CN103242367A - 2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo-phosphoramidate compound with insecticidal activity and applications thereof - Google Patents

2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo-phosphoramidate compound with insecticidal activity and applications thereof Download PDF

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CN103242367A
CN103242367A CN2013101921536A CN201310192153A CN103242367A CN 103242367 A CN103242367 A CN 103242367A CN 2013101921536 A CN2013101921536 A CN 2013101921536A CN 201310192153 A CN201310192153 A CN 201310192153A CN 103242367 A CN103242367 A CN 103242367A
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phenyl
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methyl
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phosphoramidate
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CN103242367B (en
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唐子龙
颜林
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Jiashan Linhu Xincheng Industrial Co.,Ltd.
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Hunan University of Science and Technology
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Abstract

The invention provides a novel 2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo-phosphoramidate compound, which has a structural formula (I) shown in a general formula (I). Experiments prove that the 2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo-phosphoramidate compound disclosed by the invention has certain insecticidal activity to crop diseases and pests; the raw materials are easily available; the synthesis method is simple; and therefore a new pesticide development way for solving the problems of drug resistance and the like of crop diseases and pests is provided.

Description

2-aryloxy-3-aryl-3 with insecticidal activity, 4-dihydro-2H-1,3,2-benzo phosphoramidate compounds and uses thereof
Technical field
The present invention's technical field of pesticide of serving a ball is specifically related to a kind of novel 2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate compounds and big purposes aspect the preparation bactericidal insecticidal pesticide thereof.
Background technology
Since the endoxan ester comes out as a kind of cancer therapy drug, the heterogeneous ring compound that contains N, O and P atom just enjoys the extensive concern of scientists, and 1,3,2-benzo phosphoramidate namely be a class such contain the P heterogeneous ring compound, through in recent years discover that it is all showing preferably activity aspect medicine and the agricultural chemicals, as antitumor, antibiotic, desinsection etc.Phosphamide and phosphate compounds have higher activity aspect agricultural, as desinsection, sterilization, weeding etc., the much commercializations of this two compounds are as SD-1750, iprobenfos, amiprophos etc.Yet along with the adjustment of breed structure, some high malicious phosphamides and phosphate pesticide have faced restriction and have replaced, and the development priority of organophosphorus pesticide has turned to has high reactivity and the development of the lower heterogeneous ring compound of toxicity.1,3, the 2-benzo phosphoramidate novel heterocyclic compounds that to be a class effectively combine phosphamide and phosphoric acid ester is by active substructure splicing and structural modification, the low agricultural chemicals small molecules of toxicity in the hope of obtaining active height.2008, C. Nage Raju etc. has reported a series of 6-bromine 2-replacement-3-(1-phenylethyl)-3,4-dihydro-2H-1, and 3,2-benzo phosphoramidate compounds has been studied it to the restraining effect of silkworm egg hatching and desinsection, fungicidal activity.Found that part of compounds for the better activity that has that suppresses the silkworm egg hatching, shows the activity of killing worms such as yellow rice borer preferably simultaneously.The activity of the anti-aspergillus niger fungi of part of compounds is quite active with commercial nystatin, and active even than the height of gentamicin to the inhibition of Bacillus subtilus.In the same year, they have delivered the novel 2-heterocyclic amino group-3-(4-chloro-phenyl-)-3 of a class, 4-dihydro-1,3,2-benzo phosphoramidate-2-sulfo-again at group.Discover that 2-((4-chloro-phenyl-) amino) though methylphenol has been gathered phenol, chlorine and amino isoreactivity group, does not show anti-microbial activity; Yet, after itself and phosphorus thiochloride Cheng Huanzai are by amino nucleophilic substitution, form 1,3,2-benzo phosphoramidate but shows antibacterium and anti-mycotic activity preferably.When test concentrations is 10 mg/mL, this compounds for the inhibition activity of Bacillus subtilus all greater than commercial gentamicin.
Based on above research background, proved absolutely that 1,3,2-benzo phosphoramidate and derivative thereof have biological activity widely, the present invention has synthesized 17 target compounds by two lines, and preliminary study its insecticidal activity.
Summary of the invention
The purpose of this invention is to provide a kind of novel 2-aryloxy-3-aryl-3 with insecticidal activity, 4-dihydro-2H-1,3,2-benzo phosphoramidate compounds, it has insecticidal activity.
Novel 2-aryloxy-3-aryl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate compounds has the structural formula shown in the general formula (I):
Figure 2013101921536100002DEST_PATH_IMAGE001
（I）
In the formula (I), the substituting group on three phenyl ring is respectively R 1, R 2, R 3And R 4
In the formula (I), substituent R 2Be H, R 3When being H: R 1Be CH 3, R 4Be p-OCH 3Or R 1Be H, R 4Be m-CH 3Or R 1Be H, R 4Be p-CH 3Or R 1Be H, R 4Be m-OCH 3Or R 1Be H, R 4Be p-OCH 3
In the formula (I), substituent R 1Be H, R 2When being H: R 3Be C 6H 5NHCH 2, R 4Be H; Or R 3Be 3-ClC 6H 4NHCH 2, R 4Be m-Cl; Or R 3Be 4-ClC 6H 4NHCH 2, R 4Be p-Cl; Or R3 is 2-CH 3C 6H 4NHCH 2, R 4Be o-CH 3Or R 3Be 3-CH 3C 6H 4NHCH 2, R 4Be m-CH 3Or R 3Be 4-CH 3C 6H 4NHCH 2, R 4Be p-CH 3Or R 3Be 2-OCH 3C 6H 4NHCH 2, R 4Be o-OCH 3Or R 3Be 4-OCH 3C 6H 4NHCH 2, R 4Be p-OCH 3
In the formula (I), substituent R 1Be CH 3, R 2Be CH 3The time: R 3Be 3-ClC 6H 4NHCH 2, R 4Be m-Cl; Or R 3Be 4-ClC 6H 4NHCH 2, R 4Be p-Cl; Or R 3Be 4-CH 3C 6H 4NHCH2, R 4Be p-CH 3Or R 3Be 2-OCH 3C 6H 4NHCH 2, R 4Be o-OCH 3
Novel 2-aryloxy provided by the present invention-3-aryl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate compounds comprises:
2-phenoxy group-3-(4-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 567974DEST_PATH_IMAGE002
，
2-phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 838112DEST_PATH_IMAGE004
2-phenoxy group-3-(3-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE005
2-phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(phenyl amido) methyl) phenoxy group-3-phenyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE007
2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 170315DEST_PATH_IMAGE008
2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE009
2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(3-aminomethyl phenyl amido) methyl) phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE011
2-(2-(4-aminomethyl phenyl amido) methyl) phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 492636DEST_PATH_IMAGE012
2-(2-(2-p-methoxy-phenyl amido) methyl) phenoxy group-3-(2-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(4-p-methoxy-phenyl amido) methyl) phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 103877DEST_PATH_IMAGE014
2-(2-(3-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(3-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE015
2-(2-(4-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(4-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 178143DEST_PATH_IMAGE016
2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100002DEST_PATH_IMAGE017
2-(2-(2-p-methoxy-phenyl amido) methyl-4-methyl) phenoxy group-3-(2-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 188300DEST_PATH_IMAGE018
Prove 2-aryloxy of the present invention-3-aryl-3 by experiment, 4-dihydro-2H-1,3,2-benzo phosphoramidate compounds has certain insecticidal activity to the disease and pest of farm crop, and its material is easy to get, synthetic method is simple, provides a kind of development approach of novel pesticide for solving problems such as diseases and pests of agronomic crop resistance.
Embodiment
For a better understanding of the present invention, now provide preparation 2-aryloxy-3-aryl-3,4-dihydro-2H-1, the embodiment of 3,2-benzo phosphoramidate the present invention includes but is not limited thereto the preparation method.
Embodiment 1:2-phenoxy group-3-(4-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic
Toluene with 30 mL dryings, 4-methyl-2-((4-p-methoxy-phenyl) amino) methylphenol (5 mmol) and 12 mmol triethylamines join in the there-necked flask of 100 mL successively, ice bath stirs and slowly drips the toluene solution that 10 mL contain 6 mmol phenoxy group phosphinylidyne dichloros down, be warming up to 65 ℃ of continuation reaction 5 h (TLC detection) after reacting 30 min, leave standstill cooling, remove triethylamine hydrochloride with the sand core funnel suction filtration, concentrating under reduced pressure filtrate, add 80 mL ethyl acetate again, water (40 mL * 2 time) and saturated nacl aqueous solution (40mL * 2 time) washing organic phase respectively, the organic phase anhydrous sodium sulfate drying, precipitation obtains yellow oil by column chromatography for separation, productive rate 78.8%.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.33(s,?3H,?CH 3),?3.79(s,?3H,?OCH 3),?4.52(dd,?J 1=15.5Hz,?J 2=18.5Hz,?1H),?4.85(dd,?J 1=5.5Hz,?J 2=15Hz,?1H),?6.87(d,?J=8.5Hz,?2H),?6.93(s,?1H),?6.98(d,?J=8.5Hz,?1H),?7.09(d,?J=8Hz,?1H),?7.13~7.17(m,?3H),?7.25~7.31(m,4H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.63,?53.29,?55.41,?114.56(2C),?118.55(d,?J=8.5Hz),?120.34(d,?J=4.75Hz,?2C),?122.37(d,?J=7.25Hz),?125.06,?126.43(d,?J=3.625Hz,?2C),?126.99,?129.54,?129.61(2C),?133.91,?134.67(d,?J=3Hz),?148.16(d,?J=7.875Hz),?150.58(d,?J=8Hz),?157.74.
IR(KBr,?v/cm -1):?3042,?2933,?2837,?1592,?1489,?1463,?1365,?1296,?1216,?1120,?1033,?935,?820,?770,?691,?660,?542?cm -1.
Embodiment 2:2-phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic
Toluene with 30 mL dryings, 2-((3-aminomethyl phenyl) amino) methylphenol (5 mmol) and 12 mmol triethylamines join in the there-necked flask of 100 mL successively, ice bath stirs and slowly drips the toluene solution that 10 mL contain 6 mmol phenoxy group phosphinylidyne dichloros down, be warming up to 65 ℃ of continuation reaction 5 h (TLC detection) after reacting 30 min, leave standstill cooling, remove triethylamine hydrochloride with the sand core funnel suction filtration, concentrating under reduced pressure filtrate, add 80 mL ethyl acetate again, water (40 mL * 2 time) and saturated nacl aqueous solution (40mL * 2 time) washing organic phase respectively, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 76.0%, fusing point: 79.1 ~ 80.2 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.35(s,?3H),?4.65(dd,?J 1=15Hz,?J 2=18Hz,?1H),?4.93(dd,?J 1=6Hz,?J 2=15Hz,?1H),?7.02(d,?J=7.5Hz,?1H),?7.11(d,?J=8Hz,?1H),?7.15~7.17(m,?7H),?7.22~7.24(m,?1H),?7.29~7.32(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?21.50,?52.61,?109.98,?113.72,?118.95(d,?J=8.625Hz),?120.46(d,?J=4.75Hz,?2C),?121.13(d,?J=3.75Hz),?124.47,?124.92(d,?J=3.625Hz),?125.26,?126.60,?126.75,?129.20(2C),?129.75,?139.35,?141.97(d,?J=3.5Hz),?150.37(d,?J=8.125Hz),?150.60(d,?J=8.125Hz).
IR(KBr,?v/cm -1):?3024,?2959,?2920,?2861,?1719,?1600,?1491,?1452,?1289,?1197,?1162,?1073,?1009,?963,?814,?758,?689,?512,?522?cm -1.
Embodiment 3:2-phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic
Toluene with 30 mL dryings, 2-((4-aminomethyl phenyl) amino) methylphenol (5 mmol) and 12 mmol triethylamines join in the there-necked flask of 100 mL successively, ice bath stirs and slowly drips the toluene solution that 10 mL contain 6 mmol phenoxy group phosphinylidyne dichloros down, be warming up to 65 ℃ of continuation reaction 5 h (TLC detection) after reacting 30 min, leave standstill cooling, remove triethylamine hydrochloride with the sand core funnel suction filtration, concentrating under reduced pressure filtrate, add 80 mL ethyl acetate again, water (40 mL * 2 time) and saturated nacl aqueous solution (40mL * 2 time) washing organic phase respectively, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 82.0%, fusing point: 93.0 ~ 93.9 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.33(s,?3H),?4.61(dd,?J 1=15Hz,?J 2=18.5Hz,?1H),?4.92(dd,?J 1=5.5Hz,?J 2=15Hz,?1H),?7.10(d,?J=8Hz,?1H),?7.14~7.17(m,?7H),?7.23(d,?J=8Hz,?2H),?7.28~7.33(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.94,?52.76,?118.97(d,?J=8.25Hz),?120.45(d,?J=4.625Hz,?2C),?122.99(d,?J=7.25Hz),?124.30(d,?J=3.75Hz,?2C),?124.42,?125.24,?126.75,?129.17,?129.74(2C),?130.01(2C),?135.63,?139.38(d,?J=3.5Hz),?150.39(d,?J=7.875Hz),?150.59(d,?J=8Hz).
IR(KBr,?v/cm -1):?3057,?3030,?2917,?2863,?1584,?1511,?1487,?1466,?1367,?1298,?1223,?1107,?1037,?960,?821,?773,?689,?579,?519?cm -1.
Embodiment 4:2-phenoxy group-3-(3-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic
Toluene with 30 mL dryings, 2-((3-p-methoxy-phenyl) amino) methylphenol (5 mmol) and 12 mmol triethylamines join in the there-necked flask of 100 mL successively, ice bath stirs and slowly drips the toluene solution that 10 mL contain 6 mmol phenoxy group phosphinylidyne dichloros down, be warming up to 65 ℃ of continuation reaction 5 h (TLC detection) after reacting 30 min, leave standstill cooling, remove triethylamine hydrochloride with the sand core funnel suction filtration, concentrating under reduced pressure filtrate, add 80 mL ethyl acetate again, water (40 mL * 2 time) and saturated nacl aqueous solution (40mL * 2 time) washing organic phase respectively, the organic phase anhydrous sodium sulfate drying, precipitation obtains yellow oil by column chromatography for separation, productive rate 61.7%.
1H?NMR(CDCl 3,?500?MHz)?δ:?3.78(s,?3H),?4.65(dd,?J 1=15Hz,?J 2=18Hz,?1H),?4.91(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.75(dd,?J 1=1.5Hz,?J 2=8.5Hz,?1H),?6.91(s,?1H),?6.94(d,?J=8.5Hz,?1H),?7.11(d,?J=8Hz,?1H),?7.15~7.17(m,?5H),?7.24~7.27(m,?1H),?7.28~7.33(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?52.36,?55.38,?109.87(d,?J=3.875Hz),?111.25,?115.96(d,?J=4Hz),?118.90(d,?J=8.375Hz),?120.44(d,?J=4.625Hz,?2C),?122.98(d,?J=7.125Hz),?124.57,?125.34,?126.82,?129.27,?129.79(2C),?130.03,?143.27(d,?J=4Hz),?150.25(d,?=8Hz),?150.51(d,?J=8.125Hz),?160.29.
IR(KBr,?v/cm -1):?3067,?2939,?2836,?1602,?1488,?1457,?1374,?1298,?1247,?1201,?1103,?1046,?927,?830,?761,?689,?634,?586,?516?cm -1.
Embodiment 5:2-phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic
Toluene with 30 mL dryings, 2-((4-p-methoxy-phenyl) amino) methylphenol (5 mmol) and 12 mmol triethylamines join in the there-necked flask of 100 mL successively, ice bath stirs and slowly drips the toluene solution that 10 mL contain 6 mmol phenoxy group phosphinylidyne dichloros down, be warming up to 65 ℃ of continuation reaction 5 h (TLC detection) after reacting 30 min, leave standstill cooling, remove triethylamine hydrochloride with the sand core funnel suction filtration, concentrating under reduced pressure filtrate, add 80 mL ethyl acetate again, water (40 mL * 2 time) and saturated nacl aqueous solution (40mL * 2 time) washing organic phase respectively, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 69.0%, fusing point: 124.9 ~ 126.1 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?3.79(s,?3H),?4.57(dd,?J 1=15Hz,?J 2=19Hz,?1H),?4.91(dd,?J 1=5.5Hz,?J 2=15Hz,?1H),?6.88(d,?J=8.5Hz,?2H),?7.10(d,?J=8Hz,?1H),?7.14~7.17(m,?5H),?7.25(s,?1H),?7.27~7.33(m,?4H).
13C?NMR(CDCl 3,?125?MHz)?δ:?53.38,?55.54,?114.67(2C),?119.02(d,?J=8.5Hz),?120.43(d,?J=4.875Hz,?2C),?122.89(d,?J=7.25Hz),?124.37,?125.20,?126.58(d,?J=3.625Hz,?2C),?126.71,?129.13,?129.73(2C),?134.62(d,?J=2.875Hz),?150.41(d,?J=8Hz),?150.62(d,?J=7.875Hz),?157.88.
IR(KBr,?v/cm -1):?3056,?3005,?2956,?2831,?1584,?1516,?1487,?1454,?1373,?1293,?1245,?1205,?1178,?1033,?940,?828,?769,?690,?620,?552,?513?cm -1.
Embodiment 6:2-(2-(phenyl amido) methyl) phenoxy group-3-phenyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-phenyl-2-(amino methyl) phenol (3 mmol, 0.598 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 52.1%, fusing point (mp): 145.8 ~ 148.3 ℃.
This compound 1H NMR, 13C NMR, IR, MS are as follows:
1H?NMR(CDCl 3,?500?MHz)?δ:?4.14(dd,?J 1=14.5Hz,?J 2=22.5Hz,?2H),?4.65(dd,?J 1=15Hz,?J 2=18.5Hz,?1H),?4.95(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.47(d,?J=7.5Hz,?2H),?6.69(t,?J=8Hz,?1H),?7.08~7.20(m,?7H),?7.23(dt,?J 1=1.5Hz,?J 2=7.5Hz,?1H),?7.28~7.32(m,?3H),?7.33~7.38(m,?4H).
13C?NMR(CDCl 3,?125?MHz)?δ:?43.05,?52.52,?112.99(2C),?117.61,?118.83(d,?J=8.375Hz),?120.24,?122.85(d,?J=7.125Hz),?124.31(d,?J=3.75Hz,?2C),?124.52,?125.35,?125.94,?126.76,?128.63,?129.08(2C),?129.23,?129.40(2C),?129.75,?130.10(d,?J=6.375Hz),?141.59,?147.61,?148.79(d,?J=8.25Hz),?150.11(d,?J=8.375Hz).
IR(KBr,?v/cm -1):?3435,?3049,?2860,?1603,?1510,?1488,?1453,?1373,?1328,?1301,?1280,?1189,?1167,?1103,?1088,?965,?934,?837,?803,?691,?624,?544?cm -1.
MS(ESI):?443(M+H) +.
Embodiment 7:2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(3-chloro-phenyl-)-2-(amino methyl) phenol (3 mmol, 0.701 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 45.4%, fusing point (mp): 127.2 ~ 127.6 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?4.10(dd,?J1=8.5Hz,?J2=16Hz,?2H),?6.43(dd,?J1=15Hz,?J2=18Hz,?1H),?4.93(dd,?J1=6Hz,?J2=14.5Hz,?1H),?6.41(d,?J=7.5Hz,?1H),?6.50(s,?1H),?6.71(d,?J=7.5Hz,?1H),?7.03(t,?J=8Hz,?1H),?7.11(d,?J=8.5Hz,?1H),?7.14~7.22(m,?5H),?7.28~7.29(m,?3H),?7.33~7.36(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?43.10,?52.30,?111.35,?112.53,?117.54,?118.85(d,?J=8.75Hz),?120.39,?122.31,?122.39(d,?J=3.5Hz),?124.02(d,?J=3.75Hz),?124.82,?125.67,?126.05,?126.23,?126.70,?126.84,?129.08,?129.23,?129.47,?130.06,?130.14,?130.28,?134.82(d,?J=3Hz),?142.68(d,?J=3.5Hz),?148.71(d,?J=8.375Hz),?149.88(d,?J=8.375Hz).
IR(KBr):?3336,?3064,?2921,?2860,?1597,?1489,?1455,?1287,?1215,?1168,?1090,?1035,?1010,?976,?957,?930,?843,?765,?679,?645,?595?cm -1.
Embodiment 8:2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(4-chloro-phenyl-)-2-(amino methyl) phenol (3 mmol, 0.701 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 48.6%, fusing point (mp): 133.8 ~ 134.3 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?4.08(dd,?J 1=13.5Hz,?J 2=20Hz,?2H),?4.60(dd,?J 1=15Hz,?J 2=18.5Hz,?1H),?4.92(d,?J 1=6Hz,?J 2=15Hz,?1H),?6.37(d,?J=8.5Hz,?2H),?7.06(d,?J=8.5Hz,?2H),?7.10(d,?J=8Hz,?1H),?7.13~7.19(m,?3H),?7.21~7.28(m,?6H),?7.32~7.35(m,?2H).
13C?NMR(CDCl 3,?125?MHz)?δ:?43.29,?52.59,?113.92(2C),?118.95(d,?J=8.625Hz),?120.43,?122.16,?122.51(d,?J=7.25Hz),?124.77,?125.64(d,?J=3.75Hz,?2C),?125.68,?126.85,?128.99(2C),?129.01,?129.50,?129.53(2C),?129.88(d,?J=5.875Hz),?130.10,?131.66,?140.11(d,?J=3.5Hz),?146.44,?148.80(d,?J=8.375Hz),?150.06(d,?J=8.25Hz).
IR(KBr,?v/cm -1):?3321,?3067,?2862,?1600,?1586,?1492,?1456,?1404,?1378,?1275,?1196,?1171,?1075,?1003,?968,?954,?916,?886,?862,?756,?690,?605?cm -1.
Embodiment 9:2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(2-aminomethyl phenyl)-2-(amino methyl) phenol (3 mmol, 0.640 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 54.5%, fusing point (mp): 136.1 ~ 137.0 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.04(s,?3H),?2.35(s,?3H),?4.14~4.21(m,?2H),?4.45~4.51(m,?1H),?4.77~4.78(m,?1H),?6.39(d,?J=8Hz,?1H),?6.65(t,?J=7Hz,?1H),?7.00~7.11(m,?5H),?7.12~7.17(m,?3H),?7.21~7.24(m,?2H),?7.29~7.34(m,?4H).
13C?NMR(CDCl 3,?125?MHz)?δ:?17.36,?18.03,?42.94,?53.53(d,?J=3.375Hz),?109.78(2C),?117.00(2C),?119.04(d,?8.375Hz),?120.33,?122.13,?124.39,?125.27,?126.66,?126.93(2C),?127.09,?128.03,?128.63,?129.10,?129.70,?129.92(2C),?130.28(d,?J=6.25Hz),?131.49,?139.43,?145.85,?149.10(d,?J=8.375Hz).
IR(KBr,?v/cm -1):?3446,?3048,?3014,?2911,?2853,?1605,?1584,?1515,?1486,?1454,?1369,?1303,?1268,?1213,?1187,?1169,?1099,?1044,?932,?875,?837,?769,?749,?651,?577?cm -1.
MS(ESI):?471(M+H) +.
Embodiment 10:2-(2-(3-aminomethyl phenyl amido) methyl) phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(3-aminomethyl phenyl)-2-(amino methyl) phenol (3 mmol, 0.640 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 68.0%, fusing point (mp): 83.2 ~ 84.0 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.22(s,?3H),?2.29(s,?3H),?3.94(s,?1H),?4.09(d,?J=14.5Hz,?1H),?4.13(d,?J=14Hz,?1H),?4.60(dd,?J 1=15Hz,?J 2=18.5Hz,?1H),?4.92(dd,?J 1=6.5Hz,?J 2=15Hz,?1H),?6.25~6.28(m,?2H),?6.50(d,?J=7.5Hz,?1H),?6.97~7.00(m,?2H),?7.07(t,?J=8Hz,?2H),?7.10~7.15(m,?2H),?7.16~7.23(m,?4H),?7.28~7.34(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?21.31,?21.53,?42.82,?52.56,?109.78,?113.54,?118.29,?118.77(d,?J=8.25Hz),?120.16(d,?J=2Hz),?121.35(d,?J=3.625Hz),?122.90(d,?J=7.25Hz),?124.42,?125.11(d,?J=3.75Hz),?125.24,?126.71,?126.77,?128.46,?128.90,?129.13(2C),?129.56,?130.33(d,?J=6.375Hz),?138.70,?139.33,?141.47(d,?J=3.25Hz),?147.86,?148.76(d,?J=8.25Hz),?150.08(d,?J=8.25Hz).
IR?(KBr,?v/cm -1)?v:?3352,?3033,?2918,?2855,?1606,?1586,?1528,?148,?1454,?1289,?1216,?1171,?1091,?1034,?944,?838,?756,?696,?602,?536?cm -1.
Embodiment 11:2-(2-(4-aminomethyl phenyl amido) methyl) phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(4-aminomethyl phenyl)-2-(amino methyl) phenol (3 mmol, 0.640 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate, add 60 mL ethyl acetate again, water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase respectively, organic phase anhydrous sodium sulfate drying, precipitation obtains yellow oil by column chromatography for separation, productive rate 48.9%.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.23(s,?3H,?CH 3),?2.30(s,?3H,?CH 3),?4.11(dd,?J 1=14Hz,?J 2=23Hz,?2H),?4.60(dd,?J 1=15Hz,?J 2=18.5Hz,?1H),?4.91(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.38(d,?J=8Hz,?2H),?6.92(d,?J=8Hz,?2H),?7.08~7.16(m,?6H),?7.20~7.25(m,?3H),?7.29~7.34(m,?3H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.40,?20.88,?43.25,?52.84,?113.11(2C),?118.85(d,?J=8.25Hz),?120.23,?122.92(d,?J=7.125Hz),?124.49,?124.62(d,?J=3.75Hz,?2C),?125.31,?126.59,?126.82,?128.49,?129.18,?129.57(2C),?129.70,?130.04(2C),?130.48(d,?J=6.25Hz),?135.92,?138.91,?145.54,?148.84(d,?J=8.375Hz),?150.15(d,?J=8.125Hz).
IR(KBr,?v/cm -1):?3371,?3030,?2921,?2860,?1615,?1585,?1514,?1487,?1456,?1373,?1294,?1222,?1171,?1101,?1034,?932,?816,?758,?599,?539?cm -1.
Embodiment 12:2-(2-(2-p-methoxy-phenyl amido) methyl) phenoxy group-3-(2-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(2-p-methoxy-phenyl)-2-(amino methyl) phenol (3 mmol, 0.688 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 44.0%, fusing point (mp): 105.5 ~ 108.1 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?3.66(s,?3H,?OCH 3),?3.73(s,?3H,?OCH 3),?4.20(d,?J=15Hz,?1H),?4.28(d,?J=15Hz,?1H),?4.47(t,?J=16Hz,?1H),?4.91(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.47(s,?1H),?6.68~6.78(m,?3H),?6.87~6.90(m,?2H),?7.06~7.21(m,?4H),?7.20~7.24(m,?2H),?7.28~7.30(m,?2H),?7.35(dd,?J 1=1Hz,?J 2=8Hz,?1H),?7.30(d,?J=8.5Hz,?1H).
13C?NMR(CDCl 3,?125?MHz)?δ:?42.27,?52.65,?55.27,?55.46,?109.28,?109.96,?112.08,?116.44,?118.87(d,?J=8.25Hz),?120.12,?120.97,?121.18,?123.88(d,?J=7.25Hz),?124.13,?124.87,?126.50,?128.19,?128.47,?128.75,?128.94,?129.35(d,?J=2.5Hz),?129.82(d,?J=3.875Hz),?130.28(d,?J=6.875Hz),?137.80,?146.72,?149.14(d,?J=7.375Hz),?150.61(d,?J=8Hz),?155.80(d,?J=3.875Hz).
IR(KBr,?v/cm -1):?3435,?3072,?2998,?2960,?2934,?2834,?1601,?1587,?1501,?1452,?1373,?1347,?1306,?1266,?1225,?1189,?1169,?1033,?967,?933,?866,?837,?792,?763,?734,?598,?577,?547?cm -1.
Embodiment 13:2-(2-(4-p-methoxy-phenyl amido) methyl) phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(4-p-methoxy-phenyl)-2-(amino methyl) phenol (3 mmol, 0.688 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 56.1%, fusing point (mp): 122.8 ~ 123.7 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?3.74(s,?3H,?OCH 3),?3.76(s,?3H,?OCH 3),?4.10(dd,?J 1=14Hz,?J 2=20.5Hz,?2H),?4.58(dd,?J 1=15.5Hz,?J 2=18.5Hz,?1H),?4.89(dd,?J 1=6.5Hz,?J 2=15Hz,?1H),?6.45(d,?J=9Hz,?2H),?6.72(d,?J=8.5Hz,?2H),?6.79(d,?J=9Hz,?2H),?7.09~7.17(m,?4H),?7.22~7.25(m,?1H),?7.27~7.30(m,?3H),?7.31~7.35(m,?2H).
13C?NMR(CDCl 3,?125?MHz)?δ:?44.14,?53.56,?55.45,?55.78,?114.41(2C),?114.75(4C),?118.98(d,?J=8.5Hz),?120.39,?122.94(d,?J=7.25Hz),?124.49,?125.38,?126.80,?126.92(d,?J=3.375Hz,?2C),?128.70,?129.21,?130.07,?130.40(d,?J=6.125Hz),?134.09,?142.01,?149.00(d,?J=8.25Hz),?150.24(d,?J=8.125Hz),?152.29,?158.10.
IR(KBr,?v/cm -1):?3406,?3055,?3005,?2933,?2839,?1583,?1513,?1460,?1375,?1301,?1249,?1223,?1205,?1121,?1103,?968,?932,?843,?815,?771,?735,?638,?594?cm -1.
Embodiment 14:2-(2-(3-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(3-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(3-chloro-phenyl-)-2-(amino methyl)-4-methylphenol (3 mmol, 0.743 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 52.3%, fusing point (mp): 105.3 ~ 107.5 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.28(s,?3H),?2.32(s,?3H),?3.99(dd,?J 1=13.5Hz,?J 2=21Hz,?2H),?4.56(dd,?J 1=15Hz,?J 2=17Hz,?1H),?4.84(dd,?J 1=6Hz,?J 2=14.5Hz,?1H),?6.32(d,?J=8Hz,?1H),?6.40(s,?1H),?6.65(d,?J=8Hz,?1H),?6.92(s,?1H),?6.95~7.06(m,?3H),?7.09~7.11(m,?3H),?7.14~7.22(m,?2H),?7.27(s,?1H),?7.32(s,?1H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.69,?20.74,?42.88,?52.25,?111.11,?112.29,?117.10,?118.48(d,?J=8.5Hz),?120.09,?121.91(d,?J=7.25Hz),?122.22(d,?J=3.125Hz),?123.89(d,?J=4.25Hz),?125.79,?127.22,?129.41,?129.96,?130.04,?130.23,?130.56,?130.77,?134.50,?134.74,?135.29,?136.09,?142.96(d,?J=3.5Hz),?146.52(d,?J=8.25Hz),?147.73(d,?J=8.25Hz),?149.19.
IR(KBr,?v/cm -1):?3356,?2922,?1712,?1597.?1487,?1424,?1361,?1293,?1210,?1191,?1151,?1094,?951,?919,?837,?763,?683,?594,?541?cm -1.
Embodiment 15:2-(2-(4-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(4-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(4-chloro-phenyl-)-2-(amino methyl)-4-methylphenol (3 mmol, 0.743 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains white solid by column chromatography for separation, productive rate 52.7%, fusing point (mp): 143.6 ~ 144.4 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.28(s,?3H),?2.33(s,?3H),?3.97~4.05(m,?2H),?4.54(dd,?J 1=15Hz,?J 2=18Hz,?1H),?4.85(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.35~6.38(m,?2H),?6.92(s,?1H),?6.97(d,?J=18.5Hz,?1H),?7.04~7.08(m,?3H),?7.10~7.16(m,?3H),?7.19~7.21(m,?2H),?7.24~7.27(m,?2H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.68,?20.75,?43.26,?52.52,?113.83(2C),?118.54(d,?J=8.375Hz),?120.15,?121.94,?121.01(d,?J=7.25Hz),?125.49(d,?J=3.5Hz,?2C),?127.08,?128.86(2C),?129.35,?129.38(2C),?129.41,?129.87,?130.65,?131.38,?134.35,?135.28,?140.19,?146.48,?146.53,?147.83(d,?J=8.125Hz).
IR(KBr,?v/cm -1):?3331,?3081,?2914,?2898,?2846,?1602,?1490,?1369,?1293,?1224,?1176,?1115,?950,?902,?819,?779,?701,?644,?602,?510?cm -1.
Embodiment 16:2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(4-aminomethyl phenyl)-2-(amino methyl)-4-methylphenol (3 mmol, 0.682 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate, add 60 mL ethyl acetate again, water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase respectively, organic phase anhydrous sodium sulfate drying, precipitation obtains yellow oil by column chromatography for separation, productive rate 61.8%.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.24(s,?3H,?CH 3),?2.26(s,?3H,?CH 3),?2.29(s,?3H,?CH 3),?2.32(s,?3H,?CH 3),?4.04(dd,?J 1=14.5Hz,?J 2=18Hz,?2H),?4.54(dd,?J 1=15Hz,?J 2=18Hz,?1H),?4.85(dd,?J 1=6Hz,?J 2=15Hz,?1H),?6.38(d,?J=8Hz,?2H),?6.89~6.96(m,?4H),?7.01(d,?J=8Hz,?1H),?7.06~7.09(m,?3H),?7.14(s,?1H),?7.19(d,?J=8.5Hz,?1H),?7.23(d,?J=8Hz,?2H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.13,?20.42,?20.51,?20.59,?43.17,?52.67,?112.87(2C),?118.32(d,?J=8.375Hz),?119.80,?122.25(d,?J=7.25Hz),?124.35(d,?J=3.5Hz),?126.31,?126.82,?128.77,?129.26(2C),?129.36,?129.72(3C),?130.10,?133.77,?134.61,?135.50,?138.83,?145.47,?146.44(d,?J=8.75Hz),?147.80(d,?J=8.125Hz).
IR(KBr):?3358,?3028,?2921,?2861,?1615,?1496,?1361,?1294,?1216,?1152,?1109,?960,?937,?812,?767,?729,?620,?548?cm -1.
Embodiment 17:2-(2-(2-p-methoxy-phenyl amido) methyl-4-methyl) phenoxy group-3-(2-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate synthetic.
The tetrahydrofuran (THF) that adds 30 mL dryings in the there-necked flask of 100 mL successively, N-(2-p-methoxy-phenyl)-2-(amino methyl)-4-methylphenol (3 mmol, 0.730 g) and triethylamine (5.4 mmol, 0.546 g), ice bath stirs down slowly, and dropping 10 mL contain phosphorus oxychloride (1.8 mmol, 0.276 tetrahydrofuran solution g), slowly be heated to 65 ℃ behind 30 min, continue reaction 5 h, the TLC monitoring reaction, react the back suction filtration and removed triethylamine salt, concentrating under reduced pressure filtrate adds 60 mL ethyl acetate again, respectively water (30 mL * 2 time) and saturated nacl aqueous solution (30 mL * 2 time) washing organic phase, the organic phase anhydrous sodium sulfate drying, precipitation obtains brown solid by column chromatography for separation, productive rate 54.7%, fusing point (mp): 129.1 ~ 131.6 ℃.
1H?NMR(CDCl 3,?500?MHz)?δ:?2.26(s,?3H,?CH 3),?2.29(s,?3H,?CH 3),?3.67(s,?3H,?OCH 3),?3.76(s,?3H,?OCH 3),?4.10(d,?J=15Hz,?1H),?4.18(d,?J=15Hz,?1H),?4.42(t,?J=16Hz,?1H),?4.82(dd,?J 1=6Hz,?J 2=15.5Hz,?1H),?6.38(d,?J=7.5Hz,?1H),?6.64(t,?J=7.5Hz,?1H),?6.75(q,?J=8Hz,?2H),?6.82(s,?1H),?6.85~6.89(m,?2H),?6.95(d,?J=8Hz,?1H),?7.00(d,?J=8Hz,?1H),?7.04(d,?J=8.5Hz,?1H),?7.14(s,?1H),?7.21(t,?J=8Hz,?1H),?7.30(d,?J=8.5Hz,?1H),?7.34(d,?J=8Hz,?1H).
13C?NMR(CDCl 3,?125?MHz)?δ:?20.62,?20.75,?42.33,?52.65,?55.22,?55.45,?109.17,?109.94,?112.05,?116.35,?118.56(d,?J=8.25Hz),?119.92,?120.92,?121.15,?123.29(d,?J=7.25Hz),?126.80,?128.33,?128.66,?129.18,?129.33(d,?J=1.375Hz),?129.48,?129.81(d,?J=6.375Hz),?129.91(d,?J=4Hz),?133.61,?134.37,?137.95,?146.71,?146.88(d,?J=8Hz),?148.41(d,?J=8.125Hz),?155.80(d,?J=4Hz).
IR(KBr,?v/cm -1):?3437,?3064,?2999,?2921,?2839,?1601,1524,?1491,?1461,?1351,?1297,?1248,?1209,?1184,?1145,?1106,?1051,?1027,?937,?919,?813,?797,?755,?732,?646,?568?cm -1.
Adopt China Pesticide Discovery Engineering Technical Research Centre's biological activity determination Standard operation procedure SOP (SOP) to 2-phenoxy group-3-(4-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-phenoxy group-3-(3-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(phenyl amido) methyl) phenoxy group-3-phenyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(3-aminomethyl phenyl amido) methyl) phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(4-aminomethyl phenyl amido) methyl) phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(2-p-methoxy-phenyl amido) methyl) phenoxy group-3-(2-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(4-p-methoxy-phenyl amido) methyl) phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(3-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(3-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(4-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(4-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, 2-(2-(2-p-methoxy-phenyl amido) methyl-4-methyl) phenoxy group-3-(2-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate has carried out the insecticidal activity test.
With mythimna separata ( Mythimna sepatara), the broad bean aphid ( Aphis fabae) and two-spotted spider mite ( Tetranychus urticae) try target as the confession of insecticidal activity test.Adopt spray method for mythimna separata, broad bean aphid and two-spotted spider mite are adopted pickling process, and general sieve concentration is 500mg/L, after the processing, is put into the recovery indoor cultivation, regularly observe, and check behind the 72h and the record death condition, calculate mortality ratio.The insecticidal activity test result sees Table one.
 
Table one 2-aryloxy-3-aryl-3,4-dihydro-2H-1, the insecticidal activity of 3,2-benzo phosphoramidate
Compound Mythimna separata/% Aphid/% Red spider/%
2-phenoxy group-3-(4-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 6.67 2.74
2-phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 12.60 11.67
2-phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 25.95 7.99
2-phenoxy group-3-(3-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 2.78 2.63
2-phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 15.00 5.24 3.33
2-(2-(phenyl amido) methyl) phenoxy group-3-phenyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 3.33 0.00
2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 63.46 5.42
2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 69.62 1.67
2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 52.38 4.79
2-(2-(3-aminomethyl phenyl amido) methyl) phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 30.00 14.69 3.28
2-(2-(4-aminomethyl phenyl amido) methyl) phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 29.32 4.17
2-(2-(2-p-methoxy-phenyl amido) methyl) phenoxy group-3-(2-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 0.00 41.96
2-(2-(4-p-methoxy-phenyl amido) methyl) phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 15.00 0.00
2-(2-(3-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(3-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 0.00 11.67 10.14
2-(2-(4-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(4-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 5.00 4.17 3.33
2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 85.00 6.12 4.30
2-(2-(2-p-methoxy-phenyl amido) methyl-4-methyl) phenoxy group-3-(2-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate 25.00 3.33 5.24
From table one as can be seen, part of compounds to mythimna separata ( Mythimna sepatara) show preferably active, as compound 2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate to mythimna separata ( Mythimna sepatara) cytotoxicity best, mortality ratio is up to 85.00%.Some compound to the broad bean aphid ( Aphis fabae) all have certain activity, 2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate to the broad bean aphid ( Aphis fabae) cytotoxicity best, mortality ratio is 69.62%; Next is compound 2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate and 2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate to the broad bean aphid ( Aphis fabae) the poisoning mortality ratio be respectively 63.46%, 52.38%.

Claims (3)

1. the 2-aryloxy-3-aryl-3 shown in the general formula (I), 4-dihydro-2H-1,3,2-benzo phosphoramidate compounds,
Figure 2013101921536100001DEST_PATH_IMAGE002
，
（I）
In the formula (I), the substituting group on three phenyl ring is respectively R 1, R 2, R 3And R 4
In the formula (I), substituent R 2Be H, R 3When being H: R 1Be CH 3, R 4Be p-OCH 3Or R 1Be H, R 4Be m-CH 3Or R 1Be H, R 4Be p-CH 3Or R 1Be H, R 4Be m-OCH 3Or R 1Be H, R 4Be p-OCH 3
In the formula (I), substituent R 1Be H, R 2When being H: R 3Be C 6H 5NHCH 2, R 4Be H; Or R 3Be 3-ClC 6H 4NHCH 2, R 4Be m-Cl; Or R 3Be 4-ClC 6H 4NHCH 2, R 4Be p-Cl; Or R3 is 2-CH 3C 6H 4NHCH 2, R 4Be o-CH 3Or R 3Be 3-CH 3C 6H 4NHCH 2, R 4Be m-CH 3Or R 3Be 4-CH 3C 6H 4NHCH 2, R 4Be p-CH 3Or R 3Be 2-OCH 3C 6H 4NHCH 2, R 4Be o-OCH 3Or R 3Be 4-OCH 3C 6H 4NHCH 2, R 4Be p-OCH 3
In the formula (I), substituent R 1Be CH 3, R 2Be CH 3The time: R 3Be 3-ClC 6H 4NHCH 2, R 4Be m-Cl; Or R 3Be 4-ClC 6H 4NHCH 2, R 4Be p-Cl; Or R 3Be 4-CH 3C 6H 4NHCH2, R 4Be p-CH 3Or R 3Be 2-OCH 3C 6H 4NHCH 2, R 4Be o-OCH 3
2. 2-aryloxy according to claim 1-3-aryl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate compounds is characterized in that, comprising:
2-phenoxy group-3-(4-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE004
2-phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE006
2-phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE008
2-phenoxy group-3-(3-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE012
2-(2-(phenyl amido) methyl) phenoxy group-3-phenyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE014
2-(2-(3-chloro-phenyl-amido) methyl) phenoxy group-3-(3-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(4-chloro-phenyl-amido) methyl) phenoxy group-3-(4-chloro-phenyl-)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE018
2-(2-(2-aminomethyl phenyl amido) methyl) phenoxy group-3-(2-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE020
2-(2-(3-aminomethyl phenyl amido) methyl) phenoxy group-3-(3-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE022
2-(2-(4-aminomethyl phenyl amido) methyl) phenoxy group-3-(4-aminomethyl phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE024
2-(2-(2-p-methoxy-phenyl amido) methyl) phenoxy group-3-(2-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(4-p-methoxy-phenyl amido) methyl) phenoxy group-3-(4-p-methoxy-phenyl)-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
2-(2-(3-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(3-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE030
2-(2-(4-chloro-phenyl-amido) methyl-4-methyl) phenoxy group-3-(4-chloro-phenyl-)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE032
2-(2-(4-aminomethyl phenyl amido) methyl-4-methyl) phenoxy group-3-(4-aminomethyl phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE034
2-(2-(2-p-methoxy-phenyl amido) methyl-4-methyl) phenoxy group-3-(2-p-methoxy-phenyl)-6-methyl-3,4-dihydro-2H-1,3,2-benzo phosphoramidate, structural formula is:
Figure 2013101921536100001DEST_PATH_IMAGE036
3. 2-aryloxy as claimed in claim 1-3-aryl-3,4-dihydro-2H-1, the purposes of 3,2-benzo phosphoramidate compounds aspect the preparation insecticide pesticide.
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