CN110452266A - A kind of phosphine oxide-type compound and its preparation method and application - Google Patents

A kind of phosphine oxide-type compound and its preparation method and application Download PDF

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CN110452266A
CN110452266A CN201811158498.9A CN201811158498A CN110452266A CN 110452266 A CN110452266 A CN 110452266A CN 201811158498 A CN201811158498 A CN 201811158498A CN 110452266 A CN110452266 A CN 110452266A
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compound
preparation
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贺红武
何海峰
张莎莎
彭浩
谭效松
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Huazhong Normal University
Central China Normal University
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Huazhong Normal University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5333—Arylalkane phosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring

Abstract

The present invention provides a kind of phosphine oxide-type compounds and its preparation method and application, especially compound shown in Formulas I or its stereoisomer, geometric isomer, tautomer, raceme, nitrogen oxides, hydrate, solvate, pharmaceutically acceptable salt, in formula: R1For C1‑C3Alkyl；R2For C1‑C3Alkyl；R3For C1‑C4Alkyl, furyl or the phenyl arbitrarily replaced；X, Y are the monosubstituted or multi-substituent on phenyl ring any position, such as can be replaced for contraposition or meta position, and the substituent group can be identical or different.Such compound has significant inhibiting effect to the growth of annual and perennial broadleaf weed and sedge weed, has certain control efficiency to gramineae weed.It can be used as the effective component of herbicide.

Description

A kind of phosphine oxide-type compound and its preparation method and application
Technical field
The present invention relates to pesticide fields, specifically, the present invention relates to phosphine oxide-type compound and its preparation method and application, More specifically, the present invention relates to compounds shown in compound and derivative and preparation method thereof, Formulas I shown in Formulas I removes in preparation The application of careless agent.
Background technique
Phosphate derivatives are the significant compounds of a kind of bioactivity, and are developed there are many phosphate derivatives At herbicide or plant growth regulator.Correlative study invention type-A (He Hongwu etc., Chinese invention patent, Patent No. ZL97109095.5 phosphate derivatives), they show different degrees of activity of weeding and plant growth regulating activity. But phosphate ester structure facile hydrolysis leads to active reduction, the present invention designs a kind of structure of novel not facile hydrolysis thus, that is, aoxidizes Phosphine compound.
Summary of the invention
It is an object of the invention to explore the phosphine oxide-type compound with activity of weeding, provide a kind of with activity of weeding Phosphine oxide-type compound and its synthetic method.
The present invention changes the structural framework of above compound, proposes one on the Research foundation of above-mentioned A class compound Class overcomes the phosphine oxide-type compound of above-mentioned A class compound structure facile hydrolysis, general structure I.
In formula:
R1For C1-C3Alkyl；
R2For C1-C3Alkyl；
R3For C1-C4Alkyl, furyl or the phenyl arbitrarily replaced；
X, Y are the monosubstituted or multi-substituent on phenyl ring any position, such as can be replaced for contraposition or meta position, described to take It can be identical or different for base.
According to one embodiment of present invention, R1For C1-C4Alkyl, preferred alkyl is methyl, ethyl, propyl, different Propyl, normal-butyl and isobutyl group, R2Preferably methyl, ethyl, propyl and isopropyl；R3For C1-C4Alkyl, furyl, Phenyl, at least one methyl substituted phenyl that phenyl, at least one halogen replace, preferred halogen are chlorine.It is highly preferred that R3 For methyl, ethyl, propyl, furyl, phenyl, 2,4- dichlorophenyl, 3- aminomethyl phenyl, 2,3- dichlorophenyl, 3- chlorphenyl.
According to one embodiment of present invention, compound is specially listed by table 1:
Table 1: the specific structure of compound shown in general formula I
When the phosphine oxide compound that general formula I is indicated is structure shown in number 1-69, application method A preparation: make general formula II institute The derivative of expression is reacted with derivative represented by general formula III, and chemical equation is as follows:
The reaction ratio of above-mentioned reaction alpha-hydroxyl phosphine oxide II and substituted benzene oxygen chloroacetic chloride III and alkali is 1:(1.0- 2.0): the molar ratio of (1.0-2.0), reaction dissolvent use organic solvent-acetone, chloroform, tetrahydrofuran, dichloroethanes, dichloromethane Alkane, chloroform, acetonitrile, n,N-Dimethylformamide, dimethyl sulfoxide, benzene or ethyl acetate, alkali sodium ethoxide, sodium methoxide, In the presence of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, triethylamine or pyridine, -10 DEG C to 110 DEG C reaction 1-24 hours, can be obtained higher yield.
When the phosphine oxide compound that general formula I is indicated is structure shown in number 70-105, application method B preparation: make general formula II Represented derivative is reacted with derivative represented by the following general formula IV, and chemical equation is as follows:
The reaction ratio of above-mentioned reaction alkyl phosphine oxide II and substituted phenoxy acetic acid IV, catalyst and condensing agent are 1: (1.1-2.0): the molar ratio of (0.05-0.15) (1.1-4.0), reaction dissolvent use organic solvent-acetone, chloroform, tetrahydro furan It mutters, dichloroethanes, methylene chloride, chloroform, acetonitrile, toluene, DMF, benzene or ethyl acetate, in condensing agent N, two miaow of N- carbonyl Azoles (CDI), dicyclohexylcarbodiimide (DCC), diisopropyl base carbodiimide (DIC), 1- (3- dimethylamino-propyl) -3- second Base carbodiimide (EDCI) and catalyst 4-N, in the presence of N dimethyl pyridine (DMAP), 1- hydroxy benzo triazole (HOBt), - 10 DEG C to 110 DEG C reaction 1-24 hours, can be obtained preferable yield.
Present invention discover that having the characteristics that the derivative of above-mentioned structure shown in formula I to annual and perennial broadleaf weed and Cyperaceae The growth of weeds has significant inhibiting effect, can be used as the effective component of herbicide, has for example, containing such compound and being used as The herbicide of ingredient is imitated to preventing and kill off piemarker, Amaranthus retroflexus, concave head amaranth, thorn amaranth, amaranth, field thistle, Eclipta prostrata, shepherd's purse, small Chenopodiaceae, sheep hoof, numerous A variety of weeds such as Chenopodiaceae, beggar-ticks, broom grass, arabidopsis, pharbitis nilChoisy, difformed galingale herb, cyperus iria and Herba Cyperi Glomerati have excellent Preventive effect.Has the characteristics that selective herbicide, part of compounds also has gramineae weed such as herba digitariae, barnyard grass, herba setariae viridis There is certain control efficiency.
Weeds described above illustrate the weeds type that the compounds of this invention is prevented and kill off with being merely illustrative, and should not be construed For the limitation for the weeds category prevented and kill off to the compounds of this invention.
Specific embodiment
The preparation method of Formulas I derivative of the invention is specifically described below by embodiment, these embodiments are only right The present invention is illustrated, rather than is limited the invention.
Embodiment 1
1 structural formula of compound is as follows:
The preparation method of compound 1: by 5mmol Alpha-hydroxy phosphine oxide, 5mmol potassium carbonate and 20mL benzene, ice salt bath cooling To 0 DEG C hereinafter, 5mmol 2, the 10mL benzole soln of 4- Dichlorophenoxy chloroacetic chloride is slowly added dropwise.Drop finishes, and removes ice bath, allows reaction solution It is gradually increased to room temperature, and is heated to 80 DEG C the reaction was continued.It is tracked and is reacted with lamellae (TLC), about 6h reaction is completed.End of reaction Precipitation is depressurized, 20mL methylene chloride is added, is washed with saturated potassium carbonate, dilute hydrochloric acid and sodium-chloride water solution, until solution is in neutrality. Again twice with suitable methylene chloride aqueous phase extracted, merge organic phase.It is dried overnight with anhydrous sodium sulfate, filters out anhydrous sodium sulfate Afterwards, filtrate sloughs solvent up to crude product.It is eluted through silica gel (G type) column chromatographic grade, (eluant ethyl acetate: petroleum ether volume Than=1:2) obtain sterling.Gained sterling is white solid, yield 67%；M.p.51~52 DEG C；Elemental analysis/%: calculated value: C, 46.49；H,3.44；Measured value: C, 46.26；H,3.42.
1H NMR(400MHz,CDCl3):1.42(dd,6H,2(CH3) P, J=12.6,12.7Hz), 4.61 (s, 2H, CH2), 5.42 (d, 1H, PCH, J=5.3Hz), 6.73 (d, 1H, Ar-H, J=8.9Hz), 7.09 (dd, 1H, Ar-H, J=8.7, 2.1Hz), 7.22 (d, 1H, Ar-H, J=17.0Hz), 7.30 (d, 1H, Ar-H, J=2.1Hz), 7.33 (s, 1H, Ar-H, J= 2.1H), 7.50 (d, 1H, Ar-H, J=8.4Hz)；
13C NMR(100MHz,CDCl3):171.45,152.34,134.60,133.19,132.64,130.07, 129.54,129.22,127.73,127.43,126.68,123.91,114.56,69.35,68.57,66.10,13.27, 12.63,11.66,10.99；
31P NMR(160MHz,CDCl3):51.13；
ESI-MS m/z:477.2(M+Na)+；
2 structural formula of compound is as follows:
The preparation method of compound 2 is identical as the preparation method of compound 1, is white oil object, yield 88%, refraction Rate is 1.5261；Elemental analysis/%: calculated value: C, 49.62；H,4.16；Measured value: C, 49.89；H,4.12
1H NMR(400MHz,CDCl3):1.52(dd,6H,2(CH3) P, J=12.8,12.9Hz), 2.26 (s, 3H, Ar- CH3),4.72-4.85(m,2H,CH2), 6.54 (d, 1H, PCH, J=2.4Hz), 6.59 (d, 1H, Ar-H, J=8.7Hz), 7.05 (dd, 1H, Ar-H, J=2.5,2.4Hz), 7.15 (d, 1H, Ar-H, J=2.3Hz), 7.30 (dd, 1H, Ar-H, J=2.1, 2.0Hz), 7.42 (dd, 1H, Ar-H, J=1.5,1.7Hz), 7.45 (d, 1H, Ar-H, J=1.9Hz)；
13C NMR(100MHz,CDCl3):167.46,154.17,135.83,133.64,130.89,130.26, 129.61,129.35,129.08,127.97,126.44,126.35,111.92,70.88,70.06,65.34,16.05, 14.44,14.06,13.75,13.37；31P NMR(160MHz,CDCl3):42.14；
ESI-MS m/z:457.2(M+Na)+；
3 structural formula of compound is as follows:
The preparation method of compound 3 is identical as the preparation method of compound 1, is white oil, yield 59%, refractive index For；1.5541；Elemental analysis/%: calculated value: C, 48.43；H,3.82；Measured value C, 48.31；H,3.54.
1H NMR(400MHz,CDCl3):1.52(dd,6H,2(CH3) P, J=12.8,12.8Hz), 4.70-4.83 (m, 2H,CH2), 6.81 (s, 1H, PCH), 6.83 (d, 1H, Ar-H, J=2.2Hz), 7.19 (d, 1H, Ar-H, J=8.0Hz), 7.24 (d, 2H, Ar-H, J=8.9Hz), 7.29 (dd, 1H, Ar-H, J=2.0,1.8Hz), 7.42 (d, 1H, Ar-H, J=9.6Hz), 7.45 (d, 1H, Ar-H, J=1.8Hz)；
13C NMR(100MHz,CDCl3):167.30,155.91,135.74,133.55,130.17,129.44, 129.23,129.13,127.89,126.90,115.82,70.79,70.01,65.15,14.32,13.90,13.63,13.21；
31P NMR(160MHz,CDCl3):42.38；
ESI-MS m/z:443.1(M+Na)+；
4 structural formula of compound is as follows:
The preparation method of compound 4 is identical as the preparation method of compound 1, be white solid, yield 76%, m.p.46-47℃；Elemental analysis/%: calculated value: C, 46.44；H,3.44；Measured value: C, 46.53；H,3.70.
1H NMR(400MHz,CDCl3):1.52(dd,6H,2(CH3) P, J=12.8,12.9Hz), 4.76-4.88 (m, 2H,CH2), 6.54 (d, 1H, PCH, J=2.5Hz), 6.87 (t, 1H, Ar-H, J=8.8Hz), 7.01-7.04 (m, 1H, Ar- H), 7.13 (dd, 1H, Ar-H, J=2.4,2.4Hz), 7.31 (dd, 1H, Ar-H, J=2.0,1.8Hz), 7.40-7.47 (m, 2H,Ar-H)；
13C NMR(100MHz,CDCl3):166.89,153.51,151.02,144.12,135.66,133.54, 130.10,129.50,129.34,127.85,124.30,117.43,116.89,70.97,70.19,66.46,14.40, 14.10,13.72,13.40；
31P NMR(160MHz,CDCl3):41.46；
ESI-MS m/z:461.2(M+Na)+；
The structural formula of compound 5 is as follows:
The preparation method of compound 5 is identical as the preparation method of compound 1, is white solid derivative, yield 76%； M.p.42~43C；Elemental analysis/%: calculated value: C, 53.88；H,4.77；Measured value: C, 54.08；H,4.61.
1H NMR(400MHz,CDCl3):1.43(dd,6H,2(CH3) P, J=12.8,8.8Hz), 2.35 (s, 3H, Ar- CH3),4.78-4.88(m,2H,CH2), 6.13 (d, 1H, PCH, J=6.8Hz), 6.78 (d, 1H, Ar-H, J=8.8Hz), 7.14-7.22 (m, 5H, Ar-H), 7.42 (d, 1H, Ar-H, J=2.4Hz)；
13C NMR(100MHz,CDCl3):166.41,151.52,138.38,129.71,128.98,127.20, 126.51,126.39,123.30,113.92,74.63,73.82,65.52,20.66,13.19,12.72,12.50,12.04；
31P NMR(160MHz,CDCl3):41.68；
ESI-MS m/z:423.2(M+Na)+；
The structural formula of compound 6 is as follows:
The preparation method of compound 6 is identical as the preparation method of compound 1, be white solid, yield 68%, m.p.129-131℃；Elemental analysis/%: calculated value: C, 58.94；H,5.50；Measured value: C, 58.72；H,5.74.
1H NMR(400MHz,CDCl3):1.41(dd,6H,2(CH3) P, J=12.8,8.8Hz), 2.35 (s, 3H, Ar- CH3),4.70-4.81(m,2H,CH2), 6.11 (d, 1H, PCH, J=6.1Hz), 6.83 (d, 2H, Ar-H, J=8.9Hz), 7.17-7.25(m,6H,Ar-H)；
13C NMR(100MHz,CDCl3):167.44,167.38,156.01,138.91,129.41,126.90, 126.80,115.75,74.98,74.17,65.25,21.04,13.73,13.32,13.04,12.63；
31P NMR(160MHz,CDCl3):41.10；
ESI-MS m/z:389.2(M+Na)+；
The structural formula of compound 7 is as follows:
The preparation method of compound 7 is identical as the preparation method of compound 1, is white oil, yield 69%, refractive index It is 1.5043；Elemental analysis/%: calculated value: C, 59.93；H,5.82；Measured value: C, 59.79；H,5.72.
1H NMR(400MHz,CDCl3):1.42(t,6H,2(CH3) P, J=12.6Hz), 2.27 (s, 3H, Ar-CH3), 2.35(s,3H,4-CH3-Ph),4.73-4.83(m,2H,CH2), 6.13 (d, 1H, PCH, J=6.1Hz), 6.61 (d, 1H, Ar- H, J=8.7Hz), 7.06 (dd, 1H, Ar-H, J=8.6,2.5Hz), 7.15-7.22 (m, 5H, Ar-H)；
13C NMR(100MHz,CDCl3):167.45,154.21,139.02,130.80,129.46,129.24, 128.90,126.87,126.32,126.13,111.86,74.77,73.96,65.54,65.40,21.10,16.05,13.48, 13.11,12.80,12.42；
31P NMR(160MHz,CDCl3):43.51；
ESI-MS m/z:403.3(M+Na)+；
The structural formula of compound 8 is as follows:
The preparation method of compound 8 is identical as the preparation method of compound 1, is white oil, yield 80%, refractive index It is 1.4981；Elemental analysis/%: calculated value: C, 58.94；H,5.50；Measured value: C, 58.69；H,5.31.
1H NMR(400MHz,CDCl3):1.45(dd,6H,2(CH3) P, J=13.0,12.9Hz), 2.34 (s, 3H, 4- CH3-Ph),4.82-4.96(m,2H,CH2), 6.21 (d, 1H, PCH, J=7.9Hz), 6.88 (d, 1H, Ar-H, J=8.3Hz), 6.97 (t, 1H, Ar-H, J=7.2Hz), 7.15-7.24 (m, 5H, Ar-H), 7.41 (dd, 1H, Ar-H, J=7.9,1.4Hz)；
13C NMR(100MHz,CDCl3):167.05,153.03,139.00,130.64,129.49,129.08, 127.83,126.77,122.91,122.68,113.34,77.32,77.00,76.68,74.59,73.77,65.73,21.10, 13.18,12.72,12.50,12.03；
31P NMR(160MHz,CDCl3):46.34；
ESI-MS m/z:389.2(M+Na)+；
The structural formula of compound 9 is as follows:
The preparation method of compound 9 is identical as the preparation method of compound 1, is white oil, yield 76%, refractive index It is 1.5133；Elemental analysis/%: calculated value: C, 56.19；H,4.98；；Measured value: C, 56.09；H,4.90.
1H NMR(400MHz,CDCl3):1.45(dd,6H,2(CH3) P, J=13.0,12.9Hz), 2.35 (s, 3H, 4- CH3-Ph),4.78-4.92(m,2H,CH2), 6.22 (d, 1H, PCH, J=7.3Hz), 6.85-6.94 (m, 2H, Ar-H), 7.15- 7.23(m,5H,Ar-H)；
13C NMR(100MHz,CDCl3):166.97,158.30,155.87,149.69,139.11,129.50, 129.06,126.84,117.89,117.63,114.74,114.27,74.69,73.87,66.46,21.05,13.03, 12.94,12.35,12.25；
31P NMR(160MHz,CDCl3):46.46；
ESI-MS m/z:407.2(M+Na)+；
The structural formula of compound 10 are as follows:
The preparation method of compound 10 is identical as the preparation method of compound 1, is white solid, yield 79%； M.p.67~68C.Elemental analysis/%: calculated value: C, 44.77；H,3.31；Measured value: C, 44.46；H,3.13.
1H NMR(400MHz,CDCl3):1.47(dd,6H,2(CH3) P, J=12.9,12.9Hz), 4.85 (d, 2H, CH2, ), J=2.9Hz 6.12 (d, 1H, PCH, J=7.7Hz), 6.12 (d, 1H, Ar-H, J=8.8Hz), 7.20 (dd, 2H, Ar-H, J =2.6,2.7H), 7.39 (s, 1H, Ar-H), 7.45 (t, 2H, Ar-H, J=5.7Hz)；
13C NMR(100MHz,CDCl3):166.40,151.54,133.02,132.85,132.38,130.51, 130.20,128.25,127.51,127.18,125.98,123.65,113.94,73.26,72.48,65.72,13.75, 13.07,12.60,11.92；
31P NMR(160MHz,CDCl3):42.73；
ESI-MS m/z:477.2(M+Na)+；
The structural formula of compound 11 is as follows:
The preparation method of compound 11 is identical as the preparation method of compound 1, is white solid, yield 81%； M.p.86~88C.Elemental analysis/%: calculated value: C, 49.62；H,4.16；Measured value: C, 49.87；H,4.02.
1H NMR(400MHz,CDCl3):1.42(dd,6H,2(CH3) P, J=12.9,12.9Hz), 2.28 (s, 3H, Ar- CH3),4.80(d,2H,CH2, J=3.0Hz), 6.09 (d, 1H, PCH, J=7.2Hz), 6.61 (d, 1H, Ar-H, J=8.7Hz), 7.09 (d, 1H, Ar-H, J=8.0Hz), 7.19 (d, 2H, Ar-H, J=10.7H), 7.40 (s, 1H, Ar-H), 7.45 (d, 1H, Ar-H, J=8.3Hz)；13C NMR(100MHz,CDCl3):167.31,153.96,133.17,133.01,132.55, 130.92,130.65,128.79,128.41,126.44,126.32,126.20,111.51,73.25,72.46,65.18, 15.98,14.02,13.34,12.80,12.11；31P NMR(160MHz,CDCl3):41.91；
ESI-MS m/z:457.2(M+Na)+；
The structural formula of compound 12 is as follows:
The preparation method of compound 12 is identical as the preparation method of compound 1, is white solid, yield 82%； M.p.42~43C.Elemental analysis/%: calculated value: C, 49.62；H,4.16；Measured value: C, 48.36；H,4.06.
1H NMR(400MHz,CDCl3):1.43(dd,6H,2(CH3) P, J=12.9,12.9Hz), 4.79-4.80 (d, 2H,CH2, J=3.0Hz), 6.08 (d, 1H, PCH, J=6.8Hz), 6.84 (s, 1H, Ar-H), 6.86 (d, 1H, Ar-H, J= 1.7Hz), 7.20 (dd, 1H, Ar-H, J=1.6,1.6H), 7.26 (s, 1H, Ar-H), 7.28 (d, 1H, Ar-H, J=1.8Hz), 7.39 (d, 1H, Ar-H, J=1.6Hz), 7.46 (d, 1H, Ar-H, J=8.3Hz)；
13C NMR(100MHz,CDCl3):167.17,155.80,133.19,132.96,132.44,130.62, 129.49,128.47,126.98,126.21,115.60,73.29,72.52,65.08,13.87,13.18,12.84,12.16；
31P NMR(160MHz,CDCl3):42.42；
ESI-MS m/z:421.2(M+H)+；
The structural formula of compound 13 is as follows:
The preparation method of compound 13 is identical as the preparation method of compound 1, is white solid, yield 85%； M.p.65~66C.Elemental analysis/%: calculated value: C, 46.44；H,3.44；Measured value: C, 46.73；H,3.30.
1H NMR(400MHz,CDCl3):1.51(t,6H,2(CH3) P, J=11.6Hz), 4.75-4.87 (m, 2H, CH2), 6.64 (d, 1H, PCH, J=5.8Hz), 6.86 (t, 1H, Ar-H, J=8.7Hz), 7.00-7.05 (m, 2H, Ar-H), 7.12 (d, 1H, Ar-H, J=10.9Hz), 7.21 (s, 1H, Ar-H), 7.37 (d, 1H, Ar-H, J=4.9Hz)；
31P NMR(160MHz,CDCl3):41.84；
ESI-MS m/z:461.2(M+Na)+；
The structural formula of compound 14 is as follows:
The preparation method of compound 14 is identical as the preparation method of compound 1, is yellow oily, yield 69%；Refraction Rate is 1.4987.Elemental analysis/%: calculated value: C, 47.77；H,4.01；Measured value: C, 47.70；H,4.06.
1H NMR(400MHz,CDCl3):1.57(t,6H,2(CH3) P, J=13.2,8.4Hz), 4.75-4.84 (m, 2H, CH2), 6.26 (d, 1H, PCH, J=9.8Hz), 6.42 (d, 1H, furan-H, J=1.7Hz), 6.58 (s, 2H, furan-H), 6.76 (d, 1H, Ar-H, J=8.9Hz), 7.14 (dd, 1H, Ar-H, J=2.5,2.4Hz), 7.39 (d, 1H, Ar-H, J= 2.5Hz),7.45(s,1H,furan-H)；
13C NMR(100MHz,CDCl3):166.68,151.71,145.37,143.93,129.99,127.40, 126.86,123.65,114.23,112.62,110.85,68.11,67.29,65.68,13.99,13.30；
31P NMR(160MHz,CDCl3):40.38；
ESI-MS m/z:399.2(M+Na)+；
The structural formula of compound 15 is as follows:
The preparation method of compound 15 is identical as the preparation method of compound 1, is white solid, yield 77%； M.p.75~76C.Elemental analysis/%: calculated value: C, 53.87；H,5.09；Measured value: C, 53.58；H,5.07.
1H NMR(400MHz,CDCl3):1.54(dd,6H,2(CH3) P, J=6.6,6.4Hz), 2.25 (s, 3H, Ar- CH3),4.68-4.78(m,2H,CH2), 6.25 (d, 1H, PCH, J=9.6Hz), 6.41 (d, 1H, furan-H, J=1.8Hz), 6.57 (s, 2H, furan-H), 6.59 (s, 1H, Ar-H), 7.05 (dd, 1H, Ar-H, J=2.3,2.2Hz), 7.13 (s, 1H, Ar-H),7.45(s,1H,furan-H)；
13C NMR(100MHz,CDCl3):167.47,167.41,154.15,145.66,143.99,130.71, 128.92,126.22,112.72,111.85,110.95,68.11,67.28,65.22,15.94,14.29,14.18,13.60, 13.49；
31P NMR(160MHz,CDCl3):42.05；
ESI-MS m/z:379.0(M+Na)+；
The structural formula of compound 16 is as follows:
The preparation method of compound 16 is identical as the preparation method of compound 1, is yellow oily, yield 71%；Refraction Rate is 1.5041.Elemental analysis/%: calculated value: C, 52.57；H,4.71；Measured value: C, 52.45；H,4.50.
1H NMR(400MHz,CDCl3):1.52(dd,6H,2(CH3) P, J=8.4,8.6Hz), 4.64-4.74 (m, 2H, CH2), 6.24 (d, 1H, PCH, J=9.5Hz), 6.39 (s, 1H, furan-H), 6.55 (s, 1H, furan-H), 6.77-6.82 (m,2H,Ar-H),7.18-7.22(m,2H,Ar-H),7.42(s,1H,furan-H)；
13C NMR(100MHz,CDCl3):167.26,155.89,145.53,143.93,129.28,126.64, 115.71,112.67,110.90,68.12,67.29,65.01,14.20,13.53；
31P NMR(160MHz,CDCl3):42.25；
ESI-MS m/z:365.2(M+Na)+；
The structural formula of compound 17 is as follows:
The preparation method of compound 17 is identical as the preparation method of compound 1, is yellow oily, yield 65%；Refraction Rate is 1.4933.Elemental analysis/%: calculated value: C, 49.95；H,4.19；Measured value: C, 49.80；H,4.24.
1H NMR(400MHz,CDCl3):1.56(dd,6H,2(CH3) P, J=2.9,12.3Hz), 4.74-4.84 (m, 2H, CH2), 6.27 (d, 1H, PCH, J=9.6Hz), 6.42 (d, 1H, furan-H, J=1.7Hz), 6.58 (s, 1H, furan-H), 6.86 (t, 1H, Ar-H, J=8.8Hz), 7.02 (dd, 1H, Ar-H, J=1.5,1.5Hz), 7.12 (dd, 1H, Ar-H, J= 2.5,2.4Hz),7.45(s,1H,furan-H)；
13C NMR(100MHz,CDCl3):166.91,153.39,150.90,145.50,143.94,126.84, 124.17,117.23,117.01,116.58,112.63,110.88,68.19,67.37,66.24,14.19,14.13, 13.50,13.44；
31P NMR(160MHz,CDCl3):42.25；
ESI-MS m/z:383.3(M+Na)+；
The structural formula of compound 18 is as follows:
The preparation method of compound 18 is identical as the preparation method of compound 1, is white oil, yield 65%；Refraction Rate is 1.5100.Elemental analysis/%: calculated value: C, 44.33；H,4.65；Measured value: C, 44.63；H,4.54.
1H NMR(400MHz,CDCl3):1.12-1.22(m,6H,2(CH3)P),1.53(dd,3H,PCH3, J=7.1, 7.1Hz),4.75(d,2H,COCH2, J=3.3Hz), 5.37-5.43 (m, 1H, PCH), 6.79 (d, 1H, Ar-H, J= 8.8Hz), 7.19 (dd, 1H, Ar-H, J=8.8,2.5Hz), 7.41 (d, 1H, Ar-H, J=2.5Hz)；
13C NMR(100MHz,CDCl3):167.02,151.85,130.29,127.50,127.18,123.89, 114.11,67.28,66.50,66.02,18.11,17.61,17.46,16.96,13.84；
31P NMR(160MHz,CDCl3):49.53；
ESI-MS m/z:347.3(M+Na)+；
The structural formula of compound 19 is as follows:
The preparation method of compound 19 is identical as the preparation method of compound 1, is white oil object, yield 82%；Folding Penetrating rate is 1.4973.
Elemental analysis/%: calculated value: C, 51.24；H,5.95；Measured value: C, 51.47；H,5.77；
1H NMR(400MHz,CDCl3):δ(ppm)1.47(dd,6H,2(CH3) P, J=12.7,12.7Hz), 1.55 (dd, 3H,CH3, J=7.2,7.2Hz), 2.31 (s, 3H, CH3),4.58(s,2H,CH2), 6.35 (d, 1H, PCH, J=5.4Hz), 6.93 (d, 1H, Ar-H, J=8.8Hz), 7.35 (dd, 1H, Ar-H, J=8.6 2.6Hz), 7.48 (d, 1H, Ar-H, J= 2.5Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)167.59,152.37,130.04,127.85,126.67,123.55, 114.31,68.97,66.25,66.01,15.94,15.69,14.39,14.20,13.29,13.13；
31P NMR(160MHz,CDCl3):δ(ppm)49.33
The structural formula of compound 20 is as follows:
The preparation method of compound 20 is identical as the preparation method of compound 1, is white oil object, yield 67%；Folding Penetrating rate is 1.4997.Elemental analysis/%: calculated value: C, 49.58；H,5.55；Measured value: C, 49.89；H,5.22；
1H NMR(400MHz,CDCl3):1.52(dd,6H,2(CH3) P, J=12.7,12.7Hz), 1.67 (dd, 3H, CH3, J=7.2,7.2Hz), 4.66 (s, 2H, CH2),6.83-6.89(m,2H,Ar-H),7.28-7.37(m,2H,Ar-H),
13C NMR(100MHz,CDCl3):δ(ppm)166.89,153.37,130.44,126.57,114.39,68.79, 66.75,66.13,15.89,14.19,14.06,13.09,12.99.
31P NMR(160MHz,CDCl3):δ(ppm)49.88
The structural formula of compound 21 is as follows:
The preparation method of compound 21: by 5mmol Alpha-hydroxy phosphine oxide, 10mmol pyridine and 10mL DMF, ice salt bath are cold But to 0 DEG C hereinafter, 10mmol 2, the 10mL DMF solution of 4- Dichlorophenoxy chloroacetic chloride is slowly added dropwise.Drop finishes, and removes ice bath, allows Reaction solution is gradually increased to room temperature, and 110 DEG C the reaction was continued.It is tracked and is reacted with lamellae (TLC), about 1h reaction is completed.It has reacted Finish, 20mL methylene chloride is added, is washed with saturated potassium carbonate, dilute hydrochloric acid and sodium-chloride water solution, until solution is in neutrality.Again with suitable The methylene chloride aqueous phase extracted of amount twice, merges organic phase.It is dried overnight with anhydrous sodium sulfate, after filtering out anhydrous sodium sulfate, filter Liquid sloughs solvent up to crude product.It is eluted through silica gel (G type) column chromatographic grade, (eluant ethyl acetate: petroleum ether volume ratio=1: 2) sterling is obtained.Gained sterling is white oil object, yield 78%；Refractive index is 1.4999.Elemental analysis/%: calculated value: C, 46.69；H,4.90；Measured value: C, 46.58；H,5.03；
1H NMR(400MHz,CDCl3):1.40(dd,6H,2(CH3) P, J=12.7,12.7Hz), 1.65 (dd, 3H, CH3, J=7.2,7.2Hz), 4.52 (s, 2H, CH2), 6.47 (d, 1H, PCH, J=5.4Hz), 7.09 (d, 1H, Ar-H, J= 8.8Hz), 7.45 (dd, 1H, Ar-H, J=1.5,1.4Hz), 7.58 (d, 1H, Ar-H, J=2.5,2.3Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)166.73,153.15,131.35,127.45,127.23,124.54, 114.36,68.77,66.98,66.43,15.65,14.33,14.10,13.23,13.14；
31P NMR(160MHz,CDCl3):δ(ppm)49.03
The structural formula of compound 22 is as follows:
The preparation method of compound 22 is identical as the preparation method of compound 21, is white oil object, yield 66%；Folding Penetrating rate is 1.5025.Elemental analysis/%: calculated value: C, 46.04；H,5.05；Measured value: C, 46.57；H,4.98；
1H NMR(400MHz,CDCl3):δ(ppm)1.06(s,3H,CH2CH3),1.49(dd,6H,2(CH3) P, J= 12.8,12.7Hz),1.77(dd,2H,CH2, J=7.2,7.1Hz), 4.56 (s, 2H, CH2), 6.35 (d, 1H, PCH, J= 5.2Hz), 6.92 (d, 1H, Ar-H, J=8.6Hz), 7.24 (dd, 1H, Ar-H, J=8.8 2.6Hz), 7.43 (d, 1H, Ar-H, J=2.3Hz)
13C NMR(100MHz,CDCl3):δ(ppm)167.53,152.49,130.24,127.76,126.45,123.33, 114.46,69.25,67.33,66.82,18.89,14.37,14.30,14.02,13.5,10.65
167.63,152.29,130.14,127.55,126.81,123.84,114.61,68.47,66.88,66.32, 15.89,14.19,14.13,13.50,13.4；
31P NMR(160MHz,CDCl3):δ(ppm)42.35
The structural formula of compound 23 is as follows:
The preparation method of compound 23 is identical as the preparation method of compound 21, is white oil object, yield 59%；Folding Penetrating rate is 1.5033.Elemental analysis/%: calculated value: C, 52.76；H,6.33；Measured value: C, 52.56；H,6.73；
1H NMR(400MHz,CDCl3):δ(ppm)1.17(t,3H,CH2CH3),1.52(dd,6H,2(CH3) P, J= 12.8,12.7Hz),1.66(dd,2H,CH2, J=7.4,7.2Hz), 2.37 (s, 3H, CH3),4.50(s,2H,CH2),6.27 (d, 1H, PCH, J=5.3Hz), 6.99 (d, 1H, Ar-H, J=8.8Hz), 7.25 (dd, 1H, Ar-H, J=8.62.6Hz), 7.5 (d, 1H, Ar-H, J=2.5Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)166.43,152.59,130.25,127.44,126.05,123.73, 114.76,68.25,67.55,66.58,18.99,14.99,14.25,14.20,14.0,14.05,11.75
31P NMR(160MHz,CDCl3):δ(ppm)42.89
The structural formula of compound 24 is as follows:
The preparation method of compound 24 is identical as the preparation method of compound 21, is white oil object, yield 64%；Folding Penetrating rate is 1.5010.Elemental analysis/%: calculated value: C, 51.24；H,5.95；Measured value: C, 51.79；H,6.23；
1H NMR(400MHz,CDCl3):δ(ppm)1.06(t,3H,CH2CH3),1.61(dd,6H,2(CH3) P, J= 12.8,12.7Hz),1.71(dd,2H,CH2, J=7.44,7.2Hz), 4.66 (s, 2H, CH2),6.93-6.98(m,2H,Ar- H),7.38-7.51(m,2H,Ar-H),
13C NMR(100MHz,CDCl3):δ(ppm)166.45,153.59,13124,128.37,117.46,69.73, 67.53,66.38,19.89,13.97,13.90,13.79,13.65,11.35；
31P NMR(160MHz,CDCl3):δ(ppm)43.50
The structural formula of compound 25 is as follows:
The preparation method of compound 25 is identical as the preparation method of compound 21, is white oil object, yield 72%；Folding Penetrating rate is 1.5073.Elemental analysis/%: calculated value: C, 48.39；H,5.31；Measured value: C, 48.02；H,5.77；
1H NMR(400MHz,CDCl3):δ(ppm)1.01(t,3H,CH2CH3),1.38(dd,
6H,2(CH3) P, J=12.8,12.7Hz), 1.70 (dd, 2H, CH2, J=7.4,7.2Hz), 4.55 (s, 2H, CH2),6.86(d,
1H, PCH, J=5.4Hz), 7.11 (d, 1H, Ar-H, J=8.9Hz), 7.54 (dd, 1H, Ar-H, J=1.5, 1.4Hz), 7.68 (d, 1H, Ar-H, J=2.5,2.3Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)166.34,154.09,131.04,127.01,126.95,122.33, 115.36,69.25,67.33,66.82,17.89,14.57,14.30,13.89,13.75,11.25；
31P NMR(160MHz,CDCl3):δ(ppm)43.08
The structural formula of compound 26 is as follows:
The preparation method of compound 26 is identical as the preparation method of compound 21, is white oil object, yield 77%；Folding Penetrating rate is 1.4903.Elemental analysis/%: calculated value: C, 47.61；H,5.42；Measured value: C, 45.99；H,5.13；
1H NMR(400MHz,CDCl3):δ(ppm)1.01(t,3H,CH2CH3),1.45(dd,6H,2(CH3) P, J= 12.8,12.7Hz),1.66(t,2H,CH2CH3),2.01(dd,2H,CH2, J=7.4,7.3Hz), 4.60 (s, 2H, CH2), 6.54 (d, 1H, PCH, J=5.6Hz), 6.90 (d, 1H, Ar-H, J=8.8Hz), 7.18 (dd, 1H, Ar-H, J= ), 8.82.6Hz 7.39 (d, 1H, Ar-H, J=2.3Hz)
13C NMR(100MHz,CDCl3):δ(ppm)166.43,151.59,130.26,127.67 126.54,123.29, 114.87,68.85,67.34,66.89,27.89,18.58,13.87,13.80,13.12,13.05,12.65；
31P NMR(160MHz,CDCl3):δ(ppm)48.44
The structural formula of compound 27 is as follows:
The preparation method of compound 27 is identical as the preparation method of compound 21, is white oil object, yield 80%；Folding Penetrating rate is 1.4917.
Elemental analysis/%: calculated value: C, 54.14；H,6.66；Measured value: C, 54.46；H,6.88；
1H NMR(400MHz,CDCl3):δ(ppm)1.03(t,3H,CH2CH3),1.46(dd,6H,2(CH3) P, J= 12.8,12.7Hz),1.72(t,2H,CH2CH3),2.06(dd,2H,CH2, J=7.4,7.3Hz), 4.53 (s, 2H, CH2), 6.39 (d, 1H, PCH, J=5.7Hz), 6.98 (d, 1H, Ar-H, J=8.8Hz), 7.36 (dd, 1H, Ar-H, J= ), 8.62.6Hz 7.56 (d, 1H, Ar-H, J=2.5Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)167.35,151.49,132.24,127.55,126.05,123.73, 115.46,69.55,67.53,66.92,27.19,18.99,16.57,14.47,14.33,14.01,13.85,10.55
31P NMR(160MHz,CDCl3):δ(ppm)47.67
The structural formula of compound 28 is as follows:
The preparation method of compound 28 is identical as the preparation method of compound 21, is white oil object, yield 55%；Folding Penetrating rate is 1.4957.Elemental analysis/%: calculated value: C, 52.76；H, 6.33 measured values: C, 52.54；H,6.55；
1H NMR(400MHz,CDCl3):0.97(t,3H,CH2CH3),1.58(dd,6H,2(CH3) P, J=12.8, 12.7Hz),1.76(t,2H,CH2CH3),1.97(dd,2H,CH2, J=7.4,7.3Hz), 6.97-7.09 (m, 2H, Ar-H), 7.40-7.47(m,2H,Ar-H),
13C NMR(100MHz,CDCl3):δ(ppm)167.78,150.34,130.24,127.53,114.36,69.55, 67.73,66.28,28.39,19.19,14.55,14.43,13.99,13.85,13.15
31P NMR(160MHz,CDCl3):δ(ppm)48.65
The structural formula of compound 29 is as follows:
The preparation method of compound 29 is identical as the preparation method of compound 21, is white oil object, yield 60%；Folding Penetrating rate is 1.4889.
Elemental analysis/%: calculated value: C, 49.94；H,5.69；Measured value: C, 49.47；H,5.88；
1H NMR(400MHz,CDCl3):δ(ppm)1.09(t,3H,CH2CH3),1.49(dd,6H,2(CH3) P, J= 12.7,12.7Hz),1.69(t,2H,CH2CH3),2.08(dd,2H,CH2, J=7.4,7.3Hz), 4.62 (s, 2H, CH2), 6.53 (d, 1H, PCH, J=5.6Hz), 7.12 (d, 1H, Ar-H, J=8.8Hz), 7.43 (dd, 1H, Ar-H, J=1.5, 1.4Hz), 7.55 (d, 1H, Ar-H, J=2.5,2.3Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)166.67,151.49,131.24,126.67,126.07,123.13, 114.33,69.95,67.37,66.89,26.89,18.69,14.33,14.28,14.09,13.95,11.65
31P NMR(160MHz,CDCl3):δ(ppm)47.99
The structural formula of compound 30 is as follows:
The preparation method of compound 30 is identical as the preparation method of compound 21, is yellow oil, yield 80%；Folding Penetrating rate is 1.5381.
Elemental analysis/%: calculated value: C, 48.43；H,3.83；Measured value: C, 48.87；H,4.23；
1H NMR(400MHz,CDCl3):δ(ppm)1.39(dd,6H,2(CH3) P, J=12.8,12.7Hz), 4.67 (s, 2H,CH2), 6.35 (d, 1H, PCH, J=5.4Hz), 6.67 (d, 1H, Ar-H, J=8.7Hz), 7.16-7.28 (m, 5H, Ar- ), H 7.47 (d, 1H, Ar-H, J=2.4Hz)；
13C NMR(100MHz,CDCl3):δ(ppm)166.89,151.25,138.83,129.77,128.88,127.45, 126.55,126.69,123.31,113.89,74.37,73.88,65.35,13.23,12.73,12.05,12.01；
31P NMR(160MHz,CDCl3):δ(ppm)42.65
The structural formula of compound 31 is as follows:
The preparation method of compound 31: by 5mmol Alpha-hydroxy phosphine oxide, 6mmol triethylamine and 10mL ethyl acetate, cryosel Bath is cooled to 0 DEG C hereinafter, the 10mL ethyl acetate solution of 6mmol 2- first -4- chlorine phenoxyacetyl chloride is slowly added dropwise.Drop finishes, and removes Ice bath allows reaction solution to be gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), about 6h reaction is completed.End of reaction is directly used 10mL washed reaction system, then ethyl acetate aqueous phase extracted twice, merge organic phase.It is dried overnight with anhydrous sodium sulfate, After filtering out anhydrous sodium sulfate, filtrate sloughs solvent up to crude product.It is eluted through silica gel (G type) column chromatographic grade, (eluant, eluent acetic acid second Ester: petroleum ether volume ratio=1:2) sterling is obtained, products obtained therefrom is pale yellowish oil, yield 83%；Refractive index is 1.5407.
Elemental analysis/%: calculated value: C, 53.89；H,4.77；Measured value: C, 53.67；H,4.99；
1H NMR(400MHz,CDCl3):δ(ppm)1.11(s,3H,CH3),1.40(dd,6H,2(CH3) P, J=12.8, 12.7Hz),4.61(s,2H,CH2), 6.40 (d, 1H, PCH, J=5.3Hz), 6.61 (d, 1H, Ar-H, J=8.7Hz), 7.06 (dd, 1H, Ar-H, J=8.6,2.5Hz), 7.15-7.22 (m, 5H, Ar-H)；
13C NMR(100MHz,CDCl3):δ(ppm)166.43,153.52,139.70,129.70,128.67,127.20, 126.35,126.17,123.20,113.55,74.03,73.22,65.42,16.77,13.89,13.55,12.52,12.24；
31P NMR(160MHz,CDCl3):δ(ppm)42.99
The structural formula of compound 32 is as follows:
The preparation method of compound 32 is identical as the preparation method of compound 31, is yellow oil, yield 75%；Folding Penetrating rate is 1.5389.
Elemental analysis/%: calculated value: C, 52.74；H,4.43；Measured value: C, 52.37；H,4.09；
1H NMR(400MHz,CDCl3):δ(ppm)1.46(dd,6H,2(CH3) P, J=12.7,12.7Hz), 4.45 (s, 2H,CH2), 6.67 (d, 1H, PCH, J=5.3Hz), 6.83-6.89 (m, 4H, Ar-H), 7.28-7.37 (m, 5H, Ar-H),
13C NMR(100MHz,CDCl3):δ(ppm)167.31,150.50,137.35,129.01,128.78,127.29, 126.03,123.00,113.78,74.36,73.83,65.02,13.33,12.92,12.61,12.33；
31P NMR(160MHz,CDCl3):δ(ppm)41.89
The structural formula of compound 33 is as follows:
The preparation method of compound 33 is identical as the preparation method of compound 31, is white oil object, yield 68%；Folding Penetrating rate is 1.5366.
Elemental analysis/%: calculated value: C, 50.39；H,3.98；Measured value: C, 51.18；H,4.09；
1H NMR(400MHz,CDCl3):δ(ppm)1.36(dd,6H,2(CH3) P, J=12.8,12.7Hz), 4.55 (s, 2H,CH2), 6.66 (d, 1H, PCH, J=5.4Hz), 6.87-6.96 (m, 2H, Ar-H), 7.25-7.37 (m, 5H, Ar-H)；
13C NMR(100MHz,CDCl3):δ(ppm)166.89,150.50,138.30,129.70,128.90,127.10, 126.50,126.49,123.30,113.95,74.66,73.72,65.52,13.66,12.78,12.56,12.05；
31P NMR(160MHz,CDCl3):δ(ppm)42.33
34 structural formula of compound is as follows:
The preparation method of compound 34 is identical as the preparation method of compound 31, is white oil object, yield 72%；Folding Penetrating rate is 1.5205.
Elemental analysis/%: calculated value: C, 52.74；H,4.43；Measured value: C, 53.02；H,4.59；
1H NMR(400MHz,CDCl3):δ(ppm)1.49(dd,6H,2(CH3) P, J=12.6,12.6Hz), 4.56 (s, 2H,CH2), 6.34 (d, 1H, PCH, J=5.3Hz), 6.77 (d, 1H, Ar-H, J=8.7Hz), 7.18-7.30 (m, 6H, Ar- ), H 7.49 (d, 1H, Ar-H, J=2.5Hz)
13C NMR(100MHz,CDCl3):δ(ppm)168.41,152.50,137.37,128.71,127.98,127.22, 126.41,126.59,123.37,113.99,74.53,73.84,65.62,13.16,12.62,12.53,11.97；
31P NMR(160MHz,CDCl3):δ(ppm)40.98
The structural formula of compound 35 is as follows:
The preparation method of compound 35 is identical as the preparation method of compound 31, is white oil object, yield 75%；Folding Penetrating rate is 1.5223.
Elemental analysis/%: calculated value: C, 58.95；H,5.50；Measured value: C, 58.54；H,5.25；
1H NMR(400MHz,CDCl3):δ(ppm)1.13(s,3H,CH3),1.45(dd,6H,2(CH3) P, J=12.6, 12.6Hz),4.60(s,2H,CH2), 6.57 (d, 1H, PCH, J=5.3Hz), 6.76 (d, 1H, Ar-H, J=8.7Hz), 7.06 (dd, 1H, Ar-H, J=8.6,2.5Hz), 7.35-7.52 (m, 5H, Ar-H)；
13C NMR(100MHz,CDCl3):δ(ppm)166.35,150.35,138.83,129.50,128.90,128.24, 126.67,126.02,123.03,113.39,75.63,74.82,66.52,15.33,13.88,12.92,12.70,12.34；
31P NMR(160MHz,CDCl3):δ(ppm)40.63
The structural formula of compound 36 is as follows:
The preparation method of compound 36 is identical as the preparation method of compound 31, is white oil object, yield 80%；Folding Penetrating rate is 1.5273.
Elemental analysis/%: calculated value: C, 57.88；H,5.14；Measured value: C, 57.69；H,5.22；
1H NMR(400MHz,CDCl3):δ(ppm)1.35(dd,6H,2(CH3) P, J=12.6,12.6Hz), 4.51 (s, 2H,CH2), 6.77 (d, 1H, PCH, J=5.2Hz), 6.93-7.00 (m, 5H, Ar-H), 7.35-7.47 (m, 4H, Ar-H),
13C NMR(100MHz,CDCl3):δ(ppm)166.55,151.92,138.08,129.81,128.09,127.70, 126.09,123.55,113.82,74.53,73.02,65.50,13.20,12.70,12.40,12.01；
31P NMR(160MHz,CDCl3):δ(ppm)41.04
The structural formula of compound 37 is as follows:
The preparation method of compound 37 is identical as the preparation method of compound 31, is white oil object, yield 78%；Folding Penetrating rate is 1.5199.
Elemental analysis/%: calculated value: C, 55.08；H,4.62；Measured value: C, 54.93；H,4.88；
1H NMR(400MHz,CDCl3):δ(ppm)1.47(dd,6H,2(CH3) P, J=12.6,12.6Hz), 4.56 (s, 2H,CH2), 6.72 (d, 1H, PCH, J=5.2Hz), 6.78-6.92 (m, 2H, Ar-H), 7.37-7.50 (m, 5H, Ar-H)；
13C NMR(100MHz,CDCl3):δ(ppm)167.21,152.02,137.98,129.91,128.89,127.30, 126.53,126.38,123.20,114.23,75.33,73.88,65.25,13.55,12.74,12.51,12.20；
31P NMR(160MHz,CDCl3):δ(ppm)40.21
The structural formula of compound 38 is as follows:
The preparation method of compound 38 is identical as the preparation method of compound 31, yield 79%；Elemental analysis/%: meter Calculation value: C, 54.14；H,6.66；Measured value: C, 54.18；H,6.88；ESI-MS m/z:333.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)40.51
The structural formula of compound 39 is as follows:
The preparation method of compound 39 is identical as the preparation method of compound 31, yield 76%；Elemental analysis/%: meter Calculation value: C, 52.76；H,6.32；Measured value: C, 52.77；H,6.38；ESI-MS m/z:319.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)41.52
The structural formula of compound 40 is as follows:
The preparation method of compound 40 is identical as the preparation method of compound 31, yield 61%；Elemental analysis/%: meter Calculation value: C, 49.94；H,5.69；Measured value: C, 49.99；H,5.78；ESI-MS m/z:337.2[M+1]+；
31P NMR(160MHz,CDCl3): the structural formula of 41.66 compound 41 of δ (ppm) is as follows:
The preparation method of compound 41: by 5mmol Alpha-hydroxy phosphine oxide, 6mmol triethylamine and 10mL methylene chloride, cryosel Bath is cooled to 0 DEG C hereinafter, 6mmol 2, the 10mL dichloromethane solution of 4- Dichlorophenoxy chloroacetic chloride is slowly added dropwise.Drop finishes, and removes Ice bath allows reaction solution to be gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), about 6h reaction is completed.End of reaction is directly used 10mL washed reaction system, then water phase is extracted with dichloromethane twice, merge organic phase.It is dried overnight, is filtered with anhydrous sodium sulfate Out after anhydrous sodium sulfate, filtrate sloughs solvent up to crude product.It is eluted through silica gel (G type) column chromatographic grade, (eluant, eluent acetic acid second Ester: petroleum ether volume ratio=1:2) obtain sterling.Yield is 89%；Elemental analysis/%: calculated value: C, 47.61；H,5.42；Actual measurement Value: C, 47.69；H,5.48；ESI-MS m/z:353.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)41.54
The structural formula of compound 42 is as follows:
The preparation method of compound 42 is identical as the preparation method of compound 41, yield 56%；Elemental analysis/%: meter Calculation value: C, 55.41；H,6.98；Measured value: C, 55.49；H,6.98；ESI-MS m/z:347.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)40.11
The structural formula of compound 43 is as follows:
The preparation method of compound 43 is identical as the preparation method of compound 41, yield 49%；Elemental analysis/%: meter Calculation value: C, 54.14；H,6.66；Measured value: C, 54.19；H,6.68；ESI-MS m/z:333.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)40.18
The structural formula of compound 44 is as follows:
The preparation method of compound 44 is identical as the preparation method of compound 41, yield 52%；Elemental analysis/%: meter Calculation value: C, 51.36；H,6.03；Measured value: C, 51.33；H,6.08；ESI-MS m/z:351.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)44.28
The structural formula of compound 45 is as follows:
The preparation method of compound 45 is identical as the preparation method of compound 41, yield 52%；Elemental analysis/%: meter Calculation value: C, 49.06；H,5.76；Measured value: C, 49.13；H,5.78；ESI-MS m/z:367.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)44.44
The structural formula of compound 46 is as follows:
The preparation method of compound 46 is identical as the preparation method of compound 41, yield 55%；Elemental analysis/%: meter Calculation value: C, 56.59；H,7.26；Measured value: C, 56.55；H,7.28；ESI-MS m/z:361.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)44.67
The structural formula of compound 47 is as follows:
The preparation method of compound 47 is identical as the preparation method of compound 41, yield 71%；Elemental analysis/%: meter Calculation value: C, 55.41；H,6.98；Measured value: C, 55.51；H,6.88；ESI-MS m/z:347.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)40.66
The structural formula of compound 48 is as follows:
The preparation method of compound 48 is identical as the preparation method of compound 41, yield 75%；Elemental analysis/%: meter Calculation value: C, 52.68；H,6.36；Measured value: C, 52.66；H,6.38；ESI-MS m/z:365.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)43.16
The structural formula of compound 49 is as follows:
The preparation method of compound 49 is identical as the preparation method of compound 41, yield 79%；Elemental analysis/%: meter Calculation value: C, 50.41；H,6.08；Measured value: C, 50.46；H,6.10；ESI-MS m/z:381.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)43.55
The structural formula of compound 50 is as follows:
The preparation method of compound 50 is identical as the preparation method of compound 41,
Yield is 80%；Elemental analysis/%: calculated value: C, 60.84；H,6.13；Measured value: C, 60.88；H,6.12； ESI-MS m/z:394.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)42.77
The structural formula of compound 51 is as follows:
The preparation method of compound 51 is identical as the preparation method of compound 41, yield 80%；Elemental analysis/%: meter Calculation value: C, 59.93；H,5.82；Measured value: C, 59.99；H,5.99；ESI-MS m/z:381.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)41.66
The structural formula of compound 52 is as follows:
The preparation method of compound 52 is identical as the preparation method of compound 41, yield 80%；Elemental analysis/%: meter Calculation value: C, 57.22；H,5.31；Measured value: C, 57.31；H,5.33；ESI-MS m/z:399.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)41.76
The structural formula of compound 53 is as follows:
The preparation method of compound 53 is identical as the preparation method of compound 41, yield 67%；Elemental analysis/%: meter Calculation value: C, 54.96；H,5.10；Measured value: C, 54.99；H,5.15；ESI-MS m/z:415.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)41.55
The structural formula of compound 54 is as follows:
The preparation method of compound 54 is identical as the preparation method of compound 41, yield 67%；Elemental analysis/%: meter Calculation value: C, 56.18；H,5.76；Measured value: C, 56.19；H,5.65；ESI-MS m/z:385.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)43.11
The structural formula of compound 55 is as follows:
The preparation method of compound 55 is identical as the preparation method of compound 41, yield 88%；Elemental analysis/%: meter Calculation value: C, 55.07；H,5.44；Measured value: C, 55.07；H,5.45；ESI-MS m/z:371.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)43.56
The structural formula of compound 56 is as follows:
The preparation method of compound 56 is identical as the preparation method of compound 41, yield 67%；Elemental analysis/%: meter Calculation value: C, 55.52；H,4.93；Measured value: C, 55.57；H,4.95；ESI-MS m/z:389.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)43.88
The structural formula of compound 57 is as follows:
The preparation method of compound 57 is identical as the preparation method of compound 41, yield 67%；Elemental analysis/%: meter Calculation value: C, 50.39；H,4.73；Measured value: C, 50.44；H,4.75；ESI-MS m/z:405.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)44.11
The structural formula of compound 58 is as follows:
The preparation method of compound 58 is identical as the preparation method of compound 41, yield 55%；Elemental analysis/%: meter Calculation value: C, 61.69；H,6.41；Measured value: C, 61.66；H,6.45；ESI-MS m/z:409.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)46.12
The structural formula of compound 59 is as follows:
The preparation method of compound 59 is identical as the preparation method of compound 41, yield 75%；Elemental analysis/%: meter Calculation value: C, 60.84；H,6.13；Measured value: C, 60.86；H,6.15；ESI-MS m/z:395.3[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)46.62
The structural formula of compound 60 is as follows:
The preparation method of compound 60 is identical as the preparation method of compound 41, yield 71%；Elemental analysis/%: meter Calculation value: C, 58.19；H,5.62；Measured value: C, 58.11；H,5.65；ESI-MS m/z:412.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)46.78
The structural formula of compound 61 is as follows:
The preparation method of compound 61 is identical as the preparation method of compound 41, yield 65%；Elemental analysis/%: meter Calculation value: C, 55.96；H,5.40；Measured value: C, 55.99；H,5.45；ESI-MS m/z:429.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)47.18
The structural formula of compound 62 is as follows:
The preparation method of compound 62 is identical as the preparation method of compound 41, yield 75%；Elemental analysis/%: meter Calculation value: C, 51.80；H,4.78；Measured value: C, 51.89；H,4.88；ESI-MS m/z:463.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)48.11
The structural formula of compound 63 is as follows:
The preparation method of compound 63 is identical as the preparation method of compound 41, yield 49%；Elemental analysis/%: meter Calculation value: C, 50.75；H,4.48；Measured value: C, 50.77；H,4.46；ESI-MS m/z:449.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)48.66
The structural formula of compound 64 is as follows:
The preparation method of compound 64 is identical as the preparation method of compound 41, yield 63%；Elemental analysis/%: meter Calculation value: C, 48.79；H,4.09；Measured value: C, 48.77；H,4.13；ESI-MS m/z:467.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)48.76
The structural formula of compound 65 is as follows:
The preparation method of compound 65 is identical as the preparation method of compound 41, yield 69%；Elemental analysis/%: meter Calculation value: C, 47.14；H,3.96；Measured value: C, 47.17；H,3.93；ESI-MS m/z:483.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)48.11
The structural formula of compound 66 is as follows:
The preparation method of compound 66 is identical as the preparation method of compound 41, yield 87%；Elemental analysis/%: meter Calculation value: C, 56.59；H,7.26；Measured value: C, 56.57；H,7.23；ESI-MS m/z:361.1[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)56.31
The structural formula of compound 67 is as follows:
The preparation method of compound 67 is identical as the preparation method of compound 41, yield 88%；Elemental analysis/%: meter Calculation value: C, 55.41；H,6.98；Measured value: C, 55.47；H,6.13；ESI-MS m/z:347.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)56.56
The structural formula of compound 68 is as follows:
The preparation method of compound 68 is identical as the preparation method of compound 41, yield 68%；Elemental analysis/%: meter Calculation value: C, 52.68；H,6.36；Measured value: C, 52.77；H,6.33；ESI-MS m/z:365.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)56.98
The structural formula of compound 69 is as follows:
The preparation method of compound 69 is identical as the preparation method of compound 41, yield 61%；Elemental analysis/%: meter Calculation value: C, 50.41；H,6.08；Measured value: C, 50.47；H,6.13；ESI-MS m/z:381.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)56.11
The structural formula of compound 70 is as follows:
The preparation method of compound 70: by 5.5mmol 2-methyl-4-chlorophenoxyacetic acid and 10mL tetrahydrofuran, ice salt bath 0 DEG C is cooled to hereinafter, the N of 5.5mmol, N- carbonyl dimidazoles (CDI) 10mL tetrahydrofuran solution is slowly added dropwise.Drop finishes, and removes Ice bath allows reaction solution to be gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), 5mmol Alpha-hydroxy is added in about 1h after the reaction was completed Phosphine oxide and 0.05mmol DMAP.80 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction is direct It is eluted with silica gel (G type) column chromatographic grade, (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtains sterling.Yield is 76%；Member Plain analysis/%: calculated value: C, 57.68；H,7.53；Measured value: C, 57.67；H,7.63；ESI-MS m/z:375.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.22
The structural formula of compound 71 is as follows:
The preparation method of compound 71 is identical as the preparation method of compound 70, yield 71%；Elemental analysis/%: meter Calculation value: C, 56.59；H,7.26；Measured value: C, 56.61；H,7.23；ESI-MS m/z:361.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.62
The structural formula of compound 72 is as follows:
The preparation method of compound 72 is identical as the preparation method of compound 70, yield 73%；Elemental analysis/%: meter Calculation value: C, 53.90；H,6.65；Measured value: C, 53.91；H,6.63；ESI-MS m/z:379.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.23
The structural formula of compound 73 is as follows:
The preparation method of compound 73 is identical as the preparation method of compound 70, yield 76%；Elemental analysis/%: meter Calculation value: C, 51.66；H,6.38；Measured value: C, 51.69；H,6.33；ESI-MS m/z:395.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.66
The structural formula of compound 74 is as follows:
The preparation method of compound 74 is identical as the preparation method of compound 70, yield 78%；Elemental analysis/%: meter Calculation value: C, 58.68；H,7.78；Measured value: C, 58.78；H,7.79；ESI-MS m/z:389.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.43
The structural formula of compound 75 is as follows:
The preparation method of compound 75 is identical as the preparation method of compound 70, yield 41%；Elemental analysis/%: meter Calculation value: C, 57.68；H,7.53；Measured value: C, 57.78；H,7.59；ESI-MS m/z:375.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.65
The structural formula of compound 76 is as follows:
The preparation method of compound 76 is identical as the preparation method of compound 70, yield 61%；Elemental analysis/%: meter Calculation value: C, 55.03；H,6.93；Measured value: C, 55.08；H,6.99；ESI-MS m/z:393.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.77
The structural formula of compound 77 is as follows:
The preparation method of compound 77 is identical as the preparation method of compound 70, yield 67%；Elemental analysis/%: meter Calculation value: C, 52.82；H,6.65；Measured value: C, 52.88；H,6.69；ESI-MS m/z:409.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)51.67
The structural formula of compound 78 is as follows:
The preparation method of compound 78: by -4 chlorophenoxyacetic acid of 5.5mmol 2- methyl and 10mL DMF, ice salt bath is cooling To 0 DEG C hereinafter, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide (EDCI) the 10mL DMF that 11mmol is slowly added dropwise is molten Liquid.Drop finishes, and removes ice bath, reaction solution is allowed to be gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), about 1h adds after the reaction was completed Enter 5mmol Alpha-hydroxy phosphine oxide and 0.05mmol HOBt.110 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction directly uses silica gel (G type) column chromatographic grade to elute, and (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtains sterling. Yield is 67%；Elemental analysis/%: calculated value: C, 62.48；H,6.67；Measured value: C, 62.49；H,6.69；ESI-MS m/ z:423.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.67
The structural formula of compound 79 is as follows:
The preparation method of compound 79 is identical as the preparation method of compound 78, yield 54%；Elemental analysis/%: meter Calculation value: C, 61.69；H,6.41；Measured value: C, 61.79；H,6.49；ESI-MS m/z:409.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.43
The structural formula of compound 80 is as follows:
The preparation method of compound 80 is identical as the preparation method of compound 78, yield 67%；Elemental analysis/%: meter Calculation value: C, 59.09；H,5.90；Measured value: C, 59.12；H,5.98；ESI-MS m/z:427.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.79
The structural formula of compound 81 is as follows:
The preparation method of compound 81 is identical as the preparation method of compound 78, yield 75%；Elemental analysis/%: meter Calculation value: C, 56.90；H,5.68；Measured value: C, 56.94；H,5.78；ESI-MS m/z:443.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.76
The structural formula of compound 82 is as follows:
The preparation method of compound 82 is identical as the preparation method of compound 78, yield 82%；Elemental analysis/%: meter Calculation value: C, 58.19；H,6.35；Measured value: C, 58.22；H,6.38；ESI-MS m/z:413.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.98
The structural formula of compound 83 is as follows:
The preparation method of compound 83 is identical as the preparation method of compound 78, yield 82%；Elemental analysis/%: meter Calculation value: C, 57.22；H,6.07；Measured value: C, 57.32；H,6.08；ESI-MS m/z:399.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.00
The structural formula of compound 84 is as follows:
The preparation method of compound 84 is identical as the preparation method of compound 78, yield 85%；Elemental analysis/%: meter Calculation value: C, 54.75；H,5.56；Measured value: C, 54.79；H,5.59；ESI-MS m/z:417.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.10
The structural formula of compound 85 is as follows:
The preparation method of compound 85 is identical as the preparation method of compound 78, yield 88%；Elemental analysis/%: meter Calculation value: C, 52.67；H,5.35；Measured value: C, 52.69；H,5.359；ESI-MS m/z:433.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)50.10
The structural formula of compound 86 is as follows:
The preparation method of compound 86: by 5.5mmol 2-methyl-4-chlorophenoxyacetic acid and 10mL DMF, ice salt bath is cooling To 0 DEG C hereinafter, the N of 5.5mmol, N- carbonyl dimidazoles (CDI) 10mL DMF solution is slowly added dropwise.Drop finishes, and removes ice bath, allows anti- Liquid is answered to be gradually increased to room temperature.With lamellae (TLC) track react, about 1h be added after the reaction was completed 5mmol Alpha-hydroxy phosphine oxide with 0.05mmol DMAP.80 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction directly uses silica gel (G Type) elution of column chromatographic grade, (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtains sterling.Yield is 88%；Element point Analysis/%: calculated value: C, 53.73；H,5.33；Measured value: C, 53.79；H,5.33；ESI-MS m/z:491.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)58.10
The structural formula of compound 87 is as follows:
The preparation method of compound 87 is identical as the preparation method of compound 86, yield 68%；Elemental analysis/%: meter Calculation value: C, 52.79；H,5.06；Measured value: C, 52.71；H,5.13；ESI-MS m/z:477.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)58.43
The structural formula of compound 88 is as follows:
The preparation method of compound 88 is identical as the preparation method of compound 86, yield 71%；Elemental analysis/%: meter Calculation value: C, 50.88；H,4.68；Measured value: C, 50.90；H,4.73；ESI-MS m/z:495.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)58.67
The structural formula of compound 89 is as follows:
The preparation method of compound 89 is identical as the preparation method of compound 86, yield 79%；Elemental analysis/%: meter Calculation value: C, 49.24；H,4.53；Measured value: C, 49.29；H,4.53；ESI-MS m/z:511.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)58.98
The structural formula of compound 90 is as follows:
The preparation method of compound 90: by 5.5mmol 2-methyl-4-chlorophenoxyacetic acid and 10mL acetonitrile, ice salt bath is cooling To 0 DEG C hereinafter, the N of 5.5mmol, N- carbonyl dimidazoles (CDI) 10mL acetonitrile solution is slowly added dropwise.Drop finishes, and removes ice bath, allows anti- Liquid is answered to be gradually increased to room temperature.With lamellae (TLC) track react, about 1h be added after the reaction was completed 5mmol Alpha-hydroxy phosphine oxide with 0.05mmol DMAP.80 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction directly uses silica gel (G Type) elution of column chromatographic grade, (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtains sterling.Yield is 88%；Element point Analysis/%: calculated value: C, 56.59；H,7.26；Measured value: C, 56.62；H,7.33；ESI-MS m/z:361.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)53.10
The structural formula of compound 91 is as follows:
The preparation method of compound 91 is identical as the preparation method of compound 90, yield 76%；Elemental analysis/%: meter Calculation value: C, 55.41；H,6.98；Measured value: C, 55.42；H,6.90；ESI-MS m/z:347.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)53.15
The structural formula of compound 92 is as follows:
The preparation method of compound 92 is identical as the preparation method of compound 90, yield 71%；Elemental analysis/%: meter Calculation value: C, 52.68；H,6.36；Measured value: C, 52.66；H,6.37；ESI-MS m/z:365.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)53.67
The structural formula of compound 93 is as follows:
The preparation method of compound 93 is identical as the preparation method of compound 90, yield 77%；Elemental analysis/%: meter Calculation value: C, 50.41；H,6.08；Measured value: C, 50.46；H,6.07；ESI-MS m/z:381.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)53.87
The structural formula of compound 94 is as follows:
The preparation method of compound 94: by 5.5mmol 2-methyl-4-chlorophenoxyacetic acid and 10mL tetrahydrofuran, ice salt bath 0 DEG C is cooled to hereinafter, the N of 5.5mmol, N- carbonyl dimidazoles (CDI) 10mL tetrahydrofuran solution is slowly added dropwise.Drop finishes, and removes Ice bath allows reaction solution to be gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), 5mmol Alpha-hydroxy is added in about 1h after the reaction was completed Phosphine oxide and 0.05mmol HOBt.80 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction is direct It is eluted with silica gel (G type) column chromatographic grade, (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtains sterling.Yield is 80%；Member Plain analysis/%: calculated value: C, 57.68；H,7.53；Measured value: C, 57.62；H,7.63；ESI-MS m/z:375.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.11
The structural formula of compound 95 is as follows:
The preparation method of compound 95 is identical as the preparation method of compound 94, yield 84%；Elemental analysis/%: meter Calculation value: C, 56.59；H,7.26；Measured value: C, 56.62；H,7.23；ESI-MS m/z:361.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.54
The structural formula of compound 96 is as follows:
The preparation method of compound 96 is identical as the preparation method of compound 94, yield 74%；Elemental analysis/%: meter Calculation value: C, 53.90；H,6.65；Measured value: C, 53.92；H,6.63；ESI-MS m/z:379.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.64
The structural formula of compound 97 is as follows:
The preparation method of compound 97 is identical as the preparation method of compound 94, yield 79%；Elemental analysis/%: meter Calculation value: C, 51.66；H,6.38；Measured value: C, 51.69；H,6.33；ESI-MS m/z:395.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.23
The structural formula of compound 98 is as follows:
The preparation method of compound 98 is identical as the preparation method of compound 94, yield 76%；Elemental analysis/%: meter Calculation value: C, 58.19；H,6.35；Measured value: C, 58.29；H,6.33；ESI-MS m/z:413.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.90
The structural formula of compound 99 is as follows:
The preparation method of compound 99 is identical as the preparation method of compound 94, yield 65%；Elemental analysis/%: meter Calculation value: C, 57.22；H,6.07；Measured value: C, 57.29；H,6.13；ESI-MS m/z:399.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.90
The structural formula of compound 100 is as follows:
The preparation method of compound 100 is identical as the preparation method of compound 94, yield 31%；Elemental analysis/%: meter Calculation value: C, 54.75；H,5.56；Measured value: C, 54.79；H,5.53；ESI-MS m/z:417.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.43
The structural formula of compound 101 is as follows:
The preparation method of compound 101 is identical as the preparation method of compound 94, yield 81%；Elemental analysis/%: meter Calculation value: C, 52.67；H,5.35；Measured value: C, 52.60；H,5.39；ESI-MS m/z:433.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)59.13
The structural formula of compound 102 is as follows:
The preparation method of compound 102: by 5.5mmol 2-methyl-4-chlorophenoxyacetic acid and 10mL acetonitrile, ice salt bath is cold But to 0 DEG C hereinafter, the N of 5.5mmol, N- carbonyl dimidazoles (CDI) 10mL acetonitrile solution is slowly added dropwise.Drop finishes, and removes ice bath, allows Reaction solution is gradually increased to room temperature.It is tracked and is reacted with lamellae (TLC), 5mmol Alpha-hydroxy phosphine oxide is added in about 1h after the reaction was completed With 0.05mmol HOBt.80 DEG C of reactions are slowly increased to, is tracked and is reacted with lamellae (TLC), about 1h end of reaction directly uses silica gel The elution of (G type) column chromatographic grade, (eluant, eluent acetone: petroleum ether volume ratio=1:2) obtain sterling.Yield is 80%；Element point Analysis/%: calculated value: C, 62.48；H,6.67；Measured value: C, 62.49；H,6.61；ESI-MS m/z:423.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)60.10
The structural formula of compound 103 is as follows:
The preparation method of compound 103 is identical as the preparation method of compound 102, yield 88%；Elemental analysis/%: Calculated value: C, 61.69；H,6.41；Measured value: C, 61.72；H,6.46；ESI-MS m/z:409.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)60.60
The structural formula of compound 104 is as follows:
The preparation method of compound 104 is identical as the preparation method of compound 102, yield 67%；Elemental analysis/%: Calculated value: C, 59.09；H,5.90；Measured value: C, 59.13；H,5.94；ESI-MS m/z:427.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)60.90
The structural formula of compound 105 is as follows:
The preparation method of compound 105 is identical as the preparation method of compound 102, yield 90%；Elemental analysis/%: Calculated value: C, 56.90；H,5.68；Measured value: C, 56.94；H,5.66；ESI-MS m/z:443.2[M+1]+；
31P NMR(160MHz,CDCl3):δ(ppm)60.34
2 pot-culture method activity of weeding test experiments of embodiment
(1) test medicine: weighing raw medicine with assay balance, add emulsifier (Tween-80) and solvent (DMF or DMSO or Water), it is configured to 1.0~the 5.0% small preparation of missible oil or aqua.Then it is spare 10g/ mus of concentration to be diluted to aquae destillata.
(2) test method: it will uniformly be sown into internal diameter 9cm basin alms bowl for examination weed seed, be cultivated in greenhouse.To dicotyledonous When weeds leaf period, cauline leaf spraying treatment is carried out on automatic sprayer.3 repetitions of every processing, if blank control, after processing 4~5 hours are stood, after medical fluid on blade is dry, moves into greenhouse and cultivates.Daily observation plant strain growth situation, periodic logging by Evil symptom, comprehensive activity of weeding is investigated in range estimation in 25 days after medicine.
(3) evaluation criterion: result investigation use ocular estimate, visual assessment medicament to plant strain growth inhibition, deformity, yellow, Then the influence degrees such as rotten, necrosis press 0~100% staging visual assessment activity of weeding according to comprehensive extent of injury.Evaluation Standard is specifically shown in Table 3-6.
2 activity of weeding ocular estimate evaluation criterion of table
Activity of weeding of 3 compound of embodiment to broadleaf weeds
Cauline leaf process activity of weeding (10 gram/acre) (pot-culture method) of the 3 compound 1-18 of table to broadleaf weeds
Cauline leaf process activity of weeding (10 gram/acre) of the 4 compound 18-37 of table to broadleaf weeds
Cauline leaf process activity of weeding (10 gram/acre) of the 5 compound 38-105 of table to broadleaf weeds
Soil treatment activity of weeding (10 gram/acre) of 6 part of compounds of table to broadleaf weeds
Show that phosphine oxide structures compound has good activity of weeding, portion to dicotyledonous or broadleaf weeds by above data The activity of weeding of compound is divided to be better than comparison medicament chlorine acyl grass phosphine (phosphonic acids ester structure representative compound), in addition phosphine oxide structures Compound shows new activity of weeding feature-and all has soil treatment and cauline leaf process as the effective ingredient of herbicide Activity of weeding, and the compound of phosphate ester structure type usually only has cauline leaf process activity of weeding.It should be the result shows that by first When guide structure phosphonate ester changes into new structural phosphine oxide, not only activity of weeding is improved, characteristics and application range Also changed.
4 compound of embodiment is to broadleaf weeds, sedge weed and the activity of weeding of gramineae weed
7 part of compounds of table is to broadleaf weeds, sedge weed and the activity of weeding of gramineae weed (cauline leaf process, 60 Gram/acre)
Above data shows that phosphine oxide structures compound has good preventive effect to broadleaf weeds, sedge weed, can make For selective herbicide.Part of compounds also has certain activity of weeding to gramineae weed.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any One or more embodiment or examples in can be combined in any suitable manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this The range of invention is defined by the claims and their equivalents.

Claims (10)

1. a kind of phosphine oxide-type compound, which is characterized in that the compound is compound shown in compound shown in Formulas I or Formulas I Stereoisomer, geometric isomer, tautomer, raceme, nitrogen oxides, hydrate, solvate, can pharmaceutically connect The salt received:
In formula:
R1For C1-C3Alkyl；
R2For C1-C3Alkyl；R3For C1-C4Alkyl, furyl or the phenyl arbitrarily replaced；
X, Y are the monosubstituted or multi-substituent on phenyl ring any position, such as can be replaced for contraposition or meta position, the substituent group It can be identical or different.
2. compound according to claim 1, which is characterized in that the substituent R1For C1-C3Alkyl, optionally, R1 For methyl, ethyl, propyl, isopropyl, normal-butyl and isobutyl group；R2For C1-C3Alkyl, optionally, R2For methyl, ethyl, third Base and isopropyl；R3For C1-C4Alkyl, furyl, phenyl, at least one halogen replace phenyl or at least one methyl take The phenyl in generation, optionally, R3For methyl, ethyl, propyl, furyl, phenyl, 2,4- dichlorophenyl, 3- aminomethyl phenyl, 2,3- bis- Chlorphenyl, 3- chlorphenyl.
3. compound according to claim 1, which is characterized in that the substituent X, Y are selected from hydrogen, halogen, methyl.
4. compound according to claim 1, which is characterized in that the compound is following compounds or described following Stereoisomer, geometric isomer, tautomer, raceme, nitrogen oxides, hydrate, the solvate of compound, pharmacy Upper acceptable salt:
5. a kind of method for preparing any one of Claims 1 to 4 compound, which is characterized in that make represented by general formula II Compound is reacted with compound represented by general formula III or general formula IV, to obtain compound represented by general formula I,
Wherein R1、R2、R3, X, Y have any one of claim 1-4 described in definition.
6. according to the method described in claim 5, characterized by comprising the following steps: by change represented by the general formula II Close compound represented by object, the general formula III, alkali and the mixing of the first organic solvent；
Optionally, the molar ratio of compound and alkali represented by compound and general formula III represented by the general formula II is 1: (1~2): (1~2)；
Optionally, the alkali be sodium ethoxide, sodium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, At least one of saleratus, triethylamine or pyridine；
Optionally, first organic solvent is acetone, chloroform, tetrahydrofuran, dichloroethanes, methylene chloride, chloroform, second At least one of nitrile, N,N-dimethylformamide, dimethyl sulfoxide, benzene or ethyl acetate；
Optionally, the reaction temperature is -10 DEG C to 110 DEG C；
Optionally, the reaction time is 1-24 hours.
7. according to the method described in claim 5, characterized by comprising the following steps: by change represented by the general formula II Close compound represented by object, the general formula IV, catalyst, condensing agent and the mixing of the first organic solvent；
Optionally, mole of compound, catalyst and condensing agent represented by compound, general formula IV represented by the general formula II Than for 1:1.1:0.05:(1.1~2.2)；
Optionally, the catalyst is 4-N, at least one of N dimethyl pyridine or 1- hydroxy benzo triazole；
Optionally, the condensing agent be N, N- carbonyl dimidazoles, dicyclohexylcarbodiimide, diisopropyl base carbodiimide or At least one of 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide；
Optionally, first organic solvent is n,N-Dimethylformamide, acetone, chloroform, tetrahydrofuran, dichloroethanes, two At least one of chloromethanes, chloroform, acetonitrile, toluene, benzene or ethyl acetate；
Optionally, the reaction temperature is -10 DEG C to 110 DEG C；
Optionally, the reaction time is 1-24 hours.
8. a kind of pesticide, which is characterized in that including compound defined in claim any one of 1-4.
9. a kind of method cut weeds, which is characterized in that apply in any one of claim 1-4 for the weeds cauline leaf or soil The compound or pesticide according to any one of claims 8.
10. according to the method described in claim 9, it is characterized in that, the weeds are broadleaf weeds or sedge weed；
Optionally, the weeds be piemarker, it is Amaranthus retroflexus, concave head amaranth, thorn amaranth, amaranth, field thistle, Eclipta prostrata, shepherd's purse, small Chenopodiaceae, sheep hoof, numerous Chenopodiaceae, beggar-ticks, broom grass, arabidopsis, pharbitis nilChoisy, difformed galingale herb, cyperus iria and Herba Cyperi Glomerati.
CN201811158498.9A 2018-09-30 2018-09-30 A kind of phosphine oxide-type compound and its preparation method and application Pending CN110452266A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351991A (en) * 2000-11-15 2002-06-05 华中师范大学 Substituted phenoxy acetoxyl alkyl hypophosphorous ester with herbicide activity and preparation
CN1685825A (en) * 2005-04-14 2005-10-26 华中师范大学 Substituted phenoxy acetyl oxy alkyl phospho acid and phosphonate ester possessing bactericidal insecticidal activity
CN1687086A (en) * 2005-04-26 2005-10-26 华中师范大学 Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation
CN103588814A (en) * 2012-08-13 2014-02-19 华中师范大学 Optically active isomer of substituted phenoxyl acetyloxy (amino) hydrocarbyl phosphonate with herbicidal activity and preparation thereof
CN104098603A (en) * 2013-04-02 2014-10-15 华中师范大学 O, O-dialkyl-alpha-(substituted phenoxybutyryloxy)alkyl phosphonate with herbicidal activity and preparation method thereof
CN108218919A (en) * 2016-12-14 2018-06-29 华中师范大学 Compound and its purposes as herbicide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1351991A (en) * 2000-11-15 2002-06-05 华中师范大学 Substituted phenoxy acetoxyl alkyl hypophosphorous ester with herbicide activity and preparation
CN1685825A (en) * 2005-04-14 2005-10-26 华中师范大学 Substituted phenoxy acetyl oxy alkyl phospho acid and phosphonate ester possessing bactericidal insecticidal activity
CN1687086A (en) * 2005-04-26 2005-10-26 华中师范大学 Substituted phenoxy-acetoxy-aromatic heterocyclic radical-alkyl ester phisphinic acid possessing bactericidal and herbicidal activity, and preparation
CN103588814A (en) * 2012-08-13 2014-02-19 华中师范大学 Optically active isomer of substituted phenoxyl acetyloxy (amino) hydrocarbyl phosphonate with herbicidal activity and preparation thereof
CN104098603A (en) * 2013-04-02 2014-10-15 华中师范大学 O, O-dialkyl-alpha-(substituted phenoxybutyryloxy)alkyl phosphonate with herbicidal activity and preparation method thereof
CN108218919A (en) * 2016-12-14 2018-06-29 华中师范大学 Compound and its purposes as herbicide

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