is not limited to these specific examples alone~

~ L 2 3 c3 Example 1 2~chloro-5-pyridylmethyl chloride ~16.2 9) ln a solution of acetonitrile ~30 ml) was added dxopwise to a solution of ethylenediamine 118 g) in acetonitrile (100 ml) at room temperature during 1 hour.
The reaction mixture was stirred at room temperature for an hour and next at 40 C for 2 hours.
After the stirring, acetonitril~ was evaporated under reduce pressure. Ether was added to the residue and insoluble salts were filtrated off, and then ether and excess ethylene-diamine were evaporated under reduced pressure to give N-(2-chloro-S-pyridylmethyl)ethylenediamine (16 g) of the followipg formula as colorless oil. n21.5627 Cl~C~12NH (CH2) 2NH2 ..

tCompound No. II-95) Example 2 2-bromo-5-pyridylmethyl bromide (25 g).in a solution of acetonitrile was added dropwise to a solution of ethylene diamine (30 g) in acetonitrile (80 ml) a~ O~C. After the reaction was stirred at room temperature for some time, the produced insoluble salts were filtrated off and then the filtrate was concentrated on water bath at 40C to give N-(2-bromo-5-pyridylmethyl)ethylenediamine (22 g).

n261.5586 Br~)-CH2NH tCH2 ) 2NH2 tCompound Mo. II-30) "

~ 31 ~ 7~

Example 3 6-methylpicolinic aldehyde ~12.1 g) was added to a solution of ethylenediamine 124 g) in anhydrous dioxane ~200 ml).
The mixture was stirred at room temperature for 3 hours. After the stirring, the mixture was heated and the mixture (120 ml) of the dioxane and the produced water was distilled off to complete the reaction for shiff base. The contents were cooled at room temperature and sodium boron hydride (7.6 g) was added to the contents little by lettle. ~fter the adding, the mixture were stirred at room temperature for 8 hours~ ' After the volatile matter was distilled in vaccum from the mixture, ice water was added to the residue and the product was extracted with chlorofolm. The extract was evavolated to give N-(2-methyl-6-pyridylmethyl)ethylenediamine (8.3 g).

b.p. 127-129CJOOlmmHg H3C~CH2NH (CH2 ) 2NH2 (Compound No.II-l9) Example 4 2-ethoxy-5-pyridylmethyl chloride hydrochloride (9.6 g) in an aqueous solution was added dropwise to the mixed solution of trimethylenediamine (11.1 y) and 20% aqueous solution (22 g) of sodium hydroxide at 0-5 C. After the reaction mixture was stirred at room temperature for some time~ water and excess trimethylenediamine were distilled off under reduce pressure from the contents and after the inorganic salts were filtrated of, the produced viscous and oily substance was evaporated in vaccum to give N-(2-ethoxy-5-pyridylmethyl) - ~2 trimethylene diamine (6.3 g)~
bp. 134-135~C/0.08mmHg H5C2 ~ CH2N~CH2)3N 2 (Compound No. II-52) Example 5 Table 1 below shows the compounds of general formula (II) which were synthesized by the same way as in Examples 1, 2 or 4.

~2~7~
.

~ 33 -Va1~
~ C.) C) ~u~ r- o~ ~n u~ _I o ~ ~
u~ u~
~ ~ ~ ~ 1` CD ~ ~ ~ ~
r~
O r~ ~ _I u~ u~ ,1 ~ _~
co r-_l Ll~ _l ~ U~ In ~ ~ ~ ~1 U~
r~ ~ _~ ~ ~
~> o c~ ~1 u~ u~ ~1 _I ~ I~ ~_ Tl ~`J C~ N a ~ a ~ a ~ a ~ ~
U~ ~ ~ ~ ~ P. ~

_ _ . ___ _ R _ _ $ X J m N ~) N 1i4 ~4 O -[~3 [~3 m ~ _ . _ _ _ ,,l c 1 0 o o o o ~ ~ ~ o _ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
.,, ~, ~ _I _I .,., .,, ~ _I _I
~ :: _l ~ u~ ~n u~ u~ In u~ ~ ~n c~ ~
E~ C~ h ~: O~ P O~ Q. O Q- ~ ~ ~ t 4 :1: ~ ~ ~ ~ U~ ~ L~ U~ U~ U~ ~ U~
P.
~ ___ \~; ~: :a 3: ::c :I: :~ ~ ~ m :c ~:
X _ _ ~ o o ~ o o o o o o C~

E3 ~ ~ ~ ~ ~ N t~) ~ ~`I ~
_ _ _ ___ O
Z
_l ~ o ~ ~ ~ ~r _l ~ In r~l U~ In In O l l l l l l l l l l E~ H H H H H H H H H H
C) H H H _ H H H H H _ 6~7 ___ _ ~ C~ _l G o c~
~ ~1 In O ~ ~r ~ ~0 ~ ~D
~ ~ ~:r 3 ~ G ~a __ _ X~ :~ 3~ C~
. _ o I o o o c _~ o U~ U~ U~
o o o h ~: ~ Q. Q~
.~ ~ U~ U~
. _ _ :~: 3:
.
o o o _ __ '~
__ . .
Z
~ o~ O~ r-~ U~ U~ o~

a~ H H t-l U H _ ~ , ~ 2 Example 6 Table 2 below shows the compounds of general formula (II) which were further synthesiæed by the same way as in the above Example 1, 2 or 4 for the purpose of supply~ng the ~ synthesis of the compounds of general formula (I) L

,, 36 ~ 7~c~

Table 2 Compound No. Compounds (products1 II- 3. N-(6-methyl-2-pyridylmethyl)ethylenediamine ~ II- 4. N-(6-methyl-2-pyridylmethyl)trimethylenediamine II- 5. N-~4-methyl-2-pyridylmethyl)ethylenediamine II- 6. N-(4-methyl-2-pyridylmethyl)trimethylenediamine II- 7. N-(S-ethyl-2-pyridylmethyl)ethylenediamine II- 8. N-(S-buthyl-2 pyridylmethyl)ethylenediamine II- ~. N-(4,6-dimethyl-2-pyridylmethy1)ethylenediamine II-10. N-(3-chloro-2-pyridylmethyl)ethylenediamine II-ll. N-(5-chloro-2-pyridylmethyl)ethylenediamine II-12. N-(5-chloro-2-pyridylmethyl)trimethylenediamine II-13. N-(3,5-dichloro-2-pyridylmethyl)ethylenediamine II-14. N~(S-fluoro-2-pyridylmethyl)trimethyldiamine II-15. N-(6-bromo-2-pyridylmethyl)ethylenediamine II-16. N ~2-(5-ethyl~2-pyridyl)ethyl)trimethylenediamine II-17. N-(6-chloro~4-methyl-2-pyridylmethyl)ethylenediamine II-18. N (5-methyl-3-pyridylmethyl)ethyienediamine II-21. N-(2-phenyl-5-pyridylmethyl)ethylenediamine II-22. N-(2-phenyl-5-pyridylmethyl)trimethylenediamine II~23. N-(~-benzyl-S-pyridylmethyl)ethylenediamine II-25. N-(2-chloro-3-pyridylmethyl)trimethylenediamine II-26. N-(5-chloro-3-pyridylmethyl)ethylenediamine II-27. N-(S-chloro-3-pyridylmethyl)trimethylenediamine II-28. N-(S-bromo-3-pyridylmethyl)ethylenediamine II-29. N-(5-bromo-3-pyridylmethyl)trimethylenediamine II-32. N-~5-fluoro-3-pyridylmethyl)ethylenediamine II-35. N~ (2-fluoro-S-pyridyl)ethyl~ethylenediamine ~ - 37 - ~ 2 II-36. N-~2-methyl-1-(2~fluOrO-5-pyridyl)propyl~
ethylenediamine II-37~ N-~2-(2-fluoro-5-pyridyl)ethyl)ethylenediamine II-38. N-~3-(2 bromo-5-pyridyl)propyl~trimethylenediamine II-39. N-(2-bromo-5-pyridylmethyl)tetramethylenediamine II-40. N-[4-(2-bromo-5-pyridyl)butyl)trimethylenediamine II-41. N-(2-chloro-6-methyl-3-pyridylmethyl)ethylenediamine II-42. N-(2,4-dichloro-5-pyridylmethyl)trimethylenediamine II-43. N-(2,6-dichloro-3-pyridylmethyl)ethylenediamine II-44. N-(2,4-dibromo-5-pyridylmethyl)ethylenediamine II-45. N-(2,4-di~fluoro-5-pyridylmethyl)ethylenediamine II-46. N-(2,4,5,6 tetrafluoro-3-pyridylmethyl)ethylene-diamin II-47. N-(2,4,5,6-tetrachloro-3-pyridylmethyl)ethylenediamine II-48. N-(2-methoxy-3-pyridylmethyl)trimethylenediamine II-49. N-(2-methoxy-5-pyridylmethyl)ethylenediamine II-50. N-~2~methoxy-5-pyridylmethyl)trimethylenediamine II-53. N-(2-isopropoxy-5-pyridylmethyl)ethylenediamine II-56. N-~2-(2,4-dichlorophenoxy)-5-pyridylmethyl) ethylenediamine II-57. N-(2-methy~thio-3-pyridylmethyl)ethylenediamine II-60. N-(4-methyl-2-methylthio-5-pyridylmethyl) ethylenediamine II-61. N-(2-phenylthio-5-pyridylmethyl)ethylenediamine II-62. N-~2-(4-chlorophenylthio)-5-pyridylmethyl~
ethylenediamine II-63. N-~2-ethylthio-5-pyridylmethyl)ethylenediamine II-64. N-(2-methylsulfinyl-5-pyridylmethyl)ethylenediamine II-65. N-(2-methylsulfonyl-5-pyridylmethyl)trimethylenediamine - 38 ~ .7~
I-66. N-t4-chloro-2-fluoro-5-pyridylmethyl) trimethylenediamine II-67. N-(6-chloro-2-methyl-3-pyridylmethyl)ethylenediamine II-68. N-(2-chloro-4-methyl-5-pyridylmethyl)ethylenediamine II-69. N-(2-allyl-5-pyridylmethyl~ethylenediamine II-70. N-(2-propargyl-5-pyridylmethyl)ethylenediamine II-71. N- (2,3-dichloro-5-pyridylmethyl)ethylenediamine II-72. N-(2-(1-propenyl)-5-pyridylmethyl)ethylenediamine II-73. N-(2-chloro-4-pyridylmethyl)ethylenediamine II-74. N-(2-chloro-4-pyridylmethyl)trimethylenediamine II-75. N-(2-fluoro-4-pyridylmethyl)ethylenediamine II-76. N-(2-fluoro-4-pyridylmethyl)trimethylenediamine II-77. N-(2,6-dichloro-4-pyridylmethyl)ethylenediamine II-78. N-(2,6-difluoro-4-pyridylmethyl)trimethylenediamine II-79. N-(2-methyl-4-pyridylmethyl)ethylenediamine II-80. N-(2-methyl-4-pyridylmethyl)trimethylenediamine II-81. N-(1-(2-chloro-4-pyridyl)ethyl~ethylenediamine II-82 N-(2-chloro-6 methyl-4-pyridylmethyl)ethylenediamine I-83. N-(2-chloro-6-methyl-4-pyridylmethyl) trimethylenediamine II-84. N-(2,6-dimethyl-4-pyridylmethyl)ethylenediamine II-85 n N-(2-bromo-4-pyridylmethyl)ethylenediamine II-86. N-(2,6-dibromo-4-pyridylmethyl)ethylenediamine II-87. N- (2,3,5,6-tetrafluoro-4-pyridylmethyl) ethylenediamine II-88. N-(2,3,5,6-tetrafluoro-4-pyridyl)trimethylene-diamine II-89. N-(2,6-dichloxo-4-pyridylmethyl)trimethylenediamine II-90. N-(3-chloro-2-fluoro-5-pyridylmethyl)ethylenediamine ~2~

II- gl . N- ( 3 -bromo-2 -f luoro-5-pyridylmethyl ~ ethylene-diamine II- 92. N-l2-chloro-3-fluoro-5-pyridylmethyl) ethylenediamine II- 93. N-(2,3,4~trichloro-5-pyridylmethyl~ethylenediamine II- 94. N- (3-chloro 2-methylthio-5-pyridylmethyl) ethylenediamine II- 96. N-~2-(2-chloro-5-pyridyl)ethyl)ethylenediamine II- 98. N-~2-(2-chloro-5-pyridyl)ethyl)trimethylenediamine II- 99. N-~l-(2-chloro-s-pyridyl)ethyl)trimethylenediamine II-100. N-~3-(2-chloro-5-pyridyl)propyl~trimethylenediamine II-101. N-~1-(2-chloro-5-pyridyl)ethyl~ethylenediamine~
II-102. N-(2-chloro-5-pydylmethyl)tetramethylenediamine II-103. N-t4-(2-chloro-5-pyridyl~butyl)trimethylenediamine II-104. N-~1-(2-chloro-5-pyridyl)propyl~trimethylenediamine II-105. N-~2-methyl-1-(2-chloro-5-pyridyl)propyl~
ethylenediamine The referential examples below are the synthesis ones for the compounds of general formula (IV) which are the intermediates for the aforesaid compounds of general formula (II) and part of which is new.
Referential example la 15~ methylmercaptan sodium salt (77 g) was added to 6-chloronicotinic acid (15.8 g) dissolved in 20% aqueous solution of sodium hydroxide (22 g).
The reaction mixture was stirred at 70~80C for 10 hours.

After ~he cooling, the precipitate produced by neutralization was collected by filtration and recrystallized from chloroform ~ 2 to give 6-methylthionicotinic acid (15.3 g).
mp. 186--188C

~ COOH
~`NJ

Referential example lb Thionylchloride (23.8 g) was added to 6-methyl-thionicotinic acid tl5.3 g) tfrom the above referential example la). The reaction mixture was gradually heated with stirring and refluxed until the generation of hydrogen chloride ceased. 6-methylthionicotinoylchloride was stoichiometricly obtained by distilling off excess thionylchloride under reduced pressure. 6-methylthionicotinoylchloride dissolved in ether was added dropw~se to 20% aqueous solution of sodium b~ron hydride (6.5 g) at 0^-10 C. After adding, the mixture was stirred for one hour and the ether layer was separated and dried.
Said ether layer was evaporated under reduce pressure to give 2-methylthiopyridine-5-methanol ~9.6 g).

n221.6084 Referential example lc Thionylchloride (7.7 g) was added to 2-methylthio-pyridine-5~methanol (7.8 g~ (from the above referential example lc) in chloroEorm (30 ml) at room temperature~ After the stirring for some time, the volatile matter was distilled off under reduced pressure to give 2-methylthio-5-chloromethyl pyridine hydrochloride (10.4 g) stoichiometricly.

~L2i~
~, m~. 127- 130C

~,CH2Cl H3CS ~Cl The compounds synthesized by the same way as in the above referential examples la, 1~, lc are exemplified below.
Method of referential example la ~

~ COOH ~ -COOEI

5C2~
(mpO 187-~190~C) (mp. 167~ 168QC) Method of referential example lb : -~ -CH2OH (synthesized from 6-methoxy H3CO nicotinic acid, a known compound) (bp. 95- 96~C/0.5 mmHg) ~CEI20H

(bp. 97~ 98 C/0.4 mmHg) ~n251.5960) 2 (synthesized from 2,6-~ dic~loroisonicotinic acid, C ~ 1 a known compound) (mp. 135~136C) ~gir r~1~

C~2H (synthesized from 2-chloro-~ lsonicotinic acid, a known C~ compound) (mp. 64~ 66C) Method of referential example lc : -~-CH2Cl H3C ~ ~N~
(bp. 98~ 99C/5~6 mmHg) 6J~CH 2C 1.
H5C~ ~

ibP. 68~ 70~Ctl mmHg) ~CEI2Cl (n271.6088) CE~2Cl C ~ Cl (mp. 52~ 53C) CH 2Cl ClJ ~ 3 (bp. 129~_130C/30 mmHg) ~L~62:7~5 - ~3 -Example 7 N-(2-chloro-5-pyridylmethyl)ethylenediamine (18.6 g), 1-nitro-2~2-bis(methylthio)ethylene (16.5 g) and methanol (100 ml) were mixed at room temperature.
The mixture was gradually heated with stirring and stirred at 50C until the generation of methylmercaptan ceased.
After the reaction, the reaction mixture was cooled to room temperature and the resulting crystals were collected by filtration to give 1 (2-chloro-S-pyridylmethyl)-2-(nitro-methylene)-imidazolidine (19 g) of the following ~ormula as pale yellow crystals. mp. 165-f166C

_~ , ~CHN02 2 ~
(Compound No. 95) Example 8 N-(2-fluoro-5-pyridylmethyl3ethylene diamine (1.7 g), l-nitro-2,2-bis(methylthio)ethylene ~1.7 g) and ethanol (10 ml) were mixed at room temperature.
The mixture was gradually heated with stirring and refluxed until the generation of methylmercaptan ceased. After cooling to room temperature, the resulting crystals were collected by filtration and dried to gi~e light yellow crystal 1-(2-fluoro-5-pyridylmethyl)~2-(nitromethylene)imidazolidine (1.7 y).
mp. 139~ 142~C H

C,~CHNO 2 tCompound No. 1) ~2~i;æ72~

Example 9 Table 3 below shows the compounds of general formula (I) which were synthesized by the same way as in Example 7 and 8.
Table 3 .

N
(CH ~ /=CHNO2 (CH2)n CH~XQ

C~-p~od m n R position ~ - Physical constant 2 2 O H 2-position 5~C~3 mp. 130~ 132C
3 3 0 H 2-position 5-CH3 mp. 145~ 146C
. 2 0 H 2-position 6-Br mp. 176~ 178C
2 0 H 5-position 2 C2 5 mpO 171_ 173C
3 0 H 5-position 2-OC2H5 mp. 177 ~179~C

7 2 O H 5-position 2-O ~ mp. 179~ 180C

. 3 O H 5-position 2-O ~ mp. 185~ 187 C

9 3 0 H 5-position 2-F mp. 149~ 151 C
2 0 H 3-position 2-Cl mp. 201~ 204C
11 2 0 H 3-position S-Br mp. 180 ~182 C
12 3 0 H 3-position 5-Br mp. 192 ~ 195 C
13 2 0 H 5-position 2-Br mp. 167~ 170C
14 3 ~ H 5-position 2-Br mp. 193~ 195 C
2 0 H 4-position 2-Cl mp. 177~ 179C
16 3 0 H 4-position 2-Cl mp. 219~ 222C

~ - ~5 -_ _ No. m n R position XQ Physical constant _ _ _ 17 2 O H 4-position 2,6-C12 mp. 258-~260 C

18 2 O H 2-position 6-CH3 mp. 191~ 194C

19 3 O H 2-position 6-CH3 mp. 202~ 204 C

2 O H 2-position 5-Cl mp. 145-_147~C

21 3 O H 2-position 5-C1 mp. 161_ 162 C

22 2 0 H 5-position 2-CH mp. 120~ 12~ C
23 3 O H 5-position 2-CH3 mp. 138-~40 C
24 2 O H 5-position 2-SC~3 mp. 125--126C

3 O H 5-posi-tion 2-SCH3 mp. 137-V139C

26 2 0 H 4-position 26--C13 mp. 228 ~230C

29 2 O H 5-position 2~0CH3 mp. 159 ~ 161 C

42 2 0 H 5-position 2 ~ mp. 196~ 198 C

97 3 0 H 5~position 2-Cl mp. 184--186C
. _ _ Example 10 Table 4 below shows the compounds of general formula (I) which were synthesized by reacting the compounds of general formula (II) from aforesaid Examples 1, 2, 3, 4, 5 and 6 with material Nos. (III-l), (III-2), (III-3) and ~III-4) shown below, according to the same way as in Examples 7 and 8.
Material No. (III-l) : l-nitro-2,2-bis(methylthio)ethylene No. (III-2) : 1-nitro-2,2-bis(ethylthio)ethylene No. (III-3) : 1-nitro-2,2-bis~benzylthio)ethylene No. (III-4) : 2-nitro-1,3-dithiolane Table 4 H

N
(CH ~ N'''CHN2 (C~l2)n~cH ~ XQ

Product CCNmoUnd material material _ Pyridine-. m n R bonded XQ
_ _ 27 II-84 III-2 3 O H 4-Fosition 2-C1, 6-C~I3 28 II-25 III-l 3 O H 3-position 2-C1 II-50 III-2 3 O H 5~Fsition 2-OCH3 31 II- S III-l 2 O H 2-position 4-CH3 32 II- 6 III-l 3 O H 2-position 4-CH3 33 II- 7 III-2 2 O H 2-position 5-C2H5 34 II- 8 III-l 2 O H 2-position 5~C4H9~n II- 9 III-l 2 O H 2-position- 4,6-(CH3)2 37 II-13 III-3 2 O H 2-position 3,s-C12 38 II-14 III-2 3 0 H 2-position 5-F
39 II-16 III-4 3 1 H 2-position 5-C2Hs II-17 III-l 2 O H 2-position ~-CH3, 6-Cl 41 II-18 III-2 2 O H 3-position 5-CH3 43 II-22 III-2 3 0 H 5-position 2 44 II-23 III 1 2 O H 5-position 2-CH
II-26 III-3 2 O H 3-posit.ion 5-C1 . _ - II-27 III-l 3 O 3-position 5-C1
- 4 7 ~
Table 4 (s~ont~nued) _ ~ Fr~uct Cc~i materia~ mater~al Eyridine _ . m n R F05ition X~
. , .. ~
47 II-32 III--l 2 O~I 3~sition 5-F
48 II-35 III-:I. 2 O-CH3 5-position 2-F
49 . II-36 III-2 2 03 7 5~Fsition 2-F
II-37 III-2 2 1 H 5-positiorl 2-F
51 II-38 III-3 3 2 H 5~Fsition 2~3r 52 II-39 III-l 4 OEI S position 2~r 53 II-40 III-l 3 3 H 5~Fsition 2-Br 54 II-41 III-2 2 0 H 3~osition 2~1, 6~3 II-42 III-3 3 0 H 5~Fsition 2,4-C12 56 II-43 III-l 2 O~I 3-position 2,6~12 57 II-44 III--2 2 O H 5~ositi~n 2,4~3r2 58 II-45 III-2 2 O H 5 position 2,4-F2 59 II-46 III-3 2 O H 3-position 2,4,S,6-F4 II--47 III--2 2 O H 3 positioF~ 2,4,5,6~14 61 II-48 ïII-l 3 O H 3~sition 2 OCE13 62 II-53 III~l 2 O H 5-Fosition 2{~3H7-iso 63 II-56 III~2 2 0 H 5~Fsition 2~Cl 64 II-57 III-2 2 0 H 3~Fsition 2~CH3 II-60 III-l 2 O H 5~sition 4{~I3, 2~3 66 II-61 III-l 2 O H - 5~osition 2~3 67 II~2 III-3 2 O 5~FOsition ~3Cl .

~2~i~27 ~S

Table 4 (cDntinued) . _ ~r~duct CoNmopo.und material material Pyridine-m ¦ n R Fsltion XQ
. _ _ 68 II-63 III-2 2 ¦ O H 5~Fsition 2-SC2H5 69 II-64 III-2 2 ¦ O H 5-position 2-S-CH3 l . O
II-65 III-2 3 O H 5-position 2-S-CH3 . . O
71 II-66 III-l 3 O H 5-position 4-C1, 2-F
72 II-67 III-l 2 O H 3-position 6-C1, 73 II-68 III-l 2 O H 5-position 2-C1, 74 II-69 III-l 2 O H 5-position 2 2 II-70 III-l 2 O H 5-position 2-CH2C-=CH
76 II-71 III-2 2 O H S-position 2,3-C12 77 II-72 III-2 2 O H 5-position 2-CH-CH-CH3 78 II-7s III-4 2 O H 4-position 2-F
79 II-76 III-4 3 O H 4-position 2-F
II-78 III-l 3 0 H 4-position 2,6-F2 81 II-79 III-l 2 O H 4~Fsition 2-CH3 82 II-80 III-l 3 O H 4~Fosition 2-CH3 83 II-81 III-2 2 O -CH3 4-position 2-C1 84 II-84 III-2 2 O H 4~Esition 2,6-(CH3)2II-85 III-2 2 O H 4-position 2-Br 86 II-86 III-l 2 O H 4-position 2,6-Br2 87 II-87 III-l 2 0 4-positio~ 2,3,5 t 6-F4 49 ~ ~L2~7~r3 Table 4 Pro~uct Compound material material _ _ Pyridine-m n R position XQ

88 II-88 III-l 3 O H 4-position 2,3,5,6-F4 89 II-89 III-2 3 O H 4-position 2,6-C12 II-90 III-l 2 O H 5-position 2-F, 3-C1 91 II-91 III-l 2 O H 5-position 2-F, 3-Br 92 II-92 III-1 2 O H 5-position 2-C1, 3-~
93 II-93 III-l 2 O H 5~Fsition 2,3,4-C13 94 II-94 III-l 2 O H 5-position 2-SCH3, 96 II-96 III-l 2 1 H 5-position 2-C1 98 II-98 III-2 3 1 H 5-position 2~C1 99 II~99 III-l 3 O -CH3 5-position 2-C1 100 II-100 III-l 3 2 H 5-position 2-Cl 101 II-101 III-l 2 O -CH3 5-position 2-C1 102 II-102 III-l 4 O H 5-position 2-C1 103 II-103 III-l 3 3 H 5-position 2-C1 104 II-104 III-2 3 O -C2H5 5-position 2-C1 105 II-105 III-l 2 o -C3H7 iso 5-position 2-C1 - 50- ~.2't~
ExamPle 11 ~wettable Dowder) . . _ . _ . . _ .
Flfteen parts of compound No. 95 of the invention~
80 paxts of a 1:5 mixture of powdery diatomaceous earth and powdery clay~ 2 parts of sodium alkylbenzenesulfonate, and 3 parts of a sodium alkylnaphthalenesulfonate/formaldehyde condensate are pulverized and mixed to form a wettable powder.
It is diluted with water and sprayed onto a noxious insect and/or its habitat or the locus of its occurrence.
Example 12 (emulsifiable concentrate) Thirty parts of compound No. 13 of the invention, 55 parts of exylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed with stirring to form an emulsifiable concentrate. It is diluted with water and sprayed onto a noxious insect and/or its ha~itat or the locus of its occurrence.
Example 13 (dust?
Two parts of compound No. 5 of the invention and 98 parts of powdery clay are pulverized and mixed to form a dust. It is scattered over a noxious insect and/or its habitat or the locus of its occurrence.
Example 14 (granules) ~ ater (25 parts~ is added to a mixture consisting of 10 parts of compound No. 14 of the invention, 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of a lignosulfonate, and they are well kneaded. The mixture is processed by an extrusion-type granulating machine to form granules having a size of 10 to 40 mesh which are then dried at 40 to 50C to form granules. The granules are scattered over a noxious insect and/or its habitat or the locus of i~s occurrence.

v ~ ~627:2 Example 15 (granules~
Ninety-five parts o clay mineral particles having a particle size distribution between 0.2 and ~ mm are put in a rotary mixer, and with rotation, 5 parts of compound No. 51 of the inventlon is sprayed onto the particles to wet them uniformly. The wet mixture is dried at 40 to 50C to form granules. The granules are scattered over a noxious insect, and/or its habitat or the locus of its occurrence.
Example 16 (oil preparation) Compound No. 1 of this invention ~0.5 part) and 99.5 parts of kerosene are mixed and stirred to form an oil preparation. It is sprayed onto a noxious insect, mite or nematode and/or its habitat or the locus of its occurrence.
Example 17 (biolo~ical test?
Test on Nephotettix cincticeps having resistance to organophosphorus agents:-Preparation of a test chemical Solvent~ 3.-parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether To form a suitable preparation, 1 part by weight of the active compound was mixed with the aforesaid amount of the solvent contaning the afvresaid amount of the emulsifier.
The mixture was diluted with water to a predetermined concentration~
Testing method Onto rice plants, about 10 cm tall, planted in pots each having a diameter of 12 cm was sprayed 10 ml per pot of the water-dilution of each active compound in a predetermined ~L2~25 concentration prepared as above. The sprayed chemical wasdri~d, ana a wire net having a diameter of 7 cm and a height of 14 cm was put over each pot, and 30 female imagGeS of Nephotettix cincticeps showing resistance to organophosphorus agents were released into the net. The pots were each placed in a constant temperature chamber and the number of dead insects was examined 2 days later, and the kill ratio was calculated.
The results are shown in Table 5.
Table 5 . , .
Concentration Compound of the active Kill ratio No. ingredient (%~
~ppm) 1 8 ~ 100 ~ 100 .

g7 _ 8 _ 100 Comparison A-l 40 65 B-l 40 55 Note 1) The compound numbers are the same as given above.

2) Comparisons A-l and B-l were as described above, and show the following compounds.

~ ~2~5 ~ 53 HN ~ N-CH2 ~ ~A-l~

- ~ ~H
N HN02 ~B-l) CH~ ~ -Cl In addition to the compounds exemplified in Example 17, for example, Compound Nos. 48, 49, 50, 51, 55, 96 and 98 also showed excellent insecticidal effects in the same test as Example 17.

Example 18 (biological test) Test on planthoppers:-Testing method A water dilution in a predetermined concentration ofthe active compound prepared as in Example 17 was sprayed onto rice plants/ a~out 10 cm tall, grown in pots with a diame-ter of 12 cm in an amount of 10 ml per pot. The sprayed chemical was dried, and a wire net, 7 cm in diameter and 1~ cm tall, was put over each of the pots. Thirty female imagoes of Nilaparvata lugens Stal of a s-train which showed resistance to organo-phosphorus chemicals were released in-to the net. The pots were left to stand in a cons-tant temperature chamber and the number of dead insects was examined two days later. The ~.ill ratio was then calculated.
In the same way as above, the kill ratio was calculated on Sogatella furcifera Horvath and organophosphorus-resistant aodel~hax striatellus Fallen.

.

, _ The resul-ts are shown in Table 6.

Table 6 . .
Compound Concentration Kill ratio (~) No of the active ~
. ingredient (ppm) N. L. stria- S. fur-lugens tellus cifera _ ... -- _ _ 1 40 100 10~ 100 7 ~0 100 100 100 13 40 100 100 lOU
14 ~0 100 100 100 29 40 100 10~ 100 ~5 40 100 100 100 97 40 ~00 100 ~00 .. __ . ._ . .
Compari-son ~-1 40 50 40 40 ..B-l 90 30 30 - 30 Note:
1) The compound numbers are the same as above.
~) Comparisons A-l and B-l are the same as the footnote to Table 5.

~` ~2~i~725 Examele 19 (biolo~i-c-al testl . Test on Myzus ~erisica~ (green peach aphids) having resistance to organophosphorus chemicals and carbamate chemicals:-Testing method Green peach aphids which had been bred and ha~resistance to organophosphorus chemicals and carbamate chemicals were inoculated on eggplant seedlings (black elongate eggplants), about 20 cm tall, grown in unglazed pots having a diameter of 15 cm (about 200 aphids per seedling~. One day after the inoculation, a water dilution of each active compound at a predetermined concentration prepared as in Example 17 was sprayed in a sufficient amount onto the plants using a spray gun. After the spraying, the pots were left to stand in a greenhouse at 28C. Twenty-four hours after the spraying, the kill ratio was calculated. For each compound, the test was carried out through two replicates.
The res~lts are shown in Table 7.
, .

Table 7 . , . ___ _ .
Concentration of Compound No. the active ingre- Kill ratio dient (ppm) (~) 1~ 200 100 9S 20~ 10~
9~ 200 100 Comparison A-l 1000 80 B-l 1000 60 , _ .
Estox 1000 100 (commercial product) 200 20 Note:
1) The compound numbers and comparisons A-l and B-l are the same as above.
2) Estox: S-2-ethylslllfinyl-1-methylethyldimethyl-phosphoroth~olate (45% emulsifia~le ~oncentrate).

Claims (34)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A nitromethylene derivative represented by the general formula (I) wherein R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkenyl group, a lower alkynyl group, an aryl group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group which may be optionally substituted by a halogen atom, or an aralkyl group, ? represents 1, 2, 3 or 4, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3, or a salt thereof.
2. A compound according to claim 1 wherein m is 2 or 3.
3. A compound according to claim 1 wherein R is hydrogen, X is halogen, Q
is 1, m is 2 or 3 and n is 0.
4. The compound 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine of the formula
The compound 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazoli-dine of the formula
6. The compound 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine of the formula
7. The compound 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine of the formula
8. The compound 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine of the formula
9. The compoud 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine of the formula
10. A process for preparing a nitromethylene derivative of the general for-mula I as defined in claim 1 or a salt thereof which comprises reacting a com-pound represented by the general formula II
(II) wherein R, X, ?, m and n are as defined above, with a compound represented by the general formula III

(III) wherein each R' represents a lower alkyl group, a benzyl group, or the two R' groups together represent a lower alkylene group having at least 2 carbon atoms to form a ring together with the sulfur atoms adjacent thereto.
11. A process according to claim 10 wherein in the starting materials m is 2 or 3.
12. A process according to claim 10 wherein in the starting materials R is hydrogen, X is halogen, ? is 1, m is 2 or 3 and n is 0.
13. A method of combating pests which comprises applying to the pests or to their habitat a pesticidally effective amount of a compound according to claim 1.
14. A method according to claim 13 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.
15. A method according to claim 13 wherein the active ingre-dient concentration in said composition is between 0.001 and 95%
by weight.
16. A method according to claim 13 wherein the active ingre-dient concentration in said composition is between 0.005 and 10%
by weight.
17. A method according to claim 13, 14 or 16 wherein the com-pound is applied to an area of cultivation at a rate of between 0.03 and 10kg/ha.
18. A method according to claim 13, 14 or 16 wherein the com-pound is applied to an area o-E cultivation at a rate of between 0.3 and 6 kg/ha.
19. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine.
20. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine.
21. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
22. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-imidazolidine.
23. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
24. A method according to claim 13, 14 or 16 wherein the com-pound is 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
25. A pesticidal composition comprising a pesticidally effec-tive amount of a compound according to claim 1 as an active ingre-dient in admixture with a diluent or carrier.
26. A pesticidal composition comprising a pesticidally effec-tive amount of a compound according to claim 1 as an active ingre-dient in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
27. A composition according to claim 25 or 26 wherein such com-pound is 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine.
28. A composition according to claim 25 or 26 wherein such com-pound is 1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine.
29. A composition according to claim 25 or 26 wherein such com-pound is 1.(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
30. A composition according to claim 25 or 26 wherein such com-pound is 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-imidazoli-dine.
31. A composition according to claim 25 or 26 wherein such com-pound is 1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
32. A composition according to claim 25 or 26 wherein such com-pound is 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-perhydro-1,3-diazine.
33. A compound represented by the general formula (II) (II) wherein R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkenyl group, a lower alkynyl group, an aryl group, an aryloxy group which may be optionally sub-stituted by a halogen atom, an arylthio group which may be optional-ly substituted by a halogen atom, or an aralkyl group, ? represents 1, 2, 3 or 4, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3.
34. A process for preparing a compound represented by the general formula (II) as defined in claim 33, which comprises reac-ting a compound represented by the general formula (IV) (IV) wherein R, X, ? and n are as defined above and Y represents a halogen atom or the group -OSO2R" in which R" represents a lower alkyl or an aryl group, with a compound represented by the general formula (V) H2N-(CH2)m-NH2 (V) wherein m is as defined above.
CA000478814A 1984-04-13 1985-04-11 Nitromethylene derivatives, intermediates thereof, processes for production thereof, and insecticides Expired CA1262725A (en)

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JP7296684A JPS60218386A (en) 1984-04-13 1984-04-13 Nitromethylene derivative, its intermediate, preparation thereof and insecticide
JP59-72966 1984-04-13
JP59-132943 1984-06-29
JP59132943A JPS6112682A (en) 1984-06-29 1984-06-29 Nitromethylene derivative, its intermediate, its preparation and insecticide

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