CN100388886C - Carbamate sterilization compound containing vinyl oxime ether - Google Patents

Carbamate sterilization compound containing vinyl oxime ether Download PDF

Info

Publication number
CN100388886C
CN100388886C CNB2006100314697A CN200610031469A CN100388886C CN 100388886 C CN100388886 C CN 100388886C CN B2006100314697 A CNB2006100314697 A CN B2006100314697A CN 200610031469 A CN200610031469 A CN 200610031469A CN 100388886 C CN100388886 C CN 100388886C
Authority
CN
China
Prior art keywords
oily
compound
ethyl acetate
vinyl
5mmol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CNB2006100314697A
Other languages
Chinese (zh)
Other versions
CN1843121A (en
Inventor
刘卫东
杜升华
张承来
兰世林
毛春晖
黄路
王晓光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Research Institute of Chemical Industry
Original Assignee
Hunan Research Institute of Chemical Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Research Institute of Chemical Industry filed Critical Hunan Research Institute of Chemical Industry
Priority to CNB2006100314697A priority Critical patent/CN100388886C/en
Priority to PCT/CN2006/000917 priority patent/WO2007112618A1/en
Publication of CN1843121A publication Critical patent/CN1843121A/en
Application granted granted Critical
Publication of CN100388886C publication Critical patent/CN100388886C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention discloses a compound with ethylene-oxime-ether-amino-formic-ether and a preparation method thereof. The compound is shown by general formulation(I) disclosed in the specification; in the general formulation(I), R1, R2 and R3 are alkyl, R4 and R5 respectively is hydrogen or alkyl, and R6 is substituted aryl or substituted heteroaryl. The present invention is used for controlling disease caused by various fungi such as phycomycetes, oomycetes, ascomycetes, basidiomycetes and deuteromycetes on various crops, the compounds have systematic activity and can be used for leaf surface and soil fungicide, and the present invention is especially suitable for controlling rice blast, barley and wheat powdery mildew, melon powdery mildew on cucurbitaceae crops such as cucumber, melon, towel gourds, pumpkin, etc., apple powdery mildew, grape powdery mildew, powdery mildew on other plants, grey mould on vegetables and fruit such as tomatoes, cucumber, grapes, etc., gibberellic disease on wheat and barley, capsicum phytophthira capsici leon, sclerotinia sclerotiorum, etc. The compound has the advantages of enlarged bactericidal spectrum and synergistic bactericidal effect by the mixture with other fungicides.

Description

The carbamate sterilization compound that contains vinyl oxime ether
Technical field
The present invention relates to have the carbamate compound that contains vinyl oxime ether of bactericidal activity and their preparation method.
Background technology
Have many desinsection, sterilization, weedings that substituent carbamate compound is used for crops that contain at present both at home and abroad, German patent DE 4423612 discloses N-substituted-phenyl carbamate compound, and this compounds has mycocidal characteristic.But the carbamate sterilization reactive compound that contains vinyl oxime ether that the present invention relates to does not have bibliographical information.
Summary of the invention
The purpose of this invention is to provide shown in the general formula (I) have a bactericidal activity contain carbamate compound of vinyl oxime ether and preparation method thereof, (I) is as follows for general formula:
Figure C20061003146900031
In the general formula (I): R 1, R 2, R 3It is alkyl; R 4, R 5It is respectively hydrogen or alkyl; R 6Be the aryl of replacement or the heteroaryl of replacement.
Alkyl: be meant methyl, ethyl.
Aryl: comprise phenyl and naphthyl.
Heteroaryl: contain one or more N, O, the heteroatomic five-membered ring of S, hexatomic ring or condensed hetero ring.For example furans, pyridine, pyrimidine, pyridazine, triazine, pyrazine, benzofuran, thiazole, benzothiazole or pyrazoles.
General formula (I) comprises because the two keys of carbon-nitrogen are connected the Z type of different substituting group formation and the mixture of E type geometrical isomerism and arbitrary proportion thereof with carbon-to-carbon double bond.
Further specify general formula of the present invention (I) compound with the compound of listing in the table 1, but do not limit the present invention.
Table 1: compound table
Numbering R 1 R 2 R 3 R 4 R 5 R 6 Rerum natura
1 CH 3 CH 3 CH 3 H H C 6H 5 Oily
2 CH 3 CH 3 CH 3 H H 2-Cl-C 6H 4 Oily
3 CH 3 CH 3 CH 3 H H 3-Cl-C 6H 4 Oily
4 CH 3 CH 3 CH 3 H H 4-Cl-C 6H 4 Oily
5 CH 3 CH 3 CH 3 H H 2-F-C 6H 4 Oily
6 CH 3 CH 3 CH 3 H H 3-F-C 6H 4 Oily
7 CH 3 CH 3 CH 3 H H 4-F-C 6H 4 Oily
8 CH 3 CH 3 CH 3 H H 2-Br-C 6H 4 Oily
9 CH 3 CH 3 CH 3 H H 3-Br-C 6H 4 Oily
10 CH 3 CH 3 CH 3 H H 4-Br-C 6H 4 Oily
11 CH 3 CH 3 CH 3 H H 2-Me-C 6H 4 Oily
12 CH 3 CH 3 CH 3 H H 3-Me-C 6H 4 Oily
13 CH 3 CH 3 CH 3 H H 4-Me-C 6H 4 Oily
14 CH 3 CH 3 CH 3 H H 2-CF 3-C 6H 4 Oily
15 CH 3 CH 3 CH 3 H H 3-CF 3-C 6H 4 Oily
16 CH 3 CH 3 CH 3 H H 4-CF 3-C 6H 4 Oily
17 CH 3 CH 3 CH 3 H H 2-MeO-C 6H 4 Oily
18 CH 3 CH 3 CH 3 H H 3-MeO-C 6H 4 Oily
19 CH 3 CH 3 CH 3 H H 4-MeO-C 6H 4 Oily
20 CH 3 CH 3 CH 3 H H 2-CF 3O-C 6H 4 Oily
21 CH 3 CH 3 CH 3 H H 3-CF 3O-C 6H 4 Oily
22 CH 3 CH 3 CH 3 H H 4-CF 3O-C 6H 4 Oily
23 CH 3 CH 3 CH 3 H H 4-F 2CHO-C 6H 4 Oily
24 CH 3 CH 3 CH 3 H H 2-NO 2-C 6H 4 Oily
25 CH 3 CH 3 CH 3 H H 3-NO 2-C 6H 4 Oily
26 CH 3 CH 3 CH 3 H H 4-NO 2-C 6H 4 Oily
27 CH 3 CH 3 CH 3 H H 2-NC-C 6H 4 Oily
28 CH 3 CH 3 CH 3 H H 3-NC-C 6H 4 Oily
29 CH 3 CH 3 CH 3 H H 4-NC-C 6H 4 Oily
30 CH 3 CH 3 CH 3 H H 2-N(CH 3) 2-C 6H 4 Oily
31 CH 3 CH 3 CH 3 H H 3-N(CH 3) 2-C 6H 4 Oily
32 CH 3 CH 3 CH 3 H H 4-N(CH 3) 2-C 6H 4 Oily
33 CH 3 CH 3 CH 3 H H The 2-pyridine radicals Oily
34 CH 3 CH 3 CH 3 H H The 3-pyridine radicals Oily
35 CH 3 CH 3 CH 3 H H The 2-furyl Oily
36 CH 3 CH 3 CH 3 H H The 2-thiazolyl Oily
37 CH 3 CH 3 CH 3 H H The 4-pyridine radicals Oily
38 CH 3 CH 3 CH 3 H H The 3-Cl-2-pyridine radicals Oily
39 CH 3 CH 3 CH 3 H H The 4-Cl-2-pyridine radicals Oily
40 CH 3 CH 3 CH 3 H H The 4-benzofuranyl Oily
41 CH 3 CH 3 CH 3 H H The 5-Cl-3-pyridine radicals Oily
42 CH 3 CH 3 CH 3 H H The 3-Cl-4-pyridine radicals Oily
43 CH 3 CH 3 CH 3 H H The 1-naphthyl Oily
44 CH 3 CH 3 CH 3 H H The 3-thiazolyl Oily
45 CH 3 CH 3 CH 3 H H 2，4-diCl-C 6H 3 Oily
46 CH 3 CH 3 CH 3 H H 2，6-diCl-C 6H 3 Oily
47 CH 3 CH 3 CH 3 H H 3，4-diCl-C 6H 3 Oily
48 CH 3 CH 3 CH 3 H H 2-Cl-6-F-C 6H 3 Oily
49 CH 3 CH 3 CH 3 H H 2-Cl-4-Me-C 6H 3 Oily
50 CH 3 CH 3 CH 3 H H 3-Cl-4-Me-C 6H 3 Oily
51 CH 3 CH 3 CH 3 H H 2-F-4-Me-C 6H 3 Oily
52 CH 3 CH 3 CH 3 H H 3-F-4-Me-C 6H 3 Oily
53 CH 3 CH 3 CH 3 H H 2，4-diMe-C 6H 3 Oily
54 CH 3 CH 3 CH 3 H H 2，5-diMe-C 6H 3 Oily
55 CH 3 CH 3 CH 3 H H 3，4-diMe-C 6H 3 Oily
56 CH 3 CH 3 CH 3 H H 2，4di(MeO)-C 6H 3 Oily
57 CH 3 CH 3 CH 3 H H 3，4di(MeO)-C 6H 3 Oily
58 CH 3 CH 3 CH 3 H H 3，5di(MeO)-C 6H 3 Oily
59 CH 3 CH 3 CH 3 H H 3，5di(CF 3)-C 6H 3 Oily
60 CH 3 CH 3 CH 3 H H 2，5-diCl-4-F-C 6H 2 Oily
61 CH 3 CH 3 CH 3 H H 2，4，5-tri Cl-C 6H 2 Oily
62 CH 3 CH 3 CH 3 H H 2，4，6-tri Cl-C 6H 2 Oily
63 CH 3 CH 3 CH 3 H H The 4-benzothiazolyl Oily
64 CH 3 CH 3 CH 3 H H 2，4，6-triCH 3-C 6H 2 Oily
65 C 2H 5 CH 3 CH 3 H H C 6H 5 Oily
66 C 2H 5 CH 3 CH 3 H H 2-Cl-C 6H 4 Oily
67 C 2H 5 CH 3 CH 3 H H 3-Cl-C 6H 4 Oily
68 C 2H 5 CH 3 CH 3 H H 4-Cl-C 6H 4 Oily
69 C 2H 5 CH 3 CH 3 H H 2-F-C 6H 4 Oily
70 C 2H 5 CH 3 CH 3 H H 3-F-C 6H 4 Oily
71 C 2H 5 CH 3 CH 3 H H 4-F-C 6H 4 Oily
72 C 2H 5 CH 3 CH 3 H H 2-Br-C 6H 4 Oily
73 C 2H 5 CH 3 CH 3 H H 3-Br-C 6H 4 Oily
74 C 2H 5 CH 3 CH 3 H H 4-Br-C 6H 4 Oily
75 C 2H 5 CH 3 CH 3 H H 2-Me-C 6H 4 Oily
76 C 2H 5 CH 3 CH 3 H H 3-Me-C 6H 4 Oily
77 C 2H 5 CH 3 CH 3 H H 4-Me-C 6H 4 Oily
78 C 2H 5 CH 3 CH 3 H H 2-CF 3-C 6H 4 Oily
79 C 2H 5 CH 3 CH 3 H H 3-CF 3-C 6H 4 Oily
80 C 2H 5 CH 3 CH 3 H H 4-CF 3-C 6H 4 Oily
81 C 2H 5 CH 3 CH 3 H H 2-MeO-C 6H 4 Oily
82 C 2H 5 CH 3 CH 3 H H 3-MeO-C 6H 4 Oily
83 C 2H 5 CH 3 CH 3 H H 4-MeO-C 6H 4 Oily
84 C 2H 5 CH 3 CH 3 H H 2-CF 3O-C 6H 4 Oily
85 C 2H 5 CH 3 CH 3 H H 3-CF 3O-C 6H 4 Oily
86 C 2H 5 CH 3 CH 3 H H 4-CF 3O-C 6H 4 Oily
87 C 2H 5 CH 3 CH 3 H H 4-F 2CHO-C 6H 4 Oily
88 C 2H 5 CH 3 CH 3 H H 2-NO 2-C 6H 4 Oily
89 C 2H 5 CH 3 CH 3 H H 3-NO 2-C 6H 4 Oily
90 C 2H 5 CH 3 CH 3 H H 4-NO 2-C 6H 4 Oily
91 C 2H 5 CH 3 CH 3 H H 2-NC-C 6H 4 Oily
92 C 2H 5 CH 3 CH 3 H H 3-NC-C 6H 4 Oily
93 C 2H 5 CH 3 CH 3 H H 4-NC-C 6H 4 Oily
94 C 2H 5 CH 3 CH 3 H H 2-N(CH 3) 2-C 6H 4 Oily
95 C 2H 5 CH 3 CH 3 H H 3-N(CH 3) 2-C 6H 4 Oily
96 C 2H 5 CH 3 CH 3 H H 4-N(CH 3) 2-C 6H 4 Oily
97 C 2H 5 CH 3 CH 3 H H The 2-pyridine radicals Oily
98 C 2H 5 CH 3 CH 3 H H The 3-pyridine radicals Oily
99 C 2H 5 CH 3 CH 3 H H The 2-furyl Oily
100 C 2H 5 CH 3 CH 3 H H The 2-thiazolyl Oily
101 C 2H 5 CH 3 CH 3 H H The 4-pyridine radicals Oily
102 C 2H 5 CH 3 CH 3 H H The 3-Cl-2-pyridine radicals Oily
103 C 2H 5 CH 3 CH 3 H H The 4-Cl-2-pyridine radicals Oily
104 C 2H 5 CH 3 CH 3 H H The 4-benzofuranyl Oily
105 C 2H 5 CH 3 CH 3 H H The 5-Cl-3-pyridine radicals Oily
106 C 2H 5 CH 3 CH 3 H H The 3-Cl-4-pyridine radicals Oily
107 C 2H 5 CH 3 CH 3 H H The 1-naphthyl Oily
108 C 2H 5 CH 3 CH 3 H H The 3-thiazolyl Oily
109 C 2H 5 CH 3 CH 3 H H 2，4-diCl-C 6H 3 Oily
110 C 2H 5 CH 3 CH 3 H H 2，5-diCl-C 6H 3 Oily
111 C 2H 5 CH 3 CH 3 H H 3，4-diCl-C 6H 3 Oily
112 C 2H 5 CH 3 CH 3 H H 2-Cl-6-F-C 6H 3 Oily
113 C 2H 5 CH 3 CH 3 H H 2-Cl-4-Me-C 6H 3 Oily
114 C 2H 5 CH 3 CH 3 H H 3-Cl-4-Me-C 6H 3 Oily
115 C 2H 5 CH 3 CH 3 H H 2-F-4-Me-C 6H 3 Oily
116 C 2H 5 CH 3 CH 3 H H 3-F-4-Me-C 6H 3 Oily
117 C 2H 5 CH 3 CH 3 H H 2，4-diMe-C 6H 3 Oily
118 C 2H 5 CH 3 CH 3 H H 2，5-diMe-C 6H 3 Oily
119 C 2H 5 CH 3 CH 3 H H 3，4-diMe-C 6H 3 Oily
120 C 2H 5 CH 3 CH 3 H H 2，4di(MeO)-C 6H 3 Oily
121 C 2H 5 CH 3 CH 3 H H 3，4di(MeO)-C 6H 3 Oily
122 C 2H 5 CH 3 CH 3 H H 3，5di(MeO)-C 6H 3 Oily
123 C 2H 5 CH 3 CH 3 H H 3，5di(CF 3)-C 6H 3 Oily
124 C 2H 5 CH 3 CH 3 H H 2，5-diCl-4-F-C 6H 2 Oily
125 C 2H 5 CH 3 CH 3 H H 2，4，5-tri Cl-C 6H 2 Oily
126 C 2H 5 CH 3 CH 3 H H 2，4，6-tri Cl-C 6H 2 Oily
127 C 2H 5 CH 3 CH 3 H H The 4-benzothiazolyl Oily
128 C 2H 5 CH 3 CH 3 H H 2，4，6-triCH 3-C 6H 2 Oily
129 CH 3 C 2H 5 CH 3 H H C 6H 5 Oily
130 CH 3 C 2H 5 CH 3 H H 2-Cl-C 6H 4 Oily
131 CH 3 C 2H 5 CH 3 H H 3-Cl-C 6H 4 Oily
132 CH 3 C 2H 5 CH 3 H H 4-Cl-C 6H 4 Oily
133 CH 3 C 2H 5 CH 3 H H 2-F-C 6H 4 Oily
134 CH 3 C 2H 5 CH 3 H H 3-F-C 6H 4 Oily
135 CH 3 C 2H 5 CH 3 H H 4-F-C 6H 4 Oily
136 CH 3 C 2H 5 CH 3 H H 2-Br-C 6H 4 Oily
137 CH 3 C 2H 5 CH 3 H H 3-Br-C 6H 4 Oily
138 CH 3 C 2H 5 CH 3 H H 4-Br-C 6H 4 Oily
139 CH 3 C 2H 5 CH 3 H H 2-Me-C 6H 4 Oily
140 CH 3 C 2H 5 CH 3 H H 3-Me-C 6H 4 Oily
141 CH 3 C 2H 5 CH 3 H H 4-Me-C 6H 4 Oily
142 CH 3 C 2H 5 CH 3 H H 2-CF 3-C 6H 4 Oily
143 CH 3 C 2H 5 CH 3 H H 3-CF 3-C 6H 4 Oily
144 CH 3 C 2H 5 CH 3 H H 4-CF 3-C 6H 4 Oily
145 CH 3 C 2H 5 CH 3 H H 2-MeO-C 6H 4 Oily
146 CH 3 C 2H 5 CH 3 H H 3-MeO-C 6H 4 Oily
147 CH 3 C 2H 5 CH 3 H H 4-MeO-C 6H 4 Oily
148 CH 3 C 2H 5 CH 3 H H 2-CF 3O-C 6H 4 Oily
149 CH 3 C 2H 5 CH 3 H H 3-CF 3O-C 6H 4 Oily
150 CH 3 C 2H 5 CH 3 H H 4-CF 3O-C 6H 4 Oily
151 CH 3 C 2H 5 CH 3 H H 4-F 2CHO-C 6H 4 Oily
152 CH 3 C 2H 5 CH 3 H H 2-NO 2-C 6H 4 Oily
153 CH 3 C 2H 5 CH 3 H H 3-NO 2-C 6H 4 Oily
154 CH 3 C 2H 5 CH 3 H H 4-NO 2-C 6H 4 Oily
155 CH 3 C 2H 5 CH 3 H H 2-NC-C 6H 4 Oily
156 CH 3 C 2H 5 CH 3 H H 3-NC-C 6H 4 Oily
157 CH 3 C 2H 5 CH 3 H H 4-NC-C 6H 4 Oily
158 CH 3 C 2H 5 CH 3 H H 2-N(CH 3) 2-C 6H 4 Oily
159 CH 3 C 2H 5 CH 3 H H 3-N(CH 3) 2-C 6H 4 Oily
160 CH 3 C 2H 5 CH 3 H H 4-N(CH 3) 2-C 6H 4 Oily
161 CH 3 C 2H 5 CH 3 H H The 2-pyridine radicals Oily
162 CH 3 C 2H 5 CH 3 H H The 3-pyridine radicals Oily
163 CH 3 C 2H 5 CH 3 H H The 2-furyl Oily
164 CH 3 C 2H 5 CH 3 H H The 2-thiazolyl Oily
165 CH 3 C 2H 5 CH 3 H H The 4-pyridine radicals Oily
166 CH 3 C 2H 5 CH 3 H H The 3-Cl-2-pyridine radicals Oily
167 CH 3 C 2H 5 CH 3 H H The 4-Cl-2-pyridine radicals Oily
168 CH 3 C 2H 5 CH 3 H H 4-benzo furan is fed base Oily
169 CH 3 C 2H 5 CH 3 H H The 5-Cl-3-pyridine radicals Oily
170 CH 3 C 2H 5 CH 3 H H The 3-Cl-4-pyridine radicals Oily
171 CH 3 C 2H 5 CH 3 H H The 1-naphthyl Oily
172 CH 3 C 2H 5 CH 3 H H The 3-thiazolyl Oily
173 CH 3 C 2H 5 CH 3 H H 2，4-diCl-C 6H 3 Oily
174 CH 3 C 2H 5 CH 3 H H 2，5-diCl-C 6H 3 Oily
175 CH 3 C 2H 5 CH 3 H H 3，4-diCl-C 6H 3 Oily
176 CH 3 C 2H 5 CH 3 H H 2-Cl-6-F-C 6H 3 Oily
177 CH 3 C 2H 5 CH 3 H H 2-Cl-4-Me-C 6H 3 Oily
178 CH 3 C 2H 5 CH 3 H H 3-Cl-4-Me-C 6H 3 Oily
179 CH 3 C 2H 5 CH 3 H H 2-F-4-Me-C 6H 3 Oily
180 CH 3 C 2H 5 CH 3 H H 3-F-4-Me-C 6H 3 Oily
181 CH 3 C 2H 5 CH 3 H H 2，4-diMe-C 6H 3 Oily
182 CH 3 C 2H 5 CH 3 H H 2，5-diMe-C 6H 3 Oily
183 CH 3 C 2H 5 CH 3 H H 3，4-diMe-C 6H 3 Oily
184 CH 3 C 2H 5 CH 3 H H 2，4di(MeO)-C 6H 3 Oily
165 CH 3 C 2H 5 CH 3 H H 3，4di(MeO)-C 6H 3 Oily
186 CH 3 C 2H 5 CH 3 H H 3，5di(MeO)-C 6H 3 Oily
187 CH 3 C 2H 5 CH 3 H H 3，5di(CF 3)-C 6H 3 Oily
188 CH 3 C 2H 5 CH 3 H H 2，5-diCl-4-F-C 6H 2 Oily
189 CH 3 C 2H 5 CH 3 H H 2，4，5-tri Cl-C 6H 2 Oily
190 CH 3 C 2H 5 CH 3 H H 2，4，6-tri Cl-C 6H 2 Oily
191 CH 3 C 2H 5 CH 3 H H The 4-benzothiazolyl Oily
192 CH 3 C 2H 5 CH 3 H H 2，4，6-triCH 3-C 6H 2 Oily
193 CH 3 CH 3 CH 3 CH 3 H C 6H 5 Oily
194 CH 3 CH 3 CH 3 CH 3 H 2-Cl-C 6H 4 Oily
195 CH 3 CH 3 CH 3 CH 3 H 3-Cl-C 6H 4 Oily
196 CH 3 CH 3 CH 3 CH 3 H 4-Cl-C 6H 4 Oily
197 CH 3 CH 3 CH 3 CH 3 H 2-F-C 6H 4 Oily
198 CH 3 CH 3 CH 3 CH 3 H 3-F-C 6H 4 Oily
199 CH 3 CH 3 CH 3 CH 3 H 4-F-C 6H 4 Oily
200 CH 3 CH 3 CH 3 CH 3 H 2-Br-C 6H 4 Oily
201 CH 3 CH 3 CH 3 CH 3 H 3-Br-C 6H 4 Oily
202 CH 3 CH 3 CH 3 CH 3 H 4-Br-C 6H 4 Oily
203 CH 3 CH 3 CH 3 CH 3 H 2-Me-C 6H 4 Oily
204 CH 3 CH 3 CH 3 CH 3 H 3-Me-C 6H 4 Oily
205 CH 3 CH 3 CH 3 CH 3 H 4-Me-C 6H 4 Oily
206 CH 3 CH 3 CH 3 CH 3 H 2-CF 3-C 6H 4 Oily
207 CH 3 CH 3 CH 3 CH 3 H 3-CF 3-C 6H 4 Oily
208 CH 3 CH 3 CH 3 CH 3 H 4-CF 3-C 6H 4 Oily
209 CH 3 CH 3 CH 3 CH 3 H 2-MeO-C 6H 4 Oily
210 CH 3 CH 3 CH 3 CH 3 H 3-MeO-C 6H 4 Oily
211 CH 3 CH 3 CH 3 CH 3 H 4-MeO-C 6H 4 Oily
212 CH 3 CH 3 CH 3 CH 3 H 2-CF 3O-C 6H 4 Oily
213 CH 3 CH 3 CH 3 CH 3 H 3-CF 3O-C 6H 4 Oily
214 CH 3 CH 3 CH 3 CH 3 H 4-CF 3O-C 6H 4 Oily
215 CH 3 CH 3 CH 3 CH 3 H 4-F 2CHO-C 6H 4 Oily
216 CH 3 CH 3 CH 3 CH 3 H 2-NO 2-C 6H 4 Oily
217 CH 3 CH 3 CH 3 CH 3 H 3-NO 2-C 6H 4 Oily
218 CH 3 CH 3 CH 3 CH 3 H 4-NO 2-C 6H 4 Oily
219 CH 3 CH 3 CH 3 CH 3 H 2-NC-C 6H 4 Oily
220 CH 3 CH 3 CH 3 CH 3 H 3-NC-C 6H 4 Oily
221 CH 3 CH 3 CH 3 CH 3 H 4-NC-C 6H 4 Oily
222 CH 3 CH 3 CH 3 CH 3 H 2-N(CH 3) 2-C 6H 4 Oily
223 CH 3 CH 3 CH 3 CH 3 H 3-N(CH 3) 2-C 6H 4 Oily
224 CH 3 CH 3 CH 3 CH 3 H 4-N(CH 3) 2-C 6H 4 Oily
225 CH 3 CH 3 CH 3 CH 3 H The 2-pyridine radicals Oily
226 CH 3 CH 3 CH 3 CH 3 H The 3-pyridine radicals Oily
227 CH 3 CH 3 CH 3 CH 3 H The 2-furyl Oily
228 CH 3 CH 3 CH 3 CH 3 H The 2-thiazolyl Oily
229 CH 3 CH 3 CH 3 CH 3 H The 4-pyridine radicals Oily
230 CH 3 CH 3 CH 3 CH 3 H The 3-Cl-2-pyridine radicals Oily
231 CH 3 CH 3 CH 3 CH 3 H The 4-Cl-2-pyridine radicals Oily
232 CH 3 CH 3 CH 3 CH 3 H The 4-benzofuranyl Oily
233 CH 3 CH 3 CH 3 CH 3 H The 5-Cl-3-pyridine radicals Oily
234 CH 3 CH 3 CH 3 CH 3 H The 3-Cl-4-pyridine radicals Oily
235 CH 3 CH 3 CH 3 CH 3 H The 1-naphthyl Oily
236 CH 3 CH 3 CH 3 CH 3 H The 3-thiazolyl Oily
237 CH 3 CH 3 CH 3 CH 3 H 2，4-diCl-C 6H 3 Oily
238 CH 3 CH 3 CH 3 CH 3 H 2，5-diCl-C 6H 3 Oily
239 CH 3 CH 3 CH 3 CH 3 H 3，4-diCl-C 6H 3 Oily
240 CH 3 CH 3 CH 3 CH 3 H 2-Cl-6-F-C 6H 3 Oily
241 CH 3 CH 3 CH 3 CH 3 H 2-Cl-4-Me-C 6H 3 Oily
242 CH 3 CH 3 CH 3 CH 3 H 3-Cl-4-Me-C 6H 3 Oily
243 CH 3 CH 3 CH 3 CH 3 H 2-F-4-Me-C 6H 3 Oily
244 CH 3 CH 3 CH 3 CH 3 H 3-F-4-Me-C 6H 3 Oily
245 CH 3 CH 3 CH 3 CH 3 H 2，4-diMe-C 6H 3 Oily
246 CH 3 CH 3 CH 3 CH 3 H 2，5-diMe-C 6H 3 Oily
247 CH 3 CH 3 CH 3 CH 3 H 3，4-diMe-C 6H 3 Oily
248 CH 3 CH 3 CH 3 CH 3 H 2，4di(MeO)-C 6H 3 Oily
249 CH 3 CH 3 CH 3 CH 3 H 3，4di(MeO)-C 6H 3 Oily
250 CH 3 CH 3 CH 3 CH 3 H 3，5di(MeO)-C 6H 3 Oily
251 CH 3 CH 3 CH 3 CH 3 H 3，5di(CF 3)-C 6H 3 Oily
252 CH 3 CH 3 CH 3 CH 3 H 2，5-diCl-4-F-C 6H 2 Oily
253 CH 3 CH 3 CH 3 CH 3 H 2，4，5-tri Cl-C 6H 2 Oily
254 CH 3 CH 3 CH 3 CH 3 H 2，4，6-tri Cl-C 6H 2 Oily
255 CH 3 CH 3 CH 3 CH 3 H The 4-benzothiazolyl Oily
256 CH 3 CH 3 CH 3 CH 3 H 2，4，6-triCH 3-C 6H 2 Oily
257 CH 3 CH 3 CH 3 H CH 3 C 6H 5 Oily
258 CH 3 CH 3 CH 3 H CH 3 2-Cl-C 6H 4 Oily
259 CH 3 CH 3 CH 3 H CH 3 3-Cl-C 6H 4 Oily
260 CH 3 CH 3 CH 3 H CH 3 4-Cl-C 6H 4 Oily
261 CH 3 CH 3 CH 3 H CH 3 2-F-C 6H 4 Oily
262 CH 3 CH 3 CH 3 H CH 3 3-F-C 6H 4 Oily
263 CH 3 CH 3 CH 3 H CH 3 4-F-C 6H 4 Oily
264 CH 3 CH 3 CH 3 H CH 3 2-Br-C 6H 4 Oily
265 CH 3 CH 3 CH 3 H CH 3 3-Br-C 6H 4 Oily
266 CH 3 CH 3 CH 3 H CH 3 4-Br-C 6H 4 Oily
267 CH 3 CH 3 CH 3 H CH 3 2-Me-C 6H 4 Oily
268 CH 3 CH 3 CH 3 H CH 3 3-Me-C 6H 4 Oily
269 CH 3 CH 3 CH 3 H CH 3 4-Me-C 6H 4 Oily
270 CH 3 CH 3 CH 3 H CH 3 2-CF 3-C 6H 4 Oily
271 CH 3 CH 3 CH 3 H CH 3 3-CF 3-C 6H 4 Oily
272 CH 3 CH 3 CH 3 H CH 3 4-CF 3-C 6H 4 Oily
273 CH 3 CH 3 CH 3 H CH 3 2-MeO-C 6H 4 Oily
274 CH 3 CH 3 CH 3 H CH 3 3-MeO-C 6H 4 Oily
275 CH 3 CH 3 CH 3 H CH 3 4-MeO-C 6H 4 Oily
276 CH 3 CH 3 CH 3 H CH 3 2-CF 3O-C 6H 4 Oily
277 CH 3 CH 3 CH 3 H CH 3 3-CF 3O-C 6H 4 Oily
278 CH 3 CH 3 CH 3 H CH 3 4-CF 3O-C 6H 4 Oily
279 CH 3 CH 3 CH 3 H CH 3 4-F 2CHO-C 6H 4 Oily
280 CH 3 CH 3 CH 3 H CH 3 2-NO 2-C 6H 4 Oily
281 CH 3 CH 3 CH 3 H CH 3 3-NO 2-C 6H 4 Oily
282 CH 3 CH 3 CH 3 H CH 3 4-NO 2-C 6H 4 Oily
283 CH 3 CH 3 CH 3 H CH 3 2-NC-C 6H 4 Oily
284 CH 3 CH 3 CH 3 H CH 3 3-NC-C 6H 4 Oily
285 CH 3 CH 3 CH 3 H CH 3 4-NC-C 6H 4 Oily
286 CH 3 CH 3 CH 3 H CH 3 2-N(CH 3) 2-C 6H 4 Oily
287 CH 3 CH 3 CH 3 H CH 3 3-N(CH 3) 2-C 6H 4 Oily
288 CH 3 CH 3 CH 3 H CH 3 4-N(CH 3) 2-C 6H 4 Oily
289 CH 3 CH 3 CH 3 H CH 3 The 2-pyridine radicals Oily
290 CH 3 CH 3 CH 3 H CH 3 The 3-pyridine radicals Oily
291 CH 3 CH 3 CH 3 H CH 3 The 2-furyl Oily
292 CH 3 CH 3 CH 3 H CH 3 The 2-thiazolyl Oily
293 CH 3 CH 3 CH 3 H CH 3 The 4-pyridine radicals Oily
294 CH 3 CH 3 CH 3 H CH 3 The 3-Cl-2-pyridine radicals Oily
295 CH 3 CH 3 CH 3 H CH 3 The 4-Cl-2-pyridine radicals Oily
296 CH 3 CH 3 CH 3 H CH 3 The 4-benzofuranyl Oily
297 CH 3 CH 3 CH 3 H CH 3 The 5-Cl-3-pyridine radicals Oily
298 CH 3 CH 3 CH 3 H CH 3 The 3-Cl-4-pyridine radicals Oily
299 CH 3 CH 3 CH 3 H CH 3 The 1-naphthyl Oily
300 CH 3 CH 3 CH 3 H CH 3 The 3-thiazolyl Oily
301 CH 3 CH 3 CH 3 H CH 3 2，4-diCl-C 6H 3 Oily
302 CH 3 CH 3 CH 3 H CH 3 2，5-diCl-C 6H 3 Oily
303 CH 3 CH 3 CH 3 H CH 3 3，4-diCl-C 6H 3 Oily
304 CH 3 CH 3 CH 3 H CH 3 2-Cl-6-F-C 6H 3 Oily
305 CH 3 CH 3 CH 3 H CH 3 2-Cl-4-Me-C 6H 3 Oily
306 CH 3 CH 3 CH 3 H CH 3 3-Cl-4-Me-C 6H 3 Oily
307 CH 3 CH 3 CH 3 H CH 3 2-F-4-Me-C 6H 3 Oily
308 CH 3 CH 3 CH 3 H CH 3 3-F-4-Me-C 6H 3 Oily
309 CH 3 CH 3 CH 3 H CH 3 2，4-diMe-C 6H 3 Oily
310 CH 3 CH 3 CH 3 H CH 3 2，5-diMe-C 6H 3 Oily
311 CH 3 CH 3 CH 3 H CH 3 3，4-diMe-C 6H 3 Oily
312 CH 3 CH 3 CH 3 H CH 3 2，4di(MeO)-C 6H 3 Oily
313 CH 3 CH 3 CH 3 H CH 3 3，4di(MeO)-C 6H 3 Oily
314 CH 3 CH 3 CH 3 H CH 3 3，5di(MeO)-C 6H 3 Oily
315 CH 3 CH 3 CH 3 H CH 3 3，5di(CF 3)-C 6H 3 Oily
316 CH 3 CH 3 CH 3 H CH 3 2，5-diCl-4-F-C 6H 2 Oily
317 CH 3 CH 3 CH 3 H CH 3 2，4，5-tri Cl-C 6H 2 Oily
318 CH 3 CH 3 CH 3 H CH 3 2，4，6-tri Cl-C 6H 2 Oily
319 CH 3 CH 3 CH 3 H CH 3 The 4-benzothiazolyl Oily
320 CH 3 CH 3 CH 3 H CH 3 2，4，6-triCH 3-C 6H 2 Oily
321 CH 3 CH 3 C 2H 5 H H C 6H 5 Oily
322 CH 3 CH 3 C 2H 5 H H 2-Cl-C 6H 4 Oily
323 CH 3 CH 3 C 2H 5 H H 3-Cl-C 6H 4 Oily
324 CH 3 CH 3 C 2H 5 H H 4-Cl-C 6H 4 Oily
325 CH 3 CH 3 C 2H 5 H H 2-F-C 6H 4 Oily
326 CH 3 CH 3 C 2H 5 H H 3-F-C 6H 4 Oily
327 CH 3 CH 3 C 2H 5 H H 4-F-C 6H 4 Oily
328 CH 3 CH 3 C 2H 5 H H 2-Br-C 6H 4 Oily
329 CH 3 CH 3 C 2H 5 H H 3-Br-C 6H 4 Oily
330 CH 3 CH 3 C 2H 5 H H 4-Br-C 6H 4 Oily
331 CH 3 CH 3 C 2H 5 H H 2-Me-C 6H 4 Oily
332 CH 3 CH 3 C 2H 5 H H 3-Me-C 6H 4 Oily
333 CH 3 CH 3 C 2H 5 H H 4-Me-C 6H 4 Oily
334 CH 3 CH 3 C 2H 5 H H 2-CF 3-C 6H 4 Oily
335 CH 3 CH 3 C 2H 5 H H 3-CF 3-C 6H 4 Oily
336 CH 3 CH 3 C 2H 5 H H 4-CF 3-C 6H 4 Oily
337 CH 3 CH 3 C 2H 5 H H 2-MeO-C 6H 4 Oily
338 CH 3 CH 3 C 2H 5 H H 3-MeO-C 6H 4 Oily
339 CH 3 CH 3 C 2H 5 H H 4-MeO-C 6H 4 Oily
340 CH 3 CH 3 C 2H 5 H H 2-CF 3O-C 6H 4 Oily
341 CH 3 CH 3 C 2H 5 H H 3-CF 3O-C 6H 4 Oily
342 CH 3 CH 3 C 2H 5 H H 4-CF 3O-C 6H 4 Oily
343 CH 3 CH 3 C 2H 5 H H 4-F 2CHO-C 6H 4 Oily
344 CH 3 CH 3 C 2H 5 H H 2-NO 2-C 6H 4 Oily
345 CH 3 CH 3 C 2H 5 H H 3-NO 2-C 6H 4 Oily
346 CH 3 CH 3 C 2H 5 H H 4-NO 2-C 6H 4 Oily
347 CH 3 CH 3 C 2H 5 H H 2-NC-C 6H 4 Oily
348 CH 3 CH 3 C 2H 5 H H 3-NC-C 6H 4 Oily
349 CH 3 CH 3 C 2H 5 H H 4-NC-C 6H 4 Oily
350 CH 3 CH 3 C 2H 5 H H 2-N(CH 3) 2-C 6H 4 Oily
351 CH 3 CH 3 C 2H 5 H H 3-N(CH 3) 2-C 6H 4 Oily
352 CH 3 CH 3 C 2H 5 H H 4-N(CH 3) 2-C 6H 4 Oily
353 CH 3 CH 3 C 2H 5 H H The 2-pyridine radicals Oily
354 CH 3 CH 3 C 2H 5 H H The 3-pyridine radicals Oily
355 CH 3 CH 3 C 2H 5 H H The 2-furyl Oily
356 CH 3 CH 3 C 2H 5 H H The 2-thiazolyl Oily
357 CH 3 CH 3 C 2H 5 H H The 4-pyridine radicals Oily
358 CH 3 CH 3 C 2H 5 H H The 3-Cl-2-pyridine radicals Oily
359 CH 3 CH 3 C 2H 5 H H The 4-Cl-2-pyridine radicals Oily
360 CH 3 CH 3 C 2H 5 H H The 4-benzofuranyl Oily
361 CH 3 CH 3 C 2H 5 H H The 5-Cl-3-pyridine radicals Oily
362 CH 3 CH 3 C 2H 5 H H The 3-Cl-4-pyridine radicals Oily
363 CH 3 CH 3 C 2H 5 H H The 1-naphthyl Oily
364 CH 3 CH 3 C 2H 5 H H The 3-thiazolyl Oily
365 CH 3 CH 3 C 2H 5 H H 2，4-diCl-C 6H 3 Oily
366 CH 3 CH 3 C 2H 5 H H 2，5-diCl-C 6H 3 Oily
367 CH 3 CH 3 C 2H 5 H H 3，4-diCl-C 6H 3 Oily
368 CH 3 CH 3 C 2H 5 H H 2-Cl-6-F-C 6H 3 Oily
369 CH 3 CH 3 C 2H 5 H H 2-Cl-4-Me-C 6H 3 Oily
370 CH 3 CH 3 C 2H 5 H H 3-Cl-4-Me-C 6H 3 Oily
371 CH 3 CH 3 C 2H 5 H H 2-F-4-Me-C 6H 3 Oily
372 CH 3 CH 3 C 2H 5 H H 3-F-4-Me-C 6H 3 Oily
373 CH 3 CH 3 C 2H 5 H H 2，4-diMe-C 6H 3 Oily
374 CH 3 CH 3 C 2H 5 H H 2，5-diMe-C 6H 3 Oily
375 CH 3 CH 3 C 2H 5 H H 3，4-diMe-C 6H 3 Oily
376 CH 3 CH 3 C 2H 5 H H 2，4di(MeO)-C 6H 3 Oily
377 CH 3 CH 3 C 2H 5 H H 3，4di(MeO)-C 6H 3 Oily
378 CH 3 CH 3 C 2H 5 H H 3，5di(MeO)-C 6H 3 Oily
379 CH 3 CH 3 C 2H 5 H H 3，5di(CF 3)-C 6H 3 Oily
380 CH 3 CH 3 C 2H 5 H H 2，5-diCl-4-F-C 6H 2 Oily
381 CH 3 CH 3 C 2H 5 H H 2，4，5-tri Cl-C 6H 2 Oily
382 CH 3 CH 3 C 2H 5 H H 2，4，6-tri Cl-C 6H 2 Oily
383 CH 3 CH 3 C 2H 5 H H The 4-benzothiazolyl Oily
384 CH 3 CH 3 C 2H 5 H H 2，4，6-triCH 3-C 6H 2 Oily
General formula of the present invention (I) compound can prepare by the step shown in the following reaction equation, and reaction equation is:
Figure C20061003146900121
R in the formula 1, R 2, R 3, R 4, R 5, R 6Definition the same; Z is leaving group such as halogen (chlorine, bromine or iodine).
Under alkali condition, formula (II) compound and formula (III) compound are joined in the solvent, add alkali, reacted 0.2～5 hour down at 0 ℃～80 ℃, get formula (I) compound crude product, get formula (I) compound after crude product is purified.Used solvent has benzene kind solvent, as benzene, and toluene, dimethylbenzene, chlorobenzene etc.; Varsol, as cyclohexane, benzinum, hexane, heptane etc.; Halogenated hydrocarbons, as carrene, chloroform, dichloroethane, trichloroethanes etc.; And oxolane, dimethyl formamide or dimethyl sulfoxide (DMSO) etc.; Ketones solvent, as acetone, MEK; Preferred solvent has toluene, dichloroethane, carrene, oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), MEK; Used alkali has alkali carbonate or bicarbonate, alkaline earth metal carbonate or bicarbonate, alkali metal hydroxide or alkaline earth metal hydroxide, hydrogen sodium, Sodamide, tert-butyl group potassium, tert-butyl group sodium etc.; More than preferred alkali be sodium carbonate, potash, sodium hydroxide, potassium hydroxide, hydrogen sodium or Sodamide; In 0.2～5 hour reaction time, reaction temperature is 0 ℃～100 ℃.
The preparation method of formula (II) and formula (III) compound all has bibliographical information.As Organic Synthesis CollectiveVolume III, p.668,1955 and European patent EP 0619301A 2In, the synthetic method of formula (II) compound of Z=Br has been described.
Formula (I) compound can be prevented and treated by multiple fungus-caused diseases such as Phycomycetes, Oomycete, Ascomycetes, Basidiomycetes and deuteromycetes, and they have systemic activity and can be used as the blade face and soil fungicide.Be specially adapted to prevent and treat rice blast; Powdery mildew on cucurbits powdery mildew, apple mildew, grape powdery mildew and other plant on the ground family crops such as the powdery mildew of barley and wheat, cucumber, muskmelon, sponge gourd, pumpkin; Grey mold disease on vegetables such as tomato, cucumber, grape and the fruit; The gibberellic hypha of wheat class; Phytophthora capsici germ and Sclerotinia sclerotiorum etc.
By in composition, adding other one or more fungicides, can enlarge fungicidal spectrum, and have the Synergistic sterilizing effect.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
Compound N-methoxyl group-N-2-[1-(2-phenyl vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 1)
In 20ml toluene, 1-(2-the phenyl vinyl)-acetaldoxime of adding 0.64g (4mmol) and content are 60% NaH0.25g (5mmol), at 80～100 ℃ of toluene solutions that drip N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate of 1.37g (5.0mmol) down.Drip and finish, reacted under this temperature 10～15 minutes, reactant washes with water to neutrality, anhydrous Na 2SO 4Drying, the decompression precipitation gets crude product.Crude product gets target compound 0.54g, yield 38.3% with the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.14 (s, 3H, CH3), 3.77,3.79 (2s, 6H, 2OCH3), 5.25 (s, 2H, CH2O), 6.78～6.91 (q, 2H, CH=CH), 7.25～7.55 (m, 9H, Ar-H)
Embodiment 2
N-methoxyl group-N-2-[1-(2-(3-chlorphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 3)
In the 20ml dimethyl formamide, add 1-(2-(3-chlorphenyl) vinyl)-acetaldoxime of 0.92g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 1 hour down at 25～30 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 1.16g, yield 60% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.12 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2 * OCH3), 5.25 (s, 2H, CH2O), 6.79 (s, 2H, CH=CH), 7.24～7.53 (m, 8H, Ar-H)
Embodiment 3
N-methoxyl group-N-2-[1-(2-(4-chlorphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 4)
In the 20ml dimethyl formamide, add 1-(2-(4--chlorphenyl) vinyl)-acetaldoxime of 0.92g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.
Stir half an hour down at 25～30 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 1.22g, yield 62% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.09 (s, 3H, CH3), 3.75,3.76 (2s, 6H, 2 * OCH3), 5.21 (s, 2H, CH2O), 6.82,6.88 (d, 2H, CH=CH), 7.27～7.55 (m, 8H, Ar-H)
Embodiment 4
Compound N-methoxyl group-N-2-[1-(2-(4-fluoro-phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 7)
In the 20m carrene, add 1-(2-(4-fluorophenyl) vinyl)-acetaldoxime of 0.712g (4mmol), the NaH of 0.25g60% (4.4mmol), and the N-of 1.37g (5mmol) (2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Reacted 30 minutes down at 20～25 ℃, after reaction finished, reactant washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is sloughed solvent and is got thick product.Thick product gets target compound 0.43g, yield 29.3% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.12 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2OCH3), 5.24 (s, 2H, CH2O), 6.70～6.85 (q, 2H, CH=CH), 7.00～7.52 (m, 8H, Ar-H)
Embodiment 5
N-methoxyl group-N-2-[1-(2-(4-aminomethyl phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 13)
In the 20ml dimethyl formamide, add 1-(2-(4-aminomethyl phenyl) vinyl)-acetaldoxime of 0.74g (5mmol), 0.51g (5mmol) potassium tert-butoxide, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 30 minutes down at 0～10 ℃, reactant liquor is poured in the 100ml water, and with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 0.73g, yield 40% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.12 (s, 3H, CH3), 2.35 (s, 3H, CH3Ph), 3.76,3.79 (2s, 6H, 2OCH3), 5.23 (s, 2H, CH2O), 6.74～6.88 (q, 2H, CH=CH), 7.14～7.54 (m, 8H, Ar-H)
Embodiment 6
Compound N-methoxyl group-N-2-[1-(2-(2-trifluoromethyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 14)
In the 20ml dichloroethane, add 1-(2-(2-trifluoromethyl) vinyl)-acetaldoxime of 1.14g (5mmol), N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate of the potash of 0.55g (4mmol) and 1.37g (5mmol).Reacted 40 minutes down at 50～60 ℃, after reaction finished, reactant washed with water to neutrality, through anhydrous Na 2SO 4Drying is sloughed solvent and is got thick product.Thick product gets title compound 0.75g, yield 35.9% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.13 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2OCH3), 5.26 (s, 2H, CH 2O) .87 (s, 2H, CH=CH), 7.36～7.69 (m, 8H, Ar-H)
Embodiment 7
N-methoxyl group-N-2-[1-(2-(4-methoxyphenyl)-vinyl) ethyleneimine oxygen methyl] the phenylcarbamic acid methyl esters
The preparation of (compound 19)
In the 20ml dimethyl formamide, add 1-(2-(4-methoxyphenyl) vinyl)-acetaldoxime of 0.85g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.25～30 ℃ of following stirring reactions 1 hour, then reactant mixture is poured in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 0.96g, yield 50% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 1H NMR (300MHZ, CDCl 3): 2.12 (s, 3H, CH3), 3.761,3.786,3.816 (3s, 9H, 3OCH3), 5.23 (s, 2H, CH2O), 6.66,6.71,6.79 (t, 2H, CH=CH), 7.35～7.55 (m, 8H, Ar-H)
Embodiment 8
Compound N-methoxyl group-N-2-[1-(2-(4-nitrobenzophenone)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 26)
In the 20ml dimethyl sulfoxide (DMSO), 1-(2-(4-nitrobenzophenone) the vinyl)-acetaldoxime that adds 1.03g (5mmol), 0.2g (5mmol) Sodamide, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate, stirred 1 hour down at 20～25 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, use twice of ethyl acetate extraction, ethyl acetate layer is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets title compound 1.4g, yield 70.2% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.15 (s, 3H, CH 3), 3.77,3.80 (2s, 6H, 2 * OCH 3), 5.28 (s, 2H, CH 2O), 6.85～6.99 (q, 2H, CH=CH), 7.37～8.23 (m, 8H, Ar-H)
Embodiment 9
N-methoxyl group-N-2-[1-(2-(4--cyano-phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 29)
In 20ml dimethylbenzene, add 1-(2-(4-cyano-phenyl) vinyl)-acetaldoxime of 0.93g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 1 hour down at 60～80 ℃, react the afterreaction thing that finishes and be washed with water to neutrality, again through anhydrous Na 2SO 4Drying gets thick product after the removal of solvent under reduced pressure.Thick product gets target compound 1.32g, yield 70% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.12 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2 * OCH3), 5.26 (s, 2H, CH2O), 6.84～6.93 (t, J=16.5Hz, 2H, CH=CH), 7.36～7.63 (m, 8H, Ar-H)
Embodiment 10
Compound N-methoxyl group-N-2-[1-(2-(4-N, N-dimethylaminophenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 32)
In 20ml benzene, add 1-(2-(4-N, N-dimethylaminophenyl) vinyl)-acetaldoxime of 1.03g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.25～30 ℃ of following stirring reactions 2 hours, after reaction finishes reactant is washed with water to neutrality, through anhydrous Na 2SO 4Drying gets thick product after the removal of solvent under reduced pressure.Thick product gets target compound 1.0g, yield 50.2% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.11 (s, 3H, CH3), 2.98 (s, 6H, 2 * CH3), 3.76,3.78 (2s, 6H, 2 * OCH3), 5.22 (s, 2H, CH2O), 6.60～6.69 (t, J=16.2Hz, 2H, CH=CH), 6.77～7.54 (m, 8H, Ar-H)
Embodiment 11
Compound N-methoxyl group-N-2-[1-(2-(2-furyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 35)
Under room temperature, be dissolved in 1-(2-(2-furyl) vinyl)-acetaldoxime of 0.75g (5mmol) and N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate of 1.37g (5mmol) in the 20ml dimethyl formamide, add 0.32g (0.3mmol) sodium carbonate, reacted 5 hours down at 0～5 ℃, then, reactant mixture is poured in the 100ml water, and ethyl acetate extraction twice merges organic layer, wash with water to neutrality, again through anhydrous Na 2SO 4Drying, precipitation get thick product.Thick product gets target compound 1.01g, yield 62.9% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.07 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2OCH3), 5.23 (s, 2H, CH2O), 6.39～6.41 (m, 2H, CH=CH), 6.67～7.40 (m, 7H, Ar-H)
Embodiment 12
N-methoxyl group-N-2-[1-(2-(2,4 dichloro benzene base)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 45)
In the 20ml dimethyl formamide, add 1-(2-(2,4 dichloro benzene base) vinyl)-acetaldoxime of 1.14g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stir half an hour down at 25～30 ℃, after reaction finishes reactant liquor is poured in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 1.68g, yield 80% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.15 (s, 3H, CH3), 3.76,3.79 (2s, 6H, 2 * OCH3), 5.25 (s, 2H, CH2O), 6.74,6.79 (d, 1H ,=CH-C), 7.15～7.55 (m, 8H, Ar-H, CH-Ph)
Embodiment 13
N-methoxyl group-N-2-[1-(2-(2, the 6-dichlorophenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 46)
In the 20ml oxolane, (2-(2 for the 1-of adding 1.15g (5mmol), the 6-dichlorophenyl) vinyl)-the NaOH solution of acetaldoxime and 0.4g (4mmol) 50%, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate, 20～25 ℃ of following stirring reactions 1 hour, after reaction finishes reactant liquor is poured in the 100ml water, with twice of ethyl acetate extraction, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets title compound 1.69g, yield 80.2% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.15 (s, 3H, CH3), 3.76,3.80 (2s, 6H, 2 * OCH3), 5.25 (s, 2H, CH2O), 6.81～6.88 (t, J=16.8Hz, 2H, CH=CH), 7.09～7.53 (m, 7H, Ar-H)
Embodiment 14
N-methoxyl group-N-2-[1-(2-(3, the 4--Dimethoxyphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 57)
In the 20ml dimethyl formamide, add 1-(2-(3, the 4-Dimethoxyphenyl) vinyl)-acetaldoxime of 1.11g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stir half an hour down at 25～30 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 1.66g, yield 80% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.14 (s, 3H, CH3), 3.76,3.79,3.90 (3s, 12H, 4 * OCH3), 5.25 (s, 2H, CH2O), 6.80～6.85 (t, 2H, CH=CH), 6.73,6.97～7.54 (m, 7H, Ar-H)
Embodiment 15
N-methoxyl group-N-2-[1-(2-(3,5-two trifluoromethyls)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 59)
In the 20ml chloroform, add 1-(2-(3,5-two trifluoromethyls) vinyl)-acetaldoxime of 1.48g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 1 hour down at 25～30 ℃, reactant is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets title compound 1.47g, yield 60% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 2.13 (s, 3H, CH3), 3.76,3.80 (2s, 6H, 2OCH3) 5.27 (s, 2H, CH2O), 6.90～6.92 (d, J=16.2Hz, 2H, CH=CH), 7.26～7.86 (m, 7H, Ar-H)
Embodiment 16
N-methoxyl group-N-2-[1-(2-(4-chlorphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of euphorin (compound 68)
In the 20ml dimethyl formamide, add 1-[2-(4--chlorphenyl) vinyl of 0.92g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.45g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-urethanes.Stirred 1 hour down at 25～30 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 1.11g, yield 55% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 1.61 (t, 3H, CH2CH3), 2.16 (s, 3H, N=CCH3), 3.75 (s, 3H, OCH3), 4.42 (m, 2H, CH2CH3), 5.19 (s, 2H, CH2O), 6.82,6.88 (d, 2H, CH=CH), 7.27～7.65 (m, 8H, Ar-H).
Embodiment 17
N-methoxyl group-N-2-[1-(2-(4-aminomethyl phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of euphorin (compound 75)
In the 20ml dimethyl formamide, add 1-[2-(4-aminomethyl phenyl) vinyl of 0.74g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.45g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-urethanes.Stirred 1 hour down at 0～10 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, again through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets title compound 0.72g, yield 38% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 1.62 (t, 3H, CH2CH3), 2.15 (s, 3H, N=CCH3), 2.55 (s, 3H, CH3Ph), 3.76 (s, 3H, OCH3), 4.45 (m, 2H, CH2CH3), 5.23 (s, 2H, CH2O), 6.74～6.88 (q, 2H, CH=CH), 7.14～7.54 (m, 8H, Ar-H).
Embodiment 18
N-ethyoxyl-N-2-[1-(2-(4-aminomethyl phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid second methyl esters (compound 141)
In the 20ml dimethyl formamide, add 1-[2-(4-aminomethyl phenyl) vinyl of 0.74g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.45g (5mmol) N-(2-2-bromomethylphenyl)-N-ethyoxyl-methyl carbamate.Stirred 3 hours down at 0～10 ℃, react the afterreaction liquid that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, again through using anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets title compound 0.57g, yield 30% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 1.42 (t, 3H, OCH2CH3), 2.13 (s, 3H, N=CCH3), 2.45 (s, 3H, CH3Ph), 3.77 (m, 2H, OCH2CH3), 3.86 (s, 3H, OCH3), 5.19 (s, 2H, CH2O), 6.64～6.88 (q, 2H, CH=CH), 7.16～7.56 (m, 8H, Ar-H).
Embodiment 19
N-ethyoxyl-N-2-[1-(2-(4-methoxyphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 147)
In the 20ml cyclohexane, add 1-[2-(4-methoxyphenyl) vinyl of 0.85g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.45g (5mmol) N-(2-2-bromomethylphenyl)-N-ethyoxyl-methyl carbamate.Stirred 1 hour down at 25～30 ℃, react the afterreaction thing that finishes and be washed with water to neutrality, again through anhydrous Na 2SO 4Drying gets thick product after the removal of solvent under reduced pressure.Thick product gets title compound 1.03g, yield 52% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR (300MHZ, CDCl 3): 1.41 (t, 3H, OCH2CH3), 2.23 (s, 3H, N=CCH3), 3.76 (m, 2H, OCH2CH3), 3.85 (s, 3H, OCH3), 3.93 (s, 3H, CH3OPh), 5.17 (s, 2H, CH2O), 6.64～6.87 (q, 2H, CH=CH), 7.16～7.65 (m, 8H, Ar-H).
Embodiment 20
N-methoxyl group-N-2-[1-(1-methyl-2-(4-chlorphenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 196)
In the 20ml MEK, add 1-[1-methyl-2-(4--chlorphenyl)-vinyl of 1.04g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 1 hour down at 25～30 ℃, reactant is washed with water to neutrality, through anhydrous Na 2SO 4Drying gets thick product after the removal of solvent under reduced pressure.Thick product gets target compound 0.50g, yield 25% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR:2.02 (s, 3H, C=CCH3), 2.21 (s, 3H, N=CCH3), 3.68,3.77 (2s, 6H, 2OCH3), 5.21 (s, 2H, CH2O), 6.33 (s, H, C=CH), 7.36～7.77 (m, 8H, Ar-H).
Embodiment 21
N-methoxyl group-N-2-[1-(1-methyl-2-(4-trifluoromethyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 208)
In 20ml acetone, add 1-[1-methyl-2-(4-trifluoromethyl)-vinyl of 1.21g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.25～30 ℃ of following stirring reactions 1 hour, after reaction finishes reactant liquor is poured in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 0.70g, yield 32% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR:2.01,2.20 (2s, 6H, 2CH3), 3.67,3.76 (2s, 6H, 2OCH3), 5.19 (s, 2H, CH2O), 6.31 (s, H, C=CH), 7.36～7.74 (m, 8H, Ar-H).
Embodiment 22
N-methoxyl group-N-2-[1-(2-methyl-2-phenyl-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 257)
In the 20ml dimethyl formamide, add 1-(2-methyl-2-phenyl-vinyl)-acetaldoxime of 0.87g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.25～30 ℃ of following stirring reactions 3 hours, after reaction finishes reactant is poured in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, again through anhydrous Na 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 0.61g, yield 33% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR:2.04,2.21 (2s, 6H, 2CH3), 3.69,3.80 (2s, 6H, 2OCH3), 5.18 (s, 2H, CH2O), 6.2 (s, H, C=CH), 7.35～7.65 (m, 9H, Ar-H).
Embodiment 23
N-methoxyl group-N-2-[1-(2-methyl-2-(4-methyl-phenyl)-vinyl) ethyleneimine oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 269)
In the 20ml heptane, add 1-[2-methyl-2-(4-methyl-phenyl)-vinyl of 0.94g (5mmol)]-acetaldoxime, 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stirred 2 hours down at 25～30 ℃, react the reactant that finishes and be washed with water to neutrality, again through anhydrous Na 2SO 4Drying gets thick product after the removal of solvent under reduced pressure.Thick product gets target compound 0.48g, yield 25% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR:2.05,2.22 (2s, 6H, 2CH3), 2.35 (s, 3H, CH3Ph), 3.69,3.79 (2s, 6H, 2OCH3), 5.19 (s, 2H, CH2O), 6.23 (s, H, C=CH), 7.14～7.57 (m, 8H, Ar-H).
Embodiment 24
N-methoxyl group-N-2-[1-(2-(4--chlorphenyl)-vinyl) tetrahydroform oxygen methyl] preparation of phenylcarbamic acid methyl esters (compound 324)
In the 20ml dimethyl formamide, add 1-(2-(4--chlorphenyl) vinyl)-propionaldoxime of 1.11g (5mmol), 0.42g (3mmol) potash, 1.37g (5mmol) N-(2-2-bromomethylphenyl)-N-methoxyl group-methyl carbamate.Stir half an hour down at 25～30 ℃, react the afterreaction thing that finishes and pour in the 100ml water, with ethyl acetate extraction twice, ethyl acetate layer is washed with water to neutrality, uses anhydrous Na again 2SO 4Drying is except that getting thick product after desolvating.Thick product gets target compound 0.48g, yield 23% through the mixed liquor flushing column chromatography of ethyl acetate and benzinum (1: 3).
Target compound 1H NMR:1.14 (t, 3H, CH2CH3), 1.51 (m, 2H, CH2CH3), 3.69,3.81 (2s, 6H, 2OCH3), 5.15 (s, 2H, CH2O), 5.91,6.81 (2s, 2H, 2 * C=CH), 7.21～7.65 (m, 8H, Ar-H).
As follows with formula of the present invention (I) compound to the test of the various fungal diseases of plant:
At greenhouse pot culture plant examination material, it is standby to grow to the regular period.To have general formula (I) compound small amount of N, the dinethylformamide dissolving is diluted with water to desired concn, and preparation is diluted with water to desired concn.Plant examination material being carried out spray pesticide handle, is contrast with spray clear water plant examination material, plant is tried material placement ventilation make the plant surface soup air-dry, inoculates pathogen after 24 hours.Inoculation finishes, and plant is placed in the constant temperature and humidity incubator, makes pathogen be continued to infect.A couple of days is carried out the disease index investigation of each chemicals treatment after the inoculation when contrast is fully fallen ill.
Active classification sees Table 2:
The A level: preventive effect 90%～100%, the B level: preventive effect 70%～90%, the C level: preventive effect 50～90%, the D level: preventive effect is below 50%.
Table 2: partial test result (testing compound concentration is 100ppm):
Compound number Fusarium graminearum The Phytophthora capsici germ Pyricularia oryzae Ash arrhizus bacteria Wheat powdery mildew Sclerotinia sclerotiorum
1 B B A B B C
4 A A A A A A
7 B B A A A B
13 A C A A B B
14 A A A A A B
19 B B A B A B
26 B C A A A A
29 B B A A A A
32 B A A C C B
35 A B A B A B
45 B B B B A B
59 B A B B C A
68 A A A A A A
109 B B B B A B
141 A C A A B B
147 B B A B A B
196 B B A B A C
208 B C A A A B
257 B C A B B C
324 C B A B B C
Compound among the present invention can have the Synergistic sterilizing effect with following bactericide combination: alkene azoles alcohol, nitrile bacterium azoles, the spirit of powder rust, benomyl, probenazole, carbendazim, thiophanate methyl, tpn, bordeaux mixture, the hot salt of biguanides, jinggangmeisu, hydroxyisoxazole, Sukeling, Fujione, kasugarnycin, mancozeb, maneb, zineb, Polyoxin, propineb, tmtd, tridemorph, dimethomorph, metalaxyl etc.

Claims (3)

1. the carbamate compound that contains vinyl oxime ether, the chemical constitution shown in (I) that it is characterized in that having general formula, comprising be connected the Z type of different substituting group formation and the mixture of E type geometric isomer and these geometric isomers with carbon-to-carbon double bond owing to carbon-nitrogen pair keys
Figure C2006100314690002C1
In the general formula (I): R 1, R 2, R 3It is alkyl; R 4, R 5It is respectively hydrogen or alkyl; R 6Be the aryl of replacement or the heteroaryl of replacement; Alkyl is methyl or ethyl; Aryl is a phenyl or naphthyl, and heteroaryl is for containing one or more N, O, heteroatomic five-membered ring of S or hexatomic ring.
2. the preparation method of the compound shown in the general formula described in the claim 1 (I) is characterized in that reaction equation is as follows:
Figure C2006100314690002C2
R in the formula 1, R 2, R 3, R 4, R 5.R 6Definition with described in the right 1, Z is the halogen leaving group; Formula (II) compound and formula (III) compound are joined in the solvent, add alkali reaction, used solvent is a benzene, toluene, dichloroethane, carrene, chloroform, oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), MEK; Used alkali is alkali carbonate or bicarbonate, alkaline earth metal carbonate or bicarbonate, alkali metal hydroxide or alkaline earth metal hydroxide, hydrogen sodium, Sodamide, tert-butyl group potassium; Reaction temperature: 0 ℃～80 ℃; Reaction time: 0.2～5 hour.
3. the purposes of the compound shown in the general formula described in the claim 1 (I) is characterized in that: be used for preventing and treating on various crops by the multiple fungus-caused disease of Phycomycetes, Oomycete, Ascomycetes, Basidiomycetes and deuteromycetes.
CNB2006100314697A 2006-04-05 2006-04-05 Carbamate sterilization compound containing vinyl oxime ether Active CN100388886C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CNB2006100314697A CN100388886C (en) 2006-04-05 2006-04-05 Carbamate sterilization compound containing vinyl oxime ether
PCT/CN2006/000917 WO2007112618A1 (en) 2006-04-05 2006-05-08 The vinyloximinoether-containing methyl carbamate derivatives and their use as fungicides

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100314697A CN100388886C (en) 2006-04-05 2006-04-05 Carbamate sterilization compound containing vinyl oxime ether

Publications (2)

Publication Number Publication Date
CN1843121A CN1843121A (en) 2006-10-11
CN100388886C true CN100388886C (en) 2008-05-21

Family

ID=37062114

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100314697A Active CN100388886C (en) 2006-04-05 2006-04-05 Carbamate sterilization compound containing vinyl oxime ether

Country Status (2)

Country Link
CN (1) CN100388886C (en)
WO (1) WO2007112618A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017024971A1 (en) * 2015-08-12 2017-02-16 沈阳中化农药化工研发有限公司 Unsaturated oximino ether compound and use thereof
KR20230046122A (en) * 2021-09-29 2023-04-05 주식회사 팜한농 Methods for manufacturing a n-acyl derivative with high purity

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4423612A1 (en) * 1994-07-06 1996-01-11 Basf Ag 2 - [(Dihydro) pyrazolyl-3'-oxymethylene] anilides, process for their preparation and their use
CN1401635A (en) * 2002-09-13 2003-03-12 湖南化工研究院 Sulfurous unsaturated oximinoethers with bactericidal activity and preparing process thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4441674A1 (en) * 1994-11-23 1996-05-30 Basf Ag Iminooxymethylene anilides, processes and intermediates for their preparation and compositions containing them
DE59606557D1 (en) * 1995-11-02 2001-04-12 Basf Ag PHENYLCARBAMATES, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND THEIR USE FOR COMBATING PEST AND PEST FUNGI
EP0974578A3 (en) * 1998-07-21 2003-04-02 Basf Aktiengesellschaft Phenylcarbamates. processes and intermediates for their preparation and pesticidal and fungicidal agents containing them
CN1289477C (en) * 2003-09-05 2006-12-13 湖南化工研究院 N-substituted phenyl carbamate compound with sterilization activity and method for preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4423612A1 (en) * 1994-07-06 1996-01-11 Basf Ag 2 - [(Dihydro) pyrazolyl-3'-oxymethylene] anilides, process for their preparation and their use
CN1401635A (en) * 2002-09-13 2003-03-12 湖南化工研究院 Sulfurous unsaturated oximinoethers with bactericidal activity and preparing process thereof

Also Published As

Publication number Publication date
CN1843121A (en) 2006-10-11
WO2007112618A1 (en) 2007-10-11

Similar Documents

Publication Publication Date Title
RU2194704C2 (en) Carbanilides and agent for control of insects and pathogenic fungi based on thereof
JP4559735B2 (en) Difluoromethylthiazolyl carboxanilide
RU2214403C2 (en) Isothiazole carboxylic acid amides and method for their preparing
JP4558325B2 (en) Disubstituted thiazolylcarboxyanilides and their use as microbicides
EP1178039B1 (en) Derivatives of phenyl(thio)urea and phenyl(thio)carbamate fungicides
PL184687B1 (en) Derivatives of benzamide oxime, method of obtaining them and fungicide for agricultural and horticultural use
CN1444564A (en) Biphenyl carboxamides
US11225470B2 (en) Tetrazolinone compounds and its use as pest control agents
WO1996005170A1 (en) 4-trifluoromethylbenzamides and their use as pesticides in plant and materials protection
JP2005507852A (en) Use of oxabicyclo [2.2.1] heptane derivatives as pest control agents
ES2314234T3 (en) FURANOCARBOXAMIDS.
CN100388886C (en) Carbamate sterilization compound containing vinyl oxime ether
JPH03190853A (en) Microbial insecticide
CN1356988A (en) Phenoxy fluoropyrimidines
CN1162412C (en) Thiazolylcinnamonitriles and pest controlling agents
KR20010031064A (en) Oxyranyle-triazoline thiones and their use as microbicides
CN1091444C (en) Heterocycle substituted isoxazoline compounds used as disinfectant
KR20000067942A (en) Dihydrofuran-carboxamides
JPH03153657A (en) Substituted amino acid amide derivatives and preparation and use thereof
JPH058161B2 (en)
CN1124487A (en) Carboxylic acid amide benzothiophene-S-oxides
SU1228774A3 (en) Method of fighting phytopathogenic fungi
DE19918294A1 (en) New 3-aryloxy-1,1-dioxo-1,4,2-dithiaza-heterocyclic compounds, used as pesticides, e.g. fungicides, bactericides, insecticides, acaricides or nematocides, for protection of plants or materials
甲斐浩幸 et al. Synthesis and fungicidal activity of 2-alkoxyimino-2-cyanoacetamide derivatives
EP0693877A1 (en) USE OF 7-ETHYNYL $g(a)-(METHOXYMETHYLENE) 1-NAPHTHALENE ACETIC ACID DERIVATIVES FOR PREPARING FUNGICIDAL COMPOSITIONS

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant