JPS59137462A - Novel pyrazoline derivative and insecticide - Google Patents

Abstract

NEW MATERIAL:A pyrazoline derivative shown by the formula I [X is halogen, lower alkyl, or alkoxyl; Z is halogen, CF3, A-R<1> (R<1> is lower alkyl replaced with halogen; A is O, S, sulfinyl, or sulfonyl); R is H, lower alkyl, alkenyl, or alkynyl]. EXAMPLE:1-( 4-Chlorophenylcarbamoyl )-3-phenyl-4-( 4 -difluoromethoxyphenyl )-2- pyrazoline. USE:An insecticide. Exhibiting effect on young and oil larvae. PROCESS:A 4-(4-difluoromethoxyphenyl)-2-pyrazoline derivative (novel substance) shown by the formula II is reacted with a phenyl isocyanate shown by the formula III [Z<1> is halogen, CF3, A-R<1> (R<1> as shown for R; A is O or S)] in an inert solvent or in the absence of a solvent, to give a compound shown by the formula I where Z is Z<1>.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel pyrazoline derivative, a method for producing the same, and an insecticide containing the derivative as an active ingredient.

Through many years of research and development into insecticides, a wide variety of insecticides have been put into practical use, and these insecticides have contributed to improving the productivity of agricultural and horticultural crops. However, even today, there is a demand for the development of new drugs with more excellent insecticidal properties, and the present inventors have been conducting extensive research on the insecticidal activity of pyrazoline compounds with the aim of developing new and useful insecticides. As a result, the general formula [■]: R (wherein, X represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxyl group.

2 is a halogen atom, a trifluoromethyl group, or A-
R' represents a hydrogen atom, a lower alkyl group, an alkenyl group or an alkynyl group. However, fl represents an oxygen atom, a sulfur atom, sulfy-A46, or a sulfonyl group, and R+ represents a lower alkyl group substituted with a halogen atom. The present invention was completed by discovering that a novel pyrazoline compound represented by n has excellent insecticidal activity.

As a conventional pyrazoline compound, JP-A-48-8702
No. 8, JP-A-51-41358, JP-A-52
JP-A-87166 and the like describes that 1-carbamoyl-2-pyrazoline compounds can be used as insecticides.

However, one compound of the present invention, namely the general formula [1
The compound represented by ] is a novel compound discovered for the first time by the present inventors, which has not been described in any two literatures.

The compounds of the present invention can generally be synthesized by the method shown in the reaction formula below.

(In the formula, X is according to the above definition, z゛ is a halogen atom,
Indicates a trifluoromethyl group or an AI-R1 group. However, A' represents an oxygen atom or a sulfur atom, and b' represents a lower alkyl group substituted with a -.roken atom. (In the formula, X or R' is according to the above definition, tl: 1
Indicates 1 or 2. ) (In the formula, X or 2 is according to the above definition, R represents a lower alkyl group, alkenyl group, or alkynyl group, and Y represents a halogen atom.) That is, in the general formula m [, R is a hydrogen atom and when A represents all oxygen atoms or sulfur atoms, 2 formulas (formerly represented by f 4-(4-difluoromethoxyphenyl)-2-pyrazoline derivatives and general formula (f) represented by phenyl isocyanate and It is obtained by reacting all reactants in the presence, -1: or absence of an inert solvent.

Examples of the reaction solvent include ethyl ether.

Benzene, toluene, acetonitrile, hyridine, dichloromethane, chloroform, carbon tetrachloride, etc. can be used.

The reaction temperature and reaction time can vary widely depending on the starting materials, but generally the reaction temperature is around 0°C.
~100°C2 The reaction time is preferably 0.5 hours to 24 hours.

Also, general formula [! ], when R represents a hydrogen atom and 8 represents a sulfinyl group or a sulfonyl group,
n represented by the general formula [1-B] obtained by the above method
The compound is obtained by oxidizing the compound with an oxidizing agent such as hydrogen peroxide-acetic acid or methachloroperbenzoic acid.

Furthermore, when R in general formula [I] represents a lower alkyl group, alkenyl group or alkynyl group, R'-Y Halogenated hydrocarbons represented by 4 For example, alkyl iodides, alkyl bromide compounds (?ll
(e.g. methyl iodide, ethyl iodide, ethyl bromide, etc.) or alkenyl bromide compounds (e.g. allyl bromide) or alkynyl bromide compounds (e.g. glopargyl bromide) in the presence of a base (e.g. sodium hydroxide). It is obtained by

In the above reaction formula, the starting compound 4-(4-difluoromethoxyphenyl)-2-pyrazoline derivative represented by the formula [■] is also a new compound that has not been described in the literature, but these compounds are generally as follows. It can be synthesized according to the reaction formula.

['V] [
'V] (wherein,
4-difluoromethoxybenzyl ketone represented by general formula [v] is obtained.

Next, formaldehyde is reacted in an acidic medium in the presence of a solvent and a catalyst, and the resulting product [Vl] is reacted with hydrazine in the presence of an alcohol such as ethyl alcohol or globyl alcohol to form a product [Vl] of the general formula [ A 2-pyrazoline derivative represented by n is obtained.

The method for producing 4-difluoromethoxybenzyl ketone represented by the general formula [v] is limited to the method described above.
Many methods are possible).

For example, a first-order reaction formula is exemplified.

(5) General formula [V] [where X is a chlorine atom [V-Δ]] In addition, the general formula n obtained by these reactions [2-pyrazoline derivatives shown in Although it can be purified, it is often an unstable compound and will decompose if left at room temperature.

Therefore, some compounds need to be stored at low temperatures under an atmosphere such as nitrogen. Practically speaking, in order to obtain the compound of the present invention represented by the general formula [1-A], these 2-pyrazolines [
(2) It may be reacted with the phenyl isocyanate derivative represented by the general formula [111] by the reaction described above without carrying out complete isolation and purification.

The compounds of the present invention are all listed in Table 1 below.

The present invention is not limited to these vcs.

Table 1 Note: 1. The compounds of the present invention include optical isomers based on the asymmetric carbon atom at the 4-position of the 2-pyrazoline ring, but the present invention does not include isomers such as and 11. Of course.

The compound numbers in Table 1 above refer to the following production examples.

Please refer to the formulation examples and test examples.

The compounds of the present invention are suitable for sanitary pests, paddy rice, and cane.

An extremely useful compound that can be used in non-agricultural and horticultural fields as a control agent for various agricultural and horticultural pests, forest pests, and grain storage pests that cause damage to fruit trees, cotton, other crops, flower petals, etc., or as a termite control agent. It is.

Next, examples of insect pests to which the compound of the present invention is applied will be given.

Of course, this is not limited to the following pests.

Orthoptera l German cockroach (Blattalla ger+r)
++anica) Kobane Inago (0xya ye
zoensis 1 Thrips [Thysa]
noptera) rice thrips (BaLiothr)
ips biformis, ) Hemiptera (Hem
1ptqra) Ine Kame Mushi (Lgvnotorm
s elongatus ) Ne5cra antennata ) Ocorisa chin
ensjs) Hon-heri stink bug (Riotort)
us clavatus) red-spotted stink bug (
Dy56ercus cingulatus ) Tin1acanthus s
tramincus l leafhopper (Ne
＋：＋hotettixcincti、cpos
l Laodelnhax 5tria
tqllus J' brown planthopper (Ni1at) a
rvata lugens 1.
Sogatell, a furcifera 1
Dianhorina C1tri
1-on whitefly (Trialeurod)
es vaooraTiorum) bean aphid (
Aphis craccivora l cotton aphid (Aobis gossypii)
Anhis Sρ1raac
ola l peach aphid (Yobetsu p.
Planococcus citrus
) Qudcocc (Ps+qudcocc)
us censtocki lAnoidiella aurantii
＞Sanjoze scale insect (eomst6
ckaspis psrniciosa ] Yanonensis
liA Ptera (]J3oidoptera lki/
Monhonoga (Ph 1lonor cfer ring
once engineering 1a l Citrus leafminer (Phyllo)
cnistis C1trella)
Plutella xylos
TE 1a) Cotton red beetle (Pec
tinoohora gossynella) Potato moth (Phthorimaea onercul)
Carnosina
n1oonensis 1 apple kokakumonhamaki (A(]0XOnl'ryeS 0rana,
1 Nashihimeshinkui (Graoholibo Soso Kasaakie)
0aanhalocr
ocis medinalis) Etiella zinckenella
l awa ) may power (0s
trinia furnacalis
) Zanka mei ga (j engineering Y ward and goyo a 1ncertulds l force bu)
La ya ga (k■2RI2SegQ'f; plate
) Anomis flav
d1 Ieliothis armi
gera, H, zdae or) (, virescen
s line yoto (
Sesamia 1nferens
) 5rodootcrdLitu
ra) Coleoptera (C, elsonterIa+
Do 1 Kuganepuipui (Anomala CupreR
Md1adera cas1
/1nea) Mame Ko Gane
(Popillia J+aponica,
1 Enosep
ilacbnu p-unctlita
)Urihamushi
(Au1acopnoru femordlis
l Rice beetle (Oulema oryz)
ae 1io, water weevil (Li5s
orhootr Enamel formal dress Danzo) corn rootworm fA
(Diabratj, ca 5oT),
l - Colorado Boted Beetle (Leotinota)
rsddecemlineat+a ) Hymenoptera (H
y+nent]otera l Fire Ant (S
Diptera 1 Diptera 1 Asnhondylia sp.
p, ) Mikan 3 Mi /<
Engineering (Dacus dorsalia)
l Rice leafminer (AgroLlly)
za oryzae 1taneba
HyLemya platura
Oer+atitis
capitata) Good, Goal Minoji (0r
ssolia oryzae 1i
Eba e (Musca dome)
stlcd) Akai
Eka (0ulex pipiens peX
OoDtotermes formo
1) The compound of the present invention is effective as an insecticide against young larvae and old larvae ((), and is expressed directly or by systemic transfer. 2) The compound of the present invention is effective against various insecticides. It also exhibits excellent control effects against mites and cormorants.

To fully apply the insecticide of the present invention, the active ingredient is generally 0,01
~10. OOD pT)in, preferably o, i
It is preferred to use a concentration of ~2.000 pom.

Furthermore, in the case of aquatic harmful insects, it is possible to control them by spraying a chemical solution in the concentration range mentioned above to all the places where they occur, so it is also effective in the concentration range other than the above range in water.

In applying the compounds of this invention as insecticides, a suitable carrier is generally used, such as a solid carrier such as clay, talc, bentonite, etc., or water.

Alcohols (methanol, ethanol, etc.).

Can be used in combination with liquid carriers such as ketones, ethers, aliphatic hydrocarbons, aromatic hydrocarbons (benzene, toluene, xylene, etc.), esters, nitriles, etc., and if desired, emulsifier 1 can be dispersed. agents, suspending agents, spreading agents, penetrating agents, stabilizers, etc., emulsions, oil agents, irrigation agents, powders.

1 tablet of granules, paste, flowable, poison bait.

It can be put to practical use in any form such as aerosol, atomizer, mosquito repellent, electric mosquito repellent, etc.

In addition, if necessary, other types of insecticides may be used during formulation or spraying.
It may be applied in combination or simultaneously with various fungicides, herbicides, planting agents, fertilizers, etc.

Next, the present invention will be further explained with reference to production examples, formulation examples, and test examples, but the present invention is not limited thereto.

Hm Example 1 1-(4-Chlorphenylcarbamoyl)-3-7enyl-4-(4-difluoromethoxyphenyl)-2-pyrazoline (synthesis of the present compound A1) (8) Intermediate 5-phenyl-4-( Synthesis of 4-difluoromethoxyphenyl)-2-pyrazoline α-4-hydroxyphenylacetophenone (Ber, 2.1 244
9 (188B) 2.49 to sodium hydroxide 1.
Add to a mixed solution of 6F, 10 grams of water, and 12 grams of dioxane (reaction tank A).

On the other hand, sodium hydroxide 2o2. Water 25rnl.

After heating reaction tank B to which 30 types of dioxane were added to a total temperature of 80°C, cHF and ct gas were blown into it.

The produced difluorocarbene was blown into reactor A at room temperature through a previously connected path. After confirming the completion of the reaction by gas chromatography, 50 d of water was added.

An organic layer was obtained by adding 50@/ of ethyl ether and performing an extraction operation. After drying over anhydrous sodium sulfate and distilling off the solvent, α-4-difluoromethoxyphenylacetophenone 1 was obtained.
．． 8r'e (melting point 85-91°C). This product has 6
5% formalin 252. Acetic acid 0.1. m, piperidine [117, ethyl alcohol 50 d total 77 [+, (
, and refluxed for 3 hours. After the reaction, 50% water was concentrated under plate pressure.
d. Ethyl ether 5Gd Gold was added and an extraction operation was performed to obtain an organic layer.

After drying over anhydrous sodium sulfate, the solvent was distilled off to give α-4-difluoromethoxy-phenylacrylophenone (1.65%).
'i got it. Next, add 0.8 hydrazine hydrate to this product.
rnt and 60 mef of ethyl alcohol were added, and the mixture was reacted under reflux for 2 hours.

Concentrate under reduced pressure, 3 g of water, 50 rn of ethyl ether
1 was added and an extraction operation was performed to obtain an organic layer. After drying with anhydrous sodium sulfate, the solvent was distilled off and
Phenyl-4-(4-difluoromethoxyphenyl)
-2-Hilazoline was obtained. This stuff is without refining.

This was used for the next reaction.

(b) Synthesis of compound point 1 of the present invention 6-phenyl-4-(4-difluoromethoxyphenyl)-2-pyrazoline obtained in step (a)
r and 4-chlorophenylisocyanate o, 5y
A mixed solution of i20y ethyl ether and n-hexane (
1:1) and allowed to react at room temperature for 5 hours.

The precipitated crystal IF was collected, further washed with a mixed solution of ethyl ether and n-hexane (1:112G-), and dried under reduced pressure to obtain a product of [L8F (melting point 14zO-14
60℃).

The structure of this product was determined by nuclear magnetic resonance absorption spectroscopy and mass spectrometry.
It was confirmed that it was 5-phenyl-4-(4-difluoromethoxyphenyl)-2-pyrazoline.

Nuclear magnetic resonance absorption spectrum; δ, ppm, ('!D
O4; j+c 5.98 [IH, dd, , T=1 o-5Hz),
4.35 (11-1, t, J=10Hz l.

hξV 4.74 (IH, dd, J=10+a-m5 dayszl
, 6.42 (IH; t, J=73Hzl.

6.90-7.75 (13H, ml, al2 (
IH, bsl.

Production Examples 2 to 3 Synthesis of Invention Hardware Store 7 and A8 Synthesis was performed according to Synthesis Example 1. The structure of the product was confirmed by nuclear magnetic resonance absorption spectroscopy.

Nuclear magnetic resonance absorption spectrum; δ, ppm, 0DC4
; Compound of the present invention 7: 599 (IH, dd, J=10 and 5Hzl, 4.4
0 (IH.

t, J=10Hzl, 4.77 (IH, dd,
J=10 and 5Hz), 6.45 (II(,t
, J=75)3z), A90~S80(15
H, ml, a30(IT(, bsl.

Compound of the present invention black 8°4.00 (IH, dd, J=10 and 5)+z)
, 467(II(.

t, J=10Hz +, 4.76 (IH, dd,
J=10 and 5t+zl, 6.43
(IF(,t, J=73Hz +, every 8
5-7.75 (131-1, ml, 8.17 (1B
, bsl.

Production Example 4 1-(4-promphenylcarnocumoyl)-3-(4-chlorophenyl 1-4-(4-difluoromethoxyphenyl)-2-hy-i7"S7 (Invention Hardware Shop 6) Synthesis) (a) Intermediate 3-(4-chlorophenyl)-4-(4-
Synthesis of difluoromethoxyphenyl)-2-pyrazoline 4-chlorobromobenzene 14r and magnesium 207
was reacted in ethyl ether 50d to prepare all Grignard reagents.

To this solution was added dropwise a solution of 4-difluoromethoxyphenylacetonitrile diluted with 10.55'I of ethyl ether at room temperature.

After the dropwise addition was completed, the mixture was heated under reflux for 1 hour, added to 50 g of 10% hydrochloric acid that had been allowed to cool, and then separated into 9 layers to obtain an organic layer. Dry with anhydrous sodium sulfate.

Ethyl ether was distilled off to obtain crude product 142.

By purifying with column chromatography (silica gel, benzene), 4-chloro-α-(4-
Difluoromethoxyphenyl)acetophenone was obtained (
melting point 55-75°C).

This product was mixed with 2.5 y of 35% formalin, acetic acid [11
, 6, 0.1 d of piperidine and 50-gold ethyl alcohol were added, and the mixture was refluxed for 3 hours. After reaction.

After concentrating under reduced pressure, 50 g of water, 50 g of ethyl ether
mg'i was added and an extraction operation was performed to obtain an organic layer.

After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 4-chloro-α-(4-difluoromethoxy-phenyl)acrylophenone tlyk.

Next, hydrazine hydrate Q,8-gold and ethyl alcohol 60-gold were added to this product, and the mixture was allowed to react under reflux for 2 hours. Concentrate under reduced pressure and add 60 g of water.

Ethyl/I and 50 ml of ether were added and an extraction operation was performed to obtain an organic layer. After drying over anhydrous sodium sulfate, the solvent was distilled off to give 11 g of 3-(4-chlorphenyl l-4-(
Total amount of 4-difluoromethoxyphenyl)-2-pyrazoline was obtained.

This product was used for the arrow reaction without being purified.

(b) Synthesis of compound 6 of the present invention 6-(4-chlorphenylene) obtained in the above step (11),
-4-(4-SchifAolomethoxyphenyl)-
2-Pyrazoline 1.0? and 4-bromphenyl isocyanate 0.6? f20d ethyl ether)-n-
5 at room temperature in addition to a mixed solution of hexa/ (, i : i)
Allowed time to react.

The precipitated crystals were collected, washed with a mixed solution of ethyl ether and n-hexane (1:1120-), and dried under reduced pressure to obtain an aqy product (melting point j?7.0~
120.0'Cl.

The structure of this product is shown in the nuclear magnetic resonance absorption spectrum lcf1
It was confirmed that it was -(4-bromphenylcarbamoyl1-3-[4-chlorophenyl)-4-(4-difluoromethoxyphenyl)-2-pyrazoline.

Nuclear magnetic resonance absorption spectrum, δ, opm, CDCl
, ;5.96 (IH, dd, J=10 and 5)
+z +, 4.55 (1) 1°t, J=10T(
z +, 4.68 (IH, dd, J=10 and 5T (z l, 6.41 +IH, t, J=73H
z+, 6.90-770 (12H, ml, 8.
07 (IH, bs l.

Production Example 5 Synthesis of Invention Compound 11 Synthesis was carried out according to Production Example 4. The structure of the product was confirmed by nuclear magnetic resonance absorption spectroscopy.

Nuclear magnetic resonance absorption spectrum: δ, Opm, CDC1
,';3.99 (1■4. dd, J=10 and 5)IZI, 4.36 (IH,t, J=10H
z).

4.73 (IH, dd, J=10 and 5Hzl,
6.42 (iH,t, J=73Hzl.

6.72 (IH, t, J=56Hzl, 6.9Q
~7.70 (12B; ml.

8.15 (iH, bs 1) Next, some formulation examples when the compound of the present invention is used as a total insecticide will be shown, but the present invention is not limited to these.

Hereinafter, all "parts" refer to parts by weight.

Formulation Example 1 Emulsion Compound of the present invention, 5A1-・Track・Track・Surface curve・・・
・ 10th part...Song...Song...
Song... Song... Song 80 parts Tsurupol 2680 (Toho Chemical brand name) curved surface 10 parts or more are mixed uniformly to make an emulsion. The emulsion having the above composition was diluted 50 to 50 times with water to prepare an emulsion.

Formulation Example 2 Oil Compound of the Invention Black 7...Listen/Song/Song...Song times 50 parts Methyl cellosolve...Song...Curved surface/Song/
A total of 50 parts or more is mixed to form an oil agent.

Apply oil with the above composition to grooves and puddles.01~
Apply 50rnt or 10~1 depending on the aircraft.
Spray at 00me/10a.

Formulation example 3 Wettable powder Compound of the present invention 8 ・・・・・・・・・・・・4...
-...Song/25 parts Sieglite prp (Product name)
・・・・・−・−・・・・65 part Carplex 4-8
0 (Product name) 2 parts Tsurupol 5050 (Product name) 2 parts Sodium ligninsulfonate 2 parts Sodium ligninsulfonate 2 parts Tsurupol 5050 Medium 6 parts or more is mixed and ground evenly to make an irrigation agent. When using, the water conservancy with the above composition should be mixed with water at a concentration of 100 to 250,
-t-20~5 (l G i-
Spray /10Ia.

Formulation Example 4 Powder Compound A1 of the present invention Song/Song...
...60 copies Carplex A30 (product name)...
Concave/Song/05 part v ---...Song/
Song - 95 parts diinnorovir phosphate ・・・・・・・・・・・・
・・・・・・・・・・・・- Parts i and s or more are mixed uniformly to form a powder. Combination example 5 of the above composition Poison bait bran...
・・・・・・・・・・・・・・・・・・・・・ 52
Bubei Nuka ・・・・・・・・・－・
・・・・・・・・・・・・・・・・・・・・・・・・
15 parts flour ・・・－・・・・・・・・・・・・
・・・・・・・・・・・・－・・・・・・・・・60 copies black
Sugar ・・・・・・・・・・・・・・・4・・・・・・
4. Add the present invention A8 to a uniform mixture of 3 or more parts so that the component amount becomes 0.2X, and further mix uniformly. Half of the total amount of water is added and kneaded, granulated using a beretter, and dried with warm air at 50 to 60°C. Apply the poisonous bait obtained in this way to the roots of crops. use.

Similarly, poisonous baits were prepared for the compounds of the present invention, AI, 6, and 7.11.゛Next, the usefulness of one of the compounds of the present invention will be specifically explained in the following test examples.

Test Example 1 Insecticidal test against adult house fly: 1 m7 of an acetone solution containing the compound of the present invention at a concentration of 100 ppm! was dropped onto a 9α shear plate so as to spread it evenly, and after the acetone was completely evaporated at room temperature, 10 adult house flies were placed in the flask and a glass lid with holes was placed over the flask. This petri dish i25
The plants were housed in a constant temperature room at ℃, and the number of dead insects was counted after 48 hours.The test was conducted in two sections.

As a result, the two compounds of the present invention exhibited a total mortality rate of 100X.

Test Example 2: Insecticidal test against Spodoptera nigra. Leaves of Callanus are immersed in a water emulsion of the compound of the present invention and a control compound at a predetermined concentration for about 10 seconds, air-dried, and then placed in a petri dish. The cells were released, covered with a perforated lid, and housed in a thermostatic chamber at 25°C. After 48 hours had elapsed, they were fed with Cilantro leaves that had not been treated with the compound, and after a further 120 hours, they were fed a diet with a dead shell ratio of X.

All results are shown in Table 3.

Table 3 Control Compound A (Compound described in JP-A-51-41358) Test 13
'1J3) Insecticidal test against brown planthopper diameter 8cn,
100'ppm of the compound of the present invention and the control compound to rice plants at the 6-leaf stage planted on styrocanog with a madder level of 6crn.
After spraying a concentrated emulsion and air drying, it was covered with a glass cylinder with holes.

Ten adult brown planthoppers were released and left in a constant temperature room at 25°C, and the dead insects were examined 48 hours later.

The test was conducted in two sections.

The results are shown in Table 4.

Table 4 Control Compound B (compound described in JP-A No. 57-136572) Test Example 4 Insecticidal test against lady beetles of the present invention and a control compound in an emulsion with a concentration of 1'ppm for about 10 seconds. After soaking and air-drying, the larvae were placed in a petri dish, in which 10 second instar larvae of the ladybug were placed in a petri dish, covered with a lid, and left in a constant temperature room at 25°C. Mortality rate was investigated after 48 hours. The test was conducted in two sections. All results are shown in Table 5.

Table 5 Comparative Compound A (% Compound described in Japanese Patent Publication No. 1983-41558) Test Example 5
Insecticidal test against diamondback moth A leaf of Citrus lanternis was immersed in a water emulsion with a concentration of I DDm for about 10 seconds, air-dried, and placed in a petri dish. The animals were placed in a thermostatic oven at 25°C with a lid on, and the mortality rate was investigated after 48 hours. The results are shown in Table 6.

Table 6 Control compound A N　CE(.

(Compound described in JP-A No. 51-41558) Procedural amendment (spontaneous) June 11, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case Name of case No. 11304 of 1988 Z New Pyrazoline Derivatives and Insecticides 6, Relationship with the Amendment Case Address of Patent Applicant (〒101) 3-7 Kanda Nishikicho, Chiyoda-ku, Tokyo @
Column 6 of Detailed Explanation of the Invention in Book 1 of Book I, contents of amendment (1) "R" stated in line 5 of page 10 of the specification.

R” Correct.

(2) In the table on page 10 of the specification, the "X" written in the 8th line of the bottom row is corrected to "Xl" 0 Procedural amendment March 1980 l Left eye Commissioner of the Japan Patent Office Young Kazuo Sugi 1 Description of the case Patent Application No. 11304 of 1980 2 Title of the invention New birapurin derivatives and insecticides 3 Relationship with the person making the amendment Patent applicant address 3-7 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101 Address 1
Name (398) F3 San Kagaku Kogyo Co., Ltd. 4 Date of amendment order Voluntary amendment 5 Detailed explanation of the invention in the specification subject to amendment 6 Contents of amendment (1) In the table on page 11 of the specification, "rx" written in the first line is corrected to "xl".

(2) In the table on page 12 of the specification, the procedural amendment written in the first line (fl#) July 14, 1980 Patent Office Regional Officer Kazuo Wakasugi I Indication of the case 1988 Patent Application No. 11304 2 Name of the invention: New birapurin derivatives and insecticides 3 Relationship with the case of the person making the amendment Patent applicant address: 3-7-1 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101 Name (398') Nissan Chemical Industries, Ltd. 4 Date of amendment order A.1 Voluntary amendment 5, details of the invention in the specification subject to amendment A 2 r+06 to 109°C" Tsuta 17 j+5j to 1525°C" 20 "+59 to 1466C" /l621 "Semi-crystalline" 2) In Table 1 on page 10 of the specification, 9 compounds of the present invention Following 26, the following matters are supplemented 6) Specification No. 26
Add the following information between the 4th and 5th lines of the page.

1 Production Example 6 Starting material for synthesis of the compound of the present invention/K2O'Ji
4'-methoxy-α-(4-hydroxyphenyl)
Acetophenone [J, 00C6゜52.3251 (
'67) Ite for li, manufacturing example 1. The intermediate 4'-methoxyalpha-(4-difluoronotquinphenyl)acetophenone was synthesized according to K. (t♂1 point 100-104°C)
Through this process, 20 pieces of 9 compounds of the present invention were obtained. The structure of the product was confirmed by the nuclear magnetic absorption spectrum (fc, nuclear gas absorption spectrum; Isu1 absorption spectrum; δ, ppm, CD
CA.

,'1.72 (3H,S) 3.92 (jH,dd
, J=10 and 5 Hz)4,. 50 (II-E
,t,J=10)1z) 467(i)I,act,
J−=iQ and 5H2) 668(H(,t, J=
7.5H2) 6.70-7.70 (128m) 8.0
7 (iI-■, bS) Production Examples 7 to 9 Compound of the present invention &25, Human 26.

Synthesis of kL27 It was synthesized according to Production Example 6. What is the structure of the product?

Confirmed by nuclear magnetic resonance absorption spectrum.

Nuclear magnetic resonance absorption spectrum; δ, ppm, CDC
A: Compound of the present invention l625 Ro75 (3H1S) 3.95 (H+, ad, J'=
+0 and 5Hz) 11.32 (IH,t, J=1
0Hz) 4.72 (IH, dd, J=10 and 5H2) 64'1 (1H, t, J=75H2)
6.65-7.75H2)T.

m) 8.29 (HJ, be) Medium form of the compound of the present invention 26 5.74 (5H, a) 3.96 (iH, dd, J=
10b and 5H2) 4.35 (iT-+, t, J-1
0Hz) 4.73 (1) T, dd, J=10 and 5Hz) 6.45 (+H, t, J=75Hz
) 6.70-7.70 (12H, T11) 8
．． 15 ([7, bs) Compound of the present invention μ2 no 3.72 (3H, s) 3.92 (IH, da, J
=IQand5Hz)4J2(jH,t,J=10Hz
) 4.7(1(10,CLd,,J=IOand
5) TZ) 6.42 (1) T, t, J==73Hz
) 6.65-7.60 (8H.

m) 7.65 (4H, s) 8.22 (IH
, bs, ) Production Example 10 Synthesis a of Compound 17 of the Present Invention
) Synthesis of intermediate 4'-methyl-α-(4-hydroxyphenyl)acetophenone In a 500 ml beaker, add 170 ml of stannous chloride dihydrate.
)/, @ salt e95 ml, mef/-/l/165
ml and stirred at room temperature. Into this 4/-)
f Ru α-(4-nitrophenyl)acetophenone [
C, A, record 7289"] 57? at once
The mixture was heated to ~60°C and stirring continued. Once the reaction started (with an exotherm), the temperature was returned to room temperature and the reaction was continued for 4 hours.

The liquid from the rice was added little by little to 300ml of an aqueous sodium hydroxide solution, and after confirming that the solution had a weak salt molar ratio, extraction was carried out twice with 300ml of ethyl acetate.

After drying the organic layer over anhydrous sodium chloride, the solvent was completely distilled off to obtain 4'-methyl-α-(4-aminophenyl)acetotubonone (melting point 135-141°C) 297.

4'-methyl-α-(4-aminophenyl) obtained above
Dissolve acetophenone 101F'11207d in acetic acid and add nitrite to this solution while keeping it at 20'C to 50C) IJium 65'? A solution prepared by dissolving this in 22 ml of concentrated sulfuric acid was added.

After the addition was completed, stirring was continued for 20 minutes, and then this solution was added to 500 i of water at 80°C.

Heat to reflux [~7 Jl] for 2 hours. After the reaction was completed, the cooled portion was removed by decantation and cooled in air.

By filtering the precipitated crystals and drying them, 4'
-Methyl~α-(4-hydroxy-7-enyl)7'
-Human 7 Enon 601k 7Q
7.

b) Starting ζ Of course, 4'-methyl-α synthesized in a) above
Intermediate 4'-1f-α-(4-difluoromethoxyphenyl)acetophenono (melting point 9
7 to I05''C) i to obtain the compound of the present invention, Gallo 17.

Structure of the product (1) Confirmed by nuclear magnetic resonance absorption spectrum.

Nuclear magnetic resonance absorption spectrum: δ, pI)m, cDc
i, ; Compound of the present invention 7K 17 2.30 (jH,s) 98 (iH,dd,
J = IO and 5EZ) 4.35 (IH, t, J = 10
Hz, ) 4.72 (1) T, da, J = 10 trigrams 5I-TZ) 6.40 (+H, t, J = 75'
Hz) 6.90-7.75 (12T-1, m)
8.10 (04, bs) Production Example 11 Synthesis of Compound 24 of the Present Invention Synthesis was performed according to Production Example 10. The structure of the product was confirmed by nuclear magnetic resonance absorption spectrum.

Nuclear magnetic resonance spectrum; δ+ ppm, CDCl2; Compound of the present invention 24 2.30 (51", s) 3.96 (18, act,
J=10 and s■+z), 1.34(H(,t,J-
IDHz) 4.75 (jH, da, J = 10 and 5H7) 5.80 (!T1. tt, J = 5
4 and 51H2) 6.37 (u+, t,
, :r==75+qz) 7. [10-7.70
(12H, m) soa (+n, bs) Preparation 1 night] 12 Synthesis of Present Compounds A, 2 Obtained in Preparation Example 1 fc + -(4-chlorophenylcarbamoyl)-5-phenyl-4-(4- (difluoromethoxyphenyl)-2-pyrazoline 0.9 r, potassium hydroxide 022, water 0.3 rnl, methinone iodide Q, 5f,N,N-dimethylformamide 7-Reacted at room temperature for 5 hours with stirring for 9 hours. Ta. Add this solution to 6°m of water.
After that, extraction was performed twice with 30 ml of chloroform. After drying the organic layer over anhydrous sodium sulfate, the solvent was completely distilled off to obtain a crude product of o87. This crude product was purified by total column chromatography (Nori gel, benzene; cutting etching 9=1), and was purified by n-hexane:ether (1:
1) Crystallization was carried out using 10nffl, filtered with E and dried to obtain product 042. (Melting point S06~10
9°C; Structural nuclear magnetic co-116 absorption spectrum of this product (/(J, , , 17. 1- < 4-chlorophenyl-N-methylcarbamoyl)-u-phenyl-4-
It was confirmed that it was (4-cyfluoromethoxy/phenyl)-2-pyrazoline.

Nuclear magnetic resonance absorption spectrum; δ, ppm, CDC1
”s, 57 (3FT, S) 3.75
-4.45 (5TT, m) 6.40
(iH.

t, J=75Hz) 6.95-7.50 (138,
m) Production Examples 15-14 Compound A21. Synthesis of Flat 28 Synthesis was performed according to Production Example 12. The structure of the product was confirmed by nuclear magnetic resonance absorption spectroscopy.

Nuclear magnetic resonance absorption spectrum; δ, 4opm, , CD
04 Compound of the present invention 21 Ro55 (j) I, s) 365 (58, s)
'375~4.40 (jH,
m) 6.41 (H+, t, J==July 4Z) 65 [
1 to 7.40 (121T, l11) Compound 1 of the present invention 28 1.21'l (511', t, J=7Hz
) 5.69 (3H, s) 3.70-4.
40 (5Fl, in) 6.40
(IH, t, J=75Hz'J6.50~7.50
(12H,m)' J4) In Table 5 on page 65 of the specification, 3 compounds of the present invention 1 and 11
Next, fill in all of the following items: ``Reservoir 24 of the present compound
90 Chi Invention Self-monitoring 25 100 Section

Claims (4)

[Claims] (1) General formula [1]: (wherein, X represents a hydrogen atom, a halogen atom, a lower argyl group, or an alkoxyl group.
-R' group, R represents a hydrogen atom, a lower alkyl group, an alkenyl group or an alkynyl group. However, A represents an oxygen atom, a yellow atom, a sulfinyl group, or a sulfonyl group, and R+ represents a lower alkyl group substituted with a halogen atom. ) Pyrazoline derivatives. (2) The pyrazoline derivative according to claim (1), wherein in the general formula [f], X is a hydrogen atom or a halogen atom. (3) The pyrazoline derivative according to claim (1), wherein in the general formula [1]IC, X is a lower alkyl group or an alkogyl group. (4) Range of characteristic ♂ [1lilf search terms (1) and (2)
An insecticide comprising all of the pyrazoline derivatives according to any one of items 1 to 3 as an active ingredient.