CN105131033A - N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof - Google Patents
N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt and application thereof Download PDFInfo
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- CN105131033A CN105131033A CN201510490822.7A CN201510490822A CN105131033A CN 105131033 A CN105131033 A CN 105131033A CN 201510490822 A CN201510490822 A CN 201510490822A CN 105131033 A CN105131033 A CN 105131033A
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- 241000700605 Viruses Species 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 241000723873 Tobacco mosaic virus Species 0.000 claims abstract description 29
- 201000010099 disease Diseases 0.000 claims abstract description 10
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 10
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims abstract description 8
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- 240000008574 Capsicum frutescens Species 0.000 claims abstract description 7
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 7
- 244000017020 Ipomoea batatas Species 0.000 claims abstract description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 claims abstract description 4
- 241000723994 Maize dwarf mosaic virus Species 0.000 claims abstract description 4
- 244000061456 Solanum tuberosum Species 0.000 claims abstract description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 claims abstract description 4
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- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims abstract description 3
- 244000046052 Phaseolus vulgaris Species 0.000 claims abstract description 3
- 240000003768 Solanum lycopersicum Species 0.000 claims abstract 4
- 244000061176 Nicotiana tabacum Species 0.000 claims abstract 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 41
- -1 methoxy, oxyethyl group Chemical group 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 244000241257 Cucumis melo Species 0.000 claims description 6
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 6
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 6
- 239000001390 capsicum minimum Substances 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004563 wettable powder Substances 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 3
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- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an N-(1, 2-diphenyl-2-amino)-thiophosphoramide salt compound and application thereof. The structural formula of the compound is shown as the specification (with the definitions of the groups being shown in the specification). The compound provided by the invention is applied to inhibition of tobacco mosaic virus, pepper virus, tomato virus, sweet potato virus, potato virus, cucurbit virus and maize dwarf mosaic virus, can effectively control the virus diseases of tobacco, hot pepper, tomatoes, cucurbites, grains, vegetables, beans and other crops, and is especially suitable for control of tobacco mosaic virus. (structural formula).
Description
Technical field
The present invention relates to N-(1,2-phenylbenzene-2-amino)-thiophosphoryl amine salt and as pesticides application.
Background technology
Plant virus is distributed widely in occurring in nature, and they cause serious harm to the growth of farm crop, and then cause heavy losses to modern agricultural production, and tobacco mosaic virus (TMV) (TMV) works the mischief to various crop as a kind of cause of disease physical efficiency.According to statistics, it can infect 22 kinds of monocotyledonous about 198 kinds of individualities, can cause about 5% to 90% loss (Hari, the V. do not waited; Das, P.Ultramicroscopicdetectionofplantvirusesandtheirgenepro ducts.Inplantdiseaseviruscontrol.Hadidi, A.; Khetarpal, R.K.; Koganezawa, H., Eds.; APSPress:St.Paul, MN, 1998:417-427.).Up to the present, also do not have a kind of chemical pesticide can thoroughly cover crop from the infringement of TMV.Equally, a kind of medicine is not had can to cure the crop encroached on by TMV completely yet.Although existing Antiphytoviral medicament kind is a lot, as diazosulfide (BTH), tiadinil (TDL), 4-methyl isophthalic acid, 2, pyridine alkaloid antofine, viral A, Whitfield's ointment, amino-oligosaccharide etc. in 3-thiadiazoles-5-formic acid (TDLA), DL-beta-aminobutyric acid (BABA), virazole, Ningnanmycin, phenanthro-indoles, but practical kind in these anti-plant virus agents existing is also few, field control effect is generally lower than 60%, and life-time service exists certain environmental risk.Therefore green Antiphytoviral pesticide new variety meaning that is efficient, low toxicity is designed and developed very great.
At present, containing β-thiophosphoryl amido aminated compounds is mainly used in asymmetric synthesis, straight big vast seminar reports compound N-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide is succeeded application (Lu, A.D. in asymmetric Michaeladdition addition reaction; Liu, T.; Wu, R.H.; Wang, Y.M.; Wu, G.P.; Zhou, Z.H.; Fang, J.X.; Tang, C.C.ArecyclableorganocatalystforasymmetricMichaeladditio nofacetonetonitroolefins.J.Org.Chem., 2011,76,3872 – 3879.).Owing to containing primary amine functional group in N-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thiophosphoryl amine molecule, place easily oxidized in atmosphere, thus limit the purposes of this compounds in other side.
Summary of the invention
Object of the present invention is not enough in order to solve the current stability containing β-thiophosphoryl amido aminated compounds, furthers investigate its application on agricultural chemicals, provides a kind of new N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt and application thereof.The invention provides one and prepare N-(1,2-phenylbenzene-2-is amino) method of-thiophosphoryl amine salt find that such compound has good anti-phytoviral activity, tobacco mosaic virus (TMV) (i.e. TMV), capsicum virus, tomato virus, sweet potato viruses, potato virus and melon virus and maize dwarf mosaic virus can be suppressed well, effectively can prevent and treat the virus disease of tobacco, capsicum, tomato, melon dish, grain, vegetables and legume crop, be particularly suitable for preventing and treating tobacco mosaic disease.
Technical scheme of the present invention is:
A kind of N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt compound, the following formula I of structural formula of this compound:
Wherein, R representation methoxy, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, phenoxy group, benzyloxy, methylamino-, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, phenylamino or benzyl are amino; * the configuration when carbon atom that to be connected with phenyl is chiral carbon is represented: R configuration, or S configuration, or its 1:1 mixture; HA is HCl, HBr, HI, CF
3cOOH, HCOOH, propionic acid, hexanodioic acid, phenylformic acid, lactic acid, L-TARTARIC ACID, D-tartrate, oxysuccinic acid, L-camphorsulfonic acid, Whitfield's ointment, P-hydroxybenzoic acid, succsinic acid, trans-ferulaic acid, Sulphanilic Acid, gluconic acid or Sorbic Acid.
Described N-(1,2-phenylbenzene-2-is amino) application of-thiophosphoryl amine salt compound, be applied to and suppress tobacco mosaic virus (TMV), capsicum virus, tomato virus, sweet potato viruses, potato virus and melon virus and maize dwarf mosaic virus, effectively can prevent and treat the virus disease of the various crop such as tobacco, capsicum, tomato, melon, grain, vegetables and beans; Be particularly suitable for preventing and treating tobacco mosaic disease.
The application of described N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt compound, is specially with the direct application of single compound monomer aqua, emulsion or wettable powder; Or be the application of the aqua of the mixture of multiple compounds, emulsion or wettable powder.
The invention has the beneficial effects as follows: compared with prior art, outstanding substantive distinguishing features of the present invention and marked improvement as follows:
(1) successful that N-(1,2-phenylbenzene-2-amino)-thiophosphoryl amine salt is used for activity of resisting tobacco mosaic virus is better than medicament virazole and the Ningnanmycin of prior art.Reason is: experimental results demonstrate, the phosphamide structural unit compound synthesized that combines with other group has good fungicidal activity, weeding activity and anti-phytoviral activity.
(2) with the existing medicament for activity of resisting tobacco mosaic virus or Compound Phase ratio, marked improvement of the present invention is as follows:
1. compared with virazole (Ribavirin): virazole, as the more successful plant virus inhibitor of one, is widely used in the disease that control TMV causes.When dosage is 500 μ g/mL, virazole is respectively 41%, 37%, 36% and 39% to the inhibiting rate in the isolated activity of tobacco mosaic virus (TMV), live body passivation, live body treatment and live body protection; Under same test condition, the inhibiting rate of N-of the present invention (1,2-phenylbenzene-2-is amino)-thiophosphoryl amine hydrochlorate (1) is respectively 72%, 71%, 68% and 67%, far away higher than virazole.Correlation data can see table 2 below.
2. compared with Ningnanmycin: Ningnanmycin is the best anti-plant viral disease medicament of current preventive effect, and Ningnanmycin has good preventive effect, but its result for the treatment of is poor.Under same test condition, when dosage is 500 μ g/mL, 61%, 63%, 54% and 64% is respectively to the inhibiting rate of commercial varieties Ningnanmycin in the isolated activity of tobacco mosaic virus (TMV), live body passivation, live body treatment and live body protection, although best prevention effect can reach 64%, and result for the treatment of only has 54%; Contrast N-(1 of the present invention; 2-phenylbenzene-2-is amino) isolated activity of-thiophosphoryl amine hydrochlorate (1), live body passivation, inhibiting rate in live body treatment and live body protection be respectively 72%, 71%, 68% and 67%, all exceedes commercial varieties Ningnanmycin.Correlation data can see table 2 below.
3. 3-aryl-5-methylbutyrolactone Compound Phase ratio is disclosed with CN201410344605.2; the live body treatment of the result for the treatment of reported in CN201410344605.2 and best compound 3-(4-the fluorophenyl)-5-methyl-gamma-butyrolactone of protected effect and live body protect inhibiting rate to be respectively 57% and 60%; and the present invention is containing N-(1; 2-phenylbenzene-2-is amino) the live body treatment of-thiophosphoryl amine hydrochlorate (1) and live body protect inhibiting rate to be respectively 68% and 67%, be significantly improved.
(3) compound of the present invention has good chemical stability.Owing to containing primary amine functional group in N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine molecule, easily oxidized in atmosphere, after itself and mineral acid or organic acid salify, stability strengthens greatly.Inhibiting rate in isolated activity when freshly prepd N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine hydrochlorate (1) dosage is 500 μ g/mL, live body passivation, live body treatment and live body protection is respectively 72%, 71%, 68% and 67%.Place under drying conditions after two months in atmosphere, the inhibiting rate in its isolated activity, live body passivation, live body treatment and live body protection is respectively 72%, 72%, 69% and 67%, and activity of resisting tobacco mosaic virus does not reduce.
Embodiment
The present invention is described in further detail by the following examples, but the invention is not restricted to these embodiments.
The chemical structural formula of embodiment 1, part N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt and physical constant, in table 1:
The chemical structural formula of table 1. part N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt and physical constant
Above-mentioned preferred compound and known parent compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide is compared has outstanding advantages, be in particular in: (1) light, thermostability obviously strengthen, nuclear-magnetism qualitative detection is used after continuing 24 hours with fluorescent lamp irradiation or temperature control 80 DEG C under equal conditions, above-claimed cpd does not change, and control sample N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide major part decomposes.(2) water dissolution strengthens, and control sample N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide is water-soluble hardly, and preferred compound improves water-soluble by salify or introducing modification group.Above-mentioned 2 have vital effect to the application of compound on agricultural chemicals.
The preparation of embodiment 2: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thiophosphoryl amine hydrochlorate (1)
Under 0 DEG C of condition, by (1R, 2R)-diphenyl ethylene diamine (2.12g, 0.01mmol) be dissolved in methylene dichloride (10mL), add triethylamine (1.4mL), stir in reactor, then by phenylbenzene thiophosphoryl chloride (0.252g, 0.01mmol) be dissolved in methylene dichloride (30mL), add in reaction system with constant pressure funnel, then TLC detects, after raw material phenylbenzene thiophosphoryl chloride disappears, vacuum desolvation, column chromatography is purified, product N-(the 1R obtained, 2R)-(1, 2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide.White solid, yield is 81%, and fusing point is 118-120 DEG C.[α]
2 d 0– 23.4 (c1.0, CHCl
3);
1hNMR (CDCl
3, 400MHz): 1.80 (s, 2H), 4.19 (t, J=6.8Hz, 1H), 4.25 (d, J=5.6Hz, 1H), 4.44-4.51 (m, 1H), 7.05-7.08 (m, 2H), 7.11-7.15 (m, 3H), 7.18-7.22 (m, 2H), 7.24-7.38 (m, 9H), 7.58-7.65 (m, 4H);
31pNMR (CDCl
3, 161.7MHz): 59.16;
13cNMR (CDCl
3, 100.6MHz): 61.3 (d, J=7.2Hz), 61.9,127.0,127.3,127.5,127.90,127.94,128.0,128.2,128.3,128.4,131.4,131.5,131.8,131.9,133.6,133.9,134.7,134.9,141.0,142.5. ultimate analysis Anal.calcd.forC
26h
25n
2pSm/z=428.15:C, 72.87; H, 5.88; N, 6.54; Found:C, 72.85; H, 5.90; N, 6.51.
By hydrochloric acid-ethyl acetate solution (2-3mmol, 10mL) add in 250mL there-necked flask, then N-(1R is added, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide (1mmol), after room temperature reaction 3h, vacuum desolvation obtains corresponding salt.White solid, yield is 99%, and fusing point is 155 – 158 DEG C.
1hNMR (CDCl
3, 400MHz): 4.77 (s, 1H), 4.97-5.04 (m, 1H), 6.88 (t, J=8.0Hz, 1H), (6.97-7.11 m, 5H), 7.23-7.34 (m, 8H), 7.43-7.45 (m, 2H), (7.50-7.60 m, 3H), 7.74-7.79 (m, 2H), 8.76 (s, 3H);
31pNMR (CDCl
3, 161.7MHz): 57.61;
13cNMR (CDCl
3, 100.6MHz): 59.3,59.4 (d, J=19.7Hz), 127.0,127.5,127.6,127.7,128.0,128.03,128.11,128.17,128.26,128.31,130.8,130.9,131.0,134.8,135.0,135.3,135.8,136.0,139.1; Ultimate analysis Anal.calcd.forC
26h
26clN
2pSm/z=464.12:C, 67.16; H, 5.64; N, 6.02.Found:C, 67.13; H, 5.68; N, 6.05.
The preparation of embodiment 3: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide hydrobromate (2)
By N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide (1mmol) is dissolved in trichloromethane (10mL) with the mixed solution of methyl alcohol (10mL), drip hydrobromic acid solution (48%, 1mL) after room temperature reaction 3h, add anhydrous sodium sulfate drying final vacuum precipitation and obtain corresponding salt.White solid, yield is 79%, and fusing point is 174-177 DEG C.
1hNMR (CDCl
3, 400MHz): 4.70-4.79 (m, 1H), 4.89 (s, 1H), 5.76 (t, J=10.8Hz, 1H), 6.95-6.97 (m, 2H), 7.07-7.23 (m, 10H), 7.33-7.37 (m, 1H), 7.44-7.50 (m, 3H), (7.57-7.62 m, 2H), 7.89-7.94 (m, 2H), 8.70 (s, 3H);
31pNMR (CDCl
3, 161.7MHz): 64.16;
13cNMR (CDCl
3, 100.6MHz): 59.7 (d, J=2.8Hz), 60.0,127.8,127.9,128.0,128.1,128.2,128.4,128.6,128.7,128.9,129.3,131.3,131.4,131.6,131.75,131.78,132.09,132.16,132.28,132.31,132.33,132.6,133.1,134.2,138.4 (d, J=4.5Hz); Ultimate analysis Anal.calcd.forC
26h
26brN
2pSm/z=508.07:C, 61.30; H, 5.14; N, 5.50; Found.C, 61.25; H, 5.18; N, 5.44.
The preparation of embodiment 4: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide sulfanilate (3)
Organic acid aniline sulfonic acid (1mmol) is dissolved in methyl alcohol (20mL), join in 100mL there-necked flask, then N-(1R is added, 2R)-(1,2-phenylbenzene-2-is amino) trichloromethane (50mL) mixed solution of-P, P-phenylbenzene thio-phosphamide (1mmol).In a nitrogen environment, 40-50 DEG C of reaction 3h, vacuum desolvation obtains corresponding salt.Yield is 92%, and fusing point is 120-123 DEG C.
1hNMR (CDCl
3, 400MHz): 4.67-4.80 (m, 2H), 6.12 (t, J=11.2Hz, 1H), 6.38 (t, J=8.4Hz, 2H), 6.93-7.16 (m, 16H), 7.27-7.39 (m, 6H), 7.56-7.62 (m, 2H), 7.82-7.88 (m, 2H);
31pNMR (CDCl
3, 161.7MHz): 64.16;
13cNMR (CDCl
3, 100.6MHz): 59.9 (d, J=4.6Hz), 60.4,113.9,127.4,127.5,127.6,127.8,127.9,128.1,128.3,128.47,128.56,128.63,131.1,131.19,131.28,131.30,131.8,132.0,132.4,132.9,133.5,133.6,133.9,135.7,138.7,148.1. ultimate analysis Anal.calcd.forC
32h
32n
3o
3pS
2m/z=601.16:C, 63.87; H, 5.36; N, 6.98; Found.C, 63.85; H, 5.39; N, 6.96.
The preparation of embodiment 5: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide camsilate (4)
Except organic acid is camphorsulfonic acid, the other the same as in Example 4.White solid, yield is 94%, and fusing point is 108-110 DEG C.
1hNMR (CDCl
3, 400MHz): 0.66 (s, 3H), 0.86 (s, 3H), 1.13-1.28 (m, 2H), 1.74-1.78 (m, 2H), 1.92 (t, J=4.0Hz, 1H), 1.98-2.05 (m, 1H), 2.17-2.23 (m, 1H), 2.36 (d, J=14.8Hz, 1H), 2.56 (d, J=14.8Hz, 1H), 4.78-4.88 (m, 1H), 4.86 (s, 1H), 6.31 (t, J=11.2Hz, 1H), 6.95-7.06 (m, 5H), 7.12-7.15 (m, 6H), 7.27-7.31 (m, 1H), 7.40-7.46 (m, 1H), 7.58-7.63 (m, 2H), 7.88-7.93 (m, 2H), 8.53 (brs, 2H),
31pNMR (CDCl
3, 161.7MHz): 63.36,
13cNMR (CDCl
3, 100.6MHz): 19.7,19.9,24.5,26.9,42.6,42.7,47.2,47.8,58.2,59.5 (d, J=4.6Hz), 60.3,127.5,127.8,127.9,128.0,128.1,128.3,128.4,128.5,128.7,131.2,131.3,131.4,131.6,131.7,131.8,132.1,132.3,132.6,133.0,133.6,134.0,135.2,138.6 (d, J=3.5Hz), 216.6, ultimate analysis Anal.calcd.forC
36h
41n
2o
4pS
2m/z=660.22:C, 65.43, H, 6.25, N, 4.24, Found.C, 65.41, H, 6.29, N, 4.22.
The preparation of embodiment 6: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide trifluoroacetate (5)
Except organic acid is trifluoroacetic acid, the other the same as in Example 4.Yellow solid, yield is 99%, and fusing point is 156 – 158 DEG C.
1hNMR (CDCl
3, 400MHz): 4.64 (s, 1H), 4.84-4.93 (m, 1H), 6.11 (t, J=12.0Hz, 1H), 6.96-6.98 (m, 2H), 7.13-7.28 (m, 10H), 7.40-7.46 (m, 3H), 7.51-7.55 (m, 1H), 7.62-7.68 (m, 2H), 7.81-7.86 (m, 2H), 8.77 (s, 2H), 9.40 (brs, 1H);
31pNMR (CDCl
3, 161.7MHz): 64.86;
13cNMR (CDCl
3, 100.6MHz): 60.0,60.5 (d, J=2.3Hz), 115.5 (q, J=287.5Hz), 127.6,128.3,128.4,128.5,128.6,128.7,129.2,129.6,130.9,131.0,131.5,132.0,132.2,132.3,132.5,133.3,134.5,138.1,161.5 (d, J=38.3Hz); Ultimate analysis Anal.calcd.forC
28h
26f
3n
2o
2pSm/z=542.14:C, 61.98; H, 4.83; N, 5.16; Found.C, 61.94; H, 4.87; N, 5.13.
The preparation of embodiment 7: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide Citrate trianion (6).
Except organic acid is citric acid, the other the same as in Example 4.White solid, yield is 81%, and fusing point is 93-96 DEG C.
1hNMR (CDCl
3, 400MHz): 2.28-2.42 (m, 4H), 4.72 (d, J=8.0Hz, 1H), 4.64 (d, J=10.4Hz, 1H), 4.35 (s, 1H), 6.97-7.16 (m, 11H), 7.31-7.43 (m, 5H), (7.57-7.62 m, 2H), 7.81-7.90 (m, 2H), 8.76 (brs, 5H);
31pNMR (CDCl
3, 161.7MHz): 63.32;
13cNMR (CDCl
3, 100.6MHz): 40.1,60.1,66.8,127.8,127.9,128.0,128.1,128.2,128.5,128.6,129.0,129.2,131.2,131.3,131.7,132.3,132.8,133.2,133.8,135.3,138.8,175.5,178.5; Ultimate analysis Anal.calcd.forC
32h
33n
2o
7pSm/z=620.17:C, 61.93; H, 5.36; N, 4.51; Found.C, 61.90; H, 5.38; N, 4.49.
The preparation of embodiment 8: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide malate (7)
Except organic acid is oxysuccinic acid, the other the same as in Example 4.White solid, yield is 94% fusing point is 90-94 DEG C.
1hNMR (CDCl
3, 400MHz): 2.30 (d, J=7.2Hz, 2H), 3.79 (s, 1H), 4.63 (d, J=10.0Hz, 1H), 4.82 (m, 1H), 6.68 (t, J=11.2Hz, 1H), 6.95 (m, 2H), 7.10-7.19 (m, 11H), 7.31-7.46 (m, 5H), 7.55-7.60 (m, 2H), 7.79-7.84 (m, 2H), 8.68 (brs, 4H);
31pNMR (CDCl
3, 161.7MHz): 63.32;
13cNMR (CDCl
3, 100.6MHz): 40.1,60.1,66.8,127.8,127.9,128.0,128.1,128.2,128.5,128.6,129.0,129.2,131.2,131.3,131.7,132.3,132.8,133.2,133.8,135.3,138.8,175.5,178.5; Ultimate analysis Anal.calcd.forC
30h
31n
2o
5pSm/z=562.17:C, 64.04; H, 5.55; N, 4.98; Found.C, 64.01; H, 5.59; N, 4.96.
The preparation of embodiment 9: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide p-hydroxybenzoate (8)
Except organic acid is P-hydroxybenzoic acid, the other the same as in Example 4.White solid, yield is 76%, and fusing point is 82-86 DEG C.
1hNMR (CDCl
3, 400MHz): 4.43 (d, J=8.4Hz, 1H), 4.54-4.59 (m, 1H), 5.89 (s, 1H), (6.50 d, J=7.6Hz, 2H), (6.85-7.05 m, 16H), 7.16-7.20 (m, 1H), 7.37 (d, J=8.0Hz, 2H), 7.50-7.66 (m, 8H);
31pNMR (CDCl
3, 161.7MHz): 62.59;
13cNMR (CDCl
3, 100.6MHz): 59.3,60.0,113.8,124.2,126.4,126.6,126.8,126.9,127.1,127.2,130.0,130.1,130.4,130.5,130.6,131.1,131.2,131.5,132.0,132.5,133.0,137.5,138.8,159.0,171.9; Ultimate analysis Anal.calcd.forC
33h
31n
2o
3pSm/z=566.18:C, 69.95; H, 5.51; N, 4.94; Found.C, 69.93; H, 5.55; N, 4.93.
The preparation of embodiment 10: target compound N-(1R, 2R)-(1,2-phenylbenzene-2-is amino)-P, P-phenylbenzene thio-phosphamide succinate (9)
Except organic acid is succsinic acid, the other the same as in Example 4.White solid, 94%yield, m.p.153-155 DEG C;
1hNMR (CDCl
3, 400MHz): 1.76-1.91 (m, 4H), 4.52 (d, J=10.0Hz, 1H), 4.70-4.79 (m, 1H), 6.93-6.95 (m, 2H), 7.01-7.23 (m, 11H), 7.31-7.35 (m, 1H), 7.45-7.48 (m, 3H), (7.57-7.62 m, 2H), 7.85-7.90 (m, 2H), 9.23 (brs, 4H);
31pNMR (CDCl
3, 161.7MHz): 63.59;
13cNMR (CDCl
3, 100.6MHz): 30.4,58.9,59.5,126.5,126.6,126.8,127.3,127.38,127.45,128.1,130.3,130.4,130.6,131.0,131.1,131.99,132.05,135.2,138.0,138.1,177.3; Ultimate analysis Anal.calcd.forC
30h
31n
2o
4pSm/z=546.17:C, 65.92; H, 5.72; N, 5.12; Found.C, 65.87; H, 5.76; N, 5.11.
The mensuration of embodiment 11:N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt activity of resisting tobacco mosaic virus, measures program as follows:
(1) measuring method
1.1, Virus purification and concentration determination:
Virus purification and concentration determination are given birth to reference to Nankai University's element and are surveyed room establishment tobacco mosaic virus (TMV) SOP regulation enforcement.Virus crude extract is after 2 polyoxyethylene glycol centrifugal treating, and measure concentration, 4 DEG C of refrigerations are for subsequent use.
1.2, compound solution preparation:
After weighing, former medicine adds DMF and dissolves, and obtained 1 × 10
5μ g/mL mother liquor, rear use is diluted to desired concn containing the 1 ‰ tween 80 aqueous solution; Ningnanmycin preparation is directly watered dilution.
1.3, act in vitro:
The of the right age blade of the western cigarette of frictional inoculation coral, with running water, virus concentration 10 μ g/mL.Receive after doing and cut, along arteries and veins in leaf to cuing open, left and right half leaf is dipped in 1 ‰ tween water and medicament respectively, takes out after 30min, and under suitable illumination temperature, moisturizing is cultivated, and every 3 leaves are repeat for 1 time, repeat 3 times.Record scab number after 3d, calculate preventive effect.
1.4, live body provide protection:
Select the western cigarette of 3 – 5 leaf phase coral of growing way uniformity, complete stool spray pesticide, often process 3 times and repeat, and establish 1 ‰ tween 80 aqueous solution contrasts.After 24h, blade face spreading silicon carbide (500 order), dips virus liquid with writing brush, dabs 2 times on full blade face along offshoot direction, and with palm support below blade, virus concentration 10 μ g/mL, uses running water after inoculation.Record scab number after 3d, calculate preventive effect.
1.5, live body therapeutic action:
Select the western cigarette of 3 – 5 leaf phase coral of growing way uniformity, with the full leaf virus inoculation of writing brush, virus concentration is 10 μ g/mL, uses running water after inoculation.After blade face is received and done, complete stool spray pesticide, often processes and repeats for 3 times, and establishes 1 ‰ tween 80 aqueous solution contrasts.Record scab number after 3d, calculate preventive effect.
1.6, live body passivation:
Select the western cigarette of 3 – 5 leaf phase coral of growing way uniformity, by medicament with after isopyknic viral juice mixing passivation 30min, frictional inoculation, virus concentration 20 μ g/mL, namely uses running water after inoculation, repeats 3 times, if 1 ‰ tween 80 aqueous solution contrasts.Number scab number after 3d, calculation result.
Inhibiting rate (%)=[(contrast withered spot number-process withered spot number)/contrast withered spot number] × 100%
(2) test-results
The anti-TMV active testing result that table 2N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt (1-3) obtains according to same measured method:
After tested, compound 1-3 carries out in vitro and live body (live body protection, live body treatment and live body passivation) test to TMV respectively at concentration 500 μ g/mL and 100 μ g/mL, shows outstanding anti-phytoviral activity.
The test result of table 2 part N-(1,2-phenylbenzene-2-is amino)-thio-phosphamide salt pair tobacco mosaic virus (TMV)
Visible in table 2, it is active that N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt (1-3) shows higher anti-TMV; Compound activity is obviously better than commercial varieties virazole, and particularly compound 1 activity of resisting tobacco mosaic virus under 500 μ g/mL and 100 μ g/mL concentration is obviously better than commercial varieties virazole and Ningnanmycin activity, possesses great Development volue.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. N-(1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt compound, is characterized by the following formula I of structural formula of this compound:
Wherein, R representation methoxy, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, phenoxy group, benzyloxy, methylamino-, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, phenylamino or benzyl are amino; * the configuration when carbon atom that to be connected with phenyl is chiral carbon is represented: R configuration, or S configuration, or its 1:1 mixture; HA is HCl, HBr, HI, CF3COOH, HCOOH, propionic acid, hexanodioic acid, phenylformic acid, lactic acid, L-TARTARIC ACID, D-tartrate, oxysuccinic acid, L-camphorsulfonic acid, Whitfield's ointment, P-hydroxybenzoic acid, succsinic acid, trans-ferulaic acid, Sulphanilic Acid, gluconic acid or Sorbic Acid.
2. N-(1 as claimed in claim 1,2-phenylbenzene-2-is amino) application of-thiophosphoryl amine salt compound, it is characterized by be applied to and suppress tobacco mosaic virus (TMV), capsicum virus, tomato virus, sweet potato viruses, potato virus and melon virus and maize dwarf mosaic virus, effectively can prevent and treat the virus disease of the various crop such as tobacco, capsicum tomato, melon, grain, vegetables, beans.
3. the application of N-as claimed in claim 1 (1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt compound, is characterized by and be preferred for preventing and treating tobacco mosaic disease.
4. the application of N-as claimed in claim 1 (1,2-phenylbenzene-2-is amino)-thiophosphoryl amine salt compound, is characterized by the direct application be specially with single compound monomer aqua, emulsion or wettable powder; Or be the application of the aqua of the mixture of multiple compounds, emulsion or wettable powder.
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| US3758645A (en) * | 1969-07-18 | 1973-09-11 | Sandoz Ltd | Cis thiophosphoric acid amide esters |
| US4176181A (en) * | 1977-08-19 | 1979-11-27 | Bayer Aktiengesellschaft | Combating pests with N-(aminomethylene)-(monothio and dithio)-phosphoric acid diester-amides |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044742A (en) * | 2021-11-26 | 2022-02-15 | 河北工业大学 | Chiral primary amine malonamide compound and preparation method and application thereof |
| CN114044742B (en) * | 2021-11-26 | 2023-02-10 | 河北工业大学 | Chiral primary amine malonamide compound and preparation method and application thereof |
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| CN105131033B (en) | 2017-05-31 |
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