CN103772228B - Biphenyl bisamide compounds and preparation thereof and purposes - Google Patents

Biphenyl bisamide compounds and preparation thereof and purposes Download PDF

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CN103772228B
CN103772228B CN201410018876.9A CN201410018876A CN103772228B CN 103772228 B CN103772228 B CN 103772228B CN 201410018876 A CN201410018876 A CN 201410018876A CN 103772228 B CN103772228 B CN 103772228B
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biphenyl
compound
formula
dmso
alkyl
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CN103772228A (en
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李忠
徐晓勇
刘晔
雷超
邵旭升
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East China University of Science and Technology
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Abstract

The present invention relates to a kind of biphenyl bisamide compounds and preparation thereof and purposes.Described biphenyl bisamide compounds by 2,2 '-biphenyl dicarboxylic acid acid anhydride or derivatives thereof respectively with corresponding amine (H 2nR 1and H 2nR 2) react obtained.Biphenyl bisamide compounds provided by the invention has significant insecticidal activity and selectively insecticidal spectrum, and preparation technology is succinct, is expected to be developed to low toxicity, efficient, eco-friendly novel agrochemical.

Description

Biphenyl bisamide compounds and preparation thereof and purposes
Technical field
The present invention relates to a kind of biphenyl bisamide compounds and preparation thereof and purposes.
Background technology
Sterilant is the important tool being widely used in control harmful insect in agriculture production.In 1998, Japanese agricultural chemicals company and Beyer Co., Ltd after to the screening of phthalyl aminated compounds and composition optimizes, found Flubendiamide (flubendiamide); One of them acid amides is inverted by E.I.Du Pont Company simultaneously, and obtain the O-formammidotiazol-benzamide compounds (representation compound is chlorantraniliprole) with outstanding insecticidal activity, their target is all ryanodine receptor.
But because existing sterilant action target is less, long-time a large amount of Reusability, causes pest resistance problem more and more serious.Along with environment protection and food safety more and more receive the concern of people, people propose more and more higher requirement to toxicity of pesticide and environmental friendliness, and the resistance problem of current ryanodine receptor inhibitor also becomes increasingly conspicuous.Therefore need to find low toxicity, efficient, eco-friendly novel pesticide and become technical problem in the urgent need to address with the needs meeting agriculture production.
Summary of the invention
The present inventor, through extensive and deep research, designs and synthesizes a kind of biphenyl bisamide compounds of novel structure.Through insecticidal activity test, biphenyl bisamide compounds provided by the invention has significant insecticidal activity and selectively insecticidal spectrum, and preparation technology succinctly, is expected to be developed to low toxicity, efficient, eco-friendly novel agrochemical.
One object of the present invention is, provides a kind of biphenyl bisamide compounds of novel structure.
Described biphenyl bisamide compounds is compound shown in formula I or its acceptable salt in Pesticide Science:
In formula I, R 1and R 2independently be selected from: H, C 1~ C 3alkoxyl group, C 1~ C 4the alkyl of straight or branched, the C of replacement 1~ C 4the alkyl of straight or branched, phenyl, substituted-phenyl, cyclopropyl, naphthyl, 5 ~ 6 yuan of heterocyclic radicals, by methyl substituted 5 ~ 6 yuan of heterocyclic radicals or and R 1and R 2it is asynchronously methyl;
Wherein, the C of described replacement 1~ C 4the substituting group of the alkyl of straight or branched is selected from one or two or more kinds in following groups (containing two kinds):
Halogen (F, Cl, Br or I), phenyl, cyano group (-CN), methoxyl group, ethanoyl fluoro ethanoyl,
The substituting group of described substituted-phenyl is selected from one or two or more kinds in following groups (containing two kinds):
Halogen (F, Cl, Br or I), C 1~ C 3alkyl, the C of halo 1~ C 3alkyl, C 1~ C 3alkoxyl group, the C of fluoro 1~ C 3alkoxyl group, nitro (-NO 2), hydroxyl (-OH), cyano group (-CN), amino (-NH 2), cyclopropyl, sulfonic group (-SO 3h), ethanoyl, fluoro ethanoyl,
R 11for C 1~ C 3the C of alkyl or fluoro 1~ C 3alkyl, n is 0,1 or 2,
R 12and R 13independently be selected from: H or C 1~ C 3a kind of in alkyl, and R 11and R 12in have one at least for H, or R 12, R 13with N be combined as containing N hexa-member heterocycle;
The substituting group number of described substituted-phenyl is the integer of 1 ~ 5;
The heteroatoms of described 5 ~ 6 yuan of heterocyclic radicals is selected from a kind of in N, O or S or two kinds, and heteroatomic number is 1 or 2;
R 3~ R 10independently be selected from: H, halogen (F, Cl, Br or I), nitro (-NO 2), hydroxyl (-OH), cyano group (-CN), amino (-NH 2), C 1~ C 4alkyl, the C of halo 1~ C 4alkyl, C 1~ C 3alkoxyl group, the C of halo 1~ C 3alkoxyl group, halogen (F, Cl, Br or I), ethanoyl fluoro ethanoyl, middle one;
R 14for C 1~ C 3alkyl or halo C 1~ C 3alkyl, R 15for H, C 1~ C 3alkyl or halo C 1~ C 3alkyl.
Curve mark part is the position of substitution (lower same).
Another object of the present invention is, provides a kind of composition, and in the gross weight of described composition for 100%, described composition comprises:
Compound shown in the formula I of (a) 0.001 % by weight ~ 99.99 % by weight or its acceptable salt in Pesticide Science; With
Acceptable carrier and/or vehicle in (b) Pesticide Science.
Further object of the present invention is, discloses the purposes of a kind of biphenyl bisamide compounds provided by the present invention and composition: namely biphenyl bisamide compounds provided by the present invention or composition are as the application of agricultural insecticide.
In addition, the present invention also provides the method for compound shown in a kind of preparation formula I, and the key step of described method is:
With compound shown in formula II for raw material, by compound shown in formula II respectively with corresponding amine (H 2nR 1and H 2nR 2) reaction, obtain target compound (shown in formula I compound)
Embodiment
In the present invention's preferred technical scheme, at R 1and R 2definition in:
Described C 1~ C 3alkoxyl group preferred: methoxyl group;
Described C 1~ C 4the alkyl of straight or branched is preferred: methyl, ethyl, sec.-propyl, normal-butyl, n-propyl, the tertiary butyl;
The C of described replacement 1~ C 4the alkyl of straight or branched is preferred:
The substituting group of described substituted-phenyl is selected from one or two or more kinds in following groups (containing two kinds):
Methyl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethynyl,
R 11for methyl, difluoromethyl, trifluoromethyl, n is 0,1 or 2;
R 12and R 13independently be selected from: a kind of in H, methyl or ethyl, and R 12and R 13in have one at least for H, or R 12, R 13with N be combined as containing N hexa-member heterocycle base;
The substituting group number of described substituted-phenyl is the integer of 1 ~ 3;
Described 5 ~ 6 yuan of heterocyclic radicals are preferred: pyridyl or thiazolyl.
In preferred technical scheme, described substituted-phenyl is a kind of in following groups:
In another optimal technical scheme of the present invention, R 3~ R 10independently be selected from: H, F, Cl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethynyl, sec.-propyl, vinyl, middle one.
The insecticidal activity of active substance of the present invention
Term " active substance of the present invention " or " active compound of the present invention " refer to the compounds of this invention, specific position have the biphenyl structural of bisamide, have it and have significant insecticidal activity, and insecticidal spectrum is wide, and stability is strong.
The negatively charged ion that term " in Pesticide Science acceptable salt " means this salt when forming sterilant pharmacy acceptable salt be understood with acceptable.This salt is water miscible preferably.Suitable, include by the acid salt of the compound formation of formula I the salt that mineral acid formed, such as hydrochloride, phosphoric acid salt, vitriol, nitrate; And comprise the salt of organic acid formation, and as acetate, benzoate.
Actives mass-energy of the present invention is used as to control and eliminate the insect of agriculture and forestry plant insect, stored grains widely, the insect of harm animal health and public health insect etc.In this manual, " sterilant " is the general designation of the material with the effect preventing and treating the above-mentioned all insects mentioned.The example of insect includes but not limited to: coleopteron, as sitophilus zea-mais (Sitophiluszeamais), red flour beetle (Triboliumcastaneum), potato bug (Henosepilachnavigintioctomaculata), potato ladybug (Henosepilachnasparsa), agriotes fussicollis (Agriotesfuscicollis), red pin green gold tortoise (Anomalacupripes), beautiful tortoise with four lines (Popilliaquadriguttata), colorado potato beetles (Monoleptahieroglyphica), ponderous borer (Monochamusalternatus), rice root weevil (Echinocnemussquameus), paulownia chrysomelid (Basiprionotabisignata), longicorn beetle (Anoplophorachinensis), mulberry borer (Apriponagermari), navel abdomen bark beetle (Scolytusschevy), or Agriotes subrittatus Motschulsky (Agriotesfuscicollis), lepidopterous insects, as waved malicious pretty young woman (Lymantriadispar), tent caterpillar (Malacosomaneustriatestacea), Diaphania perspectalis (Diaphaniaperspectalis), Clania variegata Snellen (Claniavariegata), cnidocampa flavescens walker (Cnidocampaflauescens), dendrolimus punctatus (Dendrolimuspunctatus), orgyia antiqua (Orgyiagonostigma), paranthrene tabaniformis (Paranthrenetabaniformis), prodenia litura (Spodopteralitura), striped rice borer (Chilosuppressalis), Pyrausta nubilalis (Hubern). (Ostrinianubilalis), meal moth (Ephestiacautella), lap moth (Adoxophyesorana), chestnut steinernema (laspyresiasplendana), black cutworm (Agrotisfucosa), greater wax moth (Galleriamellonella), diamond-back moth (Plutellaxylostella), tangerine lyonetid (Phyllocnistiscitrella), or oriental armyworm (Mythimnaseparata), Homoptera insect, as rice green leafhopper (Nephotettixcincticeps), Nilaparvata lugen (brown planthopper) (Nilaparvatalugens), Kang Shi mealybug (Pseudococcuscomstocki), arrowhead scales (Unaspisyanonensis), black peach aphid (Myzuspersicae), cotten aphid (Aphisgossydii), radish aphid (Lipaphiserysimipseudobrassicae), pears class lace bug (Stephanitisnashi), or aleyrodid (Bemisiatabaci), orthopteran, as Groton bug (Blattellagermanica), the large Lian of the U.S. (Periplanetaamerican), African mole cricket (Gryllotalpaafricana), or Asiatic migratory locust (Locusmigratoria), isoptera insect, as S.invicta Buren (Solenopsisinvicta), or Coptotermes formosanus Shtrari． (Coptotermesformosanus), dipteral insect, as housefly (Muscadomestica), Aedes aegypti (Aedesaegypti), plants fly (Deliaplatura), culex (Culexsp.), or Anopheles sinensis (Anophelessinensis), the insect of harm animal health, as boophilus microplus (Boophilusmicroplus), haemaphysalis longicornis (Haemaphysalislongicornis), hyalomma anatolicum anatolicum (Hyalommaanatolicum), bomb fly (Hypodermaspp.), liver fluke (Fasciolahepatica), bayesian moniezia (Monieziablanchard), ostertagi (Ostertagiaspp.), protozoon (Trypanosomaenansi, Babesiabigemina), rabbit coccidia (Occidiosis), tapeworm (tapeworm), coccidia (Coccidium) etc.
The compound that the present invention relates to especially to pests with chewing mouthparts as: the agriculture and forestry injurious insect such as mythimna separata, prodenia litura has special efficacy.
Containing the composition of active substance of the present invention
Active substance of the present invention can be prepared into composition in a conventional way.These active compounds can make conventional preparation, such as solution, emulsion, suspensoid, pulvis, foaming agent, paste, granule; Aerosol, with the material of the natural of active substance dipping with synthesis, microcapsule in polymer, for the dressing compound of seed, and the preparation to use with combustion unit-block, such as sootiness cartridge case, sootiness tank and sootiness dish, and the cold mist of ULV (Coldmist) and hot mist (Warmmist) preparation.
These preparations can be produced by known method, such as, active compound mix with expansion agent, these expansion agent be exactly liquid or liquefied gas or the diluent or carrier of solid, and tensio-active agent and emulsifying agent and/or dispersion agent and/or formation of foam agent can be selected arbitrarily.Such as when using water as expansion agent, organic solvent also can be used as auxiliary agent.
When making diluent or carrier with liquid solvent, be suitable substantially, as: arene, such as dimethylbenzene, toluene or alkylnaphthalene; The fragrance of chlorination or the fat hydrocarbon of chlorination, such as chlorobenzene, vinylchlorid or methylene dichloride; Fat hydrocarbon, such as hexanaphthene or paraffin, such as mineral oil fractions; Alcohols, such as ethanol or ethylene glycol and their ether and lipid; Ketone, such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or cyclohexanone; Or the polar solvent be of little use, such as dimethyl formamide and dimethyl sulfoxide (DMSO), Yi Jishui.
Diluent or carrier with regard to liquefied gas is said, refers to and will become the liquid of gas at normal temperatures and pressures, such as aerosol propellants, as hydro carbons and the butane of halogenation, propane, the mineral substance that nitrogen and carbon dioxide solid carrier can be natural with (ground) ground, such as kaolin, clay, talcum, quartz, atlapulgite, polynite, or diatomite, with the mineral substance of the synthesis ground, the silicic acid of such as high dispersing, aluminum oxide and silicate.Solid carrier for particle is that pulverize with natural announcement stone that is classification, such as calcite, marble, float stone, sepiolite and rhombspar, and the particle of inorganic and organic meal synthesis, with organic materials such as wood sawdust, Exocarpium cocois (Cocos nucifera L), the particle etc. of corn cob and tobacco stems.
Emulsification row that are non-ionic and negatively charged ion can be used as emulsifying agent and/or formation of foam agent.Such as polyoxyethylene-fatty esters of gallic acid, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyoxyethylene glycol ethers, alkyl sulfonates, alkyl sulfuric ester class, aromatic yl sulphonate class and albumin hydrolysate.Dispersion agent comprises, such as lignin sulfite waste liquor and methylcellulose gum.
Tackiness agent can be used in the formulation, such as carboxymethyl cellulose and with powder, the polymer of the natural and synthesis of particle or emulsion form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate.
Can with coloring agents as inorganic dyestuff, as ferric oxide, oxidation bore and Prussian blue; Organic dye, as organic dye, as azo dyes or metal titanium cyanine dyes; With use trace nutritional agent, as iron, suddenly, boron, copper, cobalt, the salt etc. of aluminum and zinc.
These active compounds of the present invention can be made a kind of mixture with other active compounds and be present in their commercial preparation or from use formulation prepared by these preparations, these other active compound is sterilant, close bait, sterilant, miticide, nematocides, mycocide, growth control agent etc.Sterilant comprises, such as phosphoric acid ester, amino formate, cinerins, chlorinated hydrocarbons, benzoyl area kind, and neires toxin and the material produced by microorganism, as Avrmectin.
In addition, these active compounds of the present invention also can be made a kind of mixture with synergistic agent and are present in their commercial preparation the use formulation becoming and prepare from these preparations.Synergistic agent is the compound improving active compound effect, because active compound itself has activity, also can add synergistic agent.
These preparations usually containing accounting for described composition 0.001-99.99 % by weight, preferred 0.01-99.9 % by weight.
Making from commercial preparation uses the concentration of the active compound formulation can change in wide scope.Use the concentration of the active compound in formulation can from 0.0000001-100%(g/v), preferably 0.0001 and 1%(g/v).
Shown in provided by the invention, a kind of preparation formula I, the method for compound, specifically comprises the steps:
(1) Lewis base is being had to exist and under room temperature condition, by compound shown in formula II and corresponding amine (as H 2nR 1) react in organic solvent, obtain intermediate A (means re-crystallization purify intermediates A can be adopted);
(2) Lewis base and Tosyl chloride is being had to exist and under reflux state, by intermediate A and corresponding amine (as H 2nR 2) react in organic solvent, obtain target compound (compound shown in formula I can adopt compound shown in column chromatography mode purifying I);
Wherein, described organic solvent can preferably methylene dichloride or DMF (DMF); Described Lewis base can preferably 2，4，6-trimethylpyridine or DMAP.
Major advantage of the present invention comprises:
A () the invention provides the compound of a class formation novelty, have significant insecticidal activity and selectively insecticidal spectrum;
B synthetic method that () compound provided by the invention tool is more simple and easy to get.
Below in conjunction with concrete enforcement, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number are calculated by weight, raw materials used by commercial acquisition.
Embodiment 1
(1) 2'-formyl methylamino--benzoic preparation of [1,1'-biphenyl]-2-:
Take 2,2 '-biphenyl dicarboxylic acid acid anhydride 672mg (3mmol, 1 equivalent) is loaded in round-bottomed flask, adds DMF and the 439mg (3.6mmol of 3mL, 1.2 equivalents) 2,4,6-trimethylpyridine (catalyzer), stirred after 2 minutes, add methylamine solution 0.33ml (3.3mmol, 1.1 equivalents, concentration 31%), stirring at normal temperature is after 3 hours, stopped reaction, DMF is revolved in decompression, uses acetic acid ethyl dissolution gains, is then transferred to separating funnel, wash with the HCl of 2M, separate out a large amount of solid, suction filtration recrystallization obtains white solid, productive rate 81%.
1HNMR(400MHz,DMSO)δ12.70(s,1H),8.71(d,J=4.7Hz,1H),7.59–7.46(m,3H),7.55–7.29(m,3H),7.15–7.05(m,2H),2.63(d,J=4.6Hz,3H).
HRMS:m/z calculated value C 15h 14nO 3(M+H) +256.0968, measured value 256.0967
(2) preparation of N-methyl-N'-phenyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-1 compound):
Take 2'-formyl methylamino--[1,1'-biphenyl]-2-phenylformic acid 510mg(2mmol, 1 equivalent), Tosyl chloride 456mg(2.4mmol, 1.2 equivalents), to Dimethylamino pyridine 292mg(2.4mmol, 1.2 equivalents), add methylene dichloride 4ml, reflux 5 hours.Then aniline 204mg(2.2mmol is added, 1.1 equivalents), continuation reaction stopped reaction after 5 hours, revolve and desolventize, add acetic acid ethyl dissolution residual solids, wash successively with 1M dilute hydrochloric acid, saturated aqueous common salt, through silicagel column column chromatography, with petrol ether/ethyl acetate=3:1 ~ 1:1(v/v) wash-out, obtain white solid (shown in formula I-1 compound).
1HNMR(400MHz,DMSO)δ10.70(s,1H),8.72(d,J=4.7Hz,1H),7.64(dd,J=5.8,3.2Hz,1H),7.58–7.46(m,3H),7.43–7.29(m,3H),7.21(t,J=7.9Hz,2H),7.15–7.05(m,2H),6.98(t,J=7.4Hz,1H),2.64(d,J=4.6Hz,3H).
13CNMR(101MHz,DMSO)δ168.97,168.16,139.16,139.08,138.92,137.01,136.96,129.94,129.71,129.65,129.35,129.17,128.20,128.14,127.91,127.42,124.14,119.71,22.29.
HRMS:m/z calculated value C 21h 19n 2o 2(M+H) +331.1447, measured value 331.1444.
Embodiment 2
The preparation of 4-ethylmercapto group-N-(2-p-methoxy-phenyl)-N'-methyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-2 compound):
Substitute 2 divided by 4-ethylmercapto group-2,2 '-biphenyl dicarboxylic acid acid anhydride, 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)) and 2-anisidine substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ9.70(s,1H),8.58(d,J=4.6Hz,1H),7.87(dd,J=8.0,1.4Hz,1H),7.67–7.56(m,2H),7.50–7.37(m,3H),7.13–7.08(m,1H),7.07–7.01(m,1H),7.01–6.94(m,1H),6.89–6.77(m,2H),3.56(s,3H),2.64(d,J=4.6Hz,3H).2.65(q,J=7.9Hz,2H)1.10(t,J=7.9Hz,3H)。
13CNMR(101MHz,DMSO)δ169.82,167.64,149.96,139.73,139.52,136.86,136.30,130.00,129.95,129.91,129.07,128.40,127.99,127.85,127.72,127.67,124.81,121.59,120.44,111.40,55.72,29.4,26.47,14.1
HRMS:m/z calculated value C 24h 25n 2o 3s (M+H) +421.1580, measured value 421.1582.
Embodiment 3
The preparation of N-(the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro oxyethyl group) phenyl)-N'-methyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-3 compound):
Outward, all the other steps are similar to embodiment 1, obtain title compound to substitute aniline (in step (2)) divided by the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro oxyethyl group) aniline.
1HNMR(400MHz,DMSO)δ11.20(s,1H),8.62(d,J=4.7Hz,1H),7.67–7.59(m,3H),7.59–7.47(m,3H),7.47–7.39(m,2H),7.23–7.08(m,2H),6.91(t,J=51.4Hz,1H),2.62(d,J=4.6Hz,3H).
13CNMR(101MHz,DMSO)δ170.86,168.24,139.40,139.31,138.96,136.21,136.11,136.09,130.63,130.12,130.05,130.00,129.79,128.25,128.23,128.18,127.51,119.58,26.54,22.52,14.41.
HRMS:m/z calculated value C 23h 17c l2f 4n 2o 3(M+H) +515.0552 measured values 515.0554.
Embodiment 4
The preparation of N-(the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro oxyethyl group)-phenyl)-N'-sec.-propyl-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-4 compound):
Substitute methylamine (in step (1)) and the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro oxyethyl group) aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.24(s,1H),8.30(d,J=7.8Hz,1H),7.67(s,3H),7.62–7.49(m,3H),7.43(dd,J=5.3,3.5Hz,2H),7.15(ddd,J=17.7,5.6,3.3Hz,2H),6.93(t,J=51.4Hz,1H),3.91–3.72(m,1H),0.87(s,6H).
13CNMR(101MHz,DMSO)δ170.86,168.24,139.40,139.31,138.96,136.21,136.11,136.09,130.63,130.12,130.05,130.00,129.79,128.25,128.23,128.18,127.51,119.58,41.3026.54,22.52,14.41.
HRMS:m/z calculated value C 25h 21cl 2f 4n 2o 3(M+H) +543.0860 measured values 543.0863.
Embodiment 5
The preparation of 5 '-first sulfo group-N-sec.-propyl-N-(2-p-methoxy-phenyl)-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-5 compound):
Divided by 5-first sulfo group-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with Isopropylamine and 2-anisidine substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ9.74(s,1H),8.33(d,J=7.9Hz,1H),7.75(dd,J=7.9,1.4Hz,1H),7.64(dt,J=5.6,3.2Hz,1H),7.55–7.44(m,3H),7.41–7.37(m,2H),7.16–7.11(m,1H),7.10–6.99(m,2H),6.94–6.87(m,1H),6.85–6.78(m,1H),3.80(dq,J=13.3,6.6Hz,1H),3.62(s,3H),3.41(s,3H),0.89(d,J=25.1Hz,6H).
13CNMR(101MHz,DMSO)δ168.34,168.13,150.58,139.45,139.30,137.14,136.80,129.86,129.60,129.35,128.14,127.93,127.59,127.39,125.32,122.49,120.47,111.60,55.87,49.7,41.15,22.39.
HRMS:m/z calculated value C 25h 27n 2o 5s (M+H) +467.1635 measured values 467.1633.
Embodiment 6
The preparation of 4-ethynyl-N-(3-chloro-phenyl-)-N '-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-6 compound):
Divided by 4-ethynyl-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with Isopropylamine and 2-chloroaniline substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.95(s,1H),8.40(d,J=7.7Hz,1H),7.72–7.60(m,2H),7.52(dd,J=7.0,4.0Hz,3H),7.40(dd,J=4.7,2.3Hz,2H),7.34–7.20(m,2H),7.19–6.99(m,2H),4.20(s,1H),3.83(dt,J=13.2,6.5Hz,1H),0.89(s,6H).
13CNMR(101MHz,DMSO)δ169.08,168.38,140.57,139.07,138.77,136.86,136.58,133.49,130.95,130.19,129.80,129.74,129.40,128.27,128.21,127.97,127.40,123.85,119.02,118.02,81.4,78.2,41.30,22.30.
HRMS:m/z calculated value C 25h 22clN 2o 2(M+H) +417.1364 measured values 417.1361.
Embodiment 7
The preparation of N-sec.-propyl-N '-(2-methyl-4-seven fluorine isopropyl-phenyl)-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-7 compound):
Substitute aniline (in step (2)) divided by substituting methylamine (in step (1)) and 2-methyl-4 sevoflurane isopropyl amine with Isopropylamine outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.33(s,1H),8.39(d,J=7.9Hz,1H),7.73–7.66(m,1H),7.62–7.35(m,8H),7.31–7.18(m,1H),7.16–7.07(m,1H),3.78(dd,J=14.2,6.6Hz,1H),2.06(s,3H),0.85(d,J=8.3Hz,6H).
13CNMR(101MHz,DMSO)δ168.78,168.67,139.53,139.08,138.96,137.26,136.45,133.14,130.08,129.67,129.64,129.59,128.20,128.02,127.58,125.42,123.76,123.66,122.27,121.98,121.77,119.14,41.21,22.24,18.13.
HRMS:m/z calculated value C 27h 24f 7n 2o 2(M+H) +541.1721 measured values 541.1720.
Embodiment 8
The preparation of 4-methylamino-N-(2-iodophenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-8 compound):
Divided by 4-methylamino--2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with Isopropylamine and 2-Iodoaniline substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.40(s,1H),8.14(d,J=8.0Hz,1H),7.86(d,J=7.8Hz,1H),7.73(d,J=7.1Hz,1H),7.63–7.39(m,4H),7.32(t,J=7.6Hz,1H),7.25(d,J=7.0Hz,1H),7.12(d,J=7.2Hz,1H),6.99(t,J=7.6Hz,1H),6.90(d,J=7.7Hz,1H),4.12(s,1H)3.74(dd,J=13.9,6.8Hz,1H),2.75(d,J=6.9Hz,3H),1.05–0.42(m,6H).
13CNMR(101MHz,DMSO)δ168.86,168.26,139.56,139.39,138.77,137.39,136.34,130.06,129.79,129.65,129.49,129.15,128.78,128.12,128.06,128.00,127.60,127.50,97.88,40.99,33.4,22.27.
HRMS:m/z calculated value C 24h 25iN 3o 2(M+H) +514.0986 measured values 514.0988.
Embodiment 9
The preparation of 5-vinyl-N-sec.-propyl-N'-(4-nitrophenyl)-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-9 compound):
Divided by 5-vinyl-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with Isopropylamine and p-Nitroaniline substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.39(s,1H),8.49(d,J=7.9Hz,1H),8.16(d,J=9.2Hz,2H),7.75–7.63(m,2H),7.60–7.47(m,3H),7.44–7.35(m,2H),7.20–7.08(m,2H),6.54(t,J=15.2Hz,1H),5.30(d,J=10.2Hz,2H)3.85(dq,J=13.2,6.5Hz,1H),0.93(s,6H).
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,146.10,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,111.46,40.55,40.34,40.13,39.92,39.71,39.50,39.29,23.32.
HRMS:m/z calculated value C 25h 24n 3o 4(M+H) +514.0986 measured values 514.0988.
Embodiment 10
The preparation of N-sec.-propyl-N'-benzyl-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-10 compound):
Substitute methylamine (in step (1)) and benzylamine divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ9.22(t,J=6.0Hz,1H),8.34(d,J=8.0Hz,1H),7.57–7.52(m,1H),7.50–7.39(m,5H),7.27–7.15(m,3H),7.11–7.00(m,2H),7.00–6.91(m,2H),4.29(d,J=6.0Hz,2H),3.71(dd,J=14.4,6.6Hz,1H),0.72(s,6H).
13CNMR(101MHz,DMSO)δ170.11,168.26,139.24,139.20,138.94,137.49,136.66,129.74,129.57,129.43,129.33,128.60,127.99,127.56,127.52,127.21,127.08,42.81,40.92,22.18.
HRMS:m/zcalcdforC 24H 24N 2NaO 2(M+Na) +395.1735found395.1747。
Embodiment 11
The preparation of N-(4-trifluoroacetyl group phenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-11 compound):
Substitute methylamine (in step (1)) and 4-trifluoroacetyl aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.11(s,1H),8.43(d,J=7.9Hz,1H),7.80–7.45(m,8H),7.45–7.32(m,2H),7.13(ddd,J=12.0,5.8,3.0Hz,2H),3.84(dd,J=14.1,6.8Hz,1H),0.91(s,6H).
13CNMR(101MHz,DMSO)δ179.60,168.92,168.69,139.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,41.21,22.25.
HRMS:m/zcalcdforC 25H 21F 3N 2O 3(M+H) +454.1504,found454.1502。
Embodiment 12
The preparation of 5 '-trifluoromethanesulfonic acid base-N-(fluoro-4 hydroxy-pheny of 2-)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-12 compound):
Divided by 5-fluoroform sulfo group-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2,2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), methylamine (in step (1)) is substituted and fluoro-4 hydroxyanilines of 2-substitute aniline (in step (2)) outward with Isopropylamine, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.39(s,1H),9.35(s,1H),8.39(d,J=7.9Hz,1H),7.73–7.60(m,1H),7.60–7.33(m,4H),7.24(dd,J=6.3,2.8Hz,1H),7.19–7.04(m,2H),6.98–6.85(m,1H),6.44(dt,J=8.4,3.2Hz,1H),0.91(s,6H).
13CNMR(101MHz,DMSO)δ168.92,163.69,139.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,41.21,22.25.
HRMS:m/zcalcdforC 24H 21F 4N 2O 5S(M+H) +525.1102,found525.1105。
Embodiment 13
The preparation of N-sec.-propyl-N'-(3-pyridyl)-[1,1'-xenyl]-2,2'-dibenzamides (shown in formula I-13 compound):
Divided by 3,6-bis-fluoro-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2,2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitute methylamine (in step (1)) and 3-aminopyridine with Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.97(s,1H),8.51(s,1H),8.41(d,J=7.9Hz,1H),8.23(d,J=3.5Hz,1H),7.87(d,J=8.3Hz,1H),7.60–7.47(m,2H),7.47–7.36(m,2H),7.29(dd,J=8.2,4.7Hz,1H),7.23–7.04(m,2H),3.83(dq,J=13.2,6.6Hz,1H),0.89(s,6H).。
13CNMR(101MHz,DMSO)δ169.10,168.60,154.10,152.53,139.16,138.81,136.84,136.46,135.83,130.25,129.79,129.74,129.43,128.28,128.22,127.96,127.44,126.59,124.17,41.30,22.24.
HRMS:m/zcalcdforC 22H 19F 2N 3NaO 2(M+Na) +418.1338,found418.1343。
Embodiment 14
The preparation of N-(2,3-difluorophenyl)-N'-sec.-propyl-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-14 compound):
2 are substituted, 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)) divided by 5-sec.-propyl-2,2 '-biphenyl dicarboxylic acid acid anhydride, methylamine (in step (1)) and 2 are substituted with ethamine, 3-difluoroaniline substitutes aniline (in step (2)), and outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.76(s,1H),8.44(d,J=7.8Hz,1H),7.68(dd,J=5.7,2.9Hz,1H),7.62–7.33(m,5H),7.21–7.05(m,4H),3.81(dd,J=14.0,6.7Hz,1H),3.10(m,2H),1.10(t,J=8.1Hz,3H),0.92(s,6H).
13CNMR(101MHz,DMSO)δ168.86,168.26,159.56,141.39,138.77,137.39,136.34,130.06,129.79,129.65,129.49,129.15,128.78,128.12,128.06,128.00,127.60,127.50,97.88,40.99,34.17,22.27,15.20
HRMS:m/zcalcdforC 25H 25F 2N 2O 2(M+H) +423.1879,found423.1883。
Embodiment 15
The preparation of N-(the chloro-4-trifluoromethoxy-phenyl of 2-)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-15 compound):
Substitute methylamine (in step (1)) and the chloro-4-trifluoro-methoxyaniline of 2-divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.49(s,1H),8.32(d,J=7.9Hz,1H),7.75–7.64(m,1H),7.59–7.40(m,7H),7.35(d,J=8.8Hz,1H),7.24–7.15(m,1H),7.16–7.05(m,1H),3.77(dd,J=14.1,6.7Hz,1H),0.86(s,6H).
13CNMR(101MHz,DMSO)δ168.92,168.69,156.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,41.21,22.25.
HRMS:m/zcalcdforC 24H 21ClFN 2O 3(M+H) +477.1887,found477.1886。
Embodiment 16
The preparation of N-(the bromo-4-trifluoromethyl-phenyl of 2-)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-16 compound):
Substitute methylamine (in step (1)) and the bromo-4-trifluoro-methoxyaniline of 2-divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.53(s,1H),8.30(d,J=7.9Hz,1H),7.86(d,J=8.3Hz,1H),7.78–7.66(m,1H),7.62–7.35(m,7H),7.18(ddd,J=7.0,6.0,2.2Hz,2H),3.78(dd,J=14.0,6.7Hz,1H),0.87(s,6H).
13CNMR(101MHz,DMSO)δ168.92,168.69,139.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,41.21,22.25.
HRMS:m/zcalcdforC 24H 21 79BrF 3N 2O 2(M+H) +505.0738found505.0749;m/zcalcdforC 24H 21 81BrF 3N 2O 2(M+H) +507.0718found507.0726。
Embodiment 17
The preparation of N-(2-thiazolyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-17 compound):
Substitute methylamine (in step (1)) and thiazolamine divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ12.74(s,1H),8.46(d,J=7.9Hz,1H),7.70(dd,J=5.8,3.1Hz,1H),7.64–7.48(m,3H),7.41(ddd,J=16.6,8.8,2.4Hz,3H),7.31–6.88(m,3H),3.85(dd,J=14.0,6.7Hz,1H),0.94(d,J=6.3Hz,6H).
13CNMR(101MHz,DMSO)δ169.21,167.50,157.76,139.32,138.67,138.22,136.55,134.63,130.71,129.87,129.69,129.50,128.46,128.32,127.55,114.20,41.40,22.38.
HRMS:m/zcalcdforC20H20N3O2S(M+H)+366.1271,found366.1270。
Embodiment 18
The preparation of N-(3-ethenylphenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-18 compound):
Substitute methylamine (in step (1)) and E-3-(3,3-dichloro-propenyl) aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.97(s,1H),8.51(s,1H),8.41(d,J=7.9Hz,1H),8.23(d,J=3.5Hz,1H),7.87(d,J=8.3Hz,1H),7.74–7.64(m,1H),7.60–7.47(m,3H),7.47–7.36(m,2H),7.29(dd,J=8.2,4.7Hz,1H),7.23–7.04(m,2H),6.63(t,J=16.8Hz,1H),5.61(d,J=10.6Hz),5.18(d,J=16.8Hz,1H),3.83(dq,J=13.2,6.6Hz,1H),0.89(s,6H).
13CNMR(101MHz,DMSO)δ169.08,168.38,140.57,139.07,138.77,136.86,136.58,133.49,13260,130.95,130.19,124.71,129.80,129.74,129.40,128.27,128.21,127.97,127.40,123.85,119.02,118.02,75.10,41.30,22.30.
HRMS:m/zcalcdforC 26H 24Cl 2N 2O 2(M+H) +466.1215,found466.1219。
Embodiment 19
The preparation of N-(4-acetylphenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-19 compound):
Substitute methylamine (in step (1)) and 4-ethanoyl aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.90(s,1H),8.42(d,J=7.9Hz,1H),7.70–7.64(m,1H),7.58–7.35(m,7H),7.31(d,J=8.8Hz,2H),7.22–6.95(m,2H),3.82(dq,J=13.4,6.6Hz,1H),2.50(s,3H),0.88(s,6H).
13CNMR(101MHz,DMSO)δ197.0169.04,168.22,139.08,138.80,138.11,136.93,136.70,130.10,129.76,129.69,129.35,129.13,128.25,128.18,127.93,127.72,127.39,121.12,41.26,26.6,22.28.
HRMS:m/zcalcdforC25H25N2O3(M+H) +401.1860,found401.1860
Embodiment 20
The preparation of N-(3-ethynyl phenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-20 compound):
Substitute methylamine (in step (1)) and 3-acetylenylaniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.97(s,1H),8.51(s,1H),8.41(d,J=7.9Hz,1H),8.23(d,J=3.5Hz,1H),7.87(d,J=8.3Hz,1H),7.74–7.64(m,1H),7.60–7.47(m,3H),7.47–7.36(m,2H),7.29(dd,J=8.2,4.7Hz,1H),7.23–7.04(m,2H),4.05(s,1H),5.18(d,J=16.8Hz,1H),3.83(dq,J=13.2,6.6Hz,1H),0.89(s,6H).
13CNMR(101MHz,DMSO)δ169.08,168.38,140.57,139.07,138.77,136.86,136.58,133.49,130.95,130.19,129.80,129.74,129.40,128.27,128.21,127.97,127.40,123.85,119.02,118.02,82.3,81.4,41.30,22.30.
HRMS:m/zcalcdforC 25H 23N 2O 2(M+H) +383.1754,found383.1756。
Embodiment 21
The preparation of N-(3-cyclopropyl phenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-21 compound):
Substitute methylamine (in step (1)) and 3-cyclopropyl aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.95(s,1H),8.40(d,J=7.7Hz,1H),7.72–7.60(m,2H),7.52(dd,J=7.0,4.0Hz,3H),7.40(dd,J=4.7,2.3Hz,2H),7.34–7.20(m,2H),7.19–6.99(m,3H),3.83(dt,J=13.2,6.5Hz,1H),0.89(s,6H).
13CNMR(101MHz,DMSO)δ169.08,168.38,140.57,139.07,138.77,136.86,136.58,133.49,130.95,130.19,129.80,129.74,129.40,128.27,128.21,127.97,127.40,123.85,119.02,118.02,41.30,22.30.
HRMS:m/zcalcdforC 26H 27N 2O 2(M+H) +399.2067,found399.2069。
Embodiment 22
The preparation of N-(4-methylthio group phenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-22 compound):
Substitute methylamine (in step (1)) and 4-methylthio group aniline divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.90(s,1H),8.42(d,J=7.9Hz,1H),7.70–7.64(m,1H),7.58–7.35(m,7H),7.31(d,J=8.8Hz,2H),7.22–6.95(m,2H),3.82(dq,J=13.4,6.6Hz,1H),2.57(s,3H),0.88(s,6H).
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,40.55,40.34,40.13,39.92,
HRMS:m/zcalcdforC 26H 27N 2O 2(M+H) +399.2067,found399.2069
Embodiment 23
The preparation of N-(4-difluoro first sulfo group phenyl)-N'-sec.-propyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-23 compound):
Substitute methylamine (in step (1)) and 4-difluoro first aniline sulfonic acid divided by Isopropylamine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.90(s,1H),8.42(d,J=7.9Hz,1H),7.70–7.64(m,1H),7.58–7.35(m,7H),7.31(d,J=8.8Hz,2H),7.22–6.95(m,2H),6.43(t,J=54.6Hz,1H)3.82(dq,J=13.4,6.6Hz,1H),0.88(s,6H).
13CNMR(101MHz,DMSO)δ168.92,168.69,153.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,41.21,22.25.
HRMS:m/zcalcdforC 24H 23F 2N 2O 4S(M+H) +473.1341,found473.1345
Embodiment 24
N-(4-cyano-phenyl)-N'-methoxyl group-5 ' preparation of-hydroxyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-24 compound):
Divided by 5-hydroxyl-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with Methoxyamine and substitute aniline (in step (2)) outward to cyano-aniline, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.39(s,1H),8.49(d,J=7.9Hz,1H),8.16(d,J=9.2Hz,2H),7.75–7.63(m,3H),7.60-7.35(m,4H),7.20–7.08(m,2H),5.33(s,1H),3.61(s,3H)。
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,108.21,64.40
HRMS:m/zcalcdforC 24H 23F 2N 2O 4S(M+H) +473.1341,found473.1345
Embodiment 25
The preparation of N-(4-Methylaminophenyl)-N'-proyl-4-nitro-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-25 compound):
Divided by 4 '-nitro-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2,2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitute methylamine (in step (1)) with the amino propine of 3-and aniline (in step (2)) is substituted outward to methylamino-aniline, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.20(s,1H),8.63(s,1H),8.53(d,J=7.6Hz,1H),7.67–7.59(m,2H),7.59–7.47(m,2H),7.35–6.84(m,6H),4.24(d,J=3.0Hz,2H),4.01(s,1H),3.08(s,1H),2.61(d,J=7.1Hz,3H)。
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,86.60,73.20,28.32.
HRMS:m/zcalcdforC 24H 21N 4O 4(M+H) +429.1557,found429.1559
Embodiment 26
The preparation of N-(4-trifluoroacetyl group phenyl)-N'-(formyl-2-ketone group-propylamine)-5 '-chloromethane thioether group-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-26 compound):
Divided by 5-chloromethane thioether group-2; 2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2; 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)); substitute methylamine (in step (1)) with 1-aminoacetone and aniline (in step (2)) is substituted outward to trifluoroacetyl aniline; all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.71(s,1H),8.49(d,J=7.6Hz,1H),8.20–7.70(m,4H),7.65–7.55(m,4H),7.39–7.49(m,3H),4.81(s,2H),4.20(d,J=5.2Hz,2H),2.13(s,3H)。
13CNMR(101MHz,DMSO)δ201.10,179.60,168.92,168.69,139.32,138.80,137.37,137.18,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,57.23,47.23,26.84
HRMS:m/zcalcdforC 26H 21ClF 3N 2O 4S(M+H) +549.0857,found549.0853
Embodiment 27
The preparation of 4-allyl group-N-(4-methyl sulfoxide base phenyl)-N '-(3,3,3-tri-fluoro-2 ketone-propyl group)-[1,1-biphenyl]-diformamide (shown in formula I-27 compound):
Divided by 3-allyl group-2; 2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2; 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)); methylamine (in step (1)) is substituted and 4-methyl sulfoxide base aniline substitutes aniline (in step (2)) outward with trifluoroacetyl group methylamine; all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.39(s,1H),8.49(d,J=7.9Hz,1H),7.75–7.63(m,3H),7.60-7.35(m,8H),6.01(d,J=9.2Hz,1H),4.99(d,J=9.2Hz2H),4.81(s,2H),3.10(d,J=4.2Hz,2H)，2.66(s,3H).
13CNMR(101MHz,DMSO)δ206.32,179.60,168.92,168.69,139.32,138.80,137.37,137.18,136.53,135.97,134.57,130.32,129.80,129.62,129.19,128.87,128.19,127.91,127.62,125.32,124.22,123.53,123.49,123.19,122.61,116.23,114.72,44.56,39.54,31.90,
HRMS:m/zcalcdforC 26H 21ClF 3N 2O 4S(M+H) +549.0857,found549.0853
Embodiment 28
The preparation of N-(the chloro-3-alkene of 4,4-bis--1-butyl)-N2'-(2-naphthyl)-3-methoxyl group-[1,1'-xenyl]-2,2'-diformamides (shown in formula I-28 compound):
Divided by 3-methoxyl group-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2,2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), with 4, the chloro-3-alkene of 4-bis--1-butyl-1-amine substitutes methylamine (in step (1)) and 2-amino naphthalenes substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ9.98(s,1H),8.12(t,J=6.7Hz,1H),7.70–7.64(m,2H),7.58–7.35(m,8H),7.31(m,2H),7.22–6.95(m,2H),3.85(s,3H),3.42(dq,J=12.8,6.3Hz,2H),3.42(d,J=12.8,6.3Hz,2H),2.57(d,J=5.2Hz,1H).
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,126.40,125.34,124.63,121.40,122.71,122.52,55.83,37.31,
HRMS:m/zcalcdforC 29H 25Cl 2N 2O 3(M+H) +519.1237,found519.1239
Embodiment 29
The preparation of N-(the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro ethoxyl phenenyl))-N '-(1-methylthio group-2-methyl-2-third is amino)-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-29 compound):
Substitute methylamine (in step (1)) and the chloro-4-tetrafluoro-ethoxy aniline of 3,5-divided by 2-amino-2-methyl-1-dimethyl sulfide propane to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.24(s,1H),8.04(s,1H),7.78–7.65(m,3H),7.65–7.48(m,3H),7.48–7.37(m,2H),7.29–7.08(m,2H),6.93(t,J=51.5Hz,1H),3.36(s,3H),2.78(d,J=59.1Hz,2H),2.05(s,3H),1.08–0.94(m,6H).
13CNMR(101MHz,DMSO)δ169.53,168.89,139.46,139.23,138.55,137.28,136.43,135.74,130.70,130.22,129.85,129.82,129.25,128.32,128.29,128.01,127.74,119.87,54.86,43.95,26.11,17.51.
HRMS:m/zcalcdforC27H24Cl2F4N2O3S(M+H)+602.0821found602.0820。
Embodiment 30
The preparation of N-(2-p-methoxy-phenyl)-N '-cyclopropyl-3-methyl-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-30 compound):
Divided by 2-methyl-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2, and 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), substitutes methylamine (in step (1)) with cyclopropylamine and 2-anisidine substitutes aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ9.71(s,1H),8.56(s,1H),7.80(d,J=7.5Hz,1H),7.64(d,J=5.3Hz,1H),7.57–7.44(m,3H),7.40(s,2H),7.13(s,1H),7.02(dd,J=15.3,6.6Hz,2H),6.90(d,J=7.7Hz,1H),6.82(t,J=7.3Hz,1H),3.61(s,3H),2.62(s,1H),0.57(d,J=5.3Hz,2H),2.43(s,3H)0.25(s,2H).
13CNMR(101MHz,DMSO)δ170.47,167.95,150.35,139.42,139.38,136.77,136.57,129.89,129.83,129.74,129.27,128.22,127.96,127.69,127.48,125.16,125.15,122.13,120.46,111.54,55.84,22.93,18.4,6.11.
HRMS:m/zcalcdforC 25H 25N 2O 3(M+H) +401.1860found401.1866。
Embodiment 31
The preparation of N-(the chloro-4-of 3,5-bis-(1,1,2,2-tetrafluoro ethoxyl phenenyl))-N '-(2-chloroethyl)-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-31 compound):
Divided by 4-ethanoyl-2; 2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2; 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)); methylamine (in step (1)) and the chloro-4-of 3,5-bis-(1,1 is substituted with 2-chloroethyl amine; 2; 2-tetrafluoro oxyethyl group)-aniline substitutes aniline (in step (2)) outward, all the other steps is similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.24(s,1H),8.30(d,J=7.8Hz,1H),7.67(s,3H),7.62–7.49(m,2H),7.43(dd,J=5.3,3.5Hz,2H),7.15(ddd,J=17.7,5.6,3.3Hz,2H),6.93(t,J=51.4Hz,1H),2.76(s,3H),2.09(m,2H),1.25(t,J=7.2Hz,2H).
13CNMR(101MHz,DMSO)δ197.12,169.53,168.89,139.46,139.23,138.55,137.28,136.43,135.74,130.70,130.22,129.85,129.82,129.25,128.32,128.29,128.01,127.74,119.87,44.21,43.02,26.11
HRMS:m/zcalcdforC 26H 20Cl 3F 4N 2O 4(M+H) +605.0419found605.0415。
Embodiment 32
N-(4-diethylin phenyl)-N '-(2-methoxy ethyl)-4 ' preparation of-cyano group-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-32 compound):
Divided by 4-cyano group-2,2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2,2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)), methylamine (in step (1)) is substituted and 4-diethylin aniline substitutes aniline (in step (2)) outward with 2-methoxyethyl amine, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.80(s,1H),8.42(d,J=7.9Hz,1H),7.70–7.61(m,2H),7.58–7.35(m,4H),7.31-7.25(m,2H),7.22–6.95(m,3H),3.45-3.31(m,7H),3.09(m,2H),1.25(t,J=7.2Hz,2H),1.15(t,J=7.4Hz,6H)。
13CNMR(101MHz,DMSO)δ170.26,168.09,167.73,143.25,142.15,134.09,132.84,131.67,130.85,130.44,130.42,130.22,130.17,128.56,128.34,126.64,112.34,70.21,60.73,47.10,38.63,12.85.
HRMS:m/zcalcdforC 26H 20Cl 3F 4N 2O 4(M+H) +605.0419found605.0415
Embodiment 33
N-((methyl-imino) methylene radical phenyl)-N '-(2-cyano group base ethyl)-4 ' preparation of-fluoroform acyl group-[1,1'-biphenyl]-2,2'-diformamides (shown in formula I-33 compound):
Divided by 4-fluoroform acyl group-2; 2 '-biphenyl dicarboxylic acid acid anhydride substitutes 2; 2 '-biphenyl dicarboxylic acid acid anhydride (in step (1)); methylamine (in step (1)) and 4-(methyl-imino is substituted with 2-cyano group ethamine) methylene radical aniline substitutes aniline (in step (2)) outward; all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ10.80(s,1H),8.42(d,J=7.9Hz,1H),8.20(t,J=6.8Hz,1H)7.70–7.61(m,2H),7.60–7.45(m,4H),7.31-7.25(m,2H),6.98–6.65(m,3H),3.27(d,J=6.8Hz,2H),3.09(t,J=7.2Hz,2H),3.35(t,J=7.2Hz,2H).
13CNMR(101MHz,DMSO)δ179.53,169.53,168.89,160.81,139.46,139.23,138.55,137.28,136.43,135.74,130.70,130.22,129.85,129.82,129.25,128.32,128.29,128.01,127.74,119.87,118.32,117.01,48.05,37.82,17.99.
HRMS:m/zcalcdforC 27H 22F 3N 4O 3(M+H) +507.1639found507.1642
Embodiment 34
The preparation of 2 '-(2-carboxyethyl hydrazine)-N-(4-sulfonic group-phenyl)-[1,1'-biphenyl]-methane amide (shown in formula I-34 compound):
Substitute methylamine (in step (1)) and 4-sulfoacid aniline divided by ethyl hydrazine to substitute aniline (in step (2)) outward, all the other steps are similar to embodiment 1, obtain title compound.
1HNMR(400MHz,DMSO)δ11.39(s,1H),8.49(d,J=7.9Hz,1H),8.16(d,J=9.2Hz,2H),7.75–7.63(m,3H),7.60–7.47(m,3H),7.44–7.35(m,2H),7.20–7.08(m,2H),2.68(q,J=7.9Hz,2H),1.87(s,1H),1.23(t,J=7.9Hz,3H).
13CNMR(101MHz,DMSO)δ168.97,168.16,145.16,139.08,138.92,137.01,136.96,129.94,129.71,129.65,129.35,129.17,128.20,128.14,127.91,127.42,124.14,119.71,41.23,12.29.
HRMS:m/zcalcdforC 22H 22N 3O 5S(M+H) +440.1275found440.1277。
With reference to embodiment 1 ~ 34, compound listed by all right preparation table 1.Its preparation process that this is no longer going to repeat them.
Table 1
Continued 1
Continued 1
Continued 1
Continued 1
Continued 1
Embodiment 35
The insecticidal activity test of the compounds of this invention
(1) to the insecticidal activity of aphid
Aphid belongs to homoptera pest, has piercing mouth parts, is a kind of common crop pests.With bean aphid (Aphiscraccivora) for tested object, adopt pickling process test.
Operating process: the various sample of precise, adds DMF respectively and is mixed with 10g/L mother liquor, is diluted to the concentration of 500ug/mL during experiment with the aqueous solution containing 0.2mL/LTritonX-100.Until aptery one-tenth aphid on bean sprouts stable suck after, immersing concentration together with bean sprouts is in the liquid of 500ug/mL, takes out, suck unnecessary liquid with thieving paper after 5s, moves in clean vessel and raises in 23 DEG C of constant temperature.Every concentration establishes 3 repetitions, and control group is the aqueous solution containing 0.2mL/LTritonX-100.Process after 24 hours, the dead borer population of statistics examination aphid, and calculate mortality ratio (%).
(2) to the insecticidal activity of mythimna separata
Adopt leaching leaf feeding method.Flooded 3 seconds in above-mentioned solution by fresh maize leaf, then at room temperature airing, take food for examination worm, check after 24h and calculate examination worm mortality ratio (%) (formula is the same), often process use 10 tries worm, if 3 repetitions.Make blank with clear water process, and calculate mortality ratio (%).The results are shown in Table 2.
As shown in Table 2: biphenyl bisamide compounds provided by the invention has significant insecticidal activity and selectively insecticidal spectrum, is expected to be developed to low toxicity, efficient, eco-friendly novel agrochemical.
Table 2
Continued 2

Claims (7)

1. a biphenyl bisamide compounds, described biphenyl bisamide compounds is compound shown in formula I or its acceptable salt in Pesticide Science:
In formula I, R 1and R 2independently be selected from following groups a kind of:
R 3~ R 10independently be selected from: H, halogen, nitro, hydroxyl, cyano group, amino, C 1~ C 4alkyl, the C of halo 1~ C 4alkyl, C 1~ C 3alkoxyl group, the C of halo 1~ C 3alkoxyl group, ethanoyl, fluoro ethanoyl, middle one,
R 14for C 1~ C 3alkyl or halo C 1~ C 3alkyl, R 15for H, C 1~ C 3alkyl or halo C 1~ C 3alkyl;
But, do not comprise following compounds:
2. biphenyl bisamide compounds as claimed in claim 1, is characterized in that, wherein R 3~ R 10independently be selected from following groups a kind of:
H, F, Cl, trifluoromethyl, methoxyl group, trifluoromethoxy, ethynyl, sec.-propyl, vinyl,
3. prepare a method for biphenyl bisamide compounds as claimed in claim 1 or 2, it is characterized in that, the key step of described method is: by compound shown in formula II respectively with H 2nR 1and H 2nR 2reaction, obtains target compound:
Wherein, R 1~ R 10definition identical with described in claim 1 or 2.
4. method as claimed in claim 3, it is characterized in that, described method comprises the steps:
(1) having under Lewis base existence and room temperature condition, by compound and H shown in formula II 2nR 1react in organic solvent, obtain intermediate A;
(2) Lewis base and Tosyl chloride is being had to exist and under reflux state, by intermediate A and H 2nR 2react in organic solvent, obtain target compound;
Wherein, described organic solvent is methylene dichloride or DMF; Described Lewis base is 2，4，6-trimethylpyridine or DMAP, R 1~ R 10definition identical with described in claim 1 or 2.
5. a composition, in the gross weight of described composition for 100%, described composition comprises:
Compound shown in the formula I of (a) 0.001 % by weight ~ 99.99 % by weight or its acceptable salt in Pesticide Science; With
Acceptable carrier and/or vehicle in (b) Pesticide Science;
Wherein, R 1~ R 10definition identical with described in claim 1.
6. biphenyl bisamide compounds as claimed in claim 1 or 2 is preparing the application in agricultural insecticide.
7. composition as claimed in claim 5 is as the application of agricultural insecticide.
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Title
Bis(oxazoline) Ligands Containing Four and Five Spacer Atoms: Palladium Complexes and Catalytic Behavior;Montserrat Gomez et al.;《Organometallics》;20020209;第21卷(第6期);1077-1087 *
芳杂环类多重氢键分子钳人工受体对中性分子的识别性能研究;牟其明 等;《化学学报》;20021231;第60卷(第10期);6、1841-1845 *

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