CN104418765B

CN104418765B - Aromatic aminomethane compounds and preparation method thereof and Antiphytoviral are applied

Info

Publication number: CN104418765B
Application number: CN201310375966.9A
Authority: CN
Inventors: 汪清民; 王兹稳; 魏朋; 刘玉秀; 王蕾; 郑彦龙; 马双; 王力钟
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2013-08-26
Filing date: 2013-08-26
Publication date: 2016-10-19
Anticipated expiration: 2033-08-26
Also published as: CN104418765A

Abstract

The present invention relates to the aromatic aminomethane compounds as shown in logical formula (I) and preparation thereof and the application on pesticide, the antiviral structure type that a kind of novelty of such compounds represented is succinct, synthetic method brief and practical, it is easy to industrialization is amplified.Aromatic aminomethane compounds is used as novel anti-plant virus agent, tobacco mosaic virus (TMV), Rice Virus, Fructus Capsici virus, tomato virus, sweet potato viruses, Potyvirus and melon virus and maize dwarf mosaic virus etc. can be suppressed well, can effectively prevent and treat the virosis of the various crop such as Nicotiana tabacum L., Oryza sativa L., Fructus Capsici, Fructus Lycopersici esculenti, melon dish, grain, vegetable, beans, be particularly suitable for preventing and treating tobacco mosaic disease.(wherein Ar, X, R¹And R²Meaning see description)

Description

Aromatic aminomethane compounds and preparation method thereof and Antiphytoviral are applied

Technical field

The present invention relates to a novel anti-plant virus agent of class and preparation thereof and application, be specifically related to aromatic aminomethane compounds and make For anti-plant virus agent, belong to technical field of pesticide.

Background technology

Plant virus is of a great variety, is widely distributed, and in agricultural production, virosis is the second largest class being only second to fungus Plant disease.The overwhelming majority industrial crops all because of the harm by plant virus in various degree the underproduction or quality decline, prevent and treat pole For difficulty, have the title of " plant cancer ".

Depending on substantial amounts of screening in the more degree of research and development of anti-plant virus agent, many viral inhibitors can only different journeys Degree reduces the severity of symptom.The practical kind of plant virus inhibitor is also few the most effectively and satisfactorily, especially special The therapeutic medicament of effect is less, and the medicament reported is its preventive effect (Zhang Hua, Song Bao below 60% mostly during actual application in field Peace, pesticide, 2002,41 (2), 6-9.).But, in the face of virus harm and the agriculture production modl of preventing and treating, eco-friendly natural The continuous studied discovery of source Metabolites against Plant Virus Diseases matter, it is excellent that such viral agent has timely, convenience and low cost etc. Point.

During the plant virus inhibitor of novel, efficient, the low toxicity of initiative, this seminar finds Asclepiadaceae goose first The leaching thing of floss Calamus plant Cynanchun komarovii (Cynanchum Komarovii Al.Iijiinski) is to very harmful cigarette Showy flowers of herbaceous plants mosaic virus (TMV) has high inhibitory activity (An, T.Y.；Huang, R.Q.；Yang, Z.；Zhang, D.K.；Li, G.R.；Yao,Y.C.；Gao, J.Phytochemistry2001,58,1267-1269.), biological activity tracking and enter Step separates and Structural Identification proves that active component is tylophora alkaloid antofine.This reactive compound is in 1.0 μ g/mL concentration Under TMV suppression ratio reached 60%, need concentration 1-2 the order of magnitude lower than existing plant virus inhibitor under equal inhibition. Study on mechanism shows: this Alkaloid can interact with the highest affinity and TMV RNA, so inhibit its with Glutelin assembles, final suppression TMV activity (Xi, Z.；Zhang, R.Y.；Yu, Z.H.；Ouyang, D.Bioorg.Med.Chem.Lett.2006,16,4300-4304.Gao, S.；Zhang, R.Y.；Yu, Z.H.；Xi, Z.Chembiochem.2012,13,1622-1627.).

Summary of the invention

Present invention aim at providing that a class is novel, efficient, the anti-plant virus agent of low toxicity and preparation method thereof and anti-plant Thing virus applications.The present invention on the basis of early stage finds that phenanthroindolizididerivative pyridine Alkaloid has anti-phytoviral activity, Based on antofine and TMV RNA binding mechanism model, carry out targeting appropriate design.Break through tradition limitation, be bold in innovation, first Find that series aromatic aminomethane compounds all shows good antiviral activity, and part of compounds live body activity is substantially better than business Product kind virazole is suitable with Ningnanmycin and antofine.Such compound structure is novel succinct, it is easy to preparation, photo-thermal is steady The qualitative antofine that is better than, water-soluble and in conventional organic solvent (such as dichloromethane, chloroform, toluene, ethanol etc.) Dissolubility is all better than antofine.The present invention is to formulate new and effective anti-plant virus agent to lay a good foundation, and possesses well wound The property made.

The compound that aromatic aminomethane class anti-plant virus agent general structure of the present invention is structure shown in (I):

In formula, Ar represent containing the phenyl ring of different substituents, the naphthalene nucleus containing different substituents, the phenanthrene ring containing different substituents, Ring is feared containing different substituents；X represents hydrogen or oxygen；R¹And R²Represent hydrogen, hydroxyl, alkyl, alkoxyl, alkylamino radical, alkane carboxylic respectively Base, carbalkoxy, alkylamide, 1-4 haloalkyl, the luxuriant and rich with fragrance methyl of replacement, replacement menaphthyl, substituted benzyl.

Aromatic aminomethane compounds of the present invention be structure 1-65 shown in following structural formula be the compound of representative.

Structural formula

The present invention leads to the compound of formula (I) can prepare (Scheme1) by method one: aryl formate reacts with oxalyl chloride Prepare aryl-acyl chlorides, then react to obtain target compound (I) with corresponding replacement amine.

The present invention is led to the compound of formula (I) and can be prepared (Scheme2) by method two: be dehydrated with the hydrochlorate of EDC Condensing agent, aryl formate obtains target compound (I) with corresponding replacement amine direct polycondensation.

The present invention is led to the compound of formula (I) and can be prepared (Scheme3) by method three: disubstituted derivative is by accordingly Aryl aldehyde occurs reduction amination to prepare with replacing amine in the presence of sodium cyanoborohydride.

The present invention is led to the compound of formula (I) and can be prepared (Scheme4) by method four: disubstituted for different groups Time, go up a part benzyl the most in a mild condition, then change another molecule benzyl on reaction condition.

The present invention is led to the compound of formula (I) and is had excellent anti-phytoviral activity, can suppress tobacco mosaic disease well Poison, Rice Virus, Fructus Capsici virus, tomato virus, sweet potato viruses, Potyvirus and melon virus and maize dwarf mosaic virus Deng, can effectively prevent and treat the virosis of the various crop such as Nicotiana tabacum L., Oryza sativa L., Fructus Capsici, Fructus Lycopersici esculenti, melon dish, grain, vegetable, beans, the suitableeest Together in preventing and treating tobacco mosaic disease.

The present invention is led to the compound of formula (I) and can directly be used as plant virus inhibitor, it is also possible to plus agriculturally The carrier accepted uses, it is also possible to and other anti-plant virus agents such as diazosulfide (BTH), tiadinil (TDL), 4-first Base-1,2,3-thiadiazoles-5-formic acid (TDLA), DL-beta-aminobutyric acid (BABA), virazole, Ningnanmycin, phenanthroindolizididerivative Pyridine alkaloid antofine, ter azole compounds XY-13 and XY-30, virus A, salicylic acid, polyhydroxy double naphthaldehyde, amino-oligosacchride Element forms interacting composition and uses, the performance potentiation that these compositionss have, some performance summation actions.

The viral inhibitors of the aromatic aminomethane more existing use of class anti-plant virus agent of the present invention, has the biggest advantage: change Learning simple in construction, stable chemical nature, water-soluble is good, and anti-phytoviral activity is notable, and has various plants virus and press down Make and use；Toxicity is extremely low, and environment compatibility is good, to non-target organism safety.

Detailed description of the invention

The present invention is described in further detail by the following examples, but the invention is not restricted to these embodiments.

Embodiment 1: the synthesis of aromatic aminomethane 1-3:

The synthesis of 2,3,6,7-tetramethoxy-9-phenanthrene formyl chloride (67)

2,3,6,7-tetramethoxies-9-phenanthrenecarboxylic acid (66) 0.80g (2.34mmol), 20mL is added in 100mL single port bottle Oxalyl chloride；2 DMF are added under water-bath；The most naturally being warmed to room temperature, then react 3h, normal pressure steams oxalyl chloride, obtains 0.82g yellow Solid 67；Need not process further, be directly used in the next step.

The synthesis of 2-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl acetate (1)

0.24g glycine methyl ester hydrochloride, 25mL CH is added at 100mL single port bottle₂Cl₂, 0.34g Et₃N, under water-bath It is slowly added dropwise containing 0.40g2, the CH of 3,6,7-tetramethoxies-9-phenanthrene formyl chloride (67)₂Cl₂Solution 20mL, after dropping slowly It is warmed to room temperature reaction 2h, TLC detection reaction complete.In reactant liquor, add 40mL10%HCl, add suitable quantity of water separatory；Water Use 20mL CH mutually₂Cl₂Extraction is once；Merge organic facies, wash once by saturated NaCl solution, anhydrous MgSO₄It is dried.Reduced pressure After filter reconcentration solid, then with petrol ether/ethyl acetate=1:1 recrystallization, obtain white solid, yield 86.4%, fusing point: 266-268℃。¹HNMR (400MHz, DMSO-d₆) δ 8.99 (t, J=5.6Hz, 1H), 8.06 (s, 1H), 8.03 (s, 1H), 7.85 (s, 1H), 7.79 (s, 1H), 7.47 (s, 1H), 4.10 (d, J=6.0Hz, 2H), 4.06 (s, 3H), 4.05 (s, 3H), 3.91 (s, 3H), 3.88 (s, 3H), 3.73 (s, 3H)；¹³CNMR (100MHz, DMSO-d₆) δ 170.5,169.7,150.0,149.2, 148.8,148.5,123.0,124.8,124.5,123.7,122.6,108.9,106.5,103.8,103.6,55.9,55.9, 55.5,55.3,51.8,41.1；ESI-HRMS (m/z): calcd.for C₂₂H₂₄NO₇[M+H]⁺414.1547； found414.1552.

The synthesis of 2-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) acetic acid (2)

In 100mL single port bottle, add 0.22g compound 1,15mL MeOH, 15mL4M NaOH solution, be heated to reflux 2h； TLC detection reaction is complete.Concentration of reaction solution, then adjusts pH to 5, has a large amount of white solid to separate out, stand, and reduce pressure sucking filtration, dries, Obtain light yellow solid, yield: 93.1%, fusing point: 146-148 DEG C.¹HNMR (400MHz, DMSO-d₆) δ 12.81 (s, 1H), 8.85 (t, J=5.6Hz, 1H), 8.05 (s, 1H), 8.02 (s, 1H), 7.89 (s, 1H), 7.76 (s, 1H), 7.46 (s, 1H), 4.05 (s, 6H), 3.99 (d, J=6.0Hz, 2H), 3.91 (s, 3H), 3.87 (s, 3H)；¹³C NMR (100MHz, DMSO-d₆) δ 171.5, 169.6,145.0,149.1,148.8,148.5,130.5,124.7,124.5,124.4,123.5,122.7,108.8, 106.6,103.8,103.6,56.0,55.9,55.5,55.3,41.3；ESI-HRMS (m/z): calcd.for C₂₁H₂₂NO₇[M+ H]⁺400.1391；found400.1394.

The synthesis of 2-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) ethanol (3)

In 100mL, add 0.23g compound 1,30mL THF, under ice-water bath, be dividedly in some parts 0.045g LiAlH₄, change into Ambient temperature overnight.30mL CH is added in reactant liquor₂Cl₂, then it is slowly added dropwise saturated NaOH solution, until White Flocculus disappears, Separatory；Aqueous phase uses CH again₂Cl₂(10mL × 2) extract；Merging organic facies, saturated NaCl washes twice, anhydrous Na₂SO₄It is dried.Decompression Filtering reconcentration, column chromatography obtains white solid, yield: 96.4%, fusing point: 217-219 DEG C.¹H NMR (400MHz, CDCl₃)δ 7.65 (s, 1H), 7.45 (s, 1H), 7.43 (s, 1H), 7.37 (s, 1H), 6.98 (s, 1H), 6.87 (s, 1H), 4.03 (s, 3H), 4.02 (s, 3H), 3.95 (s, 3H), 3.91 (s, 3H), 3.88-3.84 (m, 2H), 3.72-3.62 (m, 2H), 2.84 (s, 1H)；¹³C NMR (100MHz, CDCl₃) δ 171.3,149.9,149.1,148.8,148.7,129.5,125.3,124.7,124.4, 124.1,122.7,108.4,106.1,102.5,102.2,62.3,55.9,55.9,42.9；ESI-HRMS (m/z): calcd.for C₂₁H₂₄NO₆[M+H]⁺386.1598；found386.1601.

Embodiment 2: the synthesis of aromatic aminomethane 22-26:

The synthesis of 2,3,6,7-tetramethoxy-9-phenanthrene methanol (68)

2,3,6,7-tetramethoxy-9-phenanthrenecarboxylic acid (66) 1.03g, 20mL THF are added in 100mL single port bottle；Ice-water bath 0.28g LiAlH it is dividedly in some parts under cooling₄, after addition, it is heated to back flow reaction 1.5h, then naturally cools to room temperature. 20mL CH is added in reactant liquor₂Cl₂, then ice-water bath is slowly added dropwise 1mol/L HCl, until white flock precipitate disappears； Separatory, aqueous phase uses CH again₂Cl₂(10mL × 3) extract；Merging organic facies, saturated NaCl solution washed once, anhydrous Na₂SO₄Dry Dry.Filtration under diminished pressure reconcentration, obtains solid again by re-crystallizing in ethyl acetate, obtains white solid, yield 95.0%, fusing point: 183-185 ℃。¹H NMR (400MHz, CDCl₃) δ 7.83 (s, 1H), 7.78 (s, 1H), 7.59 (s, 1H), 7.55 (s, 1H), 7.21 (s, 1H), 5.13 (s, 2H), 4.13 (s, 3H), 4.13 (s, 3H), 4.07 (s, 3H), 4.03 (s, 3H), 1.75 (s, 1H).

The synthesis of 2,3,6,7-tetramethoxy-9-formaldehyde (69)

5.00g compound 68,150mL CH is added in 250mL single port bottle₂Cl₂, 10g silica gel, under agitation add 9.85g PCC, overnight, TLC detection reaction is complete for room temperature reaction.After decompression precipitation, column chromatography (CH₂Cl₂), obtain light yellow solid, Yield: 80.4%, fusing point: 227-228 DEG C.¹H NMR (400MHz, CDCl₃) δ 10.27 (s, 1H), 8.98 (s, 1H), 8.07 (s, 1H), 7.80 (s, 1H), 7.78 (s, 1H), 7.35 (s, 1H), 4.17 (s, 3H), 4.14 (s, 3H), 4.11 (s, 3H), 4.07 (s, 3H).

The synthesis of 6-(N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (22)

1.20g compound 69,40mL CH is added at 100mL single port bottle₂Cl₂, 0.42g Et₃N, 5 AcOH, under agitation Add 0.74g6-amino methyl cyclohexyl hydrochlorate, after reaction 6h, be cooled to room temperature and reduce pressure again and slough solvent；Add in reaction bulb Enter 30mL absolute methanol, 5 AcOH, 0.47gNaBH₃CN, 3h is complete in reaction.After solvent is sloughed in decompression, add 30mL CH₂Cl₂, 20mL water and appropriate saturated sodium bicarbonate solution；Separatory, aqueous phase CH₂Cl₂(10mL × 2) extract, and merge organic facies, Wash once by saturated NaCl solution again, anhydrous MgSO₄It is dried；Column chromatography obtains light yellow solid, yield: 67.9%, fusing point: 104- 106℃。¹H NMR (400MHz, CDCl₃) δ 7.75 (s, 1H), 7.67 (s, 1H), 7.58 (s, 1H), 7.42 (s, 1H), 7.18 (s, 1H), 4.16 (s, 2H), 4.08 (s, 3H), 4.07 (s, 3H), 4.06 (s, 3H), 4.02 (s, 3H), 3.64 (s, 3H), 2.79 (t, J=8.0Hz, 2H), 2.28 (t, J=8.0Hz, 2H), 1.71-1.65 (m, 2H), 1.64-1.57 (m, 2H), 1.40-1.33 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.1,149.3,149.0,148.9,148.8,130.1,126.0,125.1, 125.0,124.8,124.3,108.3,104.7,103.4,102.8,56.1,56.0,56.0,55.9,51.7,51.5,49.2, 33.9,29.2,26.8,24.7；ESI-HRMS (m/z): calcd.for C₂₆H₃₃NO₆Na[M+Na]⁺478.2200； found478.2208.

The synthesis of 6-(N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) hexanol (23)

In 100mL, add 0.30g compound 22,30mL THF, under ice-water bath, be dividedly in some parts 0.045g LiAH₄, add After change ambient temperature overnight into.30mL CH is added in reactant liquor₂Cl₂, then it is slowly added dropwise saturated NaOH solution, until White Flocculus Disappearing, separatory, aqueous phase uses CH again₂Cl₂(10mL × 2) extract: merging organic facies, saturated NaCl washes twice, anhydrous Na₂SO₄Dry Dry.Filtration under diminished pressure reconcentration, column chromatography obtains white solid, yield: 88.9%, fusing point: 83-85 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.02 (s, 1H), 7.98 (s, 1H), 7.60 (s, lH), 7.58 (s, lH), 7.34 (s, 1H), 4.34 (s, 1H), 4.13 (s, 2H), 4.03 (s, 3H), 4.02 (s, 3H), 3.92 (s, 3H), 3.90 (s, 3H), 3.40 1 3.36 (m, 2H), 2.67 (t, J=6.8Hz, 2H), 1.56-1.47 (m, 2H), 1.44-1.39 (m, 2H), 1.35-1.28 (m, 4H)；¹³C NMR (100MHz, CDCl₃) δ 149.1,148.9,148.8,148.6,130.8,126.0,125.1,125.0,124.3,124.1,108.2, 104.6,103.3,102.7,62.7,56.0,56.0,55.9,52.1,49.7,32.7,29.8,27.1,25.7；ESI-HRMS (m/z): calcd.forC₂₅H₃₄NO₅[M+H]⁺428.2431；found428.2440.

The synthesis of 6-(N-methyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (24)

In 100mL single port bottle, add 0.18g compound 22,20mL DMF, lower addition 0.03g NaH is stirred at room temperature, instead 0.10g iodomethane is added after answering 30min, complete after being then further continued for reacting 3h.Pour in 250mL separatory funnel to reactant liquor, Add a large amount of water and 50mL CH₂Cl₂, separatory；Organic facies is washed three times by saturated NaCl solution again, anhydrous MgSO₄It is dried；Column chromatography Obtain light yellow solid, yield: 89.1%, fusing point: 128-129 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.00 (s, 1H), 7.98 (s, 1H), 7.77 (s, 1H), 7.51 (s, 1H), 7.36 (s, 1H), 4.02 (s, 3H), 4.02 (s, 3H), 3.90 (s, 6H), 3.81 (s, 2H), 3.55 (s, 3H), 2.43 (t, J=8.0Hz, 2H), 2.22 (t, J=8.0Hz, 2H), 2.13 (s, 3H), 1.56-1.52 (m, 2H), 1.48-1.41 (m, 2H), 1.31-1.26 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 173.1,148.1, 147.9,147.8,147.4,124.9,124.0,123.3,107.2,104.9,102.0,101.8,56.7,55.1,55.0, 54.9,54.8,50.5,40.9,32.9,26.1,26.0,23.8；ESI-HRMS (m/z): calcd.for C₂₇H₃₅NO₆[M+Na ]⁺492.2357；found492.2361.

The synthesis of 6-(N-methyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) caproic acid (25)

In 100mL single port bottle, add 0.26g compound 24,15mL dioxane, 15mL4M NaOH solution, heat back Stream 4h, TLC detection reaction is complete.Concentration of reaction solution, to about 15mL, is then adjusted pH to 6, is now had a large amount of white solid to separate out, Placement a period of time makes precipitation complete, reduce pressure sucking filtration, drying, obtains white solid and obtains light yellow solid, yield: 59.5%, fusing point: 168-170℃。¹H NMR (400MHz, MeOH-d₄) δ 7.84 (s, 1H), 7.77 (s, 1H), 7.59 (s, 1H), 7.29 (s, 1H), 7.18 (s, 1H), 4.50 (s, 2H), 3.89 (s, 6H), 3.86 (s, 3H), 3.79 (s, 3H), 3.05-2.97 (m, 2H), 2.57 (s, 3H), 2.05 (t, J=6.4Hz, 2H), 1.70-1.62 (m, 2H), 1.48-1.40 (m, 2H), 1.26-1.19 (m, 2H)；¹³CNMR (100MHz, DMSO-d₆) δ 174.4,149.3,148.8,148.6,148.1,125.2,125.0,124.6,124.1, 108.4,106.0,104.0,103.7,62.8,56.8,55.9,55.9,55.4,55.3,40.9,33.6,26.3,24.3； ESI-HRMS (m/z): calcd.for C₂₆H₃₄NO₆[M+H]⁺456.2381；found456.2387.

The synthesis of 6-(N-methyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) hexanol (26)

In 100mL, add 0.30g compound 24,30mL THF, under ice-water bath, be dividedly in some parts 0.045g LiAH₄, add After change ambient temperature overnight into.30mL CH is added in reactant liquor₂Cl₂, then it is slowly added dropwise saturated NaOH solution, until White Flocculus Disappearing, separatory, aqueous phase uses CH again₂Cl₂(10mL × 2) extract；Merging organic facies, saturated NaCl washes twice, anhydrous Na₂SO₄Dry Dry.Filtration under diminished pressure reconcentration, obtains white solid, yield: 89.5%.Fusing point: 101-103 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.00 (s, 1H), 7.98 (s, 1H), 7.78 (s, 1H), 7.50 (s, 1H), 7.36 (s, 1H), 4.31 (t, J=4.8Hz, 1H), 4.02 (s, 6H), 3.90 (s, 6H), 3.80 (s, 2H), 3.33-3.27 (m, 2H), 2.43 (t, J=6.8Hz, 2H), 2.12 (s, 3H), 1.57-1.49 (m, 2H), 1.35-1.33 (m, 2H), 1.30-1.25 (m, 2H), 1.23-1.18 (m, 2H)；¹³CNMR (100MHz, CDCl₃) δ 149.1,148.8,148.7,148.3,130.7,126.0,126.0,125.7,125.0,124.3, 108.2,106.2,102.9,102.8,62.9,62.3,57.8,56.1,56.0,55.9,55.8,42.1,32.7,30.3, 29.7,27.5,27.3,25.6；ESI-HRMS (m/z): calcd.for C₂₆H₃₆NO₅[M+H]⁺442.2588； found442.2596.

Embodiment 3: the synthesis of aromatic aminomethane 4-21 and 27-65: (, with reference to embodiment 1 and 2, data are as follows for synthesis step)

The synthesis of 3-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl propionate (4)

White solid, yield: 90.9%, fusing point: 171-172 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.88 (s, 1H), 7.78 (s, 1H), 7.74 (s, 1H), 7.70 (s, 1H), 7.20 (s, 1H), 6.75 (t, J=5.6Hz, 1H), 4.13 (s, 6H), 4.03 (s, 6H), 3.86-3.82 (m, 2H), 3.73 (s, 3H), 2.77 (t, J=5.6Hz, 2H)；¹³C NMR (100MHz, CDCl₃) δ 173.1,170.1,150.2,149.3,148.9,129.9,125.5,125.0,124.7,124.0,123.1,108.6, 106.3,102.7,102.5,56.0,56.0,55.9,55.9,51.9,35.5,34.0；ESI-HRMS (m/z): calcd.for C₂₃H₂₆NO₇[M+H]⁺428.1704；found428.1707.

The synthesis of 3-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) propanoic acid (5)

White solid, yield: 86.2%, fusing point: 222-224 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 12.27 (s, 1H), 8.59 (t, J=5.2Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.73 (s, 1H), 7.73 (s, 1H), 7.43 (s, 1H), 4.05 (s, 6H), 3.91 (s, 3H), 3.86 (s, 3H), 3.57-3.52 (m, 2H), 2.60 (t, J=6.8Hz, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 172.9,169.1,150.0,149.1,148.8,148.4,130.4,124.7,124.5, 123.8,122.7,108.8,106.3,103.8,103.6,55.9,55.9,55.5,55.2,54.9,35.4,33.8；ESI- HRMS (m/z): calcd.forC₂₂H₂₄NO₇[M+H]⁺414.1547；found414.1549.

The synthesis of 3-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) propanol (6)

White solid, yield: 88.9%, fusing point: 94-96 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.78 (s, 1H), 7.69 (s, 1H), 7.66 (s, 1H), 7.62 (s, 1H), 7.10 (s, 1H), 6.68 (s, 1H), 4.10 (s, 6H), 4.01 (s, 3H), 3.99 (s, 3H), 3.82 (t, J=5.2Hz, 2H), 3.77-3.68 (m, 2H), 2.94 (s, 1H), 1.90-1.81 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 171.5,150.0,149.1,148.8,148.7,129.7,125.3,124.7,124.5,123.8, 122.8,108.4,106.0,102.5,102.3,59.4,55.9,55.9,55.8,55.8,36.7,32.3；ESI-HRMS(m/ Z): calcd.for C₂₂H₂₆NO₆[M+H]⁺400.1755；found400.1754.

The synthesis of 4-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl butyrate (7)

White solid, yield: 87.5%, fusing point: 160-161 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.89 (s, 1H), 7.80 (s, 1H), 7.77 (s, 1H), 7.72 (s, 1H), 7.22 (s, 1H), 6.36 (t, J=5.2Hz, 1H), 4.15 (s, 6H), 4.06 (s, 6H), 3.69 (s, 3H), 3.69-3.62 (m, 2H), 2.55 (t, J=7.2Hz, 2H), 2.11-2.05 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 173.8,170.3,150.1,149.3,148.9,148.9,130.2,125.4,124.9, 124.7,123.7,123.1,108.5,106.3,102.6,102.5,56.0,56.0,55.9,55.9,51.8,39.4,31.6, 24.9；ESI-HRMS (m/z): calcd.forC₂₄H₂NO₇[M+H]⁺442.1860；found442.1861.

The synthesis of 4-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) butanoic acid (8)

Light yellow solid, yield: 51.9%, fusing point: 208-210 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 12.14 (s, 1H), 8.60 (t, J=5.6Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.76 (s, 1H), 7.73 (s, 1H), 7.47 (s, 1H), 4.05 (s, 3H), 4.04 (s, 3H), 3.90 (s, 3H), 3.84 (s, 3H), 3.38-3.34 (m, 2H), 2.37 (t, J= 7.2Hz, 2H), 1.86-1.77 (m, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 174.2,169.2,149.9,149.0, 148.8,148.4,130.5,124.7,124.5,124.5,123.8,122.7,108.9,106.3,103.9,103.5,55.9, 55.9,55.5,55.2,38.4,31.2,24.6；ESI-HRMS (m/z): calcd.for C₂₃H₂₆NO₇[M+H]⁺428.1704； found428.1701.

The synthesis of 4-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) butanol (9)

White solid, yield: 78.3%, fusing point: 140-142 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.83 (s, 1H), 7.74 (s, 1H), 7.71 (s, 1H), 7.66 (s, 1H), 7.16 (s, 1H), 6.43 (s, 1H), 4.12 (s, 6H), 4.02 (s, 6H), 3.77 (t, J=6.0Hz, 2H), 3.61 (t, J=5.2Hz, 2H), 1.95 (s, 1H), 1.85-1.73 (m, 4H)；¹³C NMR (100MHz, CDCl₃) δ 170.4,150.1,149.2,148.9,130.3,125.3,124.9,124.7,123.7,123.0, 108.5,106.3,102.6,102.5,77.4,77.3,77.1,76.7,62.4,56.0,55.9,55.9,55.9,53.4, 39.7,29.8,26.4；ESI-HRMS (m/z): calcd.for C₂₃H₂₈NO₆[M+H]⁺414.1911；found414.1915.

The synthesis of 5-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl valerate (10)

White solid, yield 95.1%, fusing point: 151-153 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.87 (s, 1H), 7.79 (s, 1H), 7.76 (s, 1H), 7.72 (s, 1H), 7.22 (s, 1H), 6.21 (t, J=4.0Hz, 1H), 4.14 (s, 3H), 4.13 (s, 3H), 4.04 (s, 6H), 3.69 (s, 3H), 3.62-3.56 (m, 2H), 2.44 (t, J=7.2Hz, 2H), 1.85-1.73 (m, 4H)；¹³C NMR (100MHz, CDCl₃) δ 173.9,170.2,150.2,149.3,149.0,130.5,125.4,125.0, 124.8,123.7,123.1,108.5,106.4,102.7,102.6,56.0,56.0,55.9,55.9,51.6,39.5,33.6, 29.3,22.2；ESI-HRMS (m/z): calcd.for C₂₅H₃₀NO₇[M+H]⁺456.2017；found456.2021.

The synthesis of 5-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) valeric acid (11)

Gray solid, yield: 51.7%, fusing point: 110-112 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 12.05 (s, 1H), 8.56 (t, J=5.2Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.74 (s, 1H), 7.72 (s, 1H), 7.46 (s, 1H), 4.05 (s, 6H), 3.91 (s, 3H), 3.84 (s, 3H), 3.39-3.30 (m, 2H), 2.30 (t, J=6.0Hz, 2H), 1.69- 1.55 (m, 4H)；¹³CNMR (100MHz, DMSO-d₆) δ 174.4,169.1,149.9,149.0,148.8,148.4,130.7, 124.6,124.5,124.5,123.6,122.7,108.8,106.2,103.8,103.5,55.9,55.9,55.5,55.1, 38.5,33.4,28.7,22.0；ESI-HRMS (m/z): calcd.for C₂₄H₂₈NO₇[M+H]⁺442.1860； found442.1858.

The synthesis of 5-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) amylalcohol (12)

White solid, yield: 64.3%, fusing point: 177-179 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.85 (s, 1H), 7.78 (s, 1H), 7.75 (s, 1H), 7.69 (s, 1H), 7.19 (s, 1H), 6.22-6.16 (t, J=5.2Hz, 1H), 4.13 (s, 6H), 4.03 (s, 6H), 3.70 (t, J=6.4Hz, 2H), 3.61-3.56 (m, 2H), 1.78-1.72 (m, 2H), 1.69-1.64 (m, 2H), 1.60-1.54 (m, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 169.0,149.9,149.0,148.8,148.4, 130.7,124.6,124.6,124.5,123.6,122.7,108.8,106.3,103.8,103.5,60.7,55.9,55.5, 55.1,39.0,32.3,29.1,23.1；ESI-HRMS (m/z): calcd.for C₂₄H₃₀NO₆[M+H]⁺428.2068； found428.2071.

The synthesis of 6-(N-(2,3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) caproic acid (13)

Light yellow solid, yield: 85.7%, fusing point: 113-115 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 12.24 (s, 1H), 8.54 (t, J=6.4Hz, 1H), 8.04 (s, 1H), 8.01 (s, 1H), 7.74 (s, 1H), 7.72 (s, 1H), 7.46 (s, 1H), 4.05 (s, 6H), 3.91 (s, 3H), 3.84 (s, 3H), 3.35-3.30 (m, 2H), 2.24 (t, J=7.2Hz, 2H), 1.57 (m, 1.61-1.54,4H), 1.41 (m, 1.44-1.38,2H)；¹³C NMR (100MHz, DMSO-d₆) δ 174.6,169.0, 149.9,149.0,148.8,148.4,130.6,124.6,124.5,124.5,123.7,122.7,108.8,106.6, 103.8,103.5,55.9,55.8,55.5,55.1,38.8,33.8,28.9,26.1,24.3；ESI-HRMS (m/z): calcd.for C₂₅H₃₀NO₇[M+H]⁺456.2017；found456.2017.

N-n-hexyl-2, the synthesis of 3,6,7-tetramethoxies-9-phenanthrene Methanamide (14)

Light yellow solid, yield: 54.1%, fusing point: 180-182 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.84 (s, 1H), 7.76 (s, 1H), 7.73 (s, 1H), 7.67 (s, 1H), 7.18 (s, 1H), 6.15 (s, 1H), 4.12 (s, 6H), 4.02 (s, 6H), 3.58-3.54 (m, 2H), 1.73-1.65 (m, 2H), 1.51-1.43 (m, 2H), 1.40-1.31 (m, 4H), 0.92 (t, J= 5.2Hz, 3H)；¹³C NMR (100MHz, CDCl₃) δ 170.1,150.1,149.3,148.9,130.7,125.3,124.9, 124.8,123.6,123.1,108., 106.3,102.7,102.5,56.0,56.0,55.9,55.9,40.1,31.6,29.8, 26.8,22.6,14.4；ESI-HRMS (m/z): calcd.for C₂₅H₂₆NO₅[M+H]⁺426.2275；found426.2280.

The synthesis of 6-(N-(3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl caproate (15)

White solid, yield: 63.6%, fusing point: 112-114 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.86 (s, 1H), 7.85 (s, 1H), 7.80 (s, 1H), 7.78 (d, J=8.8Hz, 1H), 7.71 (s, 1H), 7.22-7.19 (m, 1H), 6.22 (s, 1H), 4.11 (s, 3H), 4.03 (s, 6H), 3.66 (s, 3H), 3.58-3.54 (m, 2H), 2.36 (t, J=7.2Hz, 2H), 1.76- 1.68 (m, 4H), 1.53-1.47 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0,170.1,159.1,149.5, 149.1,131.8,130.6,129.9,124.7,124.4,124.2,115.8,106.4,103.6,103.2,55.9,55.8, 55.5,51.5,39.7,33.9,29.4,26.5,24.5；ESI-HRMS (m/z): calcd.for C₂₅H₃₀NO₆[M+H]⁺ 440.2068；found440.2069.

The synthesis of 6-(N-(3,6,7-tetramethoxy-9-phenanthrene formoxyl) amido) hexanol (16)

White solid, yield 79.0%, fusing point: 149-151 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.54 (t, J= 5.6Hz, 1H), 8.12 (s, 1H), 8.09 (s, 1H), 7.92 (d, J=8.8Hz, 1H), 7.76 (s, 1H), 7.75 (s, 1H), 7.27-7.24 (m, 1H), 4.36 (t, J=5.2Hz, 1H), 4.05 (s, 3H), 4.01 (s, 3H), 3.85 (s, 3H), 3.42-3.38 (m, 2H), 3.36-3.33 (m, 2H), 1.61-1.56 (m, 2H), 1.48-1.34 (m, 6H)；¹³C NMR (100MHz, DMSO-d₆) δ 168.9,158.8,149.1,149.0,131.2,130.6,130.3,124.3,124.1,123.9,116.3,106.3, 104.3,104.0,60.7,55.9,55.5,55.2,39.0,32.5,29.2,26.4,25.3；ESI-HRMS (m/z): calcd.for C₂₄H₃₀NO₅[M+H]⁺412.2118；found412.2120.

The conjunction of 6-(N-(2,3-ethylenedioxy-6,7-ethylenedioxy-9-phenanthrene formoxyl) amido) methyl caproate (17) Become

White solid, yield: 60.9%, fusing point: 165-167 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.85 (s, 1H), 7.82 (s, 1H), 7.73 (s, 1H), 7.52 (s, 1H), 7.23 (s, 1H), 6.11 (s, 1H), 4.40-4.35 (m, 8H), 3.67 (s, 3H), and 3.56-3.50 (m, 2H), 2.36 (t, J=7.2Hz, 2H), 1.75-1.66 (m, 6H), 1.51-1.43 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.1,169.8,144.6,143.9,143.5,143.4,131.0,125.8,125.5, 125.1,123.7,123.2,114.7,112.7,109.3,109.3,64.6,64.6,64.4,64.4,51.5,39.7,33.9, 29.4,26.5,24.6；ESI-HRMS (m/z): calcd.for C₂₆H₂₈NO₇[M+H]⁺466.1860；found466.1869.

The synthesis of 6-(N-(2,3-ethylenedioxy-6,7-ethylenedioxy-9-phenanthrene formoxyl) amido) hexanol (18)

White solid, yield: 82.4%, fusing point: 200-202 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.49 (t, J= 5.6Hz, 1H), 8.07 (s, 1H), 8.04 (s, 1H), 7.58 (s, 1H), 7.57 (s, 1H), 7.40 (s, 1H), 4.37-4.34 (m, 9H), 3.43-3.38 (m, 2H), 3.31-3.27 (m, 2H), 1.60-1.52 (m, 2H), 1.48-1.41 (m, 2H), 1.39-1.32 (m, 4H)；¹³C NMR (100MHz, DMSO-d₆) δ 168.6,144.5,143.7,143.4,143.1,131.1,124.9, 124.9,124.8,123.4,123.0,114.4,112.2,109.5,109.4,64.2,64.1,60.7,38.9,32.5, 29.2,26.4,25.3；ESI-HRMS (m/z): calcd.for C₂₅H₂₈NO₆[M+H]⁺438.1911；found438.1915.

The synthesis of 6-(N-(2-hydroxyl-6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl caproate (19)

White solid, yield: 34.0%, fusing point: 92-94 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 9.91 (s, 1H), 8.50 (t, J=5.6Hz, 1H), 7.97-7.92 (m, 2H), 7.82 (d, J=8.8Hz, 1H), 7.75 (s, 1H), 7.71 (s, 1H), (7.14-7.12 m, 1H), 4.01 (s, 3H), 3.84 (s, 3H), 3.58 (s, 3H), 3.33-3.30 (m, 2H), 2.34 (t, J= 7.2Hz, 2H), 1.63-1.55 (m, 4H), 1.43-1.35 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.2,170.9, 155.7,149.4,148.9,132.0,130.4,129.4,124.6,124.3,123.9,123.7,116.9,106.5, 106.0,103.1,55.8,55.6,51.6,39.9,33.8,29.7,29.3,26.5,24.5；ESI-HRMS (m/z): calcd.for C₂₄H₂₈NO₆[M+H]⁺426.1911；found426.1908.

The synthesis of 6-(N-(2-hydroxyl-6,7-tetramethoxy-9-phenanthrene formoxyl) amido) methyl caproate (20)

Pale red solid, yield: 87.5%, fusing point: 158-160 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 9.91 (s, 1H), 8.50 (t, J=5.6Hz, 1H), 7.95 (d, J=4.0Hz, 2H), 7.82 (d, J=8.8Hz, 1H), 7.75 (s, 1H), 7.71 (s, 1H), 7.14-7.11 (m, 1H), 4.36 (t, J=5.2Hz, 1H), 4.01 (s, 3H), 3.84 (s, 3H), 3.42-3.38 (m, 2H), 3.35-3.30 (m, 2H), 1.62-1.55 (m, 2H), 1.48-1.43 (m, 2H), 1.39-1.31 (m, 4H)；¹³C NMR (100MHz, DMSO-d₆) δ 168.9,157.0,149.0,148.7,131.5,130.6,129.3,124.4,124.0,123.8, 123.1,117.0,106.4,106.0,103.7,60.7,55.5,55.2,39.0,32.5,29.2,26.4,25.3；ESI- HRMS (m/z): calcd.forC₂₃H₂₈NO₅[M+H]⁺398.1962；found398.1967.

N, N-dimethyl-1-(2,3,6,7-tetramethoxy-9-phenanthryl) methylamine (21)

White solid, yield: 64.3%, fusing point: 157-159 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.01 (s, 1H), 7.98 (s, 1H), 7.68 (s, 1H), 7.52 (s, 1H), 7.37 (s, 1H), 4.02 (s, 3H), 4.02 (s, 3H), 3.90 (s, 3H), 3.90 (s, 3H), 3.76 (s, 2H), 2.24 (s, 6H)；¹³C NMR (100MHz, DMSO-d₆) δ 149.0,148.7,148.6, 148.0,130.1,125.4,125.2,125.0,124.6,123.9,108.4,106.1,103.9,103.7,62.7,55.9, 55.8,55.3,55.1,45.1；ESI-HRMS (m/z): calcd.for C₂₁H₂₆NO₄[M+H]⁺356.1856； found356.1853.

The synthesis of 6-(N-benzyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (27)

Light yellow solid, yield: 95.2%, fusing point: 90-92 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.99 (s, 1H), 7.97 (s, 1H), 7.74 (s, 1H), 7.60 (s, 1H), 7.36 (s, 1H), 7.33-7.27 (m, 4H), 7.23-7.20 (m, 1H), 4.02 (s, 3H), 4.01 (s, 3H), 3.93 (s, 2H), 3.90 (s, 3H), 3.83 (s, 3H), 3.56 (s, 2H), 3.52 (s, 3H), 2.38 (t, J=8.0Hz, 2H), 2.10 (t, J=8.0Hz, 2H), 1.56-1.47 (m, 2H), 1.34-1.25 (m, 2H), 1.17- 1.09 (m, 2H)；¹³CNMR (100MHz, CDCl₃) δ 173.0,148.1,147.8,147.8,147.2,138.9,129.9, 128.1,127.1,125.8,125.2,125.0,124.0,123.3,107.2,105.5,101.9,101.9,58.2,58.0, 55.1,55.0,55.0,54.9,52.6,50.4,32.9,25.9,25.6,23.7；ESI-HRMS (m/z): calcd.for C₃₃H₃₉NO₆Na[M+Na]⁺568.2670；found568.2674.

The synthesis of 6-(N-benzyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) caproic acid (28)

White solid, yield: 73.0%, fusing point: 148-150 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 11.60 (s, 1H), 7.99 (s, 1H), 7.97 (s, 1H), 7.76 (s, 1H), 7.60 (s, 1H), 7.36 (s, 1H), 7.32-7.25 (m, 4H), 7.22-7.19 (m, 1H), 4.02 (s, 3H), 4.01 (s, 3H), 3.94 (s, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.54 (s, 2H), 2.38 (t, J=6.8Hz, 2H), 2.05 (t, J=7.2Hz, 2H), 1.58-1.50 (m, 2H), 1.35-1.27 (m, 2H), 1.18-1.10 (m, 2H)；¹³CNMR (100MHz, DMSO-d₆) δ 174.4,149.0,148.7,148.6,147.9,139.6, 130.1,128.7,128.1,126.7,125.9,125.4,125.2,124.7,123.9,108.3,106.1,103.8, 103.7,58.4,58.0,55.9,55.7,55.4,55.3,53.1,33.5,26.4,25.9,24.2；ESI-HRMS (m/z): calcd.for C₃₂H₃₈NO₆[M+H]⁺532.2694；found532.2699.

The synthesis of 6-(N-benzyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) hexanol (29)

Light yellow solid, yield: 85.7%, fusing point: 99-101 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.99 (s, 1H), 7.97 (s, 1H), 7.77 (s, 1H), 7.59 (s, 1H), 7.36 (s, 1H), 7.30-7.27 (m, 4H), 7.22-7.17 (m, 1H), 4.25 (s, 1H), 4.02 (s, 3H), 4.01 (s, 3H), 3.94 (s, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.54 (s, 2H), 3.27-3.20 (m, 2H), 2.38 (t, J=6.4Hz, 2H), 1.59-1.52 (m, 2H), 1.26-1.23 (m, 2H), 1.17- 1.12 (m, 2H), 1.09-1.03 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 148.1,147.8,147.7,147.1, 138.9,130.0,128.2,127.1,125.8,125.2,125.0,125.0,123.9,123.3,107.1,105.6, 101.8,101.7,61.8,58.3,58.0,55.1,55.0,54.9,54.9,52.5,31.7,29.3,26.0,25.9,24.4； ESI-HRMS (m/z): calcd.for C₃₂H₄₀NO₅[M+H]⁺518.2901；found518.2909.

6-N-normal-butyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) synthesis of methyl caproate (30)

Light yellow solid, yield: 80.0%, fusing point: 96-98 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.97 (s, 1H), 7.81 (s, 1H), 7.79 (s, 1H), 7.50 (s, 1H), 7.20 (s, 1H), 4.13 (s, 6H), 4.04 (s, 6H), 3.94 (s, 2H), 3.62 (s, 3H), 2.52-2.42 (m, 4H), 2.18 (t, J=7.2Hz, 2H), 1.56-1.46 (m, 6H), 1.31-1.20 (m, 4H), 0.84 (t, J=7.2Hz, 3H)；¹³C NMR (100MHz, CDCl₃) δ 174.1,149.0,148.8,148.7,148.2, 131.4,126.1,126.1,125.7,124.9,124.2,108.2,106.5,102.9,102.8,59.3,56.1,56.0, 55.9,53.9,53.5,51.4,34.0,29.4,27.0,26.7,24.8,20.7,14.1；ESI-HRMS (m/z): calcd.for C₃₀H₄₂NO₆[M+H]⁺512.3007；found512.3012.

The conjunction of 6-(N-(to methyl-benzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (31) Become

White solid, yield: 69.6%, fusing point: 88-90 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.85 (s, 1H), 7.80 (s, 1H), 7.78 (s, 1H), 7.53 (s, 1H), 7.20-7.18 (m, 3H), 7.07 (d, J=7.6Hz, 2H), 4.12 (s, 3H), 4.11 (s, 3H), 4.04 (s, 3H), 3.96 (s, 5H), 3.61 (s, 3H), 3.54 (s, 2H), 2.44 (t, J=7.2Hz, 2H), 2.31 (s, 3H), 2.15 (t, J=7.6Hz, 2H), 1.61-1.55 (m, 2H), 1.50-1.42 (m, 2H), 1.24-1.17 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.2,149.2,149.0,148.9,148.4,136.9,136.5,131.2, 129.3,128.9,126.3,126.2,126.2,125.1,124.4,108.3,106.7,103.1,103.0,59.3,58.8, 56.3,56.1,56.0,53.6,51.5,34.1,27.1,26.8,24.9,21.2；ESI-HRMS (m/z): calcd.for C₃₄H₄₂NO₆[M+H]⁺560.3007；found560.3010.

6-(N-(to t-butylbenzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (32) Synthesis

Light yellow solid, yield: 91.7%, fusing point: 84-86 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.80 (s, 1H), 7.79 (s, 1H), 7.77 (s, 1H), 7.54 (s, 1H), 7.28 (d, J=8.0Hz, 2H), 7.24 (d, J=8.0Hz, 2H), 7.20 (s, 1H), 4.12 (s, 3H), 4.11 (s, 3H), 4.04 (s, 3H), 3.96 (s, 2H), 3.93 (s, 3H), 3.61 (s, 3H), 3.56 (s, 2H), 2.46 (t, J=7.2Hz, 2H), 2.15 (t, J=7.6Hz, 2H), 1.61-1.56 (m, 2H), 1.48-1.42 (m, 2H), 1.29 (s, 9H), 1.24-1.19 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.1,149.7,149.1,148.8, 148.8,148.2,136.8,131.1,128.9,126.9,126.2,126.0,125.0,125.0,124.3,108.2, 106.6,102.9,59.2,58.7,56.1,56.1,56.0,55.9,53.7,51.4,34.4,34.0,31.4,26.9,26.7, 24.7；ESI-HRMS (m/z): calcd.for C₃₇H₄₈NO₆[M+H]⁺602.3476；found602.3481.

The synthesis of 6-(N-(to luorobenzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (33)

White solid, yield: 93.6%, fusing point: 116-118C.¹H NMR (400MHz, CDCl₃) δ 7.85 (s, 1H), 7.81 (s, 1H), 7.78 (s, 1H), 7.54 (s, 1H), 7.23-7.20 (m, 3H), 6.93 (t, J=8.8Hz, 2H), 4.13 (s, 3H), 4.12 (s, 3H), 4.04 (s, 3H), 3.98 (s, 3H), 3.98 (s, 2H), 3.62 (s, 3H), 3.52 (s, 2H), 2.45 (t, J=7.6Hz, 2H), 2.18 (t, J=7.6Hz, 2H), 1.64-1.57 (m, 2H), 1.53-1.45 (m, 2H), 1.27-1.20 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0,149.2,148.9,148.8,148.3,144.3,130.5,129.4, 129.1,128.8,128.5,128.3,126.3,125.9,125.8,125.6,125.1,125.0,125.0,124.9, 124.9,124.4,122.9,120.2,108.1,106.3,102.9,102.8,59.3,58.3,56.1,56.0,55.9, 55.9,54.3,51.5,33.9,27.0,26.8,24.7.

6-(N-(to trifluoromethyl benzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (34) Synthesis

White solid, yield: 87.5%, fusing point: 127-129 DEG C.¹H NMR (400MHz, DMSO-d₆) 67.99 (s, 1H), 7.96 (s, 1H), 7.71 (s, 1H), 7.63 (d, J=8.0Hz, 2H), 7.61 (s, 1H), 7.49 (d, J=8.0Hz, 2H), 7.36 (s, 1H), 4.02 (s, 3H), 4.01 (s, 3H), 3.97 (s, 2H), 3.90 (s, 3H), 3.84 (s, 3H), 3.64 (s, 2H), 3.52 (s, 3H), 2.41 (t, J=7.2Hz, 2H), 2.12 (t, J=7.2Hz, 2H), 1.58-1.51 (m, 2H), 1.35-1.28 (m, 2H), 1.18-1.13 (m, 2H)；¹³C NMR (100MHz, CDCl₃) 6174.0,149.2,148.9,148.8,148.3,144.3, 130.5,129.1,128.9 (q, J=31.9Hz, 1C), 126.3,125.9,125.8,125.1,124.9 (q, J=3.6Hz, 1C), 124.4,124.2 (q, J=270.1Hz, 1C), 120.2,108.1,106.3,102.9,102.8,59.3,58.3,56.1, 56.0,55.9,55.9,54.3,51.5,33.9,27.0,26.8,24.7；ESI-HRMS (m/z): calcd.for C₃₄H₃₉F₃NO₆[M+H]⁺614.2724；found614.2725.

The conjunction of 6-(N-(to nitrobenzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (35) Become

Light yellow solid, yield: 95.8%, fusing point: 132-134 DEG C.¹H NMR (400MHz, CDCl₃) δ 8.01 (d, J= 8.4Hz, 2H), 7.85 (s, 1H), 7.79 (s, 1H), 7.76 (s, lH), 7.54 (s, lH), 7.33 (d, J=8.4Hz, 2H), 7.19 (s, 1H), 4.14 (s, 3H), 4.12 (s, 3H), 4.04 (s, 8H), 3.64 (s, 3H), 3.62 (s, 2H), 2.52 (t, J=7.2Hz, 2H), 2.23 (t, J=7.2Hz, 2H), 1.71-1.64 (m, 2H), 1.59-1.53 (m, 2H), 1.33-1.25 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0,149.3,149.0,148.9,148.3,148.2,146.8,130.2,129.3,126.4, 125.9,125.7,125.1,124.5,123.2,108.1,106.2,103.0,102.8,59.5,58.0,56.1,56.0, 55.9,54.9,51.5,33.9,27.0,27.0,24.8；ESI-HRMS (m/z): calcd.for C₃₃H₃₉N₂O₈[M+H]⁺ 591.2701；found591.2711.

6-(N-(to dimethylamino benzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (36) Synthesis

Light yellow solid, yield: 37.0%, fusing point: 44-46 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.86 (s, 1H), 7.79 (s, 1H), 7.78 (s, 1H), 7.53 (s, 1H), 7.20 (s, 1H), 7.18 (d, J=8.0Hz, 2H), 6.66 (d, J= 8.0Hz, 2H), 4.12 (s, 6H), 4.04 (s, 3H), 3.95 (s, 3H), 3.94 (s, 2H), 3.61 (s, 3H), 3.50 (s, 2H), 2.91 (s, 6H), 2.43 (t, J=6.8Hz, 2H), 2.15 (t, J=7.6Hz, 2H), 1.60-1.52 (m, 2H), 1.47-1.42 (m, 2H), 1.23-1.17 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.1,149.7,149.0,148.8,148.7,148.2, 131.3,130.1,127.6,126.1,126.0,124.9,124.2,112.5,108.2,106.7,102.9,102.8,77.4, 77.3,77.1,76.7,59.0,58.3,56.1,56.1,56.0,55.9,53.2,51.4,40.8,34.0,26.9,26.6, 24.7；ESI-HRMS (m/z): calcd.for C₃₅H₄₅N₂O₆[M+H]⁺589.3272；found589.3278.

6-(N-(to methoxy-benzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (37) Synthesis

White solid, yield: 83.3%, fusing point: 92-94 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.86 (s, 1H), 7.80 (s, 1H), 7.78 (s, 1H), 7.53 (s, 1H), 7.21-7.20 (m, 3H), 6.80 (d, J=8.0Hz, 2H), 4.12 (s, 3H), 4.12 (s, 3H), 4.04 (s, 3H), 3.97 (s, 3H), 3.96 (s, 2H), 3.77 (s, 3H), 3.61 (s, 3H), 3.51 (s, 2H), 2.44 (t, J=7.2Hz, 2H), 2.16 (t, J=7.2Hz, 2H), 1.63-1.56 (m, 2H), 1.49-1.43 (m, 2H), 1.26- 1.19 (m, 2H)；¹³CNMR (100MHz, CDCl₃) δ 174.1,158.5,149.1,148.8,148.7,148.2,131.9, 131.1,130.3,128.7,126.2,126.0,125.0,124.3,113.5,108.2,106.6,102.9,102.8,59.1, 58.2,56.1,56.0,56.0,55.9,55.3,53.4,51.4,34.0,26.9,26.7,24.7；ESI-HRMS (m/z): calcd.for C₃₄H₄₂NO₇[M+H]⁺576.2956；found576.2952.

6-(N-(3,4,5-trimethoxy benzyl)-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (38) synthesis

White solid, yield: 53.6%.Fusing point: 129-131 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.89 (s, 1H), 7.81 (s, 1H), 7.77 (s, 1H), 7.55 (s, 1H), 7.19 (s, 1H), 6.42 (s, 2H), 4.12 (s, 3H), 4.11 (s, 3H), 4.03 (s, 5H), 3.99 (s, 3H), 3.76 (s, 3H), 3.71 (s, 6H), 3.63 (s, 3H), 3.48 (s, 2H), 2.56 (t, J= 7.6Hz, 2H), 2.22 (t, J=7.2Hz, 2H), 1.70-1.63 (m, 2H), 1.59-1.52 (m, 2H), 1.34-1.28 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0,152.8,149.2,148.9,148.8,148.3,136.5,136.0, 130.9,126.2,126.0,125.9,125.1,124.3,108.1,106.6,105.5,103.0,102.9,60.8,59.1, 58.7,56.1,56.0,55.9,54.6,51.5,34.0,27.1,26.9,24.8；ESI-HRMS (m/z): calcd.for C₃₆H₄₆NO₉[M+H]⁺636.3167；found636.3172.

The synthesis of 6-(2-naphthalene benzyl)-6-(N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (39)

Yellow thick liquid, yield: 69.2%.¹H NMR (400MHz, DMSO-d₆) δ 7.99 (s, 1H), 7.97 (s, 1H), 7.88-7.82 (m, 4H), 7.79 (s, 1H), 7.63 (s, 1H), 7.50-7.37 (m, 3H), 7.37 (s, 1H), 4.02 (s, 3H), 4.01 (s, 5H), 3.91 (s, 3H), 3.81 (s, 3H), 3.72 (s, 2H), 3.50 (s, 3H), 2.44 (t, J=8.0Hz, 2H), 2.09 (t, J=8.0Hz, 2H), 1.59-1.52 (m, 2H), 1.32-1.26 (m, 2H), 1.18-1.12 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0,149.2,148.9,148.8,148.3,137.5,133.3,132.6,130.9,127.7, 127.6,127.6,126.3,126.0,125.9,125.5,125.0,124.4,108.2,106.6,102.9,59.4,59.1, 56.1,56.0,55.9,53.8,51.4,33.9,27.0,26.7,24.8；ESI-HRMS (m/z): calcd.for C₃₇H₄₁NO₆Na[M+Na]⁺618.2826；found618.2832.

The synthesis of 6-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (40)

White solid, yield: 60.0%, fusing point: 191-192 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.74 (s, 2H), 7.74. (s, 2H), 7.56 (s, 2H), 7.48 (s, 2H), 7.17 (s, 2H), 4.11 (s, 6H), 4.07 (s, 6H), 4.06 (s, 4H), 4.03 (s, 6H), 3.58 (s, 3H), 3.49 (s, 6H), 2.61 (t, J=8.0Hz, 2H), 2.10 (t, J=8.0Hz, 2H), 1.78-1.69 (m, 2H), 1.48-1.39 (m, 2H), 1.22-1.16 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 174.0, 149.1,148.9,148.8,148.4,130.6,126.9,126.1,125.9,124.9,124.3,108.1,106.1, 103.0,102.8,59.6,56.1,56.0,55.9,55.4,54.5,51.4,33.9,27.1,27.0,24.7；ESI-HRMS (m/z): calcd.for C₄₅H₅₁NO₁₀Na[M+Na]⁺788.3405；found788.3405.

The synthesis of 6-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) caproic acid (41)

White solid.Yield: 92.0%, fusing point: 235 DEG C of decomposition.¹H NMR (400MHz, DMSO-d₆) δ 7.95 (s, 2H), 7.94 (s, 2H), 7.62 (s, 2H), 7.39 (s, 2H), 7.32 (s, 2H), 4.00 (s, 6H), 3.98 (s, 10H), 3.89 (s, 6H), 3.33 (s, 6H), 2.45 (t, J=8.0Hz, 2H), 1.82 (t, J=8.0Hz, 2H), 1.72-1.63 (m, 2H), 1.34- 1.25 (m, 2H), 1.15-1.05 (m, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 177.0,149.0,148.7,148.5, 148.0,129.9,126.5,125.3,125.2,124.7,123.9,108.2,105.8,103.9,103.6,58.7,55.8, 55.8,55.3,54.7,54.3,36.5,27.3,26.8,25.6；ESI-HRMS (m/z): calcd.for C₄₄H₄₉NO₁₀Na[M+ Na]⁺774.3249；found774.3247.

The synthesis of 6-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) hexanol (42)

White solid, yield: 86.2%.Fusing point: 163-165 DEG C；¹H NMR (400MHz, CDCl₃) δ 7.75 (s, 4H), 7.57 (s, 2H), 7.50 (s, 2H), 7.17 (s, 2H), 4.11 (s, 6H), 4.08 (s, 6H), 4.06 (s, 4H), 4.03 (s, 6H), 3.72 (s, 1H), 3.48 (s, 6H), 3.44-3.39 (m, 2H), 2.60 (t, J=8.0Hz, 2H), 1.77-1.68 (m, 2H), 1.36-1.29 (m, 2H), 1.23-1.17 (m, 2H), 1.14-1.09 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 148.1, 147.8,147.8,147.4,129.6,125.9,125.1,124.8,123.9,123.2,107.1,105.2,101.9, 101.7,61.7,58.6,55.1,55.0,54.8,54.4,53.4,31.6,26.2,24.4；ESI-HRMS (m/z): calcd.for C₄₄H₅₁NO₉Na[M+Na]⁺760.3456；found760.3449.

The synthesis of 5-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl valerate (43)

White solid, yield: 50.0%, fusing point: 202-204 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.72 (s, 4H), 7.53 (s, 2H), 7.44 (s, 2H), 7.15 (s, 2H), 4.09 (s, 6H), 4.06 (s, 6H), 4.02 (s, 10H), 3.57 (s, 3H), 3.48 (s, 6H), 2.59 (t, J=8.0Hz, 2H), 2.10 (t, J=8.0Hz, 2H), 1.75-1.68 (m, 2H), 1.58- 1.48 (m, 2H)；¹³CNMR (100MHz, CDCl₃) δ 173.8,149.2,148.9,148.8,148.5,130.5,126.8, 126.1,125.9,125.0,124.3,108.2,106.1,103.0,102.8,59.5,56.1,56.0,55.9,55.5, 54.4,51.4,33.7,26.7,22.9；ESI-HRMS (m/z): calcd.for C₄₄H₄₉NO₁₀Na[M+Na]⁺744.3249； found744.3246.

The synthesis of 5-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) valeric acid (44)

White solid, yield: 81.5%, fusing point: more than 300 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.91 (s, 4H), 7.53 (s, 2H), 7.33 (s, 2H), 7.29 (s, 2H), 3.98 (s, 6H), 3.96 (s, 6H), 3.88 (s, 10H), 3.28 (s, 6H), 2.44 (t, J=8.0Hz, 2H), 1.84 (t, J=8.0Hz, 2H), 1.71-1.57 (m, 2H), 1.37-1.25 (m, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 178.1,149.0,148.6,148.5,148.0,129.9,126.5,125.3,125.3, 124.6,123.9,108.2,105.7,103.9,103.6,58.5,55.8,55.7,55.3,54.7,54.4,36.7,26.8, 24.0；ESI-HRMS (m/z): calcd.for C₄₃H₄₇NO₁₀Na[M+Na]⁺760.3092；found760.3088.

The synthesis of 5-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) amylalcohol (45)

White solid, yield: 90.9%, fusing point: 156-158 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.75 (s, 2H), 7.74 (s, 2H), 7.57 (s, 2H), 7.48 (s, 2H), 7.17 (s, 2H), 4.11 (s, 6H), 4.08 (s, 6H), 4.06 (s, 4H), 4.03 (s, 6H), 3.47 (s, 6H), 3.38 (t, J=4.0Hz, 2H), 2.62 (t, J=8.0Hz, 2H), 1.79-1.72 (m, 2H), 1.53 (s, 1H), 1.32-1.20 (m, 4H)；¹³C NMR (100MHz, CDCl₃) δ 149.2,148.9,148.9,148.5, 130.7,126.9,126.1,125.9,125.0,124.3,108.2,106.2,103.0,102.9,62.8,59.7,56.1, 56.1,55.9,55.5,54.6,32.5,27.2,23.7；ESI-HRMS (m/z): calcd.for C₄₃H₄₉NO₉Na[M+Na]⁺ 746.3300；found746.3297.

The synthesis of 4-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl butyrate (46)

White solid, yield: 67.3%, fusing point: 125-127 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.75 (s, 2H), 7.74 (s, 2H), 7.57 (s, 2H), 7.46 (s, 2H), 7.17 (s, 2H), 4.11 (s, 6H), 4.08 (s, 10H), 4.03 (s, 6H), 3.49 (s, 6H), 3.45 (s, 3H), 2.65 (t, J=8.0Hz, 2H), 2.17 (t, J=8.0Hz, 2H), 2.07-2.02 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 172.6,148.2,147.9,147.8,147.5,129.3,126.05,124.9, 124.8,123.9,123.3,107.2,104.9,102.0,101.8,58.4,55.1,55.0,54.8,54.4,52.8,50.3, 30.9,21.6；ESI-HRMS (m/z): calcd.for C₄₃H₄₇NO₁₀Na[M+Na]⁺760.3092；found760.3099.

The synthesis of 4-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) butanoic acid (47)

White solid, yield: 95.0%, fusing point: 224-226 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.95 (s, 2H), 7.94 (s, 2H), 7.63 (s, 2H), 7.43 (s, 2H), 7.32 (s, 2H), 4.00 (s, 10H), 3.98 (s, 6H), 3.89 (s, 6H), 3.35 (s, 6H), 2.55 (t, J=4.0Hz, 2H), 1.95-1.88 (m, 2H), 1.86-1.79 (m, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 176.7,149.0,148.6,148.1,130.0,126.5,125.4,125.3,124.7,123.9, 108.3,105.8,104.0,103.7,58.7,55.9,55.8,55.3,54.9,54.6,35.3,23.8；ESI-HRMS(m/ Z): calcd.forC₄₂H₄₅NO₁₀Na[M+Na]⁺746.2936；found746.2938.

The synthesis of 4-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) butanol (48)

White solid, yield: 90.9%, fusing point: 134-136 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.70 (s, 4H), 7.53 (s, 2H), 7.42 (s, 2H), 7.14 (s, 2H), 4.09 (s, 6H), 4.05 (s, 6H), 4.01 (s, 10H), 3.46 (s, 6H), 3.38 (t, J=4.0Hz, 2H), 2.60 (t, J=4.0Hz, 2H), 1.80-1.71 (m, 2H), 1.47-1.38 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 148.1,147.8,147.7,147.4,129.4,125.8,125.0,124.8,123.9, 123.2,107.1,105.1,101.9,101.7,61.3,58.4,55.0,55.0,54.8,54.4,53.5,29.6,22.5； ESI-HRMS (m/z): calcd.forC₄₂H₄₇NO₉Na[M+Na]⁺732.3143；found732.3148.

The synthesis of 3-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl propionate (49)

White solid, yield: 78.5%, fusing point: 145-147 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.74 (s, 2H), 7.73 (s, 2H), 7.57 (s, 2H), 7.43 (s, 2H), 7.16 (s, 2H), 4.10 (s, 6H), 4.09 (s, 4H), 4.07 (s, 6H), 4.03 (s, 6H), 3.53 (s, 6H), 3.41 (s, 3H), 3.05 (t, J=8.0Hz, 2H), 2.62 (t, J=8.0Hz, 2H)；¹³C NMR (100MHz, CDCl₃) δ 172.9,149.3,148.9,148.8,148.6,130.0,126.9,126.0,125.8,125.0, 124.4,108.2,106.0,103.1,102.8,59.2,56.1,56.0,55.9,55.5,51.4,50.4,32.1；ESI- HRMS (m/z): calcd.forC₄₂H₄₅NO₁₀Na[M+Na]⁺746.2936；Found, 746.2935.

The synthesis of 3-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) propanoic acid (50)

Light yellow solid, yield: 97.1%, fusing point: 234-236 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.95 (s, 2H), 7.94 (s, 2H), 7.63 (s, 2H), 7.43 (s, 2H), 7.33 (s, 2H), 4.00 (s, 6H), 3.98 (s, 10H), 3.89 (s, 6H), 3.35 (s, 6H), 2.76 (t, J=8.0,2H), 2.40-2.34 (t, J=8.0,2H)；¹³C NMR (100MHz, DMSO- d₆) δ 176.4,149.0,148.7,148.5,148.0,130.1,126.4,125.4,125.3,124.7,123.8,108.2, 106.0,103.9,103.7,58.5,55.9,55.8,55.3,54.8,51.8,35.6；ESI-HRMS (m/z): calcd.for C₄₁H₄₃NO₁₀Na[M+Na]⁺732.2779；found732.2772.

The synthesis of 3-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) propanol (51)

White solid, yield: 97.4%, fusing point: 214-216 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.74 (s, 4H), 7.60 (s, 2H), 7.35 (s, 2H), 7.17 (s, 2H), 4.11 (s, 6H), 4.09 (s, 4H), 4.06 (s, 6H), 4.02 (s, 6H), 3.48 (s, 6H), 3.42 (t, J=4.0,2H), 2.89-2.81 (m, 2H), 1.94-1.86 (m, 2H), 1.43 (s, 1H)；¹³C NMR (100MHz, CDCl₃) δ 148.3,147.9,147.8,147.7,128.6,126.5,124.7,123.9,123.4,107.1, 104.5,102.1,101.8,61.7,58.4,55.1,54.9,54.9,54.3,52.5,28.1；ESI-HRMS (m/z): calcd.for C₄₁H₄₅NO₉Na[M+Na]⁺718.2987；found718.2986.

The synthesis of 2-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl acetate (52)

White solid, yield: 68.0%, fusing point: 126-128 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.96 (s, 2H), 7.95 (s, 2H), 7.63 (s, 2H), 7.52 (s, 2H), 7.34 (s, 2H), 4.20 (s, 4H), 4.01 (s, 6H), 3.99 (s, 6H), 3.90 (s, 6H), 3.57 (s, 3H), 3.43 (s, 2H), 3.38 (s, 6H)；¹³C NMR (100MHz, CDCl₃) δ 171.8,149.3, 149.0,148.8,148.7,129.8,127.0,126.0,125.8,125.0,124.5,108.2,106.4,103.0, 102.9,77.5,77.1,76.8,58.8,56.1,56.0,55.9,55.7,54.8,51.2；ESI-HRMS (m/z): calcd.for C₄₁H₄₃NO₁₀Na[M+Na]⁺732.2779；found732.2774.

The synthesis of 2-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) acetic acid (53)

With 14e as substrate, the same 15d of operating process, obtain white solid, yield: 95.7%, fusing point: more than 300 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 7.97 (s, 2H), 7.95 (s, 2H), 7.94 (s, 2H), 7.62 (s, 2H), 7.32 (s, 2H), 4.09 (s, 4H), 4.00 (s, 6H), 3.98 (s, 6H), 3.90 (s, 6H), 3.41 (s, 6H), 2.99 (s, 2H)；¹³C NMR (100MHz, DMSO-d₆) δ 174.7,148.9,148.8,148.5,148.3,130.7,126.4,125.8,125.4,124.6, 123.9,108.3,107.2,103.8,103.7,58.7,55.9,55.8,55.3,55.3；ESI-HRMS (m/z): calcd.for C₄₀H₄₁NO₁₀Na[M+Na]⁺718.2623；found718.2616.

The synthesis of 2-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) ethanol (54)

White solid, yield: 57.7%, fusing point: 246-248 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.76 (s, 2H), 7.74 (s, 2H), 7.58 (s, 2H), 7.29 (s, 2H), 7.18 (s, 2H), 4.16 (s, 4H), 4.11 (s, 6H), 4.06 (s, 6H), 4.03 (s, 6H), 3.64 (s, 2H), 3.41 (s, 6H), 2.86 (s, 2H)；¹³C NMR (100MHz, CDCl₃) δ 148.4,148.0, 147.9,147.9,128.5,126.7,124.7,124.1,123.6,107.2,104.0,102.3,101.8,58.6,57.9, 55.1,55.0,54.9,54.6,54.2；ESI-HRMS (m/z): calcd.for C₄₀H₄₃NO₉Na[M+Na]⁺704.2830； found704.2823.

The synthesis of 6-(N, N-bis-(2,3,6-trimethoxy-9-phenanthrene methyl) amido) methyl caproate (55)

White solid, yield: 65.5%, fusing point: 189-190 DEG C.¹H NMR (400MHz, CDCl₃) δ 8.04 (d, J= 8.0Hz, 2H), 7.82 (d, J=4.0Hz, 4H), 7.47 (s, 2H), 7.16 (s, 2H), 6.92 (dd, J=12.0,4.0Hz, 2H), 4.09 (s, 6H), 4.03 (s, 6H), 4.00 (s, 10H), 3.59 (s, 3H), 2.56 (t, J=8.0Hz, 2H), 2.09 (t, J= 8.0Hz, 2H), 1.68-1.61 (m, 2H), 1.46-1.39 (m, 2H), 1.18-1.10 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 173.1,156.7,148.3,147.8,130.7,130.5,127.0,126.0,124.7,124.4,123.2, 113.4,107.1,102.8,102.3,57.7,55.0,54.8,54.4,53.0,50.3,32.9,26.0,25.0,23.6； ESI-HRMS (m/z): calcd.for C₄₃H₄₇NO₈Na[M+Na]⁺728.3194；found728.3196.

The synthesis of 6-(N, N-bis-(3,6,7-trimethoxy-9-phenanthrene methyl) amido) methyl caproate (56)

White solid, yield: 62.9%, fusing point: 111-113 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.85 (s, 2H), 7.82 (s, 2H), 7.75 (d, J=8.8Hz, 2H), 7.61 (s, 2H), 7.48 (s, 2H), 7.18 (d, J=8.8Hz, 2H), 4.07 (s, 6H), 4.05 (s, 4H), 4.01 (s, 6H), 3.58 (s, 3H), 3.47 (s, 6H), 2.60 (t, J=8.0Hz, 2H), 2.09 (t, J=8.0Hz, 2H), 1.77-1.69 (m, 2H), 1.46-1.38 (m, 2H), 1.22-1.13 (m, 2H)；¹³C NMR (100MHz, CDCl₃) δ 173.9,158.2,149.2,148.7,131.0,129.9,127.4,127.3,125.7,124.8,115.4, 106.2,103.9,103.5,59.4,56.0,55.6,55.4,54.4,51.4,33.9,27.1,26.9,24.7；ESI-HRMS (m/z): calcd.for C₄₃H₄₇NO₈Na[M+Na]⁺728.3194；found728.3192.

The synthesis of 2-(N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido)-1,3-PD (57)

White solid, yield: 51.4%, fusing point: 182-184 DEG C.¹H NMR (400MHz, DMSO-d₆) δ 8.02 (s, 1H), 7.98 (s, 1H), 7.62 (s, 2H), 7.35 (s, 1H), 4.52 (s, 2H), 4.20 (s, 2H), 4.03 (s, 3H), 4.02 (s, 3H), 3.93 (s, 3H), 3.90 (s, 3H), 3.56-3.52 (m, 2H), 3.48-3.44 (m, 2H), 3.32 (s, 1H), 2.81-2.76 (m, 1H)；¹³CNMR (100MHz, DMSO-d₆) δ 148.9,148.7,148.6,148.3,125.6,124.8,124.5,123.9, 123.7,108.4,105.5,104.1,103.8,61.2,61.1,55.9,55.9,55.4,55.3,49.9；ESI-HRMS(m/ Z): calcd.forC₂₂H₂₇NO₆Na[M+Na]⁺424.1731；found424.1739.

The synthesis of 2-methyl-2-(N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido)-1,3-PD (58)

White solid, yield: 64.3%, fusing point: 108-110 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.78 (s, 1H), 7.72 (s, 1H), 7.70 (s, 1H), 7.58 (s, 1H), 7.20 (s, 1H), 4.23 (s, 2H), 4.09 (s, 6H), 4.04 (s, 3H), 4.02 (s, 3H), 3.59-3.50 (m, 4H), 1.16 (s, 3H)；¹³C NMR (100MHz, CDCl₃) δ 149.30,148.96, 148.93,148.87,130.59,126.05,125.48,125.11,125.02,124.38,108.23,104.75,103.37, 102.74,67.22,57.68,56.04,56.02,55.99,55.90,44.48,18.20；ESI-HRMS (m/z): calcd.for C₂₃H₂₉NO₆Na[M+Na]⁺438.1887；found438.1884.

The synthesis of 2-(N, N-bis-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido)-1,3-PD (59)

Light yellow solid, yield: 68.8%, fusing point: 152-154 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.75 (s, 2H), 7.73 (s, 2H), 7.59 (s, 2H), 7.23 (s, 2H), 7.16 (s, 2H), 4.40 (s, 4H), 4.12 (s, 4H), 4.11 (s, 6H), 4.06 (s, 6H), 4.02 (s, 6H), 3.42 (s, 6H), 3.30-3.23 (m, 1H), 2.36 (s, 2H)；¹³C NMR (100MHz, CDCl₃) δ 149.4,149.0,149.0,148.9,129.5,128.1,125.7,125.7,125.14,124.5,108.2, 104.8,103.4,102.8,59.7,56.1,56.0,55.9,55.1,54.6,45.7；ESI-HRMS (m/z): calcd.for C₄₁H₄₅NO₈Na[M+Na]⁺734.2936；found734.2941.

2-methyl-3-(2,3,6,7-tetramethoxy-9-phenanthrene methoxyl group)-2-((2,3,6,7-tetramethoxy-9-phenanthrene methyl) Amido) propanol (60)

White solid, yield: 56%, fusing point: 112-114C.¹H NMR (400MHz, DMSO-d₆) δ 8.02 (s, 1H), 7.99 (s, 1H), 7.97 (s, 1H), 7.95 (s, 1H), 7.65 (s, 1H), 7.55 (s, 2H), 7.35 (s, 2H), 7.26 (s, 1H), 4.96 (dd, J=28.0,12.0Hz, 2H), 4.64-4.61 (m, 1H), 4.02-4.01 (m, 14H), 3.89 (s, 3H), 3.88 (s, 3H), 3.81 (s, 3H), 3.74 (s, 3H), 3.54 (s, 2H), 3.47-3.44 (m, 2H), 1.15 (s, 3H)；¹³C NMR (100MHz, DMSO-d₆) δ 149.2,148.8,148.8,148.6,148.5,148.4,148.3,148.0,132.4,129.3, 125.6,125.2,125.0,124.9,124.6,124.5,124.2,123.7,123.6,108.5,108.2,105.5, 105.2,104.0,103.9,103.7,103.6,72.8,72.1,65.0,56.6,55.9,55.8,55.8,55.3,55.3, 55.1,55.0,44.4,19.2；ESI-HRMS (m/z): calcd.forC₄₂H₄₈NO₁₀Na[M+Na]⁺748.3092； found748.3095.

The synthesis of 6-(N, N-dibenzyl amido) methyl caproate (61)

Light yellow liquid, yield: 88.3%.¹H NMR (400MHz, CDCl₃) δ 7.34 (s, 4H), 7.32-7.30 (m, 4H), 7.24-7.18 (m, 2H), 3.65 (s, 3H), 3.54 (s, 4H), 2.40 (t, J=4.0Hz, 2H), 2.26 (t, J=8.0Hz, 2H), 1.57-1.50 (m, 4H), 1.32-1.26 (m, 2H)；ESI-HRMS (m/z): calcd.for C₂₁H₂₈NO₂[M+H]⁺ 326.2115；found326.2117.

The synthesis of 6-(N, N-dibenzyl amido) caproic acid (62)

Light yellow thick liquid, yield: 89.4%.¹H NMR (400MHz, CDCl₃) δ 7.39-7.37 (m, 4H), 7.33- 7.30 (m, 4H), 7.27-7.22 (m, 2H), 3.62 (s, 4H), 2.46 (t, J=8.0Hz, 2H), 2.29 (t, J=8.0Hz, 2H), 1.59-1.50 (m, 4H), 1.35-1.30 (m, 2H)；ESI-HRMS (m/z): calcd.for C₂₀H₂₆NO₂[M+H]⁺ 312.1958；found312.1959.

The synthesis of 6-(N, N-dibenzyl amido) hexanol (63)

Light yellow liquid, yield: 95.2%.¹H NMR (400MHz, CD₃OD) δ 7.35-7.32 (m, 5H), 7.31-7.28 (m, 3H), 7.23-7.20 (m, 2H), 3.63 (s, 2H), 3.53 (s, 4H), 2.39 (t, J=8.0Hz, 2H), 2.25 (t, J= 8.0Hz, 2H), 1.53-1.47 (m, 4H), 1.31-1.26 (m, 2H)；ESI-HRMS (m/z): calcd.for C₂₀H₂₈NO[M+ H]⁺298.2165；found298.2171.

The synthesis of 6-(N, N-bis-(2-menaphthyl) amido) methyl caproate (64)

White solid, yield: 80.1%, fusing point: 63-65 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.83-7.79 (m, 6H), 7.77 (s, 2H), 7.56 (d, J=8.4Hz, 2H), 7.49-7.41 (m, 4H), 3.73 (s, 4H), 3.62 (s, 3H), 2.49 (t, J=8.0Hz, 2H), 2.24 (t, J=8.0Hz, 2H), 1.59-1.50 (m, 4H), 1.34-1.28 (m, 2H)；¹³C NMR (100MHz, CDCl3) δ 174.2,137.6,133.4,132.8,127.9,127.7,127.3,125.9,125.5,58.6, 53.3,51.5,34.1,26.8,26.8,24.9.ESI-HRMS (m/z): calcd.for C₂₉H₃₂NO₂[M+H]⁺426.2428； found426.2424.

N₁, N₁-dimethyl-N₂, N₂The synthesis of-two (2,3,6,7-tetramethoxy-9-phenanthrene methyl) ethylenediamine (65)

Light yellow solid, yield: 38.5%, fusing point: 138-140 DEG C.¹H NMR (400MHz, CDCl₃) δ 7.73 (s, 2H), 7.72 (s, 2H), 7.58 (s, 2H), 7.45 (s, 2H), 7.17 (s, 2H), 4.10 (s, 6H), 4.07 (s, 10H), 4.03 (s, 6H), 3.52 (s, 6H), 2.85 (t, J=6.8Hz, 2H), 2.62 (t, J=6.8Hz, 2H), 2.13 (s, 6H)；¹³C NMR (100MHz, CDCl₃) δ 148.2,147.9,147.8,147.5,129.1,125.9,124.9,124.8,123.9,123.3, 107.1,105.0,102.0,101.7,58.9,56.2,55.1,55.0,54.9,54.5,51.2,44.3；ESI-HRMS(m/ Z): calcd.for C₄₂H₄₉N₂O₈[M+H]⁺709.3483；found709.3482.

Embodiment 4: the physicochemical property of compound 1-65 in embodiment 1-3

This patent aromatic aminomethane compounds 1-65 has good light, heat stability and water-soluble, is better than antofine, Conventional organic solvent (such as dichloromethane, chloroform, toluene, ethanol etc.) also have more more preferable dissolubility than antofine.? Being detected by nuclear-magnetism after irradiating sample 24h with electric filament lamp under the conditions of 50 DEG C, aromatic aminomethane compounds 1-65 is not changed in, and pacifies torr Sweet smell has 50% to decompose.The water of equal volume dissolves the quality of aromatic aminomethane compounds 1-65 far more than antofine.

Embodiment 5: as a example by biological activity is with resisting tobacco mosaic virus (Tobacco mosaic virus, TMV) activity,

The mensuration program of aromatic aminomethane compounds 1-65 activity of resisting tobacco mosaic virus is as follows:

1, Virus purification and concentration measure:

Virus purification and concentration mensuration are given birth to survey room establishment tobacco mosaic virus (TMV) SOP specification with reference to Nankai University's element and are held OK.Virus crude extract, after 2 Polyethylene Glycol centrifugal treating, measures concentration, and 4 DEG C of cold preservations are standby.

2, compound solution preparation:

After weighing, former medicine adds DMF and dissolves, and prepares 1 × 10⁵μ g/mL mother solution, afterwards with containing 1 ‰ Tween 80 aqueous solution dilutions To desired concn；Virazole preparation is directly watered dilution.

3, effect in vitro:

The of the right age blade of the western cigarette of frictional inoculation coral, rinses with flowing water, virus concentration 10 μ g/mL.Receive and cut after doing, arteries and veins along leaf To cuing open, left and right half leaf is dipped in 1 ‰ tween water and medicament respectively, takes out after 30min, and under suitable illumination temperature, moisturizing is cultivated, Every 3 leaves are to repeat for 1 time, are repeated 3 times.Record scab number after 3d, calculate preventive effect.

4, live body protective effect:

Select the 3-5 western cigarette of leaf phase coral of growing way uniformity, Herb spray pesticide, often process 3 times and repeat, and set 1 ‰ tweens 80 aqueous solution comparisons.After 24h, blade face dispenses corundum (500 mesh), dips virus liquid with brush pen, on full blade face along offshoot direction Dab 2 times, with palm support below blade, virus concentration 10 μ g/mL, rinses with flowing water after inoculation.Scab number, meter is recorded after 3d Calculate preventive effect.

5, live body therapeutical effect:

Selecting the 3-5 western cigarette of leaf phase coral of growing way uniformity, with brush pen full leaf virus inoculation, virus concentration is 10 μ g/mL, connects Rinse with flowing water after Zhong.Blade face is received after doing, Herb spray pesticide, often processes 3 times and repeats, and sets 1 ‰ Tween 80 aqueous solutions comparisons. Record scab number after 3d, calculate preventive effect.

6, live body passivation:

Select the 3-5 western cigarette of leaf phase coral of growing way uniformity, medicament is mixed passivation 30min with isopyknic virus juice After, frictional inoculation, virus concentration 20 μ g/mL, i.e. rinse with flowing water after inoculation, be repeated 3 times, if 1 ‰ Tween 80 aqueous solution comparisons. Number scab number, result of calculation after 3d.

Suppression ratio (%)=[(comparison withered spot number-process withered spot number)/comparison withered spot number] × 100%

Table 1 is resisting tobacco mosaic virus (Tobacco mosaic virus, TMV) the active testing knot of part of compounds Really:

By data in table 1 it can be seen that overwhelming majority aromatic aminomethane compounds all shows good anti-Tobacco mosaic Virus live body activity.Wherein compound 4,11,13,16,22,24,27,30,36,37,49,54,56,60 activity are substantially better than business Product kind virazole, with activity guide's antofine activity quite.

Claims

1. aromatic aminomethane class anti-plant virus agent (I), it is characterised in that the compound shown in formula I is selected from:

6-(N-benzyl-N-(2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (27)；Or 6-(N-normal-butyl-N- (2,3,6,7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (30)；Or 6-(N-(to methoxy-benzyl)-N-(2,3,6, 7-tetramethoxy-9-phenanthrene methyl) amido) methyl caproate (37).

2. the application in preventing and treating the viroses of plant of the aromatic aminomethane class anti-plant virus agent described in claim 1.