CN1733758A - Imide analog compounds and its preparation method - Google Patents

Imide analog compounds and its preparation method Download PDF

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CN1733758A
CN1733758A CN 200510014748 CN200510014748A CN1733758A CN 1733758 A CN1733758 A CN 1733758A CN 200510014748 CN200510014748 CN 200510014748 CN 200510014748 A CN200510014748 A CN 200510014748A CN 1733758 A CN1733758 A CN 1733758A
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heteroaryl
atom
tetrahydrophthalimide
scn
aryl
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CN1331863C (en
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席真
班树荣
王勇
陈文彬
李康
施捷
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Nankai University
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Abstract

The invention relates to imide compounds and method for preparation, which comprises, maintaining reaction temperature at 80-150 deg. C, at the presence of one single solvent selected from inert solvent, 1,4-dioxane, methylene chloride, chloroform, tetrahydrofuran, toluene and trimethylbenzene or their mixed solvent, reacting compound having a structural formula II with compound having a structural formula III to obtain compound having a structural formula I, wherein R1 separately selected from hydroxy, mercapto, alkyl, SCN, N3, aryl, heteroaryl, R2, R3 are separately selected from H atom, hydroxy, mercapto, halogen atom, SCN, alkyl, alkoxy, N3, aryl, heteroaryl, X is N atom or CH.

Description

A kind of imide analog compounds and preparation method thereof
Technical field
The present invention relates to imide analog compounds, particularly be applied to prepare a kind of imide analog compounds of sterilant, with and preparation method thereof.
Background technology
Imide analog compounds has had a lot of reports as sterilant, and commercialization some, for example: Vancide 89 (captan), Phaltan (folpet), tetrachloro pellet (Captafol), according to general with. (Iprodione) and exempt from gram peaceful (Vinclozolin) etc.:
Figure A20051001474800031
Figure A20051001474800032
Figure A20051001474800033
Figure A20051001474800035
But the some of them sterilant is unfriendly to environment, to people's toxic side effect.And life-time service can make bacterial strain produce tangible resistance.Therefore design synthesizing efficient, low toxicity, wide spectrum, highly selective and low residue and low resistance sterilant is a problem extremely urgent in the current pesticide research.
Summary of the invention
The invention provides a kind of imide analog compounds, have fungicidal activity, it can be applicable to prepare sterilant.
The technical solution adopted for the present invention to solve the technical problems is:
The invention provides a kind of imide analog compounds is the compound and the non-toxic salt thereof of structural formula (I) expression:
Figure A20051001474800036
Wherein, R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
The imide analog compounds and the non-toxic salt thereof of structural formula (I) expression are selected from:
N-(4, the two methylpyrimidines of 6--2-yl)-3,4,5,6-tetrahydrophthalimide (I-1)
N-(4,6-bi-methoxy pyrimidine-2-base)-3,4,5,6-tetrahydrophthalimide (I-2)
N-(4-chloro-6-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-3)
N-(4-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-4)
N-(6-picoline-2-yl)-3,4,5,6-tetrahydrophthalimide (I-5)
The preparation method of the imide analog compounds of structural formula (I) expression: at inert solvent water, 1, single solvent in 4-dioxane, methylene dichloride, chloroform, tetrahydrofuran (THF), toluene, the trimethylbenzene or mixed solvent exist down, temperature of reaction remains on 80-150 ℃, compound shown in compound shown in the structure (II) and the structural formula (III) is reacted, obtain the compound shown in the structural formula (I)
Figure A20051001474800041
Wherein: R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
General formula provided by the present invention (I) pharmacologically acceptable salts also is to belong within the scope of the invention.
The compounds of this invention can be crystalline state material or solvation material (such as hydrate), and the material of two states all belongs within the scope of the invention, and the solvation method is known to widely in the prior art, repeats no more.
Fungicidal activity
For clearly this series compound is to antimicrobial spectrum and the bacteriostatic activity thereof of various plants pathogenic bacteria, the inventor has carried out indoor bacteria inhibition assay to this series compound, and method and result are as follows:
Adopt the pastille medium method.Take by weighing medicament respectively with ten thousand/balance.Compound is taken by weighing 5mg respectively, use the 0.1mL acetone solution, it is stable to add tween 80 again, be mixed with finite concentration 250 μ g/mL diluents with quantitative aseptic distilled water then, get 4mL diluted chemical compound liquid and put into the little triangular flask of sterilization, after adding 36mL PDA substratum (10 times of the corresponding dilutions of concentration) and mixing, equalization is poured in 3 sterilization plates.Inserting diameter d after the culture medium solidifying is 5mm activatory bacterium sheet, and only adding acetone, tween 80 diluent with not dosing in the substratum, to connect the bacterium sheet be blank.Each is handled and repeats 3 times.After connecing bacterium and finishing, plate is put into 25 ℃ of constant incubators, cultivate and measured the colony radius increased value in 48 hours, calculate bacteriostasis rate (table 1).
Table 1 fungicidal activity result
Numbering Inhibiting rate
Cucumber rhizoctonia rot Cucumber fusarium axysporum Graw mold of tomato Leaf muld of tomato The asparagus lettuce sclerotium disease Capsicum epidemic disease Ring rot of apple
I-1 1 - 1 2 3 1 2
1-2 1 - 1 2 - 1 2
I-3 1 - - 1 2 1 2
I-4 1 - 1 2 - - 2
I-5 2 1 5 3 5 1 3
Annotate: inhibiting rate=0～20% o'clock is represented with 1; Inhibiting rate=20～40% o'clock is represented with 2; Inhibiting rate=40～60% o'clock is represented with 3; Inhibiting rate=60～80% o'clock is represented with 4; Inhibiting rate=80～100% o'clock is represented with 5;-expression is negative inhibiting rate or does not survey.
The above-mentioned confession found that this compounds has good fungicidal activity and fungicidal spectrum in the biological activity test of test agent.
The invention has the beneficial effects as follows that compound structure is reasonable, the raw material range of employing is extensive, and the preparation method is easy, and the synthesis technique cost is low, has good fungicidal activity and fungicidal spectrum, and product meets the requirement of environmental friendliness and Green Chemistry.
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No accompanying drawing
Embodiment
The inventor finds that through big quantity research imide analog compounds (I) has good biological activity, can directly use as medicine or sterilant, perhaps can be used as the intermediate of useful medicine or sterilant.
Wherein, R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
In order to reach synthetic purpose, the inventor has taked the method shown in the reaction process 1.
Reaction process 1
In reaction process 1, R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
In reaction process 1, the solvent that is responded all can be water, 1, single solvent in 4-dioxane, methylene dichloride, chloroform, tetrahydrofuran (THF), toluene, the trimethylbenzene or mixed solvent, and temperature of reaction remains on 80 ℃-150 ℃.
Below by embodiment the present invention is described in detail, but the present invention is not limited to these embodiment, the reagent of not mentioning among the embodiment is buied from the market and is used with former state.
Embodiment 1:N-(4, the two methylpyrimidines of 6--2-yl)-3,4,5, the preparation of 6-tetrahydrophthalimide (I-1)
Weighing 3,4,5,6-tetrahydrophthalic anhydride 152mg (about 1mmol) places the 25mL round-bottomed flask, adds the 10mL chloroform, again to wherein adding 123mg 2-amino-4, the two methylpyrimidines (about 1mmol) of 6-.Temperature of reaction remains on 80 ℃.Stirred column chromatography behind the desolventizing (40g silica gel H, 2%CH 12 hours 3OH/CH 2Cl 2Wash-out) gets white solid 171mg.Productive rate 62%.Its physicochemical data is as follows: [ 1H] NMR (400MHz, CDCl 3): δ/ppm; 6.991 (s, 1H, H-Pyrimidine), 2.470 (s, 6H, 2CH 3), 2.335 (m, 4H, 2CH 2), 1.725 (m, 4H, 2CH 2) .Mp.141-143 ℃.
Embodiment 2:N-(6-picoline-2-yl)-3,4,5, the preparation of 6-tetrahydrophthalimide (I-5)
Weighing 3,4,5,6-tetrahydrophthalic anhydride 152mg (about 1mmol) places the 25mL round-bottomed flask, adds the 10mL trimethylbenzene, again to wherein adding 108mg 2-amino-6-picoline (about 1mmol).Temperature of reaction remains on 150 ℃.Stirred column chromatography behind the desolventizing (40g silica gel H, 2%CH 10 hours 3OH/CH 2Cl 2Wash-out) gets white solid 97mg.Productive rate 40%.Its physicochemical data is as follows: [ 1H] NMR (400MHz, CDCl 3): 5/ppm; 7.703-7.664 (t, J 1=7.750Hz, J 2=7.731Hz, 1H, Py), 7.172-7.153 (d, J=7.667Hz, 1H, Py), 7.018-6.998 (d, J=7.787Hz, 1H, Py), 3.033-3.011 (m, 2H, 2CH), 2.545 (s, 3H, CH 3), 1.885 (br.s, 4H, 2CH 2), 1.478-1.471 (m, 4H, 2CH 2) .Mp.92-94 ℃.
Embodiment 3: temperature of reaction remains on 110 ℃, adds the 10mL chloroform and changes into and add 10mL toluene, and other reaction conditionss are with embodiment 1, productive rate 63%, and the product physicochemical data is with embodiment 1.
Embodiment 4: temperature of reaction remains on 120 ℃, adds the 10mL trimethylbenzene and changes into and add 7mL trimethylbenzene and 3mL chloroform, and other reaction conditionss are with embodiment 2, productive rate 44%, and the product physicochemical data is with embodiment 2.
According to example 1 and 2, can prepare compound (I) as long as change the kind of compound (II).When (II) is 2-amino-4, then generate N-(4,6-bi-methoxy pyrimidine-2-base)-3,4,5 during 6-bi-methoxy pyrimidine, 6-tetrahydrophthalimide (I-2); When being the amino 4-chloro-of 2-6-methylpyrimidine, (II) then generate N-(4-chloro-6-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-3); When being 2-amino 4-methylpyrimidine, (II) then generate N-(4-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-4).
The physicochemical data of other compound:
N-(4,6-bi-methoxy pyrimidine-2-base)-3,4,5,6-tetrahydrophthalimide (I-2)
White solid .[ 1H] NMR (400MHz, CDCl 3): δ/ppm; 5.953 (s, 1H, H-Pyrimidine), 3.070 (s, 6H, 2CH 3), 2349 (m, 4H, 2CH 2), 1.731 (m, 4H, 2CH 2) .Yield=50%Mp.115-117 ℃.
N-(4-chloro-6-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-3)
White solid .[ 1H] NMR (400MHz, CDCl 3): δ/ppm; 7.175 (s, 1H, H-Pyrimidine), 2.251 (s, 3H, CH 3), 2.350 (m, 4H, 2CH 2), 1.734 (m, 4H, 2CH 2) .Yield=36%Mp.156-158 ℃.
N-(4-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-4)
White solid .[ 1H] NMR (400MHz, CDCl 3): δ/ppm; 8.626-8.614 (d, J=4.585Hz, 1H, H-Pyrimidine), 7.126-7.114 (d, J=5.051Hz, 1H, H-Pyrimidine), 2.536 (s, 3H, CH 3), 2.365 (m, 4H, 2CH 2), 1.746 (m, 4H, 2CH 2) .Yield=40%Mp.162-164 ℃
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did.

Claims (5)

1, a kind of imide analog compounds is characterized in that: compound and non-toxic salt thereof that its structure is represented for structural formula I:
Wherein, R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
2, a kind of imide analog compounds according to claim 1 is characterized in that: compound and non-toxic salt thereof that described structural formula I represents are selected from:
N-(4, the two methylpyrimidines of 6--2-yl)-3,4,5,6-tetrahydrophthalimide (I-1)
N-(4,6-bi-methoxy pyrimidine-2-base)-3,4,5,6-tetrahydrophthalimide (I-2)
N-(4-chloro-6-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-3)
N-(4-methylpyrimidine-2-yl)-3,4,5,6-tetrahydrophthalimide (I-4)
N-(6-picoline-2-yl)-3,4,5,6-tetrahydrophthalimide (I-5)
3, the preparation method of a kind of imide analog compounds according to claim 1 is characterized in that: in the presence of inert solvent, the reaction of the compound shown in compound shown in the structure I I and the structural formula II I is obtained the compound shown in the structural formula I,
Figure A2005100147480002C2
Wherein: R 1Be independently selected from hydroxyl, sulfydryl, alkyl, SCN, N 3, aryl, heteroaryl, thick heteroaryl; R 2, R 3All be independently selected from H atom, hydroxyl, sulfydryl, halogen atom, SCN, alkyl, alkoxyl group, N 3, aryl, heteroaryl, thick heteroaryl; X is N atom or CH.
4, the preparation method of a kind of imide analog compounds according to claim 3 is characterized in that: described inert solvent is a water, 1, single solvent in 4-dioxane, methylene dichloride, chloroform, tetrahydrofuran (THF), toluene, the trimethylbenzene or mixed solvent; Temperature of reaction remains on 80 ℃-150 ℃.
5, a kind of imide analog compounds according to claim 1 and non-toxic salt thereof is characterized in that: the application in the preparation sterilant.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109453167A (en) * 2018-10-29 2019-03-12 浙江工业大学 Maleimide class compound is preparing the application in Li Shiman protozoon insecticide

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US4072499A (en) * 1976-12-22 1978-02-07 Monsanto Company Use of pyridyl phthalimides as plant growth regulants
DE3917469A1 (en) * 1989-05-30 1990-12-06 Bayer Ag Heterocyclyl-substd. pyridine derivs. - useful as herbicides, e.g. defoliants, desiccants and esp. weed-killers
WO1992000976A1 (en) * 1990-07-12 1992-01-23 Sankyo Company, Limited Pyridine derivative and selective herbicide
US6309315B1 (en) * 1999-07-13 2001-10-30 Thomas H. Adams Golf tee marking system and method of use
US7074742B2 (en) * 2000-09-18 2006-07-11 E. I. Du Pont De Nemours And Company Pyridinyl amides and imides for use as fungicides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109453167A (en) * 2018-10-29 2019-03-12 浙江工业大学 Maleimide class compound is preparing the application in Li Shiman protozoon insecticide

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