SI8411083A8 - Process for preparing derivatives of 3(2H)-pyridazinone - Google Patents

Description

A technical problem

There is a need to find a process in which, in good yield and purity, and in a technologically advantageous manner, new 3 (2H) -pyridazinone derivatives with properties that surpass those of the prior art are obtained.

The state of the art

The 3 (2H) -pyridazinone derivatives obtained by the process of the invention are novel compounds, and neither the processes nor their preparation have been described in the literature.

To date, various thioether bond 3 (2H) -pyridazinone derivatives have been reported as compounds of the present invention. Among them, the compounds listed in Table 1 below and their physiological activities were known.

The physiological activities of all the compounds listed in Table 1 are limited to fungicidal effects, depressive effects on the central nervous system and / or herbicidal effects. However, these compounds have not been reported to exhibit the excellent insecticidal and acaricidal effects found with the compounds of the present invention. The compounds of the present invention have excellent insecticidal and acaricidal activities in addition to fungicidal activity. These activities are attributed to the specific structures of the compounds of the present invention. The compounds of the invention is unique in that they have a straight or branched C2 'j ^C 5 ^_A lkilno group in position 2 of pyridazinones of the ring and also a substituted henziltio group in the 5-position of the ring. Neither the compounds of the invention nor the physiological activity, such as the insecticidal and acaricidal activities of the compounds, are described in the prior art literature.

Table 1

Compound Physiological activity Japanese Patent Publication no. R: alkyl, henzyl or 4-chloroenzyl fungicidal effect depressive effect not mid nervous system 09344/67 08860/69. griV ' ² ® ^x (V) ^R · * hydrogen a 14 halogen X: halogen or thiol increase effect pressure 71275/65 71276/65 69610/66 69612/66 69613/66 08857/67 08857/69 08859/69

- 3 Table 1 (continued)

Compound Physiological activity Japanese patent to post no. ®ΰΓ ^! · "OR" R: phenyl, furyl or thienyl R ¹ : lower alkyl the effect of the pressure increase depressive effect on central nervous system antifungal effect 71281/65 09343/66 11905/68 11908/68 --- (VII) R: halogen or lower alkylthio antifungal effect 69614/66 69615/66 08860/69 08861/69 O / ₂ , ² (vm) R: phenyl, chlorine substituted phenyl, pyridyl, furyl or thienyl pressure boost 'antifungal effect anti-acetyl cholinester effect 71277/65 71279/65, 71280/65 01302/67 69611/66 11906/68 11907/68 11909/68 08858/69 ^Hx <V ^scH O ^SCH rO (ix) X: 0 or S antifungal effect 02459/66 02788/66

--- 4Table 1 (continued)

physiological activity Japanese patent- Compound to post no. s fungicidal effect Chemical I SH Abstracts 93, V (X) 114552г Ά R: hydrogen, methyl, ethyl or benzyl • ^R , _tI 0 CN fungicidal effect Chemical A s Abstracts 91, tl x> ^{: C} A 20533h and 74637p N. 0 (XI) Vr ^CN k ^ V ^ S ^ CN (XII) R: hydrogen, alkyl, phenyl or halophenyl 0 K. C £ Jr τ ' herbicidal effect Japanese Patent Publication no. Jv (xm) 03798/65 R: R ² : hydrogen or phenyl alkyl, phenyl or -ch ₂ cooh

- 5 All the compounds represented by the general formulas IV to VIII are clearly different from the compounds of the present invention of formula I below in that the former compounds have a phenyl group in position 2. In the second p> lat <are j compounds with the general formula IX also obviously different from them t

in that their position 2 is not substituted. In addition, thiol compounds and their salts having the formula X are said to have a fucicidal effect and are different from the compounds of the present invention in that they have a substituted or unsubstituted benzylthio group in position 5 ·

We, the inventors, have intensively investigated the preparation of new compounds of the Formula I below, as well as their activities as agricultural agents, and have determined that the compounds of the Formula I are useful for controlling agricultural and horticulturally harmful insects and mites, for preventing plant rust and for expulsion common ticks on animals.

Description of solution to a technical problem with implementation examples

The 3 (2H) -pyridazinone derivatives according to the invention have the general formula (I)

2 in which R represents a linear or branched C ₂ - alkyl, R and R represent each independently hydrogen or lower alkyl, R is halogen, R is a halogen, a linear or branched - C ^ ₂ alkyl, cycloalkyl nesuhstitulran or suhstituiran with lower alkyl, straight or branched - alkoxy, lower haloalkyl, lower haloalkoxy,

-CN, -NO ₂ , —_> · Χπι / -></ Xni '·· ^-CH 2 “/ Q /' - ° - @ - ~ ^S v2 / (where X is halogen, lower alkyl, cycloalkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy, -CN or -NO ₂ , and m represents O or an integer from 1 to 5 "wherein these X are the same or different if m is an integer from 2 to 5), pyridyloxy which may be substituted by halogen and / all -CF2, quinoxalyloxy, which may be substituted by halogen and / or -CF4, lower alkenyl oxy, lower alkylthio, lower haloalkylthio, -SiCCH2), -OH.

-N (CH ^) ₂ , -SCN, -COOCH ^, or -OCH (CH ^) 0000 ^, and n denotes by an integer from 1 to 5 * where these w are the same or different if n is an integer from 2 to 5 ·

The compounds of the present invention have particularly potent insecticidal and acaryidic effects and exhibit excellent immediate effects and residual activity.

Lower alkyl, including lower alkyl moieties contained in groups such as lower alkoxy, lower haloalkyl, &quot; lower haloalkoxy, lower alkylthio, and lower haloalkylthio, are typically straight or branched alkyl having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, n-n-propyl, i-propyl, n-butyl, Isobutyl, sec-butyl or tert-butyl.

The lower alkenyl contained in fc alkenyloxy is usually straight or branched alkenyl of 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, such as ethenyl, n-propenyl, n-propadienyl, i-propenyl, n-hutenyl, n -butadienyl, n-butatrienyl, sec.butenyl and sec.butadienyl.

The term halogen and halogens in groups such as haloalkyl, haloalkoxy and haloalkylthio means a fluorine, chlorine, chromium or iodine atom or a mixture thereof.

Cycloalkyl as iP or substituent X preferably has 5 to 6 carbon atoms.

- 8 R is preferably straight or branched alkyl of 2 to 4 carbon atoms, such as ethyl, n-propyl, i-propyl, n-butyl, isobutyl, sec.butyl or ⁴ tert-butyl and most preferably tert-butyl.

Ί 2

R and R are each preferably hydrogen or straight or branched lower alkyl of 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl or i-propyl, and more preferably hydrogen, methyl or ethyl, with

R is preferably straight or branched - C8 alkyl such as i-propyl, t-butyl, i-butyl, n-hexyl, n-heptyl, n-octyl, θ2 θ8 ^a alkoxy (such as ethoxy, n-propoxy, i-propoxy , n-pentyloxy, n-hexyloxy, n-heptyloxy). Further, R ^{2 is} preferably phenyl, -O- / 0001 ^, -00 ^^? - CH (CH ₂ ) ₂ , -OCHF ₂ , cyclopropyl, cyclohexyl, allyloxy, 2-butyloxy and -Si (CH 2) ^. Most preferably, R is t-butyl, phenyl, cyclohexyl and

Preferred position R ^ is position 4.

R ^ is preferably chlorine or bromine, more preferably chlorine.

n is preferably an integer from 1 to 3, more preferably 1 or 2, and most preferably 1.

The following compounds are essential in terms of pesticide effects:

Compound no.

70. 2-tert-butyl-4-chloro-5- (4-tert-butyl-α-methylbenzylthio) -3 (2H) -pyrazoleazinone 81. 2-tert-butyl-4-chloro-5 ~ (4-tert-Butylbenzylthio) -3 (2H) -pyridinone

88. 2-tert-Butyl-4-chloro-5- (4-cyclohexylbenzylthio) -3 (2H) -pyrazole

-9-- '

95 · 2-tert-butyl-4-chloro-5- (4-phenyl-benzyl · thio) -3 (2H) -pyridazinone

105 · 2-tert-butyl 1-4-chloro-5- (4-iso-propyl-amethylbenzylthio) -3 (2H) -pyridazinone

106. 2-tert-Butyl-4-chloro-5- (4-cyclohexyl-methylbenzylthio) -3 (2H) -pyridine zinone

109. 2-tert-Butyl-4-chloro-5- (4-phenyl-α-methylbenzylthio) -3 (2H) -pyridazinone

129. 2-tert-Butyl-4-chloro-5- (4-allyloxybenzylthio) -3 (2H) -pyridazinone

133. 2-tert-Butyl-4-chloro-5- (4-trimethylsilylbenzylthio) -3 (2H) -pyridazinone

138. 2-tert-Butyl-4-chloro-5- (4-difluoromethyloxybenzylthio) -3 (2H) -pyridazinone

141. 2-tert-Butyl-4-chloro-5- (4-cyclopropylbenzylthio) -3 (2H) -pyridazinone

153. 2-tert-Butyl-4-chloro-5- (4-ethoxybenzylthio) -3 (2H) -pyridazinone

154. 2-tert. -butyl 1-4-chloro-5- (4-n-propoxybenzylthio) -3 (2H) -pyridazinone

155. 2-tert-Butyl-4-chloro-5- (4-isobutyl-1-benzyl) 3 (2H) -pyridine zinone

157 · 2-tert. -Butyl-4-chloro-5- (4-n-hexyl-1-benzylthio) 3 (2H) -pyridine zinone

158. 2-tert-Butyl-4-chloro-5- (4-n-heptyl-benzylthio) 3 (2H) -pyridine zinone

159. 2-tert-Butyl-4-chloro-5- (4-n-octyl-benzylthio) 3 (2H) -pyridazinone

163. 2-tert-Butyl-4-chloro-5- (4-iso-propoxy-benzylthio) 3 (2H) -pyridine zinone

469. 2-tert-Butyl-4-chloro-5- (4-n-pentyloxy-benzylthio) 3 (2H) -pyridazinone

470. 2-tert-Butyl-4-chloro-5 ~ (4-n-hexyloxy-benzylthio) 3 (2H) -pyridazinone

474. 2-tert-Butyl-4-chloro-5- (4-n-heptyloxy-benzylthio) 3 (2H) -pyridine

480. 2-tert-Butyl-4-chloro-5-C4- (2-butenyloxy) -benzylthio] 3 (2H) -pyridazinone

243. 2-tert. -Butyl-4-chloro-5E4 '- (4' '- trifluoromethylphenoxy) -benzylthio] -3 (2H) -pyridazinone

245. 2-1 tert-Butyl 1-4-chloro-5- C 4 '- (4 -1 tert-butyl-phenoxy) -methylbenzylthio] -3 (2H) -pyrimidinone.

More preferred compounds are compounds of numbers. 70, 84,

88, 95, 406, 409 and 243The formulas of these compounds are listed below:

oo

Φγ

M

 | 55.

o t

z>

3 '

5CH! -0-fl Ef

Setu-0-0

D i

SCH ~ {o} - \ o

”^> 4 SM i-0H O h ₇ w ₇ - 41,

IS $. + Ύ '

- * <, ήγ <Λ

000

3ra.-gJw?

' ⁿ *

SSy

We do

- Ooh

Oh

3Ϊ

S CH -Q- @

M?

is? *. ΰ

UL ·

SCHi- @ · Λλ, Cq H i?

ft

SCHi-0 - (CrtiCH = Cf ^., Λ ^ „'% XsCH.-0-> vCWh ₇

I 'l · + / υ · ^ ζ ^

-0-4 λ

- 12 is t Λ

Π0 / 7i ·? Τ>. t-g

Oh

In 'O- ^ SCHz

- @ - OCHiCH * M ^CI U ψ / Τ'Ύ ^ „n

Aa ^ A. SC-K i '^ οχ- 0 ~ l2fOF

2. ^^. -τ-γ-ν ^

OHJ

The symbol + means tert-butyl.

The compounds listed in Table 2 below are examples of compounds to be included in the present invention. However, it is self-evident that the compounds in Table 2 are merely for the purpose of explaining the Invention and not for limiting it. Incidentally, a compound of the invention comprising an asymmetric carbon atom (asymmetric carbon atoms) comprises an optically active (+) compound and a (-) compound.

Table 2

Compounds of Formula T:

[In Table 2, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, Pen is pentyl, Hex is hexyl, n is normal, t is tertiary, i is iso and s is secondary).

Num. R R ¹ R ² R ⁴ R ³ n -: - ί 1 Et H H C £ 4-t-Bu 2 Et H H Ci 4-F 3 Et H H Ci 3-CF ₃ 4 Et H H Ci ⁴ ”O.

- -r ...... R ¹ R ² R ⁴ R ³ n Num. R 5 Et H H C £ 4-OCH ₂ - <0) 6 Et H H C £ The score is now 4-0 7 Et Me H CZ 4-OCF ₂ CF ₃ 8 Et Me Me CZ 4-t-Bu 9 Et H H Nr 40 10 Et H H Nr 4-CF ₃ 11 Et H H Nr 2,3,4,5,6-F ₅ 12 Et Me H Nr 4-t-Bu 13 Et Me H Nr 4-F 14 n-Pr H H CJL 4-t-Bu 15 n-Pr H H CZ 40 16 n-Pr H H CZ , 0 17 n-Pr H H CZ 4-F 18 n-Pr H H CZ 2,4-C2_ ₂ 19 n-Pr Me H CZ 4-t-Bu 20 n-Pr Me H CZ 4-OCH ₂ / C?> CF ₃

Num. R R ¹ R ² R ⁴ R ³ n 21 n-Pr Me H C £ 2,4-C £ ₂ 22 n-Pr H H CZ 3,5-C £ ₂ 23 n-Pr H H CZ 3-CN 24 n-Pr Me H CZ 4-i-Pr 25 n-Pr Me H CZ 4-C2 26 n-Pr Me Me CZ 4-t-Bu 27 n-Pr H H Nr 2-OCF ^J Ci 28 n-Pr H H Nr 4-0CH ₂ - <^ O) -C £ 29 i-Pr H H CZ 3,4-C £ ₂ 30 i-Pr H H CZ 4-t-Bu 31 i-Pr H H CZ 2-NO ₂ 32 i-Pr H H CZ 4-OEt 33 i ~ Pr Et Me CZ 3-Nr 34 i-Pr n-Pr H CZ 4-Me 35 i-Pr H H Nr 2-OMe 36 i-Pr H H Nr ^{3 CF} 3 37 i-Pr Me H Nr 4-F 38 i-Pr Me Me Nr 4-0CH ₂ H ^ O) ~ CF ₃ 39 n-Bu H H C £ 4-Nr 40 n-Bu H H CZ 3,4-C £ ₂ 41 n-Bu H H CZ 2-CF ₃

no. R R ¹ R ² R ⁴ R ² n 42 n-Bu H H CZ 3-OCH ₂ CF ₃ 43 n-Bu Me H CZ 44 n-Bu n-Bu H CZ ⁴ -O 45 n-Bu Et Et CZ 4- <g> 46 n-3u H H Nr 3-OCF ^ j 47 n-Bu H H, Nr 4-OCH ₂ Xg> -CF ₃ 48 n-3u H H Nr 2,4-C £ ₂ 49 i-Bu H H CZ 3-Me 50 i-Bu H H CZ 3,4- (Me) ₂ 51 i-Bu H H CZ 52 i-Bu H H CZ 2-C £, 4-Me 53 i-Bu Me H CZ 2-C £, 4-F 54 i-Bu Et H CZ 2,6-CZ ₂ 55 i-Bu Et Me Nr 4-C2 56 s-Bu H H CZ 2-C2., 4-F 57 s-Bu H H CZ 2-Me, 4-G £ 58 s-3u H H Cl 4- / ηΛ

1 2 _4 _3 Num. R R R R R n 59 S-Bu H H ci. 4-t-Bu 60 s-Bu H H C £ 2,5- (Me) ₂ 61 s-Bu Me H Ci 4-F 62 s-Bu Et H Ci 4-F F 63 s-Bu H H Ci - \ 4-0CH ₂ / O / / F 64 s-Bu H H Nr 65 s-Bu H H Nr 4-CN 66 S-Bu H H Nr 3-CF ₃ 67 s-Bu H H Nr 2-F, 4-CF-j At 68 s-Bu Me H Nr 2-F, 4-Ci. 69 s-Bu i-Pr H Nr 4-OC ^f 3 70 t-Bu Me H Cit 4-t-Bu

optically active compound (+ ·) compounds of no. 70 optically active compound (-) compounds of no. 70

73 t-Bu H H Ct 74 t-Bu H H ct 75 t-Bu i. H h ' Ci

4-0-¼

Ci

-ZiT '

KoZV

CF.

Num. R R ¹ R ² R ³ n 76 t-Bu H H CZ 77 t-Bu H H CZ 2-Me 78 t-Bu H H CZ 3-Me 79 t-Bu H H CZ 4-Me 80 t-Bu H H CZ 4-i-Pr 81 t-Bu H H CZ 4-t-Bu 82 t-Bu H H CZ 2-CZ 83 t-Bu H H CZ 2 _t 4 ~ CZ ₂ 84 t-Bu H H CZ 3,4-C £ ₂ 85 t-Bu H H CZ 2-CZ, 4-Me 86 t-Bu H H CZ 2-F, 4-CZ, 87 t-Bu H H CZ 4-F ⁸⁸ t-Bu H H CZ 4- <5> 89 t-3u H H CZ Me 90 t-3u H H CZ 3-CF ₃ 91 t-3u H H CZ 3-OMe 92 t ~ Bu H H CZ 4-OCF ₃ 93 t-Bu H H CZ 2-OCF ₃ , 4-Ct 94 t-Bu II H CZ 2,3,4,5,6-F. 95 t-Bu H H Cl

Num. R R ¹ R ~ R ⁴ R ³ n 96 t-Bu H H C5. 97 t-Bu H H CZ 4-Nr 98 t-Bu H H CZ 2-0CH ₂ - ^ O ^ 99 t-Bu H H CZ ⁴ - ° ^c « ₂ - <o> 100 t-Bu H H CZ 4-0CH ₂ - \ O \ cF ₃ 101 t-Bu Me H CZ 3-Me 102 t-Bu Me H CZ 4-Me 103 t-Bu Me H CZ 4-i-Pr C S. \ 104 t-Bu H H CZ 4-O- ^ J ^ -CF ₃ 105 t-Bu Me H CZ ⁴ <3 106 t-Bu Me H CZ ⁴ <D 107 t-Bu Me H CZ 4-Nr 108 t-Bu Me H CZ 4-C £ 109 t-Bu Me H CZ

Num. 1 R R " R ⁴ R ³ n 110 t-Bu Et H CZ 4-t-Bu 111 t-Bu Me Me CZ 112 t-Bu H H CZ 2-NO ₇ 113 t-Bu H H Nr 4-Me 114 t-Bu H H Nr 4-F 115 t-Bu Et H cZ 4-CZ 116 t-Bu H H Nr 4-CF ₃ 117 t-Bu H H Nr 2-OCH ₃ CF ₃ 118 t-Bu H H Nr 4-OCF ₃ 119 t-Bu H H Nr 4-CN 120 t-Bu H H Nr 3-NO ₂ 121 t-Bu H H Nr ⁴ - <g> 122 t-Bu H H Nr 4-OCH ₂ / O> 123 t-3u Me H Nr 2-F 124 t-Bu Me H Nr 4-OC ^H 2- ^ Q> -Me 125 t-Bu n-Pr Me Nr 126 t-Bu H H CZ 4-OCH 2 ~ ^ 5) -C l

- Num. - R R ¹ ·> R R ⁴ R ^J n 127 t-Bu H H C S, 4-OCH ₂ - (Q> -Me Me \ _ 128 t-Bu H H CZ 4-OCH ₂ ^ g> 129 t-Bu H H CZ 4-OCH ₂ CH = CH ₂ 130 t-Bu H H ct 4-SC ₄ H _g -n 131 t-Bu H H CZ 4 - With Me 132 t-Bu H H CZ 3-OC ₄ H _g -n 133 t-Bu H H CZ 4-Si (Me) ₃ 134 t-Bu Me H CZ 135 t-Bu Me H CZ 136 t-Bu H H CZ 4-SCHF ₂ 137 t-Bu H H CZ 4-OCH ₂ CH ₂ CH ₂ C £ 138 t-Bu H H CZ 4-OCHF ₂ 139 t-Bu H H Nr 4-t-Bu 140 t-Bu H H Nr 4-C £ 141 t-Bu H H C £ ⁴ <l 142 t-Bu H H Ct 4-C (Me) ₂ CH ₂ C £ 143 t-3u li H CZ 4-OCHC (Me) = CH ₂

Num. R R ¹ R ² R ⁴ R ³ n 144 t-Bu H H CS, 3,5- (t-Bu) ₂ , 4-OH 145 t-Bu H H Ct 3,5- (Br) ₂ , 4-OH 146 t-Bu H H Nr 147 t-Bu H H Nr 4-n-Bu 148 t-Bu H H Nr 4-oc ₆ ^H and _3: n 149 t-Bu Me H Nr 150 t-Bu H H CS, 4-N (Me) ₂ 151 t-Bu H H CS, 3-OMe, 4-OPr-i 152 t-Bu H H CS 4-1 153 t-Bu H H CS 4-OEt 154 t-Bu H H CS 4-OPr-n 155 t-Bu H H CS 4-i-Bu 156 t-Bu H H CS 4-n-Bu 157 t-Bu H H CS 4-nC ₆ Hi ₃ 158 t-Bu H H CS 4-nC _? H ₁₅ 159 t-Bu H H CS 4-n- ^c 8H ₁₇ 160 t-Bu H H CS 4-s-Bu 161 t-Bu H H CS '- «Al 162 t-Bu H H CS. 4-COOMe 163 t-Bu H H Cl 4-OPr-i 164 t-Bu H H Cl 4-OCH ₂ CH (Et) Bu-n

Num. R R ¹ 9 R ** R ⁴ R ³ n 165 t-Bu H H CZ 4-OC ₉ H ₁₉ -n 166 t-Bu H H CZ ⁴ - ° ^C ll ^H 23- ⁿ 167 t-3u Me H CZ ^{4 OC} 10 ^H 2l “ ⁿ 168 t-Bu H H CZ 4-OC, H _n -n 4 9 169 t-Bu H H CZ 4-OC.H ..- n □ 11 170 t-Bu H H CZ 4-OC ^ H, ₀ -noi 3 171 t-Bu H H CZ 4 ° C ₇ H ₁₅ -n 172 t-Bu H H CZ 4-OC ₈ ^H and ₇ - ⁿ 173 t-Bu H H CZ 2,6- (Me), 4-t-Bu 174 t-Bu H H CZ 3,5-Br _? , 4-OPr-i 175 t-BU H H CZ 4-Ci. 176 t-Bu H H CZ 4-CF cs. \ _ 177 t-Bu H H CZ 4-0CH ₂ - <0) 178 t-Bu H H CZ ⁴ - ^ch 2 / o> 179 t-Bu H H CZ 4-OCH (Me) COOEt 180 t-Bu H H CZ 4-OCH CH = CH-Me 2 181 t-Bu H H CZ 4-SCN 182 n-Pen H H CZ 4-CS 183 n-Pen H H CZ 3-Me 184 n-? en H H CZ ⁴ <D

no. R R ¹ R ² R ⁴ -—- η _3 R n 185 n-Pen Me H Cl 4-CN 186 n-Pen Et H Ci 3-CF ₃ 187 n-Pen Et Et Ci ⁴ -O 188 n-Pen H H Nr 2-OCH ₂ - ^> - OCF ₃ 189 n-Pen H H Nr 2-Ct, 4-Me 190 n-Pen Me H Nr 2-Me, 4-C £ 191 i-Pen H H Cl 4-Nr 192 i-Pen H H Ci 4-NO ₂ 193 i-Pen H H Ci 4- \ H 194 i-Pen H H Ci • ³ - ° ^ch 2X (5} - ^cf 3 195 i-Pen Me H Ci 4-OCH ₂ / O> 196 i-Pen Et H Nr 3-OCF ₂ CF ₃ 197 n-Hex H H Ct 2-F 198 n-Hex H H Cl 4-Et F \ _ 199 n-Hex H H Ci 2-0CH ₂ -O / F 200 ί n-Hex H H a 4-OCH ₂ - / ^ 5 ^ ~ ^cn

Num. R R ¹ R ² R ⁴ R ³ n 201 n-Hex H H C £ ⁴ <D 202 n-Hex Me H Cl 4-CN 203 n-Hex Me H Ci 2-NO ₂ 204 n-Hex Et Me Ci 4-F 205 n-Hex Et Me Ci 206 n-Hex H H Nr 4-CF ₃ 207 n-Hex H H Nr 3-OCF ₃ Ci \ _ 208 n-Hex H · H Nr 4-OCHj-fo ^ ci 209 n-Hex Me H Nr A 210 n-Hex Me H Nr 3-OCF ₃ 211 n-Hex Me H Nr 4-Ct 212 n-Hex Et H Nr 2-Me 213 n-Hex Et Me Nr 2,4- (Me) ₂ 214 n-Hex Et Et Nr 3,4-Ci ₂ 215 n-Hex Et Et Nr 4-0CH ₂ ^ O ^ -C £ 216 Et H H Cl 4-O- (g) -CF ₃

Num. R R ¹ R ² R ⁴ R ³ n 217 Et H H CZ ² - ° / 5 / ^N ° 2 Ci 218 Et H H CZ 2 -C Z, 4-O-Zq \ -C £ CZ 219 E t H H CZ 2 _e 6-CZ ₂ , 3-O ^ O \ -CF ₃ 220 Et Et Me Nr 2-S0 221 i-Pr H H Nr 2-Ci, 4-0 - <^ Q ^ -CN 222 i-Pr Me Me Nr ⁴ - ^s / 50 223 i-Pr H H C £ 4-o0- _N O ₂ 224 i-Pr H H CZ 4-O0CF ₃ Me _ / 225 i-Pr Me H CZ 3-00 F \ _ 226 n-Pr Me H Nr 4-0- <0) 227 n-Pr H H Ci 4-O0CF ₃ 223 n-Pr Et H Ci

Num. R R ¹ R ² R ⁴ R ³ n 229 i-Bu n-Pr H Nr C £ 4-O - ^ - Ci 230 i-Bu Me H Nr 231 n-Bu H H Nr 2-CZ, 4-O- ^ Q ^ -NO ₂ 232 n-Bu H H CZ CZ 3-O \ Q ^ -iis 233 n-Bu H H CZ 234 n-Bu H H CZ ^4_ ° Xo) 235 s-Bu H H CZ 4-O ^> ^ 236 t-Bu H H CZ 3-0- ^ O ^ -Bu-t 237 t-Bu Me Me Nr 2,6-CZ ₂ , ⁴ “° \ O ^ ^ci 238 t ~ Bu H H Nr 3-0 ^ 5) 239 t-Bu Et H Nr ⁴ - ° aO / ^f 240 t-Bu H H 1 1 Nr 4-O- / 5)

Num. R - 'Ί R ¹ R ² R ⁴ R ³ n 241 t-Bu Me Me Nr 4-0- <θ) 242 t-Bu H H Ci 4-0- ^ 243 t-Bu H H Ci 4-o / O> CF ₃ CZ \ _ 244 t-Bu H H Cl 4-O ^) - _C F ₃ 245 t-Bu Me H CZ 4-O- ^ Q ^ -Bu-t 246 t-Bu H H Cl 4-0H ^ O} -C £ 247 t-Bu H H Cl 4-o- ^ Č? X ^F CZ \ _ 248 t-Bu H H Cl o-s / o} - «'., 249 t-3u H H CZ ⁴ -s- <§> 250 i-Pen H H CZ 3-o) C £ \ _ 251 i-Pen H H CZ 3-C £, 4-OhQ> -CF ₃

Num. • '1 R R ¹ R ² R ⁴ R ³ n 252 i-Pen Me H Ci 2,4-Ct ₂ , 4-O-iQ> -CN 253 i-Pen Et Me Nr 2- ° 5O> 254 i-Pen Me Me Ct 255 i-Pen Et Et Nr 256 n-Pen H H Ci ³ - ° Xo) 257 n-Hex H H Cl ⁴ '°'<§> - ^CP 3 258 n-Hex H H Ci 2-Cl, 4-S- ^ Q ^ -Br 259 n-Hex H H Nr 3,5-CZ ₂ , 4-0 ~ (o} -CF ₃ 260 t-Bu H H Ci 4- ° - ^ Q ^ ^ch 2 ^c £

Compounds of formula I can be prepared by reacting a compound of formula HA

in which R and R ² * ^- have the same meanings as formula I, and Y denotes -SH, a halogen or a lower alkyl) with a compound of the formula III defined in -OR ^ (where R represents

wherein R, R, R ⁷ and n have the same meanings as defined in formula I, and Z is halogen or -SH, wherein Z is halogen if Y is -SH, and Z is -SH if Y is halogen or -OR ^.

In particular, the compounds of the present invention can be prepared according to the following reactions (1), (2) or (3):

Reaction (1):

o

(m)

(XIV)

Reaction (5) »

N

(I)

- 32 with | p Z h wherein R, R, R, R ² , R and n in the above reactions (1) to (3) have the same meanings as defined above, hal means halogen and TS? means lower alkyl.

Namely, the compounds of the invention can be prepared by reacting the 3 (2H) -pyridazinone derivative of formula II, XVIII or XV, as one of the raw materials, with the hensyl compound of formula III or XIV, as another material, in a suitable solvent in the presence of hydrogen halide bonding agents or alcohol removal agents.

Lower alcohols such as methanol, ethanol, ketones such as acetone, methylethyl ketone, hydrocarbons such as benzene, toluene, ethers such as isopropyl ether, tetrahydrofuran,

1,4-dioxane, amides such as Ν, Ν-dimethyloformamide, hexamethylphosphoryltr ⁴ amide, and halogenated hydrocarbons such as dichloromethane.

If necessary, these solvents can be used as a mixture with water.

Inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and organic bases such as triethylamine, pyridine can be used as hydrogen halide bonding agents. If necessary, a catalyst such as tetraammonium salts (eg triethylbenzylammonium chloride) may be added to the reaction system.

The reaction temperature ranges from room temperature to the boiling point of the solvent used in the reaction.

The raw material ratio can be selected as desired. However, it is advantageous to perform the metabolism using equimolar or approximately equimolar amounts of materials.

- 55 By the way, the compounds of formula (II) above can be prepared by a process according to the following reaction:

where S, H and Hal have the same meanings as defined above.

The preparation of compounds I of the invention is described in more detail by the following examples, which should not be construed as limiting the invention.

- 34 Synthesis Example 1

Synthesis of 2-tert-butyl-4-chloro-5-mercapto-3 (2H) pyridazinone

66.3 g of 2-tert-butyl 4,5-dichloro-3 (2H) -pyridazinone and 48.0 g of 70% sodium hydrosulfide were added to 560 ml of water. After stirring at 60 ° C for 4 hours, activated charcoal was added. The resulting mixture was allowed to cool and then filtered. Concentrated hydrochloric acid was added to the resulting filtrate until its pH was reduced to 2 or less. The resulting solid was filtered off, washed with water, dried and then recrystallized from a mixed solvent of benzene and n-hexane to give the desired product as white needle crystals from the ground. 112 to 113 ° C (Yield: 81.5%) ·

The compound thus obtained was analyzed by H-NMR spectra in deuterium chloroform (CDCl2) to give the following results:

¹ H-NMR (CDCl 3, δ (ppm):

1.61 (9H, s, 2-t-Bu), 4.04 (1H, s, -SH), 7.56 (1H, s, 6-H).

Synthesis Example 2:

Synthesis of 2-tert-butyl-4-bromo-5-mercapto-3 (2H) · pyridazinone

31 »0 g of 2-tert-butyl-4,5 dibromo-3 (2H) -pyridazinone and 15.8 g of 7θ% sodium were added to 200 ml of water.

- 35 Hydrosulfides. After stirring at 60 ° C for 4 hours, the resulting mixture was allowed to cool to room temperature and about 8 ml of concentrated hydrochloric acid was added to reduce the pH of the solution to no more than 2. The resulting solid was filtered off, washed with water, dried and then recrystallized from benzene / n-hexane to give 0.8 g of the desired product as white crystals from the ground. 107 to 110 ° C (yield: 30.4%)

The compound thus obtained was analyzed by means of zl

H-NMR spectrum in deuterium chloroform (CDCl2) to give the following results:

(CDCip, $ (ppm):

1.63 (9H, s, 2-t-Bu), 4.18 (1H, s, -SH),

7.53 (1H, s, 6-H).

Synthesis Example 3 "

Synthesis of 2-tert-butyl-4-chloro-5- (2-methylbenzylthio) 3 (2H) -pyridazinone (compound no. 77) ^:

V. Dissolve 1.5 ml of 2-tert-butyl-4-chloro-5-mercapto-3 (2H) -pyrazinone in 10 ml of Ν, dim-dimethylformamide and add 1.2 g of anhydrous potassium carbonate and 1 , 0 g of α-chloro o-xylene. The resulting mixture was heated for 2 hours at stirring

- 36 80 to 110 ° C. After allowing it to cool to room temperature, 100 ml of water was added to the mixture and then stirred. The precipitated solid was filtered off, washed with water, dried and recrystallized from ethanol to give white needle crystals having the following physical properties (yield: 72.7%):

mp: 138.0 to 139.0 ° C. H-NMR (CDCl3), < 5 (ppm):

1.62 (9H, s, 2-t-Bu), 2.40 (3H, s, 2'-CHp, 4.21 (2H, s, -SCH ₂ -), 7.18 (4H, m. phenyl), 7.61 (1H, s, 6 -H).

Synthesis Example 4:

Synthesis of 2-ter c. butes 1-4-clom-5- (4-tert-butylbenzylthio) -3 (2H) -pyridazinone (compound no. 81):

A procedure similar to that in Synthesis Example 3, 1® was performed to use 2.0 g of 2-tert-butyl-4-chloro-mercapto-3 (2H) -pyridazinone, 15 ml of N, N-dimethylformamide,

1.3 g of anhydrous sodium carbonate and 1.6 g of 4-tert.butylbenzyl chloride to give white needle crystals having the following physical characteristics (yield: 87.9%):

- 37 mp: 111.0 to 112.0 ° C. ¹ H-NMR (CDO3), $ (ppm):

1.29 (9H, s, 4'-t-Bu), 1.60 (9H, s, 2-t-Bu), 4.21 (2H, s, -S0H ₂ -), 7.32 (4H , m, phenyl),

7.61 (1H, s, 6-H).

Synthesis Example 5 ^;

Synthesis of 2-tert-butyl-4-chloro-5- (4-tert-butyl-ethylbenzylthio) -3 (2H) -pyridazinone (Compound No. 70)

A procedure similar to the procedure in Synthesis Example 3 was performed except that 1.5 g of 2-tert-butyl-4-chloro-5-mercapto-3 (2H) -pyridazinone, 10 ml of N, N-dimethylformamide were used,

1.0 g of anhydrous sodium carbonate and 1.4 g of 4-tert-butylα-methylbenzyl chloride to give white needle crystals having the following physical properties (yield: 72.7%) m.p .: 100.0 to 106, 0 ° C ¹ H-NMR (CDCl 3, S (ppm):

1.29 (9H, s, 4'-t-Bu), 1.58 (9H, s, 2-t-Bu), 1.70 (3H, d, J = 7Hz, <x-CH ₅ ),

4.58 (1H, q, -SCH <), 7.33 (4H, m, phenyl), 7.56 (1H, s, 6-H).

- 38 Synthesis Example 6:

Synthesis of (+) - 2-tert-butyl-4-chloro-5- (4-tert-butyl-methylbenzylthio) -3 (2H) -pyridazinone (Compound No. 71)

17.0 g (77> 2 mmol) of p-tetec.butyl-α-methylbenzyl acetate were suspended in 3θ0 ml of 0.2 l disodium hydrogen phosphate aqueous solution (pH 9.1) and 1.00 g of bovine liver acetone powder was added. After stirring at room temperature for 77 hours, the reaction liquid was extracted twice with 200 ml ethyl acetate each (insoluble by filtration through Celite). The ethyl acetate layer was dried over anhydrous sodium sulfate and the solvent was removed by distillation to give 16.1 g of an almost colorless oily residue.

The oily residue was fractionated by silica gel column chromatography [developer: benzene / ethyl acetate mixture 20: 1 (v / v)] to give 3.60 g (+) - p-tert.butyl-a-methylbenzyl alcohol as colorless crystals having a soil. 85 ° C (yield: 26.2%); · [ref. ⁵ + 47.8 ⁰ (C = 1.01, ΟθΗ ^), ^{98% e, e} ·

A portion of the product (3.49 g) was recrystallized from 10.5 S hexane to give 3 »06 g crystals with 100% ee, [<x] j 7 + 48.9 ° (C = 1.05, C ₆ H ₁₂ > ·

12.16 g of (-) - p-tert.butyl-α-methylbenzyl acetate were also obtained as an almost colorless oil (yield: 71> 5%) with [cd ^ ⁵ - 36.9 ⁰ (C = 1.09. C ₆ H ₁₂ ), 35.6% ee

- 59 To 25 ml of ethyl ether was added 1.78 g (+) - 4-tert-butyl-α-methylbenzyl alcohol with 100% e.e. and 1.8 g of dry pyridine. The resulting solution was maintained at -25 ° C while stirring, and a solution of 5 "1 g of phosphorus tribromide dissolved in 18 ml of ethyl ether (at -15 to -25 ° C) was added dropwise. After complete addition, the resulting mixture was stirred at -10 ° C for 1 hour and then allowed to stand for 2 days at 5 ° C. We added ice water to it. The resulting organic layer was washed successively with saturated aqueous sodium bicarbonate solution and ice water, dried with anhydrous Glauber salt and the solvent removed under reduced pressure to give 1.6 g of 4-tert-butyl-a-methylbenzyl bromide.

0.96 g of the obtained product was added while stirring to a solution of 0.87 g of 2-tert-butyl-4-chloro-5-mercapto5 (2H) -pyridazinone, 20 ml of hexamethylphosphorylthriamide and 0.25 g of anhydrous sodium carbonate at -20 ° C. The resulting mixture was allowed to stand at room temperature for 2 days. Then, 500 ml of benzene was added to the mixture and washed twice with water. The resulting organic layer was dried with anhydrous Glauber salt and the solvent was removed by distillation to give the crude product. The crude product was purified by thin layer chromatography (using a mixture of benzene / ethyl acetate 5θ * · 1 »= 0.5).

Hexane was added to 1.1 g of the product thus obtained to give 0.85 S crystals.

The compound thus obtained was, in accordance with the measured H-NMR, identical to the compound obtained in the synthesis case 5 ·

- 40 tal. 102.3 to 104.3 ° 0 [m / z + 0.96 ° (C = 1.0, OHCl3).

Synthesis Example 7 ^:

Synthesis of (-) - 2-tert-butyl-4-chloro-5- (4-tert-butyl-methylbenzylthio) -3 (2H) -pyridazinone (Compound No. 72)

22.6 g of (-) - p-tert.butyl-ocmethylbenzyl acetate with -50.9 ° (C = 1 »®g ^ 12 ^ ^o P ^ purity were suspended in 400 ml of 0.2 M aqueous disodium hydrogen phosphate solution. 35.6% ee obtained in Synthesis Example 6 and 1.35 S hen liver acetone powder was added The resulting mixture was digested at 25 ° C for 76 hours The reaction liquid was extracted twice with 400 ml ethyl acetate (insoluble The ethyl acetate layer was dried over anhydrous sodium sulphate and the solvent was removed by distillation. v / v) eluted p-tert.butyl-a-methylbenzyl acetate and then with a 10: 1 benzene / ethyl acetate mixture (v / v) p-tert.butyl-a-methylbenzyl alcohol, and then a solvent was distilled from each eluate Thus, 14.01-g (yield: 62%) of (-) - p-tert.butyl-α-methylbenzyl acetate were obtained with Cajp-85 »5 ⁰ (C = 1.07, 'opt. east 82.6% ee, and 6.25 S (yield: 34%) (+) - p- 41 tert-butyl-α-methylbenzyl alcohol with [α] + + 23.1 ⁰ (C = 1.07. θ6 ^ 12 ^ 'optical purity 47.2% ee

In 33.6 ml of methanol, 13.79 6 (82.6 mmol) of 2 5 o (-) - p-tert.butyl-α-methylbenzyl acetate was dissolved with [from _D -85.5 (0 = 1.07, optical purity 82.6% ee After stirring the solution and cooling it with ice, 21.7 S of 45% aqueous sodium hydroxide solution (sodium hydroxide 81.4 mmol) was added over 5 minutes.

After allowing the resulting mixture to cool to room temperature, it was stirred for one hour and then 100 ml of water and 100 ml of benzene were extracted for extraction. The aqueous layer was re-extracted with 30 ml of benzene. The benzene layers were combined, washed with water, dried over anhydrous sodium sulfate and the solvent removed by distillation to give 10.86 g (yield: 97%) of colorless (-) - p-tert.butylamethylbenzyl alcohol; [from jp - 41.1 ⁰ (C = 1.03, C ^ H ^),

84,0% e.e.

A portion (10.6 g) of the product was recrystallized from 31.8 g of hexane to give 8.20 g of (-) - p-tert.butyl-amethylbenzyl alcohol with [α] -47.8 ^O (C = 1 , 00, ΟθΗ ^), optical purity 97.8% ee

We then performed a procedure similar to the procedure in synthesis case 6. Namely, we performed a metabolism and purification similar to those in synthesis case 6, except that 1.78 g (-) - 4-tert-butyl-oc-methylbenzyl alcohol ( the enantiomer of the product in synthesis case 6) having optical

- 42 rotation (-) and. an optical purity of 97.8% ee instead of 1.78 g of its (+) isomer to give 0.62 g of crystals for the desired compound. According to the H-Nlffl measurement, the compound was identical to the compound obtained in the 5 · melt synthesis case. 102.2 to 106.7 ° C [ref ⁵ - 1.14 ⁰ (C = 1.0, CHCl 2).

Synthesis Example 8:

Synthesis of 2-tert-Butyl-4-chloro-5- [4 '- (4-trifluoromethylphenoxy) -benzylthio] -5 (2H) -pyridazinone (Compound No. 245)

2.2 g (0.01 mol) of 2-tert-butyl-4-chloro-5-mercapto-5 (2H) -pyridazinone and 5.5 S (0.0105 mo) were dissolved in 5θ ml of Ν, dim-dimethylformamide. ) 4- (4'-trifluoromethylphenoxy) benzyl bromide, and 2.1 g (0.02 mol) of anhydrous sodium carbonate were added to metabolize at 85 to 90 ° C for 4 hours. After the reaction, the reaction liquid was allowed to cool, poured into water and then extracted with benzene. The benzene layer was washed with 5% aqueous sodium hydroxide solution and then with water, dried over anhydrous sodium sulfate, and then the benzene was removed by distillation under reduced pressure. N-Hexane was added to the oily residue and the precipitated crystals were filtered to give white crystals (yield: 85.5%) · mp. 152.0 to 155.5 ° C. ¹ H-NMR (CDCl 3, (ppm):

1.60 (9H, s, 2-t-Bu), 4.22 (2H, s, -SCH ₂ -),

6.92 to 7.60 (9H, m, phenyl and 6-H).

- 43 Synthesis Example 9:

Synthesis of 2-tert-butyl-4-bromo-5- (4-tert-butylbenzylthio) -3 (2H) -pyridazinone (Compound No. 139) Dimethylformamide solution 4.4 g of 2-tert-butyl-4-bromo-5-mercapto -3 (2H) -pyridazinone and 4.7 S 4-tert-butylbenzyl bromide were added 3.5 S sodium carbonate. The resulting reaction liquid was stirred at 80 ° C for 4 hours, allowed to cool to room temperature, stirred with water and extracted with benzene. The benzene layer was washed with 3% aqueous sodium hydroxide solution and then with water, dried and then removed with benzene by distillation to give a yellowish brown solid. The solid was recrystallized from a mixed solvent of benzene and n-hexane to give white crystals (yield: 64%).

m.p. 137.0 to 139.0 ° C (ODOip, S ⁷ (ppm):

1.53 (9H, s, 4'-t-Bu), 1.62 (9H, s, 2-t-Bu), 4.21 (2H, s, -SCH ₂ -), 7.33 (4H, m , phenyl),

7.54 (1H, s, 6-H).

Synthesis Example 10:

Synthesis of 2-tert-butyl-4-chloro-5- (4-tert-butylbenzylthio) -3 (2H) -pyridazinone (Compound No. 81)

A mixture of 1.5 6 2-tert-butyl-4-chloro-5-mercapto-3 (2H) pyridazinone, 200 ml of benzene, 1.5 S of anhydrous potassium carbonate and 1.4 g of 4-tert-butyl-benzyl chloride was obtained. metabolized

- 44 at reflux temperature for 6 hours. Then, a procedure similar to that in Synthesis Example 5 was performed to give white crystals (yield: 60%).

The compound thus obtained was, according to measurementA, H-NMR identical to the compound obtained in synthesis case 4.

Synthesis Example 11:

Synthesis of 2-tert-butyl-4-chloro-5- (4-chlorobenzylthio) -5 (2H) -pyridazinone (compound no. 175)

0.7 S of sodium hydroxide was dissolved in ml of water and 100 ml of benzene, 5.5 S 2-tert-butyl-4,5 dichloro-5 (2H) -pyridazinone and 0.15 S triethylbenzylammonium chloride were added. The resulting solution was stirred at room temperature for 2.4 g of 4-chlorobenzyl mercaptan and then stirred for 15 hours. After the digestion was completed, the sano organic layer was separated, washed with 5% aqueous sodium hydroxide solution and then with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. Hexane was added to the resulting oily residue to give crystals. The crystals were filtered off to give 5.3 S of the desired compound (yield:

%).

m.p. 142.0 to 145.0 ° C. ¹ H-NMR (CDO?, <0 (ppm):

1.60 (9H, s, t-Bu), 4.20 (2H, s, -S0H ₂ -),

7.52 (4H, s, phenyl), 7.5θ (1H, s, 6-H)

- 45 Synthesis Example 12:

Synthesis of 2-tert-butyl-4-bromo-5 "( ^with f" tert-butylbenzylthio) -5 (2H) -pyridazinone (Compound No. 139) 0.22 g of sodium hydroxide was dissolved in 5 ml of water and 10 ml was added of dichloromethane, 1.55 S 2-tert-butyl-4,5dibromo-3 (2H) -pyridazinone and 0.05 S triethylbenzylammonium chloride. The resulting solution was stirred at room temperature 0.83 S with 4-tert-butyl-benzyl mercaptan and then stirred for 10 hours. After the digestion was completed, about 50 ml of Cl2 Clg was added to the solution and the organic layer was separated, washed with 5% aqueous sodium hydroxide solution and then with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the resulting solid was recrystallized from benzene / n-hexane mixed solvent to give 1.32 g of the desired compound (yield: 65%).

m.p. 137.0 to 139.0 ° C (CDCl 3, q) (ppm):

1.55 (9H, s, t-Bu), 1.62 (9H, s, t-Bu),

4.21 (2H, s, -SCH ₂ -), 7.33 (4H, s, phenyl),

7.5 (1H, s, 6-H).

Synthesis Example 13:

Synthesis of 2-tert-butyl-4-chloro-5- (4-tert-butylbenzylthio-3 (2H) -pyridazinone (compound no. 81)

0.7 g of sodium hydroxide was dissolved in 15 ml of water and 30 ml of dichloromethane, 3.5 S 2-tert-butyl-4,5di chloro-5 (2H) -pyridazinone and 0.13 S triethylbenzylammonium chloride were added. The resulting solution was stirred at room temperature at 2.7 g of 4-butylbenzyl mercaptan and then stirred for 15 hours. Po

- The 46 completed metabolites separated the organic layer only, washed with 5% aqueous sodium hydroxide solution and then with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the resulting oily residue was mixed with hexane to give crystals. The crystals were filtered off to give 3.8 6 desired compounds (yield:

%).

The physical properties of the compound were identical to those of Synthesis Example 4.

Compounds prepared according to one of the processes in synthesis cases 3 to 10 are listed in Table 3 below. By the way, compounds produced in synthesis cases 3 to 10 are included in Table 3.

TABLE 3

Compounds of Formula I:

EV in Table 3 mentions Me methyl, Et stands for ethyl, Pr 'stands for propyl, Bu stands for butyl, n stands for normal, t stands for tertiary, i stands for iso and s stands for secondary].

Compound šL · ...... ......... ' R R ¹ V R ³ n Tal. (° C) 1 Et H H if 4-t-Bu 123,0-124,5 2 Et H H c 4 4-F 106,0-108,5 4 Et H H cl ^ Q> 140.0-143, 0 14 n-Pr H H cl 4-t-Bu 159,0-161,0 29 i-Pr H H CZ 3 _r 4-C £ 2 181,0-187,0 30 i-Pr H H CZ 4-t-Bu 141,0-142,0 70 t-Bu Me H CZ 4-t-Bu 100,0-106,0 71 optically active compound of no. 70 (+) compounds 102, 3-104, 3 72 optically active number 70 compound () compounds 102: 2-106, 7 73 t-Bu H H CZ .N 170, 0-176, 0 4-0- 74 t-Bu H H CZ 4-0 ^ Z ^N > / V ^CF 1 if T ³ 160, 1-171.5 75 t-Bu H H CZ 4-0- O- «, 112,1-113,5 = / 76 t-Bu H H CZ ^x H i 198, 2-199, 6 4-Cr 'tt 77 t-Bu H H CZ 2-Me 138, 0-139, 0 78 t-Bu H H CZ 3-Me 86,5-87,5 79 t-Bu H H c z 4-Me Π9, 0-120, 0 80 t-Bu H H cz 4-i-Pr K 96,5-98,0 81 t-Bu H H CZ 4-t-Bu 111, 0-112.0 84 t-Bu H H CZ 3,4-C £ ₀ 111, 0-112, 0 87 t-Bu H H ' CZ 4-F 112,5-114,0 88 t-Bu H H c z • A) 157,0-159,0

TABLE 3 (continued)

Compound no. R R ¹ R ² R ⁴ Rn Tal. (° C) 95 t-Bu H H Cit 4- <O) 169,0-171,0 97 t-Bu H H CZ 4-Nr 144, 0-146, 0 101 t-Bu Me H Cit 3-Me 118, 0-119, 0 102 t-Bu Me H Cii 4-Me 83, 0-84.0 103 t-Bu Me H Cit 4-i-? R Cž \ _ 73,0-74,5 104 t-Bu H H Cit 4-0-O-CF, 129,0-131,0 106 t-Bu Me H CZ The score is now 4-0 102,0-104,0 107 t-Bu Me H CZ 4 -No 122,5-123,5 108 t-Bu Me H CZ 4-CJt 98, 5-99, 5 109 t-Bu Me H CZ 0 140, 0-142, 0 110 t-Bu Et H CZ 4-t-Bu oil 112 t-Bu H H CZ 2-NO ₂ 121,0 115 t-Bu Et H CZ 4-C Z oil 126 t-Bu H H CZ 4-OCH ₂ - <0>) -Ct 143,0-146,0 127 t-Bu H H CZ 4-OCH _? - ^^ - Me Me \ _ 120,0-122,2 128 t-Bu H H CZ __ 4-0CH ₂ ^ O) 110, 0-111, 0

TABLE 3 (continued)

Compounds st. R 1 R ^x R ² R ⁴ _n 3 R n Tal. (° C) 129 t-Bu H H Ci. 4-OCH ₂ CH = CH ₂ 59, 0-68.0 130 t-Bu H H Cit 4-SC4H ₉ -n oil 131 t-Bu H H ci. 4-SMe semi-solid 132 t-Bu II II ci. 3-OC.H _n -n 4 9 semi-solid snoV 133 t-Bu H H Cl 4-Si (Me) ₃ 99,6-101,4 134 t-Bu Me H Ct 149,0-150,0 135 t-Bu Me H Ci ⁴ © ^H 118.0-120, 0 136 t-Bu H H Ci 4-SCHF _? 77, 0-77, 5 137 t-Bu H H Ci 4-OCH CH ₂ CH ₂ CZ semi-solid 138 t-Bu II H Ci 4-OCHF ₂ 75,0-78,0 139 t-Bu H H Nr 4-t-Bu 137.0-139, 0 140 t-Bu H H Nr 4-Ci. 163,0-165,0 141 t-Bu H H CJt 4- <f 68,0-68,3 142 t-Bu H H CJt 4-C (Me) ₂ CH ₂ C £. 127, 0-129, 0 143 t-Bu II. H Cit 4-OCHC (Me) = CH ₂ 98,6-100,0 144 t-Bu H H ci. 3,5- (t-Bu) ₂ , 4-OH 164.7-166, 3 145 t-Bu H H C £ 3,5- (Br) ₂ , 4-OH 191,7 193,4 146 t-Bu H H Nr ⁴ <E> 147,0-152,0 14 7 and t-Bu H H Nr 4-nC ₄ H _g L -. _. 84, 0-86, 0 l

- 50 TABLE 5 (continued)

Compound no .. R R ¹ R ² R ⁴ R ³ n Tal. (° C) 148 t-Bu H H Nr 4-OC ^ H, -, - n 6 13 71 * 0-73.0 149 t-Bu He H Nr ⁴ XQ> oil 150 t-Bu H H Cl 4-N (Me) ₂ 136, 5-140, 0 151 t-Bu H H C2, 3-OMe, 4-OPr-i 86, 0-88.0 152 t-Bu H H C £ 4-1 117, 0-118.0 153 t-Bu H H Cl 4-OEt 90, 0-91.0 154 t-Bu H H Cl 4-OC ₃ H ₇ -n 105,0-106,0 155 t-Bu H H Cl 4-i-Bu 125,0-129,0 156 t-Bu H H Cl 4-n-Bu 92,0-94,0 157 t-Bu H H Cl 4-- ^c 6H ₁₃ 304,0-106,0 158 t-Bu H H Cl 4-nC _? H ₁₅ / semi-solid (position 4 80%, position 2 20%) ' 159 t-Bu H H Cl ⁴ ~ ⁿ “ ^C 8 ^H 17 55, 0-65.0 (position 4 70%, position 2 30%) 160 t-Bu H H ci 4 sec. -I will 95, 0-97.0 161 t-Bu H H Cl 4-t-C.H .. o 11 142,0-143,0 162 t-Bu H H Cl 4-COOMe 117, 0-122.0 163 t-Bu H H Cl 4-OPr-i 131, 0-132, 5 164 t-Bu H H Cl 4-OCH ₂ CH (Et) Bu-U oil 165 t-Bu H H Cl ⁴ “ ^OC 9 ^H 19 ' ⁿ oil 166 t-Bu H H Cl ⁴ - ° ^C IN ^H 23- ⁿ oil

- 51 TABLE 5 (continued)

Compound St. R R ¹ R ² R ⁴ R ³ n Tal. (° C) · 167 t-Bu Me H CS 4- ° ^c 10 ^H 21-n oil 168 t-Bu H H CS 4-OC ₄ H ₉ -n 89,0-89,5 169 t-Bu H ' H CS 4-OC ₅ II ₁₁ -n 88,0-88,5 170 t-Bu H H CS 4-OC ₆ ^H and ₃ -n 85.0-86, 0 171 t-Bu H H CS 4-OC ₇ H ₁₅ -n 77,0-78,0 172 t-Bu H H CS 4-OCgH ^ ₇ ~ n 64, 0-66.0 173 t-Bu H H CS 2,6- (Me) 2> 4-t-Bu 207.0-208, 5 174 t-Bu H H CS 3,5-Br ₂ , 4-OPr-i 46, 0-48.0 175 t-Bu H H CS 4-CS 142, 0-143, 0 176 t-Bu H H CS 4-CFg CS \ _ 125,0-127,0 177 t-Bu H H CS 4-ΟΟΗ ₂ -φ) 132,0-133,0 178 t-Bu H H CS 4-CH ₂ - (5) oil 179 t-Bu H H CS 4-OCH (MejCOOEt 111,0-113,0 180 t-Bu H H CS 4-OCH ₂ CH = CH-Me 64.0-66, 0 181 t-Bu H H CS 4-SCN 104, 5-109.0 216 Et H H CS 4-0 ^ 0) -CF ₃ 127, 0-131.0 224 i-Pr II H CS 4-OH @> - CF ₃ 133, 0-135, 0 227 n-Pr H II CS «-O- (5 / cf ₃ 137, 0-140.0

- 52 TABLE 3 (continued)

Sggjina R R ¹ R ² R ⁴ R ³ n Tal. (° G) 243 t-Bu H H cs ^ -o / o / cFj 152.0-155, 5 CZ 244 t-Bu H H cs 4-O ^ -CF ₃ 109, 0-110, 0 245 t-Bu Me H cs 4 —O - ^^^^ - Bu— t oil 246 t-Bu H H cs 4i ₀ - (O> -01 146.0.-147, 0 249 t-Bu H H cs oil 260 t-Bu H H cs 4-O4g> CH ₂ CS i '20 ile (n _D 1 6073)

- 53 When using compounds according to the present invention for insecticidal, acaricidal and / or fungicidal agents for agricultural and horticultural purposes or for exterminating agents?

animal parasites, generally mixed with suitable carriers, e.g. solid carriers such as clay, talc, bentonite or diatomaceous earth, or liquid carriers such as water, alcohols (eg methanol and ethanol), aromatic hydrocarbons (eg benzene, toluene and xylene), chlorinated hydrocarbons, ethers, ketones, acid amides (e.g. dimethylformamide) or esters (e.g. ethyl acetate). If desired, emulsifiers, dispersing agents, suspending agents, penetrating agents, spraying agents, stabilizers and the like can be added to these mixtures to put them into practical use in the form of a liquid preparation, emulsifiable concentrate, wettable powder, powder, granules, liquids or sub. . In addition, other herbicides, various insecticides, bactericides, plant growth regulators and / or synergists may be present in the mixture ^{in <} ^ ® ^ ^a during their preparation or use.

The amount of compounds of the invention to be used as an active ingredient is suitably in the range of 0.005 to 5 kg per hectare, although it varies depending on the place and time of use of the compounds, methods of use, diseases and harmful insects in which they are used , Polish crops to be protected, and under ..

The following are examples of formulations of fungicidal, insecticidal and acaricidal preparations and exterminant parasite preparations for animal ticks, these compositions comprising the compound of the present invention as the active ingredient. These examples are for illustrative purposes only and not to limit the invention. In the following cases, the part means the mass part

Formulation Example 1: Emulsifiable concentrates active ingredient ... 25 parts xylene ... 55 parts

N, N-dimethylformamide ... 20 parts

Solpol 2680 (trademark, a mixture of non-ionic surfactant and anionic surfactant, manufactured by Toho Chemicals, Co.,

Ltd., Japan) ... 5 parts

The above ingredients are thoroughly mixed together to form an emulsifiable concentrate. When used, dilute the emulsifiable concentrate with water at a concentration of 1: 500 to 1:20 000 and apply in an amount of 0.005 to 5 kg of active ingredient per hectare.

Formulation Example 2: Wetting Powders

Active ingredient ... 25 parts

Siegreit PFP (Trademark, kaolin based clay, manufacturer Siegreit Mining Industries Co *, Ltd.) ... 69 parts

Solpol 5059 (trademark, a mixture of ndcnske8 surfactant and anionic surfactant, manufactured by Toho Chemical Co.,

Ltd., Japan) ... 5 parts

- 55 Carplex (Blank Marks, Coagulation Anti-Aggregate, Mixture of Surfactant and White Sessions, Manufacturer Shionogi Seiyaku K.K., Japan ^ ... 3 parts.

The above ingredients are mixed homogeneously and ground to form a wettable powder. When used, dilute the wettable powder with water from 1: 500 to 1:20 000 and apply in the amount of 0.005 to 5 kg of the active ingredient not hectare.

Formulation Example 3 ^: Oily solutions

Active ingredient ... 10 parts

Methylcellosolve ... 9θ parts.

The above components are homogeneously mixed to form an oily solution. Apply an oily solution of 0.005 to 5 kg of active ingredient per hectare when used.

Formulation Example 4: Dust

The active ingredient ... 3, θ works

Carplex (trademark, anti-coagulation agent as mentioned above) ... 0.5 parts clay ... 95.0 parts diisopropyl phosphate _t 1.5 parts.

The above ingredients are homogeneously mixed and ground to form a powder. When used, powder is applied in an amount of 0.005 to 5 kg of active ingredient per hectare.

- 56 Formulation Example 5: Granules

Active ingredient ... 5 parts bentonite ... 54 parts talc ... 40 parts calcium lignin sulfonate ... 1 part

The above ingredients are thoroughly mixed and ground, mixed with a small amount of water and mixed while stirring. The resulting mixture was granulated using an extrusion granulator and dried to form granules. Granules in the amount of 0.005 to 5 kg of active ingredient per hectare are applied.

Formulation Example 6: Liquid preparations

Active ingredient ... 25 parts

Solpol 3355 (brand, non-ionic surfactant, manufacturer)

Toho Chemicals, Co., Ltd., Japan) ... 10 parts

Lunox 1000C (trademark, anionic surfactant, manufacturer of Toho Chemicals, Co., Ltd., Japan) ... 0.5 parts aqueous xanthan gum (natural high molecular weight compound) ... 20 parts water .. .44.5 parts.

The above ingredients, except the active ingredient, are mixed uniformly to form a solution, and to this the active ingredient is added. The resulting mixture was thoroughly mixed, wet-milled using a sand mill to form a liquid preparation. When used, dilute

- 57 Liquid preparation with water 1:50 to 1:20 000 and applied in an amount of 0.005 to 10 kg of active ingredient per hectare.

The compounds of the present invention not only show a stronger insecticidal effect on Hemiptera insects, such as ricehopper (Nephotettix cincticeps), Lepidoptera, such as Plutella xylostella, and sanitary insects such as Culex pipiens mosquitoes, but are also useful for parasite extermination and vegetables such as red spider Tetranychus urticae, Tetranychus kanzawai, Tetranychus cinnabarinus, Panonychus citri and Panonychus ulmi, as well as parasitic ticks on animals such as Boophilus microplus, Boophilus annulatus, Amblyomma maculatum, Rhipicephalus appendiculatus and Haem8physalis longicornis. The main feature of the compounds of the present invention is that the compounds are useful for preventing or controlling plant rust (or disease) on fruits and vegetables such as Sphaerotheca fuliginea, Pseudoperonospora cubensis, etc., in addition to having the aforementioned insecticidal, acericidal and fungicidal effects. Accordingly, the compounds of the present invention are excellent agri-cultural agents that allow pest and plant rust (or disease) control at the same time. In addition, they are excellent as a means of eradicating parasitic ticks on animals such as pets (eg cattle, horses, sheep and pigs ^, domestic poultry and other animals such as dogs, cats, rabbits, etc.).

The invention will be further explained by the following test examples.

- 58 Test Example 1: An insecticide test on adult domestic flies (Musca domestica) ml of acetone solution containing 1000 ppm of the test compound of the invention was dropwise applied to a 9 cm diameter laboratory beaker by distributing the solution evenly over cups. After the acetone had completely evaporated at room temperature, we placed 10 adult house flies in a cup and covered the cup with a plastic cap fitted with a few holes. The cup containing the nozzle was placed / thermostated chamber which was maintained at

25 ° C. The assessment was carried out after 48 hours by counting the killed dead insects and calculating the mortality of the insects according to the following formula mortality (%) = number of killed insects' number of animals per animal ^{x 100}

By the way, the test was repeated twice for each compound. The test results are listed in Table 4.

Test case 2: Insecticide test on Culex pipiens larvae

200 ml of an aqueous solution of 10 ppm of each compound of the invention was placed in a tall cup 9 cm in diameter and 6 cm high. We then dropped into each cup 10 Culex pipiens larvae in the posterior stage. The high cup was placed in a thermostatic chamber maintained at 25 ° C and counted after 96 hours. Mortality was determined as in test case 1.

- 59 The above test was repeated twice for each compound. The results are shown in Table 4.

Test case 3: Contact insecticide test for Plutella xylostella

The cabbage leaf was immersed for about 10 seconds in an aqueous emulsion containing 1000 ppm of each compound of the invention and then air-dried. The leaf thus treated was then placed in a cup, into which 10 Plutella xylostella larvae in the second stage were dropped. The cup was fitted with a lid that had a few holes and was then placed in a thermostatic chamber maintained at 25 ° C. In the same manner as in test case 1, we determined Plutella xylostelle mortality after 96 hours. By the way, the test was repeated twice for each compound.

The test results are shown in Table 4.

Test Example 4: Contact Insecticide Test on Henosepilachna vigintioctopunctata

The tomato leaf was immersed in an aqueous emulsion containing 1000 ppm of each compound of the invention and then air-dried. The leaf thus treated was placed in a laboratory cup into which 10 larvae of Henosepilachre vigintioctopunctata were dropped in the second stage. The cup was then covered with a cap fitted with holes and then placed in a thermostated chamber, maintained at 25 ° C. The number of destroyed larvae was controlled after 96 hours and their mortality was determined

- 60 in the same manner as in test case 1. Incidentally, the test was repeated twice for each compound.

The test results are shown in Table 4.

Test case 5: Acaricidal test on Tetr8nychus kanzawai

A 1.5 cm diameter round cutter was cut from a sheet of low beans and then placed on a moistened filter paper which was given / a 7 cm diameter styrene beaker. Each piece of leaf was inoculated with 10 Tetranychus kanzawai bugs. Half a day after inoculation, a 2 ml aqueous emulsion containing 1000 ppm of the compound of the invention was sprayed onto each styrene beaker using a rotary spray column diluted with a spray. The number of killed beetles was checked after 96 hours and the mortality was determined as in test case 1. Incidentally, the test was repeated twice for each compound.

The results are shown in Table 4.

Test Example 6: Acaricidal test on Panonychus citra

A round piece of 1.5 cm diameter was cut from the mandarin leaf with a punch and then placed on moistened filter paper, which was placed on a 7 cm diameter styrene beaker. Each piece of leaf was inoculated with 10 beads of Panonychus citri. Half a day after inoculation, a 2 ml aqueous emulsion containing 1000 ppm of the active substance with the spray was applied to each styrene beaker using a rotary spray column. The number of killed beetles was checked after 96 hours and the mortality was determined as in test case 1.

The results are shown in Table 4.

Test Case 7: Insecticide test on Nephotettix cincticeps

The stems and leaves of p8ddy rice were immersed for 10 seconds in an emulsion of 1000 ppm of each compound of the invention, and then the stems and leaves were placed in a glass cylinder. cover the glass cylinder with a lid that had a few holes and place it in a thermostated chamber which was maintained at 25 ° C. 96 hours later, mortality was determined as in test case 1. Incidentally, the test was repeated twice for each compound.

The results are shown in Table 4.

Test Example 8: Nonmeticidal test for Meloidogyne spp.

Finger infected with Meloidogyne spp. _; was placed in an 8 cm diameter styrene beaker. A liquid containing 1000 ppm of active ingredient was prepared by diluting the emulsifiable concentrate according to the present invention with water and then spraying it. The nematode-infected finger, which was placed in a styrene beaker, was impregnated with 50 ml of the resulting fluid. After 48 hours, we transplanted tomato seedlings into the treated soil as an indicator. We are roots 30 days after the transplant

- 62 tomatoes were washed with water and root parasitism checked by observation and evaluation in accordance with the following assessment:

Assessment of root parasitism

... no nodes are seen at the roots

... there are some knots on the roots

... the mean number of nslsorenin nodes is observed

... there are many knots at the roots

... a lot of knots are seen on the roots.

By the way, the test was repeated twice for each compound. The results are shown in Table 4.

Test Case 9: Pseudoperonospora cubensis suppression test on cucumbers

Cucumbers (Cucumis sativus L.: var. Sagamihanjiro) were used and were grown for about 2 weeks. They were sprayed with a solution of the emulsifiable concentrate according to the invention which was adjusted to a predetermined concentration (1000 ppm) in an amount of 20 ml per crucible. After placing each crucible overnight in the greenhouse, the cucumbers were sprayed with Pseudoperonospora cubensis spores for inoculation (with spore concentrations such that 15 individual spores were visible under microscope magnification at 150 times magnification). Cucumbers inoculated with Pseudoperonospora cubensis spores were left in a 25 ° C and 100% relative humidity room for 24 hours and then transferred to observe the disease on the greenhouse.

- 63 7 days after inoculation, percentages of disease onset were measured and evaluated according to the following assessment:

... is not a disease

... onset of disease in no more than 5% of inoculated leaves

... onset of disease in 6 to 20% of inoculated leaves

... onset of disease in 21 to 50% of inoculated leaves

... onset of disease in 51 to 90% of inoculated leaves

... onset of disease in not less than 9% of inoculated leaves,

The results are shown in Table 5-1 ·

Test case 10: The test for the destruction of Sphaerotheca fuliginea does not pickle

We used cucumbers (Cucumis sativus L.: var. Sagamihanjiro) grown in pots for about 2 weeks and then sprayed with a solution of emulsifiable concentrate of the present invention that was adjusted to a predetermined concentration of 20 ml. on the pot. After placing each crucible overnight in the greenhouse), the cucumbers were sprayed onto the inoculation with a suspension of Sphaerotheca fuliginea spores (with spore concentration such that 25 individual spores were visible under observation at 150 × magnification with a microscope). To monitor the onset of the disease, cucumbers were placed in 25 to 30 ° C plants. 10 days after inoculation, percentages of disease onset were measured and evaluated according to the same assessment as in test case 9 ·

- 64 The results are shown in Table 5-H ·

We will now explain in detail the following, by way of the following test examples, the extrinsic effect of the compounds of the invention on the gastropods in animals.

Test case 11: Acaricidal test ns Haemaphysalis longicornis

An acetone solution of 1000 ppm of the compound of the invention was prepared and, as a control, an acetone solution. A cylindrical filter was fitted inside the cylindrical glass vessel (2.8 cm in diameter and 10.5 cm in height) as a test vessel, which had an internal filter

2 area 142.9 cm, lateral area 130.6 cm and total p

the surface of the bottom and the lid being 24.6 cm, the filter being previously immersed in one of the solutions mentioned above and then sufficiently dried. After dropping 20 bub into this test container, we provided the filter with a lid fitted with a filter and covered with a cotton stopper. After a predetermined time, the filter was removed from the vessel, illuminated using a microscopic capacitor under a binocular stereomicroscope, and the movement of the ticks body and legs was observed. The evaluation of live and dead ticks was performed by considering ticks that move the body and legs as alive.

By the way, the tested tick is a tick-free beetle of a tick that was incubated from an egg hatched by an adult parthenogenetic female tick of the Haemaphysalis longicornis tick of the Okayama strain, which was previously allowed to drink from rabbit domestic blood.

The results are shown in Table 6.

Table 4

* P xa 4) fl • H • O Oh o. <Q Musca domestica (1000 ppm) Culex pipiens (10 ppm) 03 t — and r — 4 Φ Ul o T— <S > CL X cx ca o r-4 O i-4 C3 OJ r-4 ul □ <—4 O-. <Ie u) <0 4-J a «C -c s e .c a, o. a o c. G u r-1 G O • H O O £ j'H O <3J 4-1 -). Λ C About t4 g ca. O · Η => ra 'e ϋ o. rt o. ϋ U _o b® § dso <0 CO ri dn (£ di ra a • H Ul Ui rt Z — S D 6 1 (Λ O. ³ x | o U | O ds o GJ X ω cx φ in Ή Ul U c • H U X • H Ul Ul a) Ul Oh X Ο- Ο Z (1000 ppm) Meloidogyne sp. (1000 ppm) 1 100 100 100 100 100 100 100 0 4 100 100 100 100 90 100 100 1 14 - 65 95 100 95 100 100 ¹ 70 100 100 100 100 100 100 100 0 72 100 100 100 100 100 100 100 0 73 - - - 100 100 100 - 0 75 100 100 - 100 100 100 100 0 78 70 90 80 100 100 100 100 0 79 75 95 85 100 100 100 100 0 80 100 100 100 100 100 100 100 0 81 100 100 100 100 100 100 100 0

Table 4 (continued)

• P KQ Φ a Ή T3 Oh P · 02 Musca domcstlca. (1000 pptn) Culex pipiens (10 ppm) a r-H e) o rH β a. Xf cx <3 O ΓΜ O rH O O r- ( M 3 »-4 Henosepilachna vigintioctopunctata (1000 ppm) OT a ^e λ S «• H> jC0 o ® ® 2 PN d · Pd Φ® • n U P4 o S cu 2 x o u o C jr-1 Oh c <3 P- □ 3 Cm (U in Ή U a c * T- » U X Ή U 4-J 0) in o τ- Ή- φ z (1000 ppm) 4 tn E ai ct c c. hi o o TJ o • rt irt Oh rrt a) s 84 100 100 100 75 100 100 100 1 87 100 100 100 100 100 100 100 1 88 100 100 100 100 100 100 100 0 95 100 100 100 100 100 100 100 0 97 80 90 100 100 95 100 100 0 101 100 100 100 100 70 100 100 0 102 100 100 100 100 100 100 100 0 103 100 100 100 100 100 100 100 0 104 100 100 100 100 100 100 100 0 106 100 100 100 100 100 100 100 0 107 100 100 100 100 85 100 100 0 1 108 j 100 100 100 100 100 100 100 0

- 67 Table 4 (continued)

• • P XQ Φ ΰ H Ό Oh P * CQ Musca doir.es you ca. (1000 ppm) Culex pipiens. (10 ppm) rt garden 1-4 Oh w 0 i-H 2 > <O. X | Λ rt (O irt iO, rrt | O D rrt 4-1 □ t — M lenosepi lachna vigintioctopunctata (1000 ppm) ra o Λ | · · Η &? § ra ra 3 A M <hour E4-M ' • rt U -rd z— \ υ e Cu »2 ⁰⁴ -C ouo> iO o« «rt V) O- ω in -rt U □ C • rt U X • rt U m) U Oh Έ- rt z; (1000 ppm) Meloidogyne sp. (1000 ppm) 109 100 100 100 100 100 100 100 0 110 - | 70 90 100 100 100 0 115 100 100 85 70 90 100 100 1 126 - 100 - 100 100 100 100 1 127 - 100 - 100 100 100 100 1 128 - 100 - 100 100 100 100 0 129 100 100 100 100 100 100 100 0 130 100 100 100 100 100 100 100 0 131 100 100 - 100 100 100 100 0 132 100 100 100 100 100 100 100 0 133 100 100 - 100 100 100 100 0 134 100 100 100 100 100 100 100 0

Table 4 (continued)

• 43 «O Φ d • H t * 3 Oh P> CQ C3 C ε Ώ CU Φ O. ε O O ^! Q O (tf rri U X X M r * C δ cU o. 'SJ ° · X | 2 Ol'- ' ul Plutella xylostella (1000 ppm) fl3 AJ AJ C (Ϊ C c z; s X ct ου 0 CL C3 Ari rri C O • H O G O. Ή O O -U r-i c 0 three C co 0) · £ CQ -X 0 1 § d% Ov4 h® lo d> jo toro o A »d ¹ « uro 1 £ 444 i three | l-i Ari - · ίο C | 5 o. ω c □ X o o O> sO C -ri. o <- cu Ifl o. Φ in three Ari C C three C X three Ari Ari C Ari Oh t * · * Ή. OJ ΞΪ χ-χ Mr Rücker Ou & Oh o o rri Χ-Χ Meloldogyne sp, (1000 ppm) 135 100 100 100 100 100 100 100 0 136 100 100 - 100 100 100 100 0 137 100 100 100 100 100 100 100 0 138 100 100 100 100 100 100 100 0 139 - - - 100 100 100 100 0 141 100 100 - 100 100 100 100 0 142 100 100 - 100 100 100 100 0 143 - 100 - 100 100 100 100 0 146 100 100 - 100 100 100 100 0 147 - 100 - 100 100 100 100 0 143 100 100 - 100 100 100 100 0 149 100 100 100 100 100 100 100 0

- 69 Table 4 (continued)

• • P > w ω (4 • H T3 Oh P » QQ «3 U - »- i in g W CL a £ 0 o 73 C About ca i-i a 2 X 0) c Ci T-l 2 Ct Q • H C. eU o X r — 1 4J r * H □ Oh ca. i — 4 r — 1 a 4-1 0) Oh i-ι e> cx X cx Hello r-1 | O 1—1 I O O r-4 -J cl, 1 ilenosepi lachna vigintioctopunctata (1000 ppm) » 3 1 = · O. O-H k, ® „rt> g« C0! O P NI'- ' -p D (D i en mi • »4 4J * 1 * 4 υ e o. 03 C- and O In O p ^ o C —1 C '' S <5 - i [Nephotettix cincticeps? (1000 ppm) Meloldogyne sp. (1000 ppm) 150 100 100 -. - 100 100 100 1 151 100 100 100 100 100 100 100 0 152 - 100 - 100 - 100 100 0 153 100 100 100 100 100 100 100 0 154 100 100 100 100 100 100 100 0 155 100 100 100 100 100 100 100 0 156 100 100 100 100 100 100 100 0 157 100 100 100 100 100 100 100 0 158 100 100 - 100 100 100 100 0 159 100 - - 100 100 100 100 0 160 100 100 - 100 100 100 100 0 161 100 - - 100 100 100 100 0

Table 4 (continued)

« p no § • H • m Oh £> ca. d υ • rt '' 'o 4 ~> S Cft CL O SL p: 0 o o o o o Draw (J, Cfl Cfl c •no (X £ X -H O. Oh Oh X rH OJ ' t— ( 3 Oh 'Plutella xylostella (1000 ppm) .Henosepilachna vigintioctopunctata (1000 ppm) co g 'e ^ 3 o. O-H O. t * i <0 0 ° me § f4 N r-l P d Φ co. • rt rt in • rt α ε CL o) a. 3 & O a o C rrt Oh c C0 (rt and sd33T5auya χτη3ΐοΐ {α3ψ 1 j ................ '' ¹ 1 (uidd 0001) Meloidogyne sp. (1000 ppm) 162 100 100 - - - - 100 0 163 100 100 100 100 100 100 100 0 164 100 100 - 100 100 100 - 0 165 100 100 - 100 100 100 100 0 166 - 100 100 100 100 100 0 167 - - 100 100 100 100 100 0 168 100 100 100 100 100 100 100 0 169 100 100 100 100 100 100 100 0 170 100 100 100 100 100 100 100 0 171 100 100 - 100 100 100 100 0 172 100 100 - 100 100 100 100 0 174 100 100 1 100 100 0

Table 4 (continued)

& Φ rt • rl T3 Oh P * CQ this one in • H in Ξ CO Cl D O- e o o • o o, O <9 Jr-i In j '*' w □ Culex pipiens. (10 ppm) Plutella xylostella. (1000 ppm) , Henosepilachna viglntloctopunctata. (1000 ppm) ca d ^Ξ rt o. c, OM H® o co a 2 rt NO • p «φ ra Panonychus citri (1000 ppm) (Λ 0- Φ U • Ή • U C C Oh X • H LJ LJ Φ U Oh X CL, o (rndd 0001) J cnp ~ - E OJ o. e o. 600 o o o o • H r — i Oh <U s 176 - 100 100 100 100 100 100 0 177 - 100 100 100 100 100 100 0 178 100 100 - 100 - loo 100 - 180 100 100 100 100 100 100 100 0 216 100 100 100 100 70 100 100 1 224 100 100 95 100. 100 100 100 1 227 100 100 95 100 100 100 100 0 243 100 100 100 100 100 100 100 0 244 100 100 100 100 100 100 100 0 245 100 100 100 100 100 100 - 0 246 - - - - 100 100 100 0 249 100 100 95 100 100 100 100 1

- 72 Table 5-1 (Pseudoperonospora cubensis suppression test)

Compounds no. The rate of occurrence will- | creep (1000 ppm) ' 1 0 4 0 30 0 81 0 95 0 97 0 102 0 70 0 109 0 127 0 131 0 Ϊ34 0 136 0 138 0 152 0 153 0 176 0 181 0 '227 0 243 0

- 73 Tables 5-11 (Sphaerotbeca fuligine harvesting test)

Compound no. Occurrence rate (1000 ppm) 1 0 78 0 80 0 81 0 87 0 95 0 70 0 112 0 133 0 138 0 139 0 141 0 149 0 176 0

- 74 Table 6

Acaricidal test for Haemaphysalis longicornis

Compound no. Concentration Benches destroyed after treatment (%) solutions (ppm) 24 hours after processing 48 hours after processing 70 1,000 100 100 81 1,000 100 100 106 1,000 100 100 109 1,000 100 100 Control (Only eceton) - 0 0

• _v

An indication of the best, applicant-known way to economically Utilize the claimed invention

Synthesis of 2-tert-butyl-4-chloro-5- (4-tert-butylbenzylthio) 3 (2H) -pyridazinone

2.0 g of 2-tert-butyl-4-chloro-5-mercapto-3 (2H) -pyridazinone were dissolved in 15 acres of Ν, dim-dimethylformamide and 1.3 g of anhydrous sodium carbonate was added and

1.6 g of 4-tert.butylbenzyl chloride. The resulting mixture was heated to 80-100 ° C for 2 hours while stirring. After allowing it to cool to room temperature, 100 ml of water was added to the mixture and then stirred. The precipitated solid was filtered off, washed with water, dried and recrystallized from ethanol to give white needle crystals having the following physical characteristics (yield 87.9%):

mp: 111.0 to 112.0 ° C. ¹ H-NMR (CDCl 3, S (ppm):

1.29 (9H, s, 4'-t-Bu), 1.60 (9H, s, 2-t-Bu), 4.21 (2H, s, -SCH ₂ -), 7.32 (4H , m, phenyl), 7.61 (1H, s, 6-H).

For

Claims (1)

PATENT APPLICATION A process for preparing a 3 (2H) -pyridazinone derivative of general formula (I) 1 in which R is straight or branched alkyl, R and R are each independently hydrogen or alkyl, R is chlorine or bromine, R is halogen, straight or branched (C 1 -C 6 alkyl, C 1 -C 8 cycloalkyl which is unsubstituted or substituted by lower alkyl, straight or branched C 1 -C 4 alkoxy, haloalkyl, C 1 -C 4 haloalkoxy, -NO 4, (where X is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl and m represents 0 or an integer 1 or 2, wherein these X are the same or different if m is an integer 2), pyridyloxy which may be substituted by halogen and / or -CF2, quinoxalyloxy which may be substituted by halogen and / or -CF 4, C 1 -C 4 alkenyloxy, C 1 -C 4 alkylthio, halomethylthio, -Si (CH ₂ ) ₂ , -OH, -N (CH ₃ ) ₂ , -SCN, -COOCH ₃ or -OCH ( CH ^ COOC ^ and n denote an integer from 1 to 3, where R is the same or different if n is an integer 2 or 3, - 7f characterized in that a compound of general formula IIA (IIA) wherein R and R have the same meanings as defined in formula I and Y is -SH or halogen is reacted with a compound of general formula IIIA (IIIA) 1 2 3 wherein R, R, R and n have the same meanings as defined above and Z is halogen or -SH, where Z is halogen if Y in formula IIA is -SH and Z is -SH , if Y is halogen, in a solvent selected from the lower alcohols, ketones, aromatic hydrocarbons, ethers, amides, halogenated hydrocarbons in inorganic bases or organic bases or mixtures of these solvents with water in the presence of a hydrogen halide acceptor in the absence or presence of a quaternary catalyst salts at the reaction temperature between room temperature and the boiling point of the solvent. For NISSAN CHEMICAL INDUSTRIES, LTD. 18985-VIII-86-MS