CN1043120C - Bactericide of phosphate (phosphinium) ester - Google Patents

Bactericide of phosphate (phosphinium) ester Download PDF

Info

Publication number
CN1043120C
CN1043120C CN94103709A CN94103709A CN1043120C CN 1043120 C CN1043120 C CN 1043120C CN 94103709 A CN94103709 A CN 94103709A CN 94103709 A CN94103709 A CN 94103709A CN 1043120 C CN1043120 C CN 1043120C
Authority
CN
China
Prior art keywords
phosphorus
ester
phosphine
bactericide
phosphinium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN94103709A
Other languages
Chinese (zh)
Other versions
CN1096161A (en
Inventor
唐除痴
金桂玉
李树正
吴桂萍
张素华
李秉武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN94103709A priority Critical patent/CN1043120C/en
Publication of CN1096161A publication Critical patent/CN1096161A/en
Application granted granted Critical
Publication of CN1043120C publication Critical patent/CN1043120C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a germicide containing an organophosphorus compound, namely S-alkyl O-poly-hologenophenyl-thiophosphate with the general formula 1, wherein R=an alkyl group from C1 to C6, or a 2-chloroethyl; R'= a benzene group, a methyl group, an alkoxyl group, an alkylthio, an aryloxy, an arylthioyl or an amino; n= 2 to 5. The compound of the formula 1 is synthesized by a method of the isomerization and the chlorination of dialkyl thiophosphate, and the present invention has good germicidal activity.

Description

Phosphorus (phosphine) bactericide of phosphate (phosphinium) ester
The present invention relates to contain the bactericide class of organic phosphorus compound.
Commercial organophosphorus fungicide mostly has symmetrical structure, as kitazine, Hinosan, tolelofos-methyl etc.
Figure C9410370900031
Kitazine Hinosan tolelofos-methyl
We find recently, and S-alkyl 0-many halobenzenes base sulfo-phosphorus (phosphine) acid 1 with dissymmetrical structure has excellent bactericidal activity.
Its chemical structural formula is:
R=C 1-6Alkyl, the 2-chloroethyl;
R '=phenyl, methyl, alkoxyl, alkylthio group, aryloxy group, arylthio, amido;
n=2～5
Compound with formula structure, can with the method for the isomerization chlorination of sulfo-phosphorus (phosphine) acid dialkyl ester of this experiment in recent years invention (see Chinese patent 91101697, X191101698 X) prepares, and course of reaction is as follows:
Figure C9410370900033
Figure C9410370900041
Sulfo-phosphorus (phosphine) acid dialkyl ester 2 carries out in the time of 60-100 ℃ with the isomerization chlorination of phosphorus oxychloride, after having reacted accessory substance 0-alkyl phosphinylidyne dichloro-4,4 is steamed under reducing pressure, excess obtains product 1 without separating to purify directly to react in the presence of the acid binding agent in solvent with many halophenols.
Compound with 1 formula structure, in the plate test, 12.5 under the concentration of～50ppm, mostly has the broad-spectrum sterilization activity, these phytopathogens comprise: gibberella saubinetii (Giberella zeae), apple wheel spot (Alternaria mali}, cucumber anthrax (Collototrochum lagenarium), paddy rice rice blast (Piricularia oryzae), peanut foxiness (Cercospora arachidicala), tomato is epidemic disease (Alternariasolani) early, vegetables grey mold (Botrytis cinerae), cotton standing dead (Rhizoctoniasolami), apple wheel line (Physalospora piricola), withered (Helminthosporium oryzne) the rape sclerotium of paddy rice oriental sesame leaf (Sclerotiniasclerotiorum), apple anthrax (Glomerella cingulata) etc.Wherein work as R '=methyl, phenyl, alkylthio group, aryloxy group, arylthio in 1 formula, the R=alkyl, many alkylhalide groups, Cln n=3, You Ji are to work as R=Me, R '=Ph, Cln=2,4,5-Cl 3The time, bactericidal activity is more outstanding.Table 1 has exemplified the antibacterial activity of part of compounds to above-mentioned several plant disease fungus, and concentration is 50ppm, serves as the contrast medicament with carbendazim (M.B.C).
Example 1 S-(2-chloroethyl) O-(2,4, the 5-trichlorophenyl) phenylphosphonothioic acid acid (1, R=ClCH 2CH 2, R ＇=C 6H 6, Cln=2,4,5-Cl 3) synthetic
3.5g (0.0117mol) 0, and 0-two (2-chloroethyl) phenylphosphonothioic acid ester (2, R=CH 2ClCH 2R ＇=Ph) and 1.9g (0.0117mol) phosphorus trichloride are in 80-85 ℃ of stirring reaction 12h, (detect until reactant 2 disappearances with TLC, silica gel plate, petrol ether/ethyl acetate (V/V) is launched at 10: 1, iodine vapor colour developing) 0.7/1mmHg that reduces pressure after having reacted bathes outward and steams accessory substance 4 (R=ClCH about 80 ℃ 2CH 2), excess adds 25ml chloroform and 2.3g (0,0117mol) 2,4, the 5-trichlorophenol drips 1.42g (0.014mol) triethylamine under the room temperature, be warming up to 50-60 ℃ of reaction 4h, can add a small amount of triethylamine and reach about 9 until pH if reactant is acidity, the Lu is crossed in cold back, boil off solvent and get crude product 4.0g, with silica gel column chromatography (200-300 order, petrol ether/ethyl acetate (V/V), gradient elution in 10: 1～1: 1) purifies, get product 2.6g, productive rate 53.4% (two step gross production rates), n D 251.6125, 1H NMR δ (ppm): 3.14 (dt, 2H, J PH=14,8Hz), 3,50 (t, 2H), 7.46-8.08 (m, 7H).IR(cm -1):1235(s,P=O）。Elementary analysis: C 14H 11Cl 4O 2PS (FM, 416.1) calculated value: C%40.41, H%2.66; Measured value: C%40.64, H%2.58.
Example 2 S-amyl group O-(2,4, the 5-trichlorophenyl) methyl Thiophosphonate (1, R=C 8H 11R ＇=Me, Cln=2,4,5-Cl 3) synthetic
Operation is with example 1,7.48g (0.0297mol) 2 (R=C 6H 11, R ＇=Me) and 4.56g (0.0297mol) POCl 3In 100 ℃ of reaction 20h, pressure reducing and steaming accessory substance 4 (R=C 5H 11) after, crude product is purified through decompression distillation, collects b.p.99-102 ℃/0.5mmHg, n D 251.5084 get 4.03g 3 (R=C 5H 11, R ＇=Me), productive rate 67.7%.
Get 3 (R=C of above-mentioned gained 5H 11, 2.51g (0.0126mol) of R ＇=Me) and 2.47g (0.0125mol) 2,4,5-trichlorophenol, 2,4,6,-T and 1.25g (0.0125mol) triethylamine reacts in 50ml toluene, crude product 4.0g, through silica gel column chromatography purify product 2.36g productive rate 52.2%, n D 251.5640. 1H NHR δ (ppm), 0.8 (t, 3H), 1.03-1.26 (m, 4H), 1.52 (m, 2H), 2.05 (d, 3H, J PH=15.1Hz), 2.80 (dt, 2H, J PH=13.2Hz), 7.50 (m, 2H) IR (cm -1): 1237 (s, P=O), elementary analysis, C 12H 16Cl 3O 2PS (FW:361.6) calculated value: C%39.86, H%4.46, measured value: C%39.87%.H%4.58%,
Example 3 S-ethyl O-(4-chlorphenyl) 0-(2,4, and 5-trichlorophenyl thiophosphate (1, R=Et, R ＇=4-ClC 5H 4O, Cln=2,4,5-Cl 3) synthetic
Operation is with example 1.4.2g (0.015mol) 2 (R=Et, R ＇=4-C 8H 4O) and phosphorus oxychloride 90-96 ℃ of 2.3g (0.015mol) reaction 64h until raw material disappear (TLC monitoring).Pressure reducing and steaming accessory substance 4 (R=Et), excess is dissolved in the 10ml chloroform, drips 2.8g (0.014mol) 2,4, and the mixture of 5-trichlorophenol, 3.1g (0.03mol) triethylamine and 10ml chloroform is warming up to 30-45 ℃ of stirring reaction 4h after adding.Cold back is washed with 2 * 15mL, and drying boils off chloroform, and crude product is purified with silica gel column chromatography, gets product 1 (R=Et, R ＇=4-ClC 5H 4O, Cln=2,4,5-Cl 3) 2.8g, productive rate 43.1% (three step gross production rates), n D 251.5921. 1H NMRδ(ppm):1.36(t,3H),3.06(dq,2H,J PH=16.6Hz),7.28～7.72(m,6H)。IR(cm -1):1239(s,P=O)。Elementary analysis C 14H 11C 14O 3PS (FW:432.1) calculated value: C%38.92, H%2.57, measured value: C%38.45, H%2.41,
Example 4 S-methyl S-propyl group O-(2,4, and 5-trichlorophenyl phosphorodithioate (1, R=Me, R ＇=PrS, Cln=2,4,5-Cl 3Synthetic
Operation is with example 1.3.4g (0.017mol) 2 (R=Me, R ＇=PrS) in about 65 ℃, react 4.5h with 2.8g (0.018mol) phosphorus oxychloride, boil off accessory substance 4 (R=Me) after, add the 20ml chloroform, drip 3.4g (0.015mol) 2,4 under the stirring at room, 5-trichlorophenol, 2,4,6,-T, 2.0g (0.02mol) triethylamine and 15ml chloroformic solution are warming up to 40-45 ℃ of reaction 3h, washing after adding, dry, boil off solvent, crude product, purify with silicagel column, get product 1 (R=Me, R ＇=PrS, Cln=2,4,5-Cl 3) 2.2g, productive rate 35.5% (two step gross production rates) n D 251.5885 1H NMR δ (ppm): 1.04 (t, 3H), 1.80 (m, 2H), 2.50 (d, 3H, J PH=16.6Hz), 3.02 (dt, 2H, J PH=14.4Hz), and 7.53-7.72 (m, 2H), IR (cm -1): 1229 (s, P=O).Elementary analysis C 10H 12Cl aO 2PS 2(FW:365.7), calculated value: C%32.85, H%3.31, measured value: C%32.87, H%3.22.
Example 5 S-ethyl S-phenyl O-(2,4, the 5-trichlorophenyl) phosphorodithioates (1, R=Et, R ＇=PhS, Cln=2,4,5-Cl 3) synthetic
Operation is with example 1.By 2.5g (0.0095mol) 2 (R=Et, R ＇=PhS) and the crude product 3 (R=Ets of 1.6g (0.0104mol) phosphorus oxychloride in 70 ℃ of reaction 7h gained, R ＇=PhS) adds 1.9g (0.0095mol) 2,4, the mixture of 5-trichlorophenol, 1.1g (0.011mol) triethylamine and 20mL chloroform, 40-50 ℃ of reaction 6h, crude product purify through silica gel osmanthus product 1 (R=Et, R ＇=PhS, Cln=2,4,5-Cl 3) 1.9g, productive rate 48.2% (two step gross production rates), n D 251.6092. 1H NMRδ(ppm):1.22(t,3H),2.83(dq,2H,J PH=16.2),7.00-7.62(m,7H)IR(cm -1):1232(s,P=O)。Elementary analysis C 14H 12Cl 3O 2PS 2(FW:413.7), calculated value: C%40.65, H%2.92, measured value: C%40.62, H%2.77.
Example 6 N, and N-diethyl S-methyl O-(2,3, the 5-trichlorophenyl) thio-phosphamide ester (1, R=Me, R ＇=Et 2N, Cln=2,3,5-Cl 3) synthetic
Operation is with example 1.2 (R=Me, R ＇=Et 2N) react 11h, b.p.80-82 ℃/0.2mmHg of decompression distillation collection with waiting mole phosphorus oxychloride in 60-65 ℃.Get this product of distillation 3 (R=Me, R ＇=Et 2N) 2.1g (0.0104mol) is dissolved in the 15mL chloroform, agitation and dropping 2.1g (0.0106mol) 2 in the time of 15 ℃, 3, the mixture of 5-trichlorophenol, 1.5g (0.015mol) triethylamine and 10mL chloroform adds the back in 45 ℃ of reaction 4h, washing, dry, steam solvent, crude product is purified with silica gel column chromatography, gets product 1 (R=Me, R ＇=Et 2N, Cln=2,3,5-Cl 3) 2.0g, productive rate 53.0% (single step reaction), n D 251.5590, 1H NMR δ (ppm): 120 (t, 6H), 2.32 (d, 3H, J PH=15.1Hz) .3.33 (dq, 4H, J PH=13.0Hz), and 7.54-7.80 (m, 2H).IR(cm -1):1239(s,P=O)。Elementary analysis C 11H 15Cl aNO 2PS (FW:362.6), calculated value: C%36.43, H%4.17, N%3.86, measured value: C%36.57, H%4.04, N%3.74.
Example 7 adds a little organic solvent (0.5mL) respectively with 1 all compounds, and each medicine is got 1mL and is placed in the culture dish, adds the 9mL agar medium, treats inoculating block (three repetitions, a contrast) after the medium drying.After spending 48 hours, survey bacterium colony expansion diameter, ask relative inhibition.Test result sees Table 1
Table 1
Compound R R ＇ Cln Gibberella saubinetii Apple wheel spot The cucumber anthrax The paddy rice rice blast The peanut foxiness Tomato is epidemic disease early The vegetables grey mold Cotton standing dead Apple wheel line The paddy rice leaf is withered fiber crops recklessly The rape sclerotium The apple anthrax
ClCH 2CH 2 Ph 2,4,5-Cl 3Me Ph 2,4.5-Cl 3Et Ph 2,4,5-Cl 3Pr Ph 2,4,5-Cl 3Bu Ph 2,4,5-Cl 3Et Ph 2,3,5-Cl 3Et Ph Cl 3CH 2CH 2Cl Me 2,4,5-Cl 3Me Me 2,4,5-Cl 3Et Me 2,4,5-Cl 3Pr Me 2,4,5-Cl 3Bu Me 2,4,5-Cl 3Armyl Me 2,4,5-Cl 3 100 100 83.3 80.8 100 83.3 83.0 100 100 100 100 100 100 100 100 100 100 100 100 73.8 - - - - - - 100 100 100 100 89.0 100 67.5 - - - - - - 100 100 100 100 - 100 100 - - - - - - 100 100 100 100 100 100 78.6 100 100 - - 100 100 100 100 100 100 58.0 100 61.0 100 100 100 100 100 100 100 100 100 100 - 100 100 - - - - - - 61.9 100 100 57.1 100 82.5 82.5 100 100 100 100 100 100 100 100 100 74.0 100 100 84.0 100 100 100 100 100 100 100 100 80.8 100 - 84.6 61.5 - - - - - - 100 100 100 100 - 100 100 - - - - - - 100 100 100 100 - 100 76.0 - - - - - -
Table 1 is continuous
Et PhO 2,4,5-Cl 3Et 4-ClC 3H 4O 2,4,5-Cl 3Pr 4-ClC 3H 4O 2,4,5-Cl 3Et 2,4,5-Cl 3C 6H 2O 2,4,5-Cl 3Pr 2,4,5-Cl 3C 6H 2O 2,4,5-Cl 3Pr Cl 5C 5O Cl 5Me PrS 2,4,5-Cl 3Et PrS 2,4,5-Cl 3Et BuS 2,4,5-Cl 3Et PhCH 2S 2,4,5-Cl 3Et PhS 2,4,5-Cl 3Me Et 2N 2,4,5-Cl 3Pr Et 2N 2,4,5-Cl 3Me Et 2N 2,3,5-Cl 3Me Et 2N Cl 5Many bacterium phosphorus (MBC) 73.3 26.7 26.7 80.0 100 73.3 81.7 100 20.0 100 100 50.0 30.0 83.3 13.3 100 79.1 25.0 8.3 83.3 - 55.8 100 100 27.1 100 100 45.8 45.8 33.3 25.0 0.0 100 28.0 25.0 100 - 63.2 100 100 29.2 74.0 100 33.3 100 33.3 37.5 12.5 100 100 100 100 - 100 100 100 100 - - 100 100 100 50.0 100 100 45.7 28.6 100 - 53.1 100 100 42.9 100 100 31.4 60.0 20.6 11.4 100 100 31.6 28.9 100 100 56.8 100 100 23.7 100 100 36.8 31.6 31.6 0.0 0.0 100 21.2 20.4 71.4 - 100 100 100 12.5 - - 60.0 42.9 49.3 40.8 100 48.4 11.1 0.0 52.4 100 72.2 76.2 100 39.7 100 100 76.2 49.2 77.8 19.8 100 76.0 24.0 24.0 68.0 100 76.0 100 100 32.0 100 100 44.0 56.0 44.0 0.0 100 69.2 53.8 53.8 80.8 - 69.2 80.8 100 57.7 - - 61.5 57.7 42.3 38.5 7.7 100 65.1 65.1 84.1 - 100 100 100 74.2 - - 87.9 87.9 79.5 51.5 100 100 52.0 48.0 100 - 76.0 100 100 52.0 - - 56.0 100 46.0 32.0 100

Claims (4)

1. a phosphorus (phosphine) bactericide of phosphate (phosphinium) ester is characterized in that its general formula is: Wherein, R=methyl, ethyl, propyl group, butyl, amyl group, 2-chloroethyl; R '=methyl, 4-chlorophenoxy, 2,4,5-Trichlorophenoxy, pentachloro-phenoxy group, rosickyite base, butylthio, benzylthio, diethylin; Cln=2,4,5-Cl 3, 2,3,5-Cl 3, Cl 5
2. according to the said phosphorus of claim 1 (phosphine) bactericide of phosphate (phosphinium) ester, it is characterized in that the R=ethyl, R '=propyl group, Cln=2,4,5-Cl 3
3. the synthetic method of the said phosphorus of claim 1 (phosphine) bactericide of phosphate (phosphinium) ester, the synthesis step that it is characterized in that it is, under 60-100 ℃, carry out isomerization chlorination with sulfo-phosphorus (phosphine) acid dialkyl ester 2 and phosphorus oxychloride, after the reaction accessory substance 0-alkyl phosphinylidyne dichloro is under reduced pressure steamed, excess is purified without separating, and directly obtains product in the presence of the acid binding agent with many halophenols in solvent.
4. the application of the said phosphorus of claim 1 (phosphine) bactericide of phosphate (phosphinium) ester is characterized in that it can be used to kill fusarium graminearum, apple zonate spot bacterium, cucumber anthracnose, Pyricularia oryzae Cav bacterium, peanut Cercospora bacteria, tomato early blight bacterium, eliminating vegetable botrytis bacterium, cotton rhizoctonia solani, ring rot of apple bacterium, paddy rice flax leaf spoting bacteria, rape sclerotium and apple anthrax bacteria.
CN94103709A 1994-04-04 1994-04-04 Bactericide of phosphate (phosphinium) ester Expired - Fee Related CN1043120C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN94103709A CN1043120C (en) 1994-04-04 1994-04-04 Bactericide of phosphate (phosphinium) ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN94103709A CN1043120C (en) 1994-04-04 1994-04-04 Bactericide of phosphate (phosphinium) ester

Publications (2)

Publication Number Publication Date
CN1096161A CN1096161A (en) 1994-12-14
CN1043120C true CN1043120C (en) 1999-04-28

Family

ID=5031230

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94103709A Expired - Fee Related CN1043120C (en) 1994-04-04 1994-04-04 Bactericide of phosphate (phosphinium) ester

Country Status (1)

Country Link
CN (1) CN1043120C (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663665A (en) * 1968-06-18 1972-05-16 Bayer Ag O-cycloalkyl-s-alkyl-o-halophenyl-phosphorothiolates
US3839563A (en) * 1968-06-18 1974-10-01 Bayer Ag Fungicidal o-alkyl(-cycloalkyl)-s-alkyl-o-halophenyl-phosphorothiolates
DE2440761A1 (en) * 1973-08-29 1975-03-13 Ciba Geigy Ag Biocidal phosphonates esp. active against cotton pests, flies and aphi - prepd. by reaction of substd. phosphorohalide with substd. phenol and acid-binding agent
US3954919A (en) * 1970-12-26 1976-05-04 Bayer Aktiengesellschaft O-ethyl-S-N-propyl-O-(substituted pheny)-phosphorothiolates
US4006229A (en) * 1970-10-26 1977-02-01 Ciba-Geigy Ag Insecticidal and acaricidal trihalophenyl thiophosphates
FR2516517A1 (en) * 1981-11-19 1983-05-20 Rhone Poulenc Agrochimie O-aryl and o-alkyl s tertiary-alkyl alkyl:phosphono:thionate(s) - insecticide and nematocide plant protection agents, esp. active against coleoptera, dibrotica spp, and lepidoptera

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3663665A (en) * 1968-06-18 1972-05-16 Bayer Ag O-cycloalkyl-s-alkyl-o-halophenyl-phosphorothiolates
US3839563A (en) * 1968-06-18 1974-10-01 Bayer Ag Fungicidal o-alkyl(-cycloalkyl)-s-alkyl-o-halophenyl-phosphorothiolates
US4006229A (en) * 1970-10-26 1977-02-01 Ciba-Geigy Ag Insecticidal and acaricidal trihalophenyl thiophosphates
US3954919A (en) * 1970-12-26 1976-05-04 Bayer Aktiengesellschaft O-ethyl-S-N-propyl-O-(substituted pheny)-phosphorothiolates
DE2440761A1 (en) * 1973-08-29 1975-03-13 Ciba Geigy Ag Biocidal phosphonates esp. active against cotton pests, flies and aphi - prepd. by reaction of substd. phosphorohalide with substd. phenol and acid-binding agent
FR2516517A1 (en) * 1981-11-19 1983-05-20 Rhone Poulenc Agrochimie O-aryl and o-alkyl s tertiary-alkyl alkyl:phosphono:thionate(s) - insecticide and nematocide plant protection agents, esp. active against coleoptera, dibrotica spp, and lepidoptera

Also Published As

Publication number Publication date
CN1096161A (en) 1994-12-14

Similar Documents

Publication Publication Date Title
US5312814A (en) α-phosphonocarboxylate squalene synthetase inhibitors
CN1043120C (en) Bactericide of phosphate (phosphinium) ester
Hoffmann et al. Organic Phosphorus Compounds. II. 1 Isomeric Alkyl Phosphoro-and Phosphonothioates
O'Neal et al. Oxidation and methylation reactions of PH-substituted (silylamino) phosphines
Lin et al. Phospholipids chiral at phosphorus. 18. Stereochemistry of phosphatidylinositide-specific phospholipase C
Satish Kumar et al. Pentacoordinate phosphoranes with reversed apicophilicity as stable intermediates in a Mitsunobu-type reaction
Wallace et al. Species specificity in the chemical mechanisms of organophosphorus anticholinesterase activity
Cristau et al. Synthesis of bis (hydroxymethyl) phosphorylated compounds, analogs of α-aminophosphonic acids or alkylidenebisphosphonic acids
US3658953A (en) Process for the preparation of substituted vinyl esters of acids of phosphorus
NL8302353A (en) PHOSPHORIZATION AGENT; METHOD FOR PREPARING THEREOF METHOD FOR PHOSPHORYLATING AN ORGANIC HYDROXYL OR AMINE COMPOUND
US3660543A (en) S-2-hydrocarbylthio-alkyl esters of thiophosphorus acids
KOBAYASHI et al. Synthesis and biological activities as insecticides and fungicides of saligenin cyclic phosphorothiolates
US6147244A (en) Preparations of thiophosphites and thiophosphonates
Quin et al. Generation of Ethyl Metathiophosphate by Thermal Fragmentation of O-Ethyl N-Substituted Phosphoramidothioates
US2912450A (en) Reaction products of dialkyl phosphorothiolothionates and acetylenic compounds
Drábek et al. Synthesis and biological properties of dinitroarylphosphates
US3644598A (en) 1 - alkoxy(-alkenyloxy -phenoxy) - 1-thiono-3-chloro(3-alkyl)phospholines
US3705217A (en) Production of haloethylphosphonate diesters
US2957019A (en) O, o-dialkyl s-(2-cyano-haloalkyl) phosphorothiolothionates
Li et al. Synthesis of N-(alkoxycarbonyl or alkoxycarbonyl-methyl-alkoxyphosphonyl)-α-amino-O, O-diphenyl phosphonates and their bioactivities
Xu et al. Synthesis of 1‐(N‐perfluoroalkanesulfonylamino)‐2, 2, 2‐(trichloroethyl) dialkylphosphonates and phosphonic Acids
US3336314A (en) O-quinolinyl s-alkyl-alkylphos-phonodithioates
Szabo et al. Synthesis and biological properties of insecticidal S-(phthalimidomethyl) O-alkyl alkylphosphonodithioates and thiolates
Blair et al. Insecticide Screening, Synthesis and Insecticide Activity of Methyl 2, 4, 5-Trichlorophenyl Phosphoramidates
KR20040104506A (en) Improved method for the production of bisphosphites

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee