AU2015401326B2

AU2015401326B2 - Benzylhydrazone compounds and preparation method and application thereof

Info

Publication number: AU2015401326B2
Application number: AU2015401326A
Authority: AU
Inventors: Changqing JIA; Yongqiang Ma; Zhaohai Qin; Yumei Xiao; Xiaoyong YUAN
Original assignee: China Agricultural University
Current assignee: China Agricultural University
Priority date: 2015-07-03
Filing date: 2015-07-03
Publication date: 2018-07-26
Anticipated expiration: 2035-07-03
Also published as: WO2017004734A1; AU2015401326A1

Abstract

Disclosed are a compound represented by formula I, a preparation method therefor, and a use thereof. See the specification for the definition of each substituent group in formula I. The preparation method comprises the following step: performing, in the presence of a catalyst in an organic solution, a condensation reaction on a compound represented by formula IV and a compound represented by formula V to obtain the compound represented by formula I. The preparation method is simple, and the resulting compound represented by formula I is applicable to prevention of a number of plant diseases caused by pathogenic fungi, such as oomycetes, basidiomycetes, ascomycetes, and imperfect fungi, and can effectively prevent powdery mildew on wheat, maize rust, and watermelon anthracnose in particular. Using a low concentration of the compound achieves a good prevention effect. Moreover, a part of the compound represented by formula I has excellent insecticidal activity and acaricidal activity and is capable of protecting crops from a number of pests and mites. Therefore, the compound can be used as a germicide or a pesticide in agriculture or other fields.

Description

The present invention belongs to the field of preparation of agricultural fungicide and 5 insecticide and application thereof, particularly to a benzylhydrazone compound and preparation method and application thereof.

Background

Methoxyacrylate fungicides are a kind of agricultural fungicides having excellent effect, which is derived from a natural antibiotic Strobilurin A having fungicidal activity, this kind of fungicides are broad spectrum and high effect, exhibit an excellent activity on almost all the fungal diseases, and play an important role for protecting agricultural production.

There are a number of structural modifications for methoxyacrylate compounds. These modifications mostly are changes on side chains, but the structures are only of three types of diarylethers, benzylethers and benzyloximeethers, with limited structural types and application ranges. Meanwhile, as fungicide, this kind of compounds generate a serious resistance problem.

Summary of Invention

In one or more aspects, the present invention provides a benzylhydrazone compound and preparation method thereof.

In particular, in one aspect the present invention provides benzylhydrazone compounds of formula I:

C:\Interwoven\NRPortbl\DCC\RBR\l 7219907_ I .docx-26/06/2018

2015401326 26 Jun 2018 in the formula I, X is selected from CH orN; Y is selected from any one of O, S andNH; Ri is cyano; R2 is selected from any one of C1-C12 alkyl, Qi and Q2; R3 is selected from any one of hydrogen, C1-C5 alkyl, Qi and Q2;

wherein, in the Qi and Q2, both R4 and R5 are selected from at least one of hydrogen, CiC5 alkyl, C1-C5 alkoxy, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, mesyl and trifluoromesyl; the halogen is selected from any one of fluorine, chlorine, bromine and iodine; m=0-5; n=0-4;

the binding site of R4 is at least one of the five remaining binding sites, in which R4 may be same or not when m>l; the binding site of R5 is at least one of the four remaining binding sites, in which R5 may be same or not when n>l, wherein, in Q2, N may be located at any one of sites 2, 3, and 4.

In other aspects, the present invention provides benzylhydrazone compounds of the general formula:

COYCH3 formula I.

1A

Description

Z16111319CPAU

In the formula I, X is selected from CH or N; Y is selected from any one of O, S and NH; Ri is selected from any one of Ci-C₈ alkyl, allyl, propargyl, benzyl, benzoyl, Ci-C₅ fatty acyl, Ci-C₅ alkoxycarbonyl, cyano, carbamoyl, and thiocarbamoyl; R₂ is selected from any one of C1-C12 alkyl, Q_b and Q₂; R₃ is selected from any one of hydrogen, Ci-C₅ alkyl, Q_b and Q₂;

>5<>l

Ql= (I-J-(R₄)m Q₂= P^(^R5)n wherein, in the Qi and Q₂, both R4 and R₅ are selected from at least one of hydrogen, Ci-C₅ alkyl, Ci-C₅ alkoxy, Ci-C₅ fluoroalkyl, Ci-C₅ fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, mesyl, and trifluoromesyl, the halogen is selected from any one of fluorine, chlorine, bromine, and iodine; m=0-5; n=0-4.

The binding site of R4 is at least one of the five remaining binding sites, in which R4 may be same or not when m>l; the binding site of R₅ is at least one of the four remaining binding sites, in which R₅ may be same or not when n>l, wherein, in Q₂, N may be located at any one of sites 2, 3, and 4.

The general structure formula of the benzylhydrazone compounds provided by the present invention is shown as formula I, preferably the following structures: in the formula I, X is selected from CH or N; Y is selected from 0 or NH; Ri is selected from any one of C|~C₄ straight chain or branched chain alkoxycarbonyl, benzoyl, cyano, carbamoyl, and thiocarbamoyl; R₂ is selected from Qi or Q₂; R₃ is selected from hydrogen or C_rC₂ alkyl;

wherein, in the Qi and Q₂, both R4 and R₅ are selected from at least one of Ci-C₅ alkyl, trifluoromethyl, trifluoromethoxy, phenoxy, halogen, nitro, cyano, pyridyloxy, mesyl, and trifluoromesyl; m=0-3; n=0-2.

The general structure formula of the benzylhydrazone compounds provided by the present invention is shown as formula I, further preferably the following structures: in the formula I, X is selected from CH or N; Y is selected from 0 or NH; R| is selected from C|~C₄ straight chain or branched chain alkoxycarbonyl, cyano; R₂ is selected from Qi or Q₂; R₃ is elected from hydrogen or methyl;

wherein, in the Qi and Q₂, both R4 and R₅ are selected from at least one of trifluoromethyl, trifluoromethoxy, phenoxy, fluorine, chlorine, nitro, cyano, pyridyloxy, mesyl, and trifluoromesyl; m=0-3, n=0-2.

100002

2010.2

Description

Z16111319CPAU

The term to which the definition of the compound of formula I of the present invention is related refers to the following substituents:

Halogen refers to fluorine, chlorine, bromine, and iodine.

Alkyl: straight chain or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, «-butyl, isobutyl, /-butyl, and /-pentyl.

Aryl and the aryl portion in aryloxy includes phenyl, pyridyl, furyl, etc. Furthermore, in the compound of formula I of the present invention, geometrical isomers are generated because different substituents are coupled via carbon-carbon double bond or carbon-nitrogen double bond (the different configurations respectively represents as Z and E). The compound of formula I of the present invention may be Z-isomer or E-isomer, or a mixture of the both in any ratio.

The compound of formula I of the present invention can be particularly selected from the compounds with the following numbers:

Wt

la lb Ic Id

Number	Ri	r₃	(ROm
Ia-l~Id-l	ch₃	H	H
Ia-2~Id-2	2-C1
Ia-3~Id-3	4-C1
Ia-4~Id-4	ch₃	H
Ia-5~Id-5	2-C1
Ia-6~Id-6	4-C1
Ia-7~Id-7	2,4-20
Ia-8~Id-8	(CH₃)₃C	H	H
Ia-9~Id-9	2-0
Ia-10~Id-10	4-0
Ia-ll~Id-ll	ch₃	H
Ia-12~Id-12	2-0
Ia-13~Id-13	4-0

100002

2010. 2

Description

Z16111319CPAU

Ia-14~Id-14			2,4-20
Ia-15~Id-15	CH₃OCO	H	H
Ia-16~Id-16	2-0
Ia-17~Id-17	3-0
Ia-18~Id-18	4-0
Ia-19~Id-19	2,4-20
Ia-20~Id-20	2,6-20
Ia-21~Id-21	4-CN
Ia-22~Id-22	3-CN
Ia23~Id-23	2-CH₃
Ia-24~Id-24	3-CH₃
Ia-25~Id-25	4-CH₃
Ia-26~Id-26	2,4-2CH₃
Ia-27~Id-27	3,5-2CH₃
Ia-28~Id-28	2,6-2CH₃
Ia-29~Id-29	3-F
Ia-30~Id-30	4-F
Ia-31~Id-31	4-CHF₂
Ia-32~Id-32	3-CF₃
Ia-33~Id-33	4-CF₃
Ia-34~Id-34	3-OCF₃
Ia-35~Id-35	4-OCF₃
Ia-36~Id-36	4-OCH₂CHF₂
Ia-37~Id-37	2,4-2F
Ia-38~Id-38	3,5-2OCH₃
Ia-39~Id-39	3,4,5-3OCH₃
Ia-40~Id-40	3,4-(CH₂)₂O
Ia-41~Id-41	2-NO₂
Ia-42~Id-42	3-NO₂
Ia-43~Id-43	4-NO₂
Ia-44~Id-44	3-OPh
Ia-45~Id-45	ch₃	H
Ia-46~Id-46	2-0
Ia-47~Id-47	3-0

100002

2010. 2

Description

Z16111319CPAU

Ia-48~Id-48			4-C1
Ia-49~Id-49	2,4-20
Ia-50~Id-50	2,6-20
Ia-51~Id-51	4-CN
Ia-52~Id-52	3-CN
Ia-53~Id-53	2-CH₃
Ia-54~Id-54	3-CH₃
Ia-55~Id-55	4-CH₃
Ia-56~Id-56	2,4-2CH₃
Ia-57~Id-57	3,5-2CH₃
Ia-58~Id-58	2,6-2CH₃
Ia-59~Id-59	3-F
Ia-60~Id-60	4-F
Ia-61~Id-61	4-CHF₂
Ia-62~Id-62	3-CF₃
Ia-63~Id-63	4-CF₃
Ia-64~Id-64	3-OCF₃
Ia-65~Id-65	4-OCF₃
Ia-66~Id-66	4-OCH₂CHF₂
Ia-67~Id-67	2,4-2F
Ia-68~Id-68	3,5-2OCH₃
Ia-69~Id-69	3,4,5-3OCH₃
Ia-70~Id-70	3,4-(CH₂)₂O
Ia-71~Id-71	2-NO₂
Ia-72~Id-72	3-NO₂
Ia-73~Id-73	4-NO₂
Ia-74~Id-74	3-OPh
Ia-75~Id-75	2-Cl-4-OPh
Ia-76~Id-76	C₂H₅OCO	H	H
Ia-77~Id-77	2-0
Ia-78~Id-78	3-0
Ia-79~Id-79	4-0
Ia-80~Id-80	2,4-20
Ia-81~Id-81	2,6-20

100002

2010. 2

Description

Z16111319CPAU

Ia-82~Id-82			4-CN
Ia-83~Id-83	3-CN
Ia-84~Id-84	2-CH₃
Ia-85~Id-85	3-CH₃
Ia-86~Id-86	4-CH₃
Ia-87~Id-87	2,4-2CH₃
Ia-88~Id-88	3,5-2CH₃
Ia-89~Id-89	2,6-2CH₃
Ia-90~Id-90	3-F
Ia-91~Id-91	4-F
Ia-92~Id-92	4-CHF₂
Ia-93~Id-93	3-CF₃
Ia-94~Id-94	4-CF₃
Ia-95~Id-95	3-OCF₃
Ia-96~Id-96	4-OCF₃
Ia-97~Id-97	4-OCH₂CHF₂
Ia-98~Id-98	2,4-2F
Ia-99~Id-99	3,5-2OCH₃
Ia-100~Id-100	3,4,5-3OCH₃
Ia-101~Id-101	3,4-(CH₂)₂O
Ia-102~Id-102	2-NO₂
Ia-103~Id-103	3-NO₂
Ia-104~Id-104	4-NO₂
Ia-105~Id-105	3-OPh
Ia-106~Id-106	ch₃	H
Ia-107~Id-107	2-C1
Ia-108~Id-108	3-C1
Ia-109~Id-109	4-C1
Ia-110~Id-110	2,4-20
Ia-lll~Id-lll	2,6-20
Ia-112~Id-112	4-CN
Ia-113~Id-113	3-CN
Ia-114~Id-114	2-CH₃
Ia-115~Id-115	3-CH₃

100002

2010. 2

Description

Z16111319CPAU

Ia-116~Id-116			4-CH₃
Ia-117~Id-117	2,4-2CH₃
Ia-118~Id-118	3,5-2CH₃
Ia-119~Id-119	2,6-2CH₃
Ia-120~Id-120	3-F
Ia-121~Id-121	4-F
Ia-122~Id-122	4-CHF₂
Ia-123~Id-123	3-CF₃
Ia-124~Id-124	4-CF₃
Ia-125~Id-125	3-OCF₃
Ia-126~Id-126	4-OCF₃
Ia-127~Id-127	4-OCH₂CHF₂
Ia-128~Id-128	2,4-2F
Ia-129~Id-129	3,5-2OCH₃
Ia-130~Id-130	3,4,5-3OCH₃
Ia-131~Id-131	3,4-(CH₂)₂O
Ia-132~Id-132	2-NO₂
Ia-133~Id-133	3-NO₂
Ia-134~Id-134	4-NO₂
Ia-135~Id-135	3-OPh
Ia-136~Id-136	2-Cl-4-OPh
Ia-137~Id-137	(CH₃)₂CHOCO	H	H
Ia-138~Id-138	2-C1
Ia-139~Id-139	3-C1
Ia-140~Id-140	4-C1
Ia-141~Id-141	2,4-20
Ia-142~Id-142	2,6-20
Ia-143~Id-143	4-CN
Ia-144~Id-144	3-CN
Ia-145~Id-145	2-CH₃
Ia-146~Id-146	3-CH₃
Ia-147~Id-147	4-CH₃
Ia-148~Id-148	2,4-2CH₃
Ia-149~Id-149	3,5-2CH₃

100002

2010. 2

Description

Z16111319CPAU

Ia-150~Id-150			2,6-2CH₃
la-15 l—Id-151	3-F
Ia-152~Id-152	4-F
Ia-153~Id-153	4-CHF₂
Ia-154~Id-154	3-CF₃
Ia-155~Id-155	4-CF₃
Ia-156~Id-156	3-OCF₃
Ia-157~Id-157	4-OCF₃
Ia-158~Id-158	4-OCH₂CHF₂
Ia-159~Id-159	2,4-2F
Ia-160~Id-160	3,5-2OCH₃
Ia-161~Id-161	3,4,5-3OCH₃
Ia-162~Id-162	3,4-(CH₂)₂O
Ia-163~Id-163	2-NO₂
Ia-164~Id-164	3-NO₂
Ia-165~Id-165	4-NO₂
Ia-166~Id-166	3-OPh
Ia-167~Id-167	ch₃	H
Ia-168~Id-168	2-C1
Ia-169~Id-169	3-C1
Ia-170~Id-170	4-C1
Ia-171~Id-171	2,4-20
Ia-172~Id-172	2,6-20
Ia-173~Id-173	4-CN
Ia-174~Id-174	3-CN
Ia-175~Id-175	2-CH₃
Ia-176~Id-176	3-CH₃
Ia-177~Id-177	4-CH₃
Ia-178~Id-178	2,4-2CH₃
Ia-179~Id-179	3,5-2CH₃
Ia-180~Id-180	2,6-2CH₃
Ia-181~Id-181	3-F
Ia-182~Id-182	4-F
Ia-183~Id-183	4-CHF₂

100002

2010. 2

Description

Z16111319CPAU

Ia-184~Id-184			3-CF₃
Ia-185~Id-185	4-CF₃
Ia-186~Id-186	3-OCF₃
Ia-187~Id-187	4-OCF₃
Ia-188~Id-188	4-OCH₂CHF₂
Ia-189~Id-189	2,4-2F
Ia-190~Id-190	3,5-2OCH₃
Ia-191~Id-191	3,4,5-3OCH₃
Ia-192~Id-192	3,4-(CH₂)₂O
Ia-193~Id-193	2-NO₂
Ia-194~Id-194	3-NO₂
Ia-195~Id-195	4-NO₂
Ia-196~Id-196	3-OPh
Ia-197~Id-197	2-Cl-4-OPh
Ia-198~Id-198	3-SCH₃
Ia-199~Id-199	3-SO₂CH₃
Ia-200~Id-200	4-SO₂CF₃
Ia-201~Id-201	(CH₃)₃COCO	H	H
Ia-202~Id-202	2-C1
Ia-203~Id-203	3-C1
Ia-204~Id-204	4-C1
Ia-205~Id-205	2,4-20
Ia-206~Id-206	2,6-20
Ia-207~Id-207	4-CN
Ia-208~Id-208	3-CN
Ia-209~Id-209	2-CH₃
Ia-210~Id-210	3-CH₃
Ia-211~Id-211	4-CH₃
Ia-212~Id-212	2,4-2CH₃
Ia-213~Id-213	3,5-2CH₃
Ia-214~Id-214	2,6-2CH₃
Ia-215~Id-215	3-F
Ia-216~Id-216	4-F
Ia-217~Id-217	4-CHF₂

100002

2010. 2

Description

Z16111319CPAU

Ia-218~Id-218			3-CF₃
Ia-219~Id-219	4-CF₃
Ia-220~Id-220	3-OCF₃
Ia-221~Id-221	4-OCF₃
Ia-222~Id-222	4-OCH₂CHF₂
Ia-223~Id-223	2,4-2F
Ia-224~Id-224	3,5-2OCH₃
Ia-225~Id-225	3,4,5-3OCH₃
Ia-226~Id-226	3,4-(CH₂)₂O
Ia-227~Id-227	2-NO₂
Ia-228~Id-228	3-NO₂
Ia-229~Id-229	4-NO₂
Ia-230~Id-230	3-OPh
Ia-231~Id-231	ch₃	H
Ia-232~Id-232	2-C1
Ia-233~Id-233	3-C1
Ia-234~Id-234	4-C1
Ia-235~Id-235	2,4-20
Ia-236~Id-236	2,6-20
Ia-237~Id-237	4-CN
Ia-238~Id-238	3-CN
Ia-239~Id-239	2-CH₃
Ia-240~Id-240	3-CH₃
Ia-241~Id-241	4-CH₃
Ia-242~Id-242	2,4-2CH₃
Ia-243~Id-243	3,5-2CH₃
Ia-244~Id-244	2,6-2CH₃
Ia-245~Id-245	3-F
Ia-246~Id-246	4-F
Ia-247~Id-247	4-CHF₂
Ia-248~Id-248	3-CF₃
Ia-249~Id-249	4-CF₃
Ia-250~Id-250	3-OCF₃
Ia-251~Id-251	4-OCF₃

100002

2010. 2

Description

Z16111319CPAU

Ia-252~Id-252			4-OCH₂CHF₂
Ia-253~Id-253	2,4-2F
Ia-254~Id-254	3,5-2OCH₃
Ia-255~Id-255	3,4,5-3OCH₃
Ia-256~Id-256	3,4-(CH₂)₂O
Ia-257~Id-257	2-NO₂
Ia-258~Id-258	3-NO₂
Ia-259~Id-259	4-NO₂
Ia-260~Id-260	3-OPh
Ia-261~Id-261	2-Cl-4-OPh
Ia-262~Id-262	3-SCH₃
Ia-263~Id-263	3-SO₂CH₃
Ia-264~Id-264	4-SO₂CF₃
Ia-265~Id-265	CN	H	H
Ia-267~Id-267	2-C1
Ia-268~Id-268	3-C1
Ia-269~Id-269	4-C1
Ia-270~Id-270	2,4-20
Ia-271~Id-271	2,6-20
Ia-272~Id-272	4-CN
Ia-273~Id-273	3-CN
Ia-274~Id-274	2-CH₃
Ia-275~Id-275	3-CH₃
Ia-276~Id-276	4-CH₃
Ia-277~Id-277	2,4-2CH₃
Ia-278~Id-278	3,5-2CH₃
Ia-279~Id-279	2,6-2CH₃
Ia-280~Id-280	3-F
Ia-281~Id-281	4-F
Ia-282~Id-282	4-CHF₂
Ia-283~Id-283	3-CF₃
Ia-284~Id-284	4-CF₃
Ia-285~Id-285	3-OCF₃
Ia-286~Id-286	4-OCF₃

100002

2010. 2

Description

Z16111319CPAU

Ia-287~Id-287			4-OCH₂CHF₂
Ia-288~Id-288	2,4-2F
Ia-289~Id-289	3,5-2OCH₃
Ia-290~Id-290	3,4,5-3OCH₃
Ia-291~Id-291	3,4-(CH₂)₂O
Ia-292~Id-292	2-NO₂
Ia-293~Id-293	3-NO₂
Ia-294~Id-294	4-NO₂
Ia-295~Id-295	3-OPh
Ia-296~Id-296	ch₃	H
Ia-297~Id-297	2-C1
Ia-298~Id-298	3-C1
Ia-299~Id-299	4-C1
Ia-300~Id-300	2,4-20
Ia-301~Id-301	2,6-20
Ia-302~Id-302	4-CN
Ia-303~Id-303	3-CN
Ia-304~Id-304	2-CH₃
Ia-306~Id-305	3-CH₃
Ia-307~Id-307	4-CH₃
Ia-308~Id-308	2,4-2CH₃
Ia-309~Id-309	3,5-2CH₃
Ia-310~Id-310	2,6-2CH₃
Ia-311~Id-311	3-F
Ia-312~Id-312	4-F
Ia-313~Id-313	4-CHF₂
Ia-314~Id-314	3-CF₃
Ia-315~Id-315	4-CF₃
Ia-316~Id-316	3-OCF₃
Ia-317~Id-317	4-OCF₃
la-318~Id-318	4-OCH₂CHF₂
Ia-319~Id-319	2,4-2F
Ia-320~Id-320	3,5-2OCH₃
Ia-321~Id-321	3,4,5-3OCH₃

100002

2010. 2

Description

Z16111319CPAU

Ia-322~Id-322			3,4-(CH₂)₂O
Ia-323~Id-323	2-NO₂
Ia-324~Id-324	3-NO₂
Ia-325~Id-325	4-NO₂
Ia-326~Id-326	3-OPh
Ia-327~Id-327	2-Cl-4-OPh
Ia-328~Id-328	3-SCH₃
Ia-329~Id-329	3-SO₂CH₃
Ia-330~Id-330	4-SO₂CF₃
Ia-331~Id-331	h₂nco	H	H
la-332—Id-332	2-C1
Ia-333~Id-333	3-C1
Ia-334~Id-334	4-C1
Ia-335~Id-335	2,4-20
Ia-336~Id-336	2,6-20
Ia-337~Id-337	4-CN
Ia-338~Id-338	3-CN
Ia-339~Id-339	2-CH₃
Ia-34(Md-340	3-CH₃
Ia-341~Id-341	4-CH₃
Ia-342~Id-342	2,4-2CH₃
Ia-343~Id-343	3,5-2CH₃
l_a 344ffld 344	2,6-2CH₃
Ia-345~Id-345	3-F
Ia-346~Id-346	4-F
Ia-347~Id-347	4-CHF₂
Ia-348~Id-348	3-CF₃
Ia-349~Id-349	4-CF₃
Ia-35(Md-350	3-OCF₃
Ia-351~Id-351	4-OCF₃
la-352—Id-352	4-OCH₂CHF₂
Ia-353~Id-353	2,4-2F
Ia-354~Id-354	3,5-2OCH₃
Ia-355~Id-355	3,4,5-3OCH₃

100002

2010. 2

Description

Z16111319CPAU

Ia-356~Id-356			3,4-(CH₂)₂O
Ia-357~Id-357	2-NO₂
Ia-358~Id-358	3-NO₂
Ia-359~Id-359	4-NO₂
Ia-360~Id-360	3-OPh
Ia-361~Id-361	ch₃	H
Ia-362~Id-362	2-C1
Ia-363~Id-363	3-C1
Ia-364~Id-364	4-C1
Ia-365~Id-365	2,4-20
Ia-366~Id-366	2,6-20
Ia-367~Id-367	4-CN
Ia-368~Id-368	3-CN
Ia-369~Id-369	2-CH₃
Ia-370~Id-370	3-CH₃
Ia-371~Id-371	4-CH₃
Ia-372~Id-372	2,4-2CH₃
Ia-373~Id-373	3,5-2CH₃
Ia-374~Id-374	2,6-2CH₃
Ia-375~Id-375	3-F
Ia-376~Id-376	4-F
Ia-377~Id-377	4-CHF₂
Ia-378~Id-378	3-CF₃
Ia-379~Id-379	4-CF₃
Ia-380~Id-380	3-OCF₃
Ia-381~Id-381	4-OCF₃
Ia-382~Id-382	4-OCH₂CHF₂
Ia-383~Id-383	2,4-2F
Ia-384~Id-384	3,5-2OCH₃
Ia-385~Id-385	3,4,5-3OCH₃
Ia-386~Id-386	3,4-(CH₂)₂O
Ia-387~Id-387	2-NO₂
Ia-388~Id-388	3-NO₂
Ia-389~Id-389	4-NO₂

100002

2010. 2

Description

Z16111319CPAU

Ia-390~Id-390			3-OPh
Ia-391~Id-391	2-Cl-4-OPh
Ia-392~Id-392	3-SCH₃
Ia-393~Id-393	3-SO₂CH₃
Ia-394~Id-394	4-SO₂CF₃
Ia-395~Id-395	H₂NCS	H	H
Ia-396~Id-396	4-C1
Ia-397~Id-397	4-NO₂
Ia-398~Id-398	3-OPh
Ia-399~Id-399	ch₃	H
Ia-400~Id-400	4-C1
Ia-401~Id-401	4-CH₃
Ia-402~Id-402	2,4-201
Ia-403~Id-403	ch₃co	ch₃	H
Ia-404~Id-404	(CH₃)₃CO	ch₃	4-C1
Ia-405~Id-405	PhCO	ch₃	H

Ο

CONHCHg

Ο

CONHCH₃

Ie If

Ig

Ih

Number	Ri	r₃	Site of N	(R₅)n
Ie-l~Ih-l	ch₃oco	H	2	H
Ie-2~Ih-2	4-C1
Ie-3~Ih-3	5-C1
Ie-4~Ih-4	3,5-201
Ie-5~Ih-5	4-CH₃
Ie-6~Ih-6	6-F
Ie-7~Ih-7	4-NO₂
Ie-8~Ih-8	4-CF₃
Ie-9~Ih-9	4-OCH₃
Ie-10~Ih-10	4-OCF₃
Ie-ll~Ih-ll	3	H
Ie-12~Ih-12	4-C1

100002

2010. 2

Description

Z16111319CPAU

100002

2010. 2

Description

Z16111319CPAU

Ie-47Oh-47				4-NO₂
Ie-48Oh-48	4-CF₃
Ie-49Oh-49	4-OCH₃
Ie-500h-50	4-OCF₃
Ie-51 Oh-51	4	H
Ie-52Oh-52	3-C1
Ie-53Oh-53	5-C1
Ie-54Oh-54	3,5-20
Ie-55Oh-55	3-CH₃
Ie-56Oh-56	6-F
Ie-57Oh-57	3-NO₂
Ie-58Oh-58	5-CF₃
Ie-59Oh-59	2-OCH₃
Ie-600h-60	5-OCF₃
Ie-61 Oh-61	C₂H₅OCO	H	2	H
Ie-62Oh-62	4-0
Ie-63Oh-63	5-0
Ie-64Oh-64	3,5-20
Ie-65Oh-65	4-CH₃
Ie-66Oh-66	6-F
Ie-67Oh-67	4-NO₂
Ie-68Oh-68	4-CF₃
Ie-69Oh-69	4-OCH₃
Ie-700h-70	4-OCF₃
Ie-71 Oh-71	3	H
Ie-72Oh-72	4-0
Ie-73Oh-73	2-0
Ie-74Oh-74	2,5-20
Ie-75Oh-75	4-CH₃
Ie-76Oh-76	6-F
Ie-77Oh-77	4-NO₂
Ie-78Oh-78	4-CF₃
Ie-79Oh-79	4-OCH₃
Ie-800h-80	4-OCF₃

100002

2010. 2

Description

Z16111319CPAU

Ie-81~Ih-81

Ie-82~Ih-82

Ie-83~Ih-83

Ie-84~Ih-84

Ie-85~Ih-85

Ie-86~Ih-86

Ie-87~Ih-87

Ie-88~Ih-88

Ie-89~Ih-89

Ie-90~Ih-90

Ie-91~Ih-91

Ie-92~Ih-92

Ie-93~Ih-93

Ie-94~Ih-94

Ie-95~Ih-95

Ie-96~Ih-96

Ie-97~Ih-97

Ie-98~Ih-98

Ie-99~Ih-99

Ie-100~Ih-100

Ie-1010h-101

Ie-102~Ih-102

Ie-103~Ih-103

Ie-104~Ih-104

Ie-105~Ih-105

Ie-106~Ih-106

Ie-107~Ih-107

Ie-108~Ih-108

Ie-109~Ih-109

Ie-1100h-110

Ie-lllOh-111

Ie-112~Ih-112

Ie-113~Ih-113

Ie-114~Ih-114

ch₃

3-C1

5-C1

3,5-20

3-CH₃

6-F

3-NO₂

5-CF₃

2-OCFF

5-OCF,

4-C1

5-C1

3,5-20

4-CFF

6-F

4-NO,

4-CF₃

4-OCFF

4-OCF,

4-0

2-0

2,5-20

4-CFF

6-F

4-NO?

4-CF?

4-OCFF

4-OCF,

3-0

5-0

3,5-20

100002

2010.2

Description

Z16111319CPAU

100002

2010. 2

Description

Z16111319CPAU

Ie-149~Ih-149				2-OCH₃
Ie-150~Ih-150	5-OCF₃
Ie-151~Ih-151	ch₃	2	H
Ie-152~Ih-152	4-C1
Ie-153~Ih-153	5-C1
Ie-154~Ih-154	3,5-201
Ie-155~Ih-155	4-CH₃
Ie-156~Ih-156	6-F
Ie-157~Ih-157	4-NO₂
Ie-158~Ih-158	4-CF₃
Ie-159~Ih-159	4-OCH₃
Ie-160~Ih-160	4-OCF₃
Ie-161~Ih-161	3	H
Ie-162~Ih-162	4-C1
Ie-163~Ih-163	2-C1
Ie-164~Ih-164	2,5-201
Ie-165~Ih-165	4-CH₃
Ie-166~Ih-166	6-F
Ie-167~Ih-167	4-NO₂
Ie-168~Ih-168	4-CF₃
Ie-169~Ih-169	4-OCH₃
Ie-170~Ih-170	4-OCF₃
Ie-171~Ih-171	4	H
Ie-172~Ih-172	3-C1
Ie-173~Ih-173	5-C1
Ie-174~Ih-174	3,5-201
Ie-175~Ih-175	3-CH₃
Ie-176~Ih-176	6-F
Ie-177~Ih-177	3-NO₂
Ie-178~Ih-178	5-CF₃
Ie-179~Ih-179	2-OCH₃
Ie-180~Ih-180	5-OCF₃
Ie-181~Ih-181	(CH₃)₃COCO	H	2	H
Ie-182~Ih-182	4-C1

100002

2010. 2

Description

Z16111319CPAU

100002

2010. 2

Description

Z16111319CPAU

100002

2010. 2

Description

Z16111319CPAU

Ie-251 Oh-251

Ie-252~Ih-252

Ie-253~Ih-253

Ie-254~Ih-254

Ie-255~Ih-255

Ie-256~Ih-256

Ie-257~Ih-257

Ie-258~Ih-258

Ie-259~Ih-259

Ie-260~Ih-260

Ie-261 Oh-261

Ie-262~Ih-262

Ie-263~Ih-263

Ie-264~Ih-264

Ie-265~Ih-265

Ie-267~Ih-267

Ie-268~Ih-268

Ie-269~Ih-269

Ie-270~Ih-270

Ie-271 Oh-271

Ie-272~Ih-272

Ie-273~Ih-273

Ie-274~Ih-274

Ie-275~Ih-275

Ie-276~Ih-276

Ie-277~Ih-277

Ie-278~Ih-278

Ie-279~Ih-279

Ie-280~Ih-280

Ie-281~Ih-281

Ie-282~Ih-282

Ie-283~Ih-283

Ie-284~Ih-284

Ie-285~Ih-285

ch₃

4-0

2-0

2,5-20

4-CH,

6-F

4-NO?

4-CF,

4-OCFF

4-OCF,

3-0

5-0

3,5-20

3-CH,

6-F

3-NO,

5-CF,

2-OCH,

5-OCF,

4-0

5-0

3,5-20

4-CH,

6-F

4-NCF

4-CF,

4-OCH,

4-OCF,

4-0

2-0

2,5-20

100002

2010.2

Description

Z16111319CPAU

Ie-286~Ih-286				4-CH₃
Ie-287~Ih-287	6-F
Ie-288~Ih-288	4-NO₂
Ie-289~Ih-289	4-CF₃
Ie-290~Ih-290	4-OCH₃
Ie-291 Oh-291	4-OCF₃
Ie-292Oh-292	4	H
Ie-293Oh-293	3-C1
Ie-294Oh-294	5-C1
Ie-295Oh-295	3,5-20
Ie-296Oh-296	3-CH₃
Ie-297Oh-297	6-F
Ie-298Oh-298	3-NO₂
Ie-299Oh-299	5-CF₃
Ie-3000h-300	2-OCH₃
Ie-3010h-301	5-OCF₃
Ie-3020h-302	NH₂CO	H	2	H
Ie-3030h-303	4-0
Ie-3040h-304	5-0
Ie-3060h-305	3,5-20
Ie-3070h-307	4-CH₃
Ie-3080h-308	6-F
Ie-3090h-309	4-NO₂
Ie-3100h-310	4-CF₃
Ie-311Oh-311	4-OCH₃
Ie-312Oh-312	4-OCF₃
Ie-313Oh-313	3	H
Ie-314Oh-314	4-0
Ie-315Oh-315	2-0
Ie-316Oh-316	2,5-20
Ie-317Oh-317	4-CH₃
Ie-318Oh-318	6-F
Ie-319Oh-319	4-NO₂
Ie-3200h-320	4-CF₃

100002

2010. 2

Description

Z16111319CPAU

Ie-321 Oh-321

Ie-322Oh-322

Ie-323Oh-323

Ie-324Oh-324

Ie-325Oh-325

Ie-326Oh-326

Ie-327Oh-327

Ie-328Oh-328

Ie-329Oh-329

Ie-3300h-330

Ie-331Oh-331

Ie-332Oh-332

Ie-333Oh-333

Ie-334Oh-334

Ie-335Oh-335

Ie-336Oh-336

Ie-337Oh-337

Ie-338Oh-338

Ie-339Oh-339

Ie-3400h-340

Ie-341 Oh-341

Ie-342Oh-342

Ie-343Oh-343

Ie-344Oh-344

Ie-345Oh-345

Ie-346Oh-346

Ie-347Oh-347

Ie-348Oh-348

Ie-349Oh-349

Ie-3500h-350

Ie-351Oh-351

Ie-352Oh-352

Ie-353Oh-353

Ie-354Oh-354

4-OCH,

4-OCF,

3-C1

5-C1

3,5-20

3-CFF

6-F

3-NO?

5-CF₃

2-OCFF

5-OCF,

4-0

5-0

3,5-20

4-CFF

6-F

4-NO?

4-OF

4-OCFF

4-OCF, ch₃

4-0

2-0

2,5-20

4-CFF

6-F

4-NCF

4-CF,

4-OCFF

4-OCF,

3-0

100002

2010. 2

Description

Z16111319CPAU

Note: N in pyridine ring coupled with (R₅)_n may be located at site 2, 3 or 4 in above table.

The preparation method of benzylhydrazone compounds (compounds shown as formula I) provided by the present invention includes the following steps: in the presence of catalyst, condensation reaction is performed to the compound shown as formula IV and the compound shown as formula V in organic solvent, to yield the compound shown as formula I.

ii ,R₂

Br .J r °

COYCHy formula I formula V io In the formula IV, the definitions to R_b R₂ and R₃ are same as formula I; in the formula V, the definitions to X and Y are same as formula I.

In the above preparation method, the catalyst is base, and the base is selected from at least one of sodium hydride, sodium amide, lithium amide, lithium diisopropylamide, n-butyllithium and phenyllithium.

The molar ratio of the catalyst to the compound shown as formula IV is 1 :

(1.2-3).

The reaction temperature of the condensation reaction is -5-100 °C, preferably 10-50°C, and particularly 25°C. The reaction time is 2-12 h, and particularly 4-9 h.

The molar ratio of the compound shown as formula IV to the compound shown as formula V is 1 : (1-2), and particularly 1 : (1-1.3).

The organic solvent is selected from at least one of N,N-Dimethylformamide

100002

2010. 2

C:\Interwoven\NRPortbl\DCC\RBR\l 7219907_l.docx-26/06/2018

2015401326 26 Jun2018

Bi ,NH2 H formula II (DMF), N-methylpyrrolidone and dimethoxyethane.

The condensation reaction is preferably performed according to the following steps: dissolving the catalyst and the compound shown as formula IV into organic solvent, stirring at -10-5°C for 0.5-2h, and then adding the compound shown as formula V thereto and reacting at

-5~100°C for 2-12 h, to yield the compound shown as formula I.

In the above preparation method, the compound shown as formula IV is prepared in accordance with the following method: reacting the compound shown as formula II with the compound shown as formula III in organic solvent, to yield the compound shown as formula IV,

R2COR3 formula III

In the formula II, the definition to Ri is same as formula I; In the formula III, the definitions to both R₂ and R3 are same as formula I.

Wherein, the molar ratio of the compound shown as formula II to the compound shown 15 as formula III is 1 : (1-2), and particularly 1:1.

The reaction temperature of the reaction is -20~50°C, and the reaction time is 1-6 h.

The organic solvent is methanol or ethanol.

The compounds shown as formula II, formula III and formula V are all commercially available, for example, the compound shown as formula II maybe particularly alkylhydrazine, arylhydrazine, acylhydrazine, alkoxycarbonylhydrazine, semicarbazide, thiosemicarbazide or cyanohydrazine, etc.

Another object of the present invention is to provide fixngicide and/or insecticide composition and preparation method thereof. This composition comprises benzylhydrazone compounds (the compound shown as formula I) and agriculturally acceptable carrier, wherein, the weight percentage of benzylhydrazone compounds (active component) is 0.1-99%, particularly 30-60% in this composition.

Description

Z16111319CPAU

The preparation method of the fungicide and/or insecticide composition provided by the present invention comprises the following steps: mixing the benzylhydrazone compounds (the compound shown as formula I) with the agriculturally acceptable carrier, to yield the composition.

The benzylhydrazone compounds not only may be a single compound of the present invention, but also may be a mixture of several compounds of the present invention.

The agriculturally acceptable carrier has features as follows: 1) easy to apply to a site to be treated after formulating with an active component, such as plant, seed, or soil; 2) advantageous to store, transport or operate; 3) can be solid or liquid, comprising substances that are typically a gas but have been compressed into liquid. In a word, any carrier, which is commonly used to formulate the agriculturally available insecticidal and fungicidal composition, can be used.

The agriculturally acceptable carrier can be particularly selected from solid carrier and/or liquid carrier.

The solid carrier is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminosilicate oxide, natural or synthetic resin, polychlorophenol, starch, bentonite and wax, wherein the natural or synthetic silicate may be particularly selected from at least one of attapulgite, talc, aluminosilicate, diatomite, mica, montmorillonite and calcium silicate. The natural or synthetic resin may be particularly selected from at least one of benzofuran resin, styrene polymer (with a molecular weight of 50,000-200,000) and styrene copolymer(e.g., styrene-butadiene copolymer); The wax may be particularly selected from beeswax and/or paraffin.

The liquid carrier is selected from at least one of water, Ci-C₄ alcohol, C₃-C₈ ketone, aromatic hydrocarbon, petroleum fraction and C₆-C_i2 chlorinated hydrocarbon, wherein the alcohol may be particularly ethanol and/or ethylene glycol; the ketone may be particularly at least one of acetophenone, propanone, methyl ethyl ketone and cyclohexanone; the aromatic hydrocarbon may be particularly at least one of benzene, toluene, and xylene; the petroleum fraction may be particularly kerosene and/or mineral oil; the chlorinated hydrocarbon may be particularly at least one of tetrachloromethane, dichloromethane and

100002

2010. 2

Description

Z16111319CPAU trichloroethane.

Generally, the fungicide and/or insecticide composition is typically processed into a form of concentrate for transporting, and is diluted by the user before application.

In order to facilitate diluting, the fungicide and/or insecticide composition provided by the present invention may also comprise surfactant.

The addition amount of the surfactant can be an amount that is acceptable for the use of fungicide and/or insecticide in agriculture.

The surfactant is selected from at least one of emulsifier, dispersant, wetting 10 agent and penetrant.

The emulsifier may be particularly selected from at least one of agricultural emulsifier 500# (calcium alkylbenzene sulfonate), agricultural emulsifier 600# phosphate (phenyl-phenol polyoxyethylene ether), agricultural emulsifier 700# (alkyl-phenol formaldehyde resin polyoxyethylene ether), agricultural emulsifier

1600# (phenylethylphenol polyoxyethylene polypropylene ether), polyoxyalkylene alkylarylether and ethylene oxide-propylene oxide block copolymer.

The dispersant may be particularly selected from at least one of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate salt, benzene sulfonic acid formaldehyde condensate sodium salts, sodium lauryl sulfate, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester and ester polyoxyethylene ether.

The wetting agent may be particularly selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, Nekal BX, shikakai powder, silkworm excrement and sapindus mukurossi powder.

The penetrant may be particularly selected from at least one of siloxane polyoxyethylene ether, alkylaryl sulfonate, alcohol ether succinate and phenol ether succinate.

Certainly, other aids may be appropriately added into the fungicide and/or insecticide composition of the present invention.

The addition amount of other aids can be an amount that is acceptable for the use of fungicide and/or insecticide in agriculture.

100002

2010. 2

Description

Z16111319CPAU

The other aids may be selected from at least one of disintegrant, defoamer, cryoprotectant and thickener.

The disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, aluminium chloride and glucose.

The defoamer is selected from at least one of silicone oil, silicone compounds,

C10-C20 saturated fatty acid compounds, C8-C10 fatty alcohol compounds.

The cryoprotectant is selected from at least one of ethylene glycol, propylene glycol, glycerol and polyethylene glycol.

The thickener is selected from at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.

Corresponding components may be added into the fungicide and/or insecticide composition prepared in the present invention in accordance with the method well known for those skilled in the art, thereby preparing various dosage forms such as wettable powder, powder, granule, concentrated emulsion, emulsified oil, suspension, aerosol or smoke agent, etc.

Meanwhile, an effective amount of the fungicide and/or insecticide composition of the present invention can be applied according to different plants and diseases, and such application may be performed by foliar spraying, seed treatment or soil treatment.

In certain aspects, one or more other fungicides may be added into the fungicide and/or insecticide composition of the present invention, so as to generate additional advantages and effects; the compound shown as formula I provided by the present invention may be also mixed with other fungicides and/or insecticides.

Additionally, the use of the compound shown as formula I provided by the present invention and the composition thereof in preparation of botanical fungicides and/or insecticides also belongs to the protection scope of the present invention.

The compound shown as formula I provided by the present invention has a broad spectrum and excellent fungicidal activity, and can be used in preventing and treating diseases on many plants resulting from four pathogenic eumycetes: ascomycetes, basidiomycetes, deuteromycetes and oomycete diseases. A good preventing and treating effect can be obtained at a very low dose. At the same

100002

2010. 2

Description

Z16111319CPAU time, this kind of compounds shown as formula I have a certain systemic and can be used as leaf surface and soil fungicide for preventing and treating diseases on many plants. It can particularly prevent and treat the following diseases: pepper phytophthora blight, tomato early blight, tomato late blight, rice blast, wheat leaf rust, apple ring rot, rice sheath blight, rice blast, ustilaginoidea virens, rice bakanae disease, wheat powdery mildew, sclerotinia sclerotiorum, cucumber downy mildew, cucumber fusarium wilt, botrytis cinerea, cucumber powdery mildew or apple powdery mildew.

Furthermore, a portion of compounds shown as formula I of the present invention also have a better insecticidal and acaricidal activity, e.g.: Ia-84, Id-397, Ih-259, etc. which can be used to prevent and treat insects and mites on plants.

The side chain of the benzylhydrazone compounds prepared in the present invention is benzylhydrazone structure, and these benzylhydrazone compounds and the composition thereof can prevent and treat harmful fungi and insects (e.g., mythimna separata, plutella xylostella, myzus persicae and carmine spider mite) of plant (e.g., crop: pepper, tomato, rice, wheat, apple, rape and cucumber, etc.), and have a broad spectrum and excellent insecticidal effect.

Description of drawings

Fig. 1 is a flow chart of preparation of the compound shown as formula I.

Preferred embodiments of the invention

The present invention will be described in detail according to Examples below, but the present invention is limited thereto.

The methods in the following examples are all the common method, unless specially stated; the reagents and materials are all commercially available, unless specially stated.

I. Preparation Example of the compound shown as formula I is as follows, and the corresponding preparation flow chart is shown as figure 1:

Example 1. Preparation of compound la-4:

In a 100 mL 3-neck flask, 15 mL DMF solution containing 0.93 g (6.9mmol) l-benzylidene-2-methylhydrazine was added, and then the temperature is cooled

100002

2010. 2

C:\Intcrwovcn\NRPortbl\DCC\RBR\l 72I99O7_ I .docx-26/06/2018

2015401326 26 Jun2018 below 5°C; 0.53g (12 mmol) NaH oil dispersible granule with a mass fraction of 70% was added, after stirring for lh, 2.35g (8.2 mmol) (£)-2-(2-bromomethyl)phenyl-2methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 8h. The reaction was quenched with water and gray solid was precipitated out; the precipitate was purified with column chromatography to yield 2.2 g white powder, yield: 82%, melting point: 78-80°C.

‘HNMR(300MHz, CDC1₃) δ, 2.93(s, 3H), 3.04(s, 3H), 3.75(s, 3H), 3.8l(s, 3H), 3.85(s, 2H), 7.22-7.95(m, 9H), 8.1 l(s, 1H).

¹³C NMR (75MHz, CDC1₃) δ 23.0, 44.2, 50.6, 59.1, 60.2, 104.6, 126.2, 126.8, 127.4, 10 128.2, 128.6, 128.9, 130.8, 133.0, 137.5, 158.4, 164.0, 168.5.

The compounds of numbers Ia-l~Ia-14 to Id-1—Id-14 were all prepared in accordance with the method in example 1.

Wherein, the compound la-11: greyish-white powder, yield: 77%, melting point: 77-79°C , ‘H NMR and ¹³C NMR are as follows:

‘HNMR(300MHz, CDC1₃) δ 1.23(S, 9H), 2.95(s, 3H), 3.77(S, 3H), 3.80(s, 3H), 3.8l(s,

2H), 7.21-7.89(m, 9H), 8.13(s, 1H).

¹³C NMR (75MHz, CDC1₃) δ 17.7, 28.1, 52.5, 52.8, 60.0, 77.2, 104.6, 126.2, 126.8, 127.4, 128.4, 128.8, 128.9, 130.5, 131.1, 133.6, 137.2, 158.4, 164.0, 168.8.

The compound Ib-11: white powder, melting point: 102-104°C, yield: 82%,¹ HNMR and 20 ¹³C NMR are as follows:

‘HNMR(300MHz, CDC1₃) δ 1.27(s, 9H), 2.73(s, 3H), 2.95(s, 3H), 3.80(s, 3H), 3.81(s, 2H), 7.21-7.95(m, 9H), 8.01(s, 1H).

¹³C NMR (75MHz, CDC1₃) δ 17.5, 26.3, 28.7, 51.4, 59.8, 77.6, 104.1, 126.1, 126.8, 127.9, 128.0, 128.8, 128.9, 130.7, 131.2, 133.4, 137.6, 158.4, 168.2, 172.5.

The compound Ic-11: light yellow powder, melting point: 86-88°C, yield: 73%, ‘HNMR and ¹³C NMR are as follows:

‘HNMR(300MHz, CDC1₃) δ 1.28(s, 9H), 2.97(s, 3H), 3.72(s, 3H), 3.80(s, 2H), 3.96(s, 3H), 7.24-7.96(m, 9H);

¹³C NMR(75MHz, CDC1₃) δ 17.3,28.3,52.5,52.7,64.3,77.4,123.0,125.3,127.1,128.2, 30 128.8, 130.8, 131.0, 131.1, 131.7, 137.5, 149.7, 163.7, 168.8.

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The compound Id-11: white powder, melting point: 108-110°C, yield: 89%, 'HNMRand ¹³C NMR are as follows:

'HNMR(300MHz, CDCIs) δ 1.32(s, 9H), 2.66(s, 3H), 2.98(s, 3H), 3.82(s, 2H), 3.96(s, 3H), 7.50-7.93(m, 9H);

¹³C NMR(75MHz, CDC1₃) δ 17.8, 26.2, 28.6, 64.4, 77.5, 123.7, 125.0, 127.4, 128.2,

128.6, 130.8, 131.2, 131.4, 131.9, 137.1, 151.7, 164.2, 168.8.

Example 2: Preparation of compound Ic-109:

In a 100 mL 3-neck flask, ethyl 2-(l-(4-chlorophenyl) ethylidene)hydrazinocarboxylate (0.5g, 0.0021mol) and 15 mL DMF were added and the temperature was cooled below 5°C;

0.13g (0.00315 mol) NaH oil dispersable granule with a mass fraction of 70% was added, after stirring for lh, 0.72 g (0.0025 mol) (£)-2-(2-bromomethyl)phenyl-2-methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 9h. The reaction was quenched with water and solid was precipitated out; the precipitate was purified with column chromatography to yield 0.71 g light yellow solid, yield: 77%, melting point: 123-125°C, *H NMR and ¹³C NMR are as follows:

*H NMR (300 MHz, DMSO) δ 7.80 (d, J = 8.6 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H),

7.39-7.34 (m„ 3H), 7.16-7.15 (m, 1H), 4.62 (s, 2H), 4.08 (q, J= 7.0 Hz, 2H), 3.93 (s, 3H), 3.66 (s, 3H), 1.99 (s, 3H), 1.17 (t, 7= 7.1 Hz, 3H).

¹³C NMR (75 MHz, DMSO) δ 169.65, 162.93, 152.44, 148.94, 135.86, 135.80, 135.61,

130.08, 129.42, 128.88, 128.71, 128.65, 127.38, 63.52, 61.89, 52.65, 52.20, 40.62, 40.34,

40.07, 39.79, 39.51, 39.23, 38.95, 16.82, 14.56.

The compounds of numbers Ia-15~Ia-264 to Id-15~Id-264 and Ie-l~Ie-240 to Ih-1—Ih240 were all prepared in accordance with the method in example 2.

Wherein, the compound Ic-228: white powder, melting point: 126-128°C, yield: 70%, *H

NMR and ¹³C NMR are as follows:

'HNMR(300 MHz, DMSO) δ 8.26 (d,7=9.1 Hz, 2H), 8.01 (d,7=9.1 Hz, 2H), 7.427.26 (m, 3H), 7.14 (m, 1H), 4.64 (s, 2H), 3.93 (s, 3H), 3.66 (s, 3H), 2.04 (s, 3H), 1.39 (s, 9H).

¹³CNMR(75 MHz, DMSO) δ 168.25, 162.95, 151.06, 148.96, 148.65, 143.16, 135.95, 130.09, 129.37, 128.88, 128.72, 128.27, 127.37, 123.72, 81.12, 63.55, 52.67, 27.99, 17.35.

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The compound Ic-259: white solid, melting point: 149-151°C, yield: 79%, *HNMR and ¹³C NMR are as follows:

*H NMR (300 MHz, CDC1₃) δ 8.38 - 8.30 (m, IH), 8.14-8.12 (m, IH), 8.02-7.99 (m, IH), 7.53-7.50 (m, 2H), 7.42 - 7.29 (m, 2H), 7.17-7.13 (m, 2H), 4.99 (s, 2H), 4.14 (s, 3H),

3.96 (s, 3H), 1.62 (s, 9H).

¹³CNMR(75 MHz, DMSO) δ 163.07, 152.96, 148.75, 148.39, 138.12, 136.76, 133.58, 132.69,130.62,129.93,129.51, 128.84,127.47,125.78,123.82,120.84, 81.92, 63.77, 52.97, 45.88,28.02.

The compound If-222: white solid, melting point: 162-164°C, yield: 76%, *H NMR and 10 ¹³C NMR are as follows:

‘HNMR(300 MHz, CDCI3) δ 1.38(s, 9H), 2.95(s, 3H), 3.68(s, 3H), 3.93(s, 3H), 6.10(s, 2H), 7.10-7.71(m, 5H), 8.54(d, IH), 9.04(d, IH);

¹³C NMR (75 MHz, DMSO) δ 17.3, 28.5, 51.4, 52.8, 64.1, 84.4, 121.5, 124.3, 125.0, 125.2, 126.8, 130.0, 130.6, 136.9, 139.1, 149.7, 152.4, 153.4, 154.7, 163.5, 168.8.

Example 3: Preparation of compound If-283:

In a 100 mL 3-neck flask, (0.5g, 2.3 mmol) 2-((6-chloropyridine-3-yl)methylene)-lcyanohydrazine and 15 mL DMF were added and the temperature was cooled below 5°C; 0.12g (3.3 mmol) NaH oil dispersable granule with a mass fraction of 70% was added, after stirring for lh, 0.79 g (2.8 mmol) (£)-2-(2-bromomethyl)phenyl-2-methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 5h. The reaction was quenched with water and solid was precipitated out; the precipitate was purified with column chromatography to yield 0.73 g yellow powder, yield: 80%, melting point: 170-172°C, 'HNMRand ¹³C NMR are as follows:

‘HNMR (300 MHz, DMSO) δ 8.69 (d, J= 1.9 Hz, IH), 8.12 (dd, J= 8.4, 2.6 Hz, IH),

7.60 (d, J= 8.5 Hz, IH), 7.50-40 (m, 3H), 7.26-7.21 (m, IH), 4.60 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.38 (s, 3H).

¹³CNMR(75 MHz, DMSO) δ 162.86, 162.06, 152.22, 148.84, 148.43, 137.94, 132.94, 131.80, 130.82, 130.23, 129.73, 129.20, 128.65, 124.39, 112.95, 63.72, 58.31, 52.86, 15.96.

The compounds of numbers Ia-265~Ia-330 to Id-265~Id-330 and Ie-241~Ie-301 to Ih30 241 —Ih-301 were all prepared in accordance with the method in example 3.

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Wherein, the compound Ic-296: white solid, melting point: 156-158°C, yield: 71%, *H NMR and ¹³C NMR are as follows:

'HNMR (300 MHz, DMSO) δ 7.71-7.58 (m, 2H), 7.54-7.35 (m„ 6H), 7.31 - 7.14 (m, 1H), 4.57 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.35 (s, 3H).

¹³C NMR (75 MHz, DMSO) δ 165.61, 162.85, 148.87, 136.54, 133.09, 130.94, 130.83,

130.17, 129.68, 129.19, 128.74, 128.56, 127.03, 113.53, 63.70, 58.18, 52.82, 16.22.

The compound Ic-315: white solid, melting point: 172-174°C, yield: 73%, *HNMR and ¹³C NMR are as follows:

*H NMR (300 MHz, DMSO) δ 7.91 (d, J = 8.3 Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H),

7.55-7.49 (m, 3H), 7.29 - 7.26 (m, 1H), 4.62 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.40 (s, 3H).

¹³C NMR (75 MHz, DMSO) δ 163.73, 162.85, 148.85, 140.46, 132.96, 130.94, 130.81,

130.52, 130.15, 129.71, 129.22, 128.62, 127.85, 126.00, 125.67, 125.62, 122.39, 112.97, 63.70,58.38,52.65, 16.33.

Example 4: Preparation of compound Ic-361:

In a 100 mL 3-neck flask, 15 mL DMF solution containing 0.41g (2.3mmol) 2-(1phenylethylidene)hydrazinoformamide was added and the temperature was cooled below 5°C; 0.12g (3.3 mmol) NaH oil dispersable granule with a mass fraction of 70% was added, after stirring for lh, 0.79 g (2.8 mmol) (£)-2-(2-bromomethyl)phenyl-2-methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 4h. The reaction was quenched with water and solid was precipitated out; the precipitate was purified with column chromatography to yield a white powder, yield: 65%, melting point: 184-186°C, *H NMR and ¹³C NMR are as follows:

‘HNMR (300 MHz, DMSO) δ 2.93(s, 3H), 3.62(s, 3H), 3.95(s, 3H), 5.92(s, 2H), 7.127.86(m, 9H), 8.11(bs, 2H);

¹³C NMR (75 MHz, DMSO) δ 19.3, 51.2, 52.8, 64.4, 122.7, 125.6, 126.8, 128.0, 129.0,

130.5, 130.8, 131.1, 136.9, 137.4, 149.0, 155.2, 163.3, 170.0.

The compounds of numbers Ia-331~Ia-394 to Id-331—Id-394 and Ie-302~Ie-362 to Ih302-IH-362 were all prepared in accordance with the method in example 4.

Wherein the compound la-336: white solid, yield: 74%, mp 207-209°C, *HNMR and ¹³C

NMR are as follows:

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2015401326 26 Jun 2018 *H NMR (300 MHz, DMSO) δ 3.23 (s, 3H), 3.76 (s, 3H), 6.31 (s, 2H), 7.18-7.75 (m, 10H), 8.41 (bs, 1H);

¹³CNMR(75 MHz, DMSO) δ49.5, 50.6, 59.1,104.7,125.6,126.5,127.7,128.2,129.1, 129.8, 130.0, 130.6, 133.5, 134.6, 143.5, 155.4, 158.2, 164.7.

The compound Ie-331: white solid, yield: 56%, mp 241-243°C, *H NMR and ¹³C NMR are as follows:

'HNMR (300 MHz, DMSO) δ 3.36 (s, 3H), 3.62 (s, 3H), 3.77 (s, 3H), 6.34 (s, 2H), 7.03 (s, 1H), 7.21-7.74 (m, 9H), 8.49 (s, 1H);

¹³CNMR(75 MHz, DMSO) δ 49.4, 50.3, 54.1, 59.5, 104.2, 115.6, 116.2, 126.2, 126.6,

127.7, 129.9, 134.1, 134.6, 140.5, 146.9, 155.3, 157.1, 158.3, 164.5.

Example 5: Preparation of compound Ic-400:

In a 100 mL 3-neck flask, 15 mL DMF solution containing 0.64 g(2.3 mmol) 2-(1-(4chlorophenyl)ethylidene) hydrazinothioformamide was added and the temperature was cooled below 5°C; 0.12g (3.3 mmol) NaH oil dispersable granule with a mass fraction of 70% was added, after stirring for lh, 0.79 g (2.8 mmol) (F)-2-(2-bromomethyl)phenyl-2-methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 4h. The reaction was quenched with water and solid was precipitated out; the precipitate was purified with column chromatography to yield white powder, yield: 72%, melting point: 178-180°C, *H NMR and ¹³C NMR are as follows:

‘HNMR (300 MHz, DMSO) δ 2.90(s, 3H), 3.58(s, 3H), 3.63(s, 3H), 5.69(s, 2H), 7.217.86(m, 8H), 8.01(bs, 2H);

¹³C NMR (75 MHz, DMSO) δ 20.3, 52.0, 56.4, 64.0, 121.4, 125.3, 126.5, 128.1, 128.8, 130.0, 130.7, 135.4, 136.8, 136.9, 149.2, 163.6, 170.1, 176.6.

The compounds of numbers Ia-395~Ia-402 to Id-395~Id-402 were all prepared in accordance with the method in example 5.

Wherein the compound la-400: white solid, yield: 70%, mp 211-213°C, *H

Description

Z16111319CPAU

NMR and ¹³C NMR are as follows:

NMR (300 MHz, DMSO) δ 2.95(s, 3H), 3.53 (s, 3H), 3.72 (s, 3H), 5.60 (s, 2H), 7.12 (s, 1H), 7.20-7.94 (m, 8H), 8.41 (bs, 2H);

¹³C NMR (75 MHz, DMSO) δ 21.1, 50.7, 57.2, 59.6, 105.0, 126.0, 126.4,

127.3, 128.2, 128.9, 129.9, 132.5, 134.1, 135.6, 136.6, 158.4, 164.3, 170.0, 176.2.

The compound Ic-397: white solid, yield: 64%, mp 257-259Ό, ^JH NMR and ¹³C NMR are as follows:

*H NMR (300 MHz, DMSO) δ 3.64 (s, 3H), 4.00 (s, 3H), 5.85 (s, 2H), 7.23-8.62 (m, 11H).

io ¹³C NMR (75 MHz, DMSO) δ 50.7, 56.6, 64.3, 121.5, 123.7, 124.0, 124.9, 126.0, 129.6, 131.1, 136.3, 139.3, 146.2, 149.7, 150.0, 163.5, 176.0.

Example 6: Preparation of compound Ic-404:

In a 100 mL 3-neck flask, 15 mL ML solution containing 0.58 g(2.3 mmol) N'-(l-(4-chlorophenyl) ethylidene) pivaloylhydrazine was added and the temperature was cooled below 5°C; 0.12g (3.3 mmol) NaH oil dispersable granule with a mass fraction of 70% was added, after stirring for lh, 0.79 g (2.8 mmol) (£)-2-(2-bromomethyl)phenyl-2-methoxyimino methyl acetate was added and the temperature was increased to room temperature (25°C) for subsequently reacting for 4h. The reaction was quenched with water and white solid was precipitated out; the precipitate was purified with column chromatography to yield white powder, yield: 46%, melting point: 148-150 °C, ^JH NMR and ¹³C NMR are as follows:

*H NMR (300 MHz, CDC1₃) δ 1.24(s, 9H), 2.90(s, 3H), 3.65(s, 3H), 3.88(s, 3H), 6.04(s, 2H), 7.20-7.88(m, 8H);

¹³C NMR (75 MHz, CDC1₃) δ 20.0, 28.6, 39.5, 50.7, 52.7, 64.3, 122.0, 125.3,

126.8, 128.2, 128.9, 130.1, 130.8, 135.6, 136.6, 136.9, 149.7, 163.7, 170.1, 183.0.

The compounds of numbers Ia-403~Ia-405 to Id-403~Id-405 were all prepared in accordance with the method in example 6.

Wherein, the compound Ic-403: white solid, yield: 78%, mp 195-197 °C, ^JH

NMR and ¹³C NMR are as follows:

*H NMR (300 MHz, CDC1₃) δ 2.16(s, 3H), 2.91 (s, 3H), 3.66 (s, 3H), 3.92 (s,

3H), 6.14 (s, 2H), 7.21-7.954 (m, 9H).

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Description

Z16111319CPAU ¹³C NMR (75 MHz, CDC1₃) δ 20.0, 24.6, 49.4, 52.8, 64.5, 120.9, 125.2, 126.5, 128.0, 128.4, 130.0, 130.7, 130.9, 136.3, 136.9, 149.1, 163.0, 168.2, 170.3.

The compound Id-403: white solid, yield: 68%, mp 207-209°C, NMR and ¹³C NMR are as follows:

NMR (300 MHz, CDC1₃) δ 2.14 (s, 3H), 2.77 (s, 3H), 3.00 (s, 3H), 3.92 (s,

3H), 6.19 (s, 2H), 7.28-8.06 (m, 10H).

¹³CNMR(75 MHz, CDCl₃)6 20.2, 24.9,26.0, 49.8, 63.8, 120.6, 125.0, 126.1, 128.2, 128.7, 130.5, 131.1, 132.8, 136.3, 137.2, 151.4, 163.6, 168.7, 170.3.

II. Examples of compositions containing the compounds shown as formula I io are as follows: (the content of each of the following components was in weight percentage, the active component was added after the amount thereof was converted into percentage content)

Example 7: Preparation of a wettable powder containing 50% of compound shown as formula I:

The composition of the wettable powder: 50% of the compound shown as formula I, 5% of disperant polycarboxylate, 3% of wetting agent sodium dodecyl sulfate, 42% of solid carrier or disintegrant bentonite; a mixture was obtained by mixing each of the above components in accordance with the described ratio, and jet milled, to yield 50% of wettable powder.

Example 8: Preparation of an emulsified oil containing 30% of compound shown as formula I:

The composition of the emulsified oil: 30% of the compound shown as formula I, 12% of emulsifier polyoxyalkylene alkylarylether, 10% of penetrant alkylaryl sulfonate, 48% of liquid carrier cyclohexanone; a clear solution containing 30% of the compound was obtained by mixing each of the above components in accordance with the described ratio.

Example 9: Preparation of a water dispersable granule containing 60% of compound shown as formula I:

The composition of water dispersable granule: 70% of the compound shown 30 as formula I, 3% of disperant calcium alkylbenzene sulfonate salt, 3% of disperant lignosulfonate, 4% of wetting agent sodium dodecyl sulfate, 20% of solid carrier or filler starch; water dispersable granule containing 70% of the compound shown as

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Description

Z16111319CPAU formula I was obtained by mixing each of the above components in accordance with the described ratio.

III. Determination of bioactivity:

Example 10. determination of fungicidal activity:

The experiment was performed to various diseases of plants using the compound of formula I of the present invention, wherein the experimental process was as follows:

Determination method for living potting: dissolving the raw pesticide of compound of formula I (i.e., pure compound of formula I) to be tested with a little amount of Ν,Ν-Dimethylformamide, and diluting to a desired scale with water. Experimental group and control group: in the experimental group, the resultant was sprayed onto the plant sample, and disease inoculation was performed after 24h; in the experimental group, no resultant was sprayed onto the plant sample, and disease inoculation was performed after 24h; two groups of plant samples were both placed in a constant temperature and humidity incubator (25±2°C, the relative humidity is 60%), allowing for infecting continuously After the control group fully suffered from diseases (typically one week), an evaluation was performed, and part of the test results are as follows:

When the dose of pesticide spraying is 500ppm, a majority of compounds in la-1 —Id-1 and Ia-405~Id-405 have a control efficiency of 100% on pepper blight and wheat powdery mildew; when the dose of pesticide spraying is 50ppm, the compounds la-1 —Id-1 to Ia-405~Id-405 have a control efficiency of 70-100%.

When the dose of pesticide spraying is lOOppm, the compounds la-66, la-87, Ib-75, Ic-124, Ic-299, Id-238, Ifl82, Ig217, Ih-261, and Ij-53 etc. have a control efficiency of 100% on both pepper blight and wheat powdery mildew, the calculation equation of the control efficiency is as follows:

control efficiency=(l-disease index after pesticide treatment/disease index of blank control) X 100%

Ic-299 and the existing product azoxystrobin were selected to perform a fungicidal activity test respectively, and the test results were shown in table 1 below:

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Z16111319CPAU table 1. Result of the fungicidal activity comparative test

Inhibition rate (%) (lOOmg/L, living spraying)

compound	cotton rhizoctoniosis	pepper blight	tomato late blight	apple ring rot	watermelon anthracnose	pythium aphanidermatum	cucumber gray mold
azoxystrobin	46.2	37.0	62.2	62.5	51.1	49.3	51.1
Ic-299	64.2	44.7	55.1	82.1	47.2	58.3	75.0

When the dose of pesticide spraying is 50ppm, compounds la-87, Ic-124, and Ih-261 have a control efficiency of greater than 80% on all of tomato early blight, rice blast, wheat leaf rust, apple ring rot, rice sheath blight, rice blast, ustilaginoidea virens, rice bakanae disease, sclerotinia sclerotiorum, cucumber downy mildew, cucumber gray mold and cucumber powdery mildew.

Example 11. Determination of insecticidal and acaricidal activities:

A determination of insecticidal activity was performed on insects and mites, and the determination process was as follows: dissolving the compound of formula io I with a little amount of Ν,Ν-Dimethylformamide, and diluting to a desired scale with water.

Mythimna separata, plutella xylostella, myzus persicae and carmine spider mite were used as testing sample, and the determination of insecticidal activity was performed by airbrush spraying method, wherein the pressure of airbrush spraying treatment was 10 psi, and the spraying amount was 0.5ml. The death rates of these testing samples were investigated after treating for 2-3 days, and part of the testing results is as follows:

When the application dose of airbrush spraying method is 500 ppm, compounds Ic-315, Ih246, and Id-374 all have a death rate of greater than 60% on mythimna separata, plutella xylostella, myzus persicae, carmine spider mite.

Industrial application

The compound shown as formula I provided by the present invention has a broad spectrum and excellent fungicidal activity, and can be used in preventing and treating diseases on many plants resulting from four pathogenic eumycetes: ascomycetes, basidiomycetes, deuteromycetes and oomycete diseases. A good preventing and treating effect can be obtained at a low dose. It is widely used in

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2015401326 26 Jun 2018 botanical fungicide and/or insecticide.

The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word comprise, and variations such as comprises and comprising, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

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Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

2015401326 26 Jun 2018

1. A compound shown as formula I:

COYCH₃ formula I in the formula I, X is selected from CH orN; Y is selected from any one of O, S andNH; Ri is cyano; R₂ is selected from any one of C1-C12 alkyl, Qi and Q₂; R3 is selected from any one of hydrogen, C1-C5 alkyl, Qi and Q₂;

wherein, in the Qi and Q₂, both R4 and R5 are selected from at least one of hydrogen, CiC5 alkyl, C1-C5 alkoxy, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, halogen, nitro, cyano, phenoxy, pyridyloxy, mesyl and trifluoromesyl; the halogen is selected from any one of fluorine, chlorine, bromine and iodine; m=0-5; n=0-4;

the binding site of R4 is at least one of the five remaining binding sites, in which R4 may be same or not when m>l; the binding site of R5 is at least one of the four remaining binding sites, in which R₅ may be same or not when n>l, wherein, in Q₂, N may be located at any one of sites 2, 3, and 4.
2. The compound shown as formula I of Claim 1, wherein Y is selected from O or NH; Ri is cyano; R₂ is selected from Qi or Q₂; R₃ is selected from hydrogen or Ci-C₂ alkyl;

wherein, in the Qi and Q₂, both R4 and R5 are selected from at least one of C1-C5 alkyl, trifluoromethyl, trifluoromethoxy, phenoxy, halogen, nitro, cyano, pyridyloxy, mesyl and trifluoromesyl; m=0-3; n=0-2.
3. The compound shown as formula I of Claim 2, wherein Ri is cyano; R3 is selected from hydrogen or methyl;

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2015401326 26 Jun2018 wherein, in the Qi and Q₂, both R
4 and R5 are selected from at least one of trifluoromethyl, trifluoromethoxy, phenoxy, fluorine, chlorine, nitro, cyano, pyridyloxy, mesyl and trifluoromesyl.
5 4. A composition, comprising the compound shown as formula I of any one of Claims 1 3 and agriculturally acceptable carrier, wherein the weight percentage of the compound shown as formula I in the composition is 0.1-99%.

5. The composition of Claim 4, wherein the agriculturally acceptable carrier is selected 10 from solid carrier and/or liquid carrier;

the solid carrier is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminosilicate oxide, natural or synthetic resin, polychlorophenol, starch, bentonite and wax, wherein the natural or synthetic silicate is selected from at least one of attapulgite, talc, aluminosilicate, diatomite, mica, montmorillonite and calcium silicate, the

15 natural or synthetic resin is selected from at least one of benzofuran resin, styrene polymer and styrene copolymer, the wax is selected from beeswax and/or paraffin;

the liquid carrier is selected from at least one of water, C1-C4 alcohol, C3-C8 ketone, aromatic hydrocarbon, petroleum fraction and Ce-Cn chlorinated hydrocarbon, wherein the alcohol is ethanol and/or ethylene glycol; the ketone is at least one of acetophenone,

20 propanone, methyl ethyl ketone and cyclohexanone; the aromatic hydrocarbon is at least one of benzene, toluene, and xylene; the petroleum fraction is kerosene and/or mineral oil; the chlorinated hydrocarbon is at least one of tetrachloromethane, dichloromethane and trichloroethane.

25
6. The composition of Claim 4 or 5, wherein the composition further comprises surfactant;

the surfactant is selected from at least one of emulsifier, dispersant, wetting agent and penetrant;

The emulsifier is selected from at least one of calcium alkylbenzene sulfonate, phenyl30 phenol polyoxyethylene ether, alkyl-phenol formaldehyde resin polyoxyethylene ether,

C:\Intcrwovcn\NRPortbl\DCC\RBR\l 72Ι9907_ 1 .docx-26/06/2018

2015401326 26 Jun 2018 phenylethylphenol polyoxyethylene polyoxypropylene ether, polyoxyalkylene alkylarylether and ethylene oxide-propylene oxide block copolymer;

the dispersant is selected from at least one of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene

5 sulfonate salt, benzene sulfonic acid formaldehyde condensate sodium salts, sodium lauryl sulfate, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester and ester polyoxyethylene ether;

the wetting agent is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, Nekal BX, shikakai powder, silkworm excrement and sapindus mukurossi

10 powder;

the composition further comprises other aids;

the other aids are selected from at least one of disintegrant, defoamer, cryoprotectant and thickener;

the disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, 15 aluminium chloride and glucose;

the defoamer is selected from at least one of silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds, C8-C10 fatty alcohol compounds;

the cryoprotectant is selected from at least one of ethylene glycol, propylene glycol, glycerol and polyethylene glycol;

20 the thickener is selected from at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
7. Use of the compound shown as formula I of any one of Claims 1-3 and/or the composition of any one of Claims 4-6 in preparation of botanical fungicides and/or

25 insecticides.

Figure of the Description

Z16111319CPAU

ΪΖ r₂ccr₃

III

II

IV

Fig.l

1/1