O-烷基S-烷基(芳基)硫代磷(膦)酸衍生物与三氯氧磷的氯化反应──合成S-烷基(芳基)硫代磷(膦)酰氯酯的新方法

在研究O,O二烷基O芳基硫代磷酸酯(1)与三氯氧磷的异构化氯化反应机理时,发现1的异构化产物O,S二烷基硫代磷酸酯(4)能顺利地与三氯氧磷反应,4中的烷氧基被氯原子取代,得到的产物S烷基硫代磷酰氯酯(2)和O烷基磷酰二氯酯3.当4中的R为烷基或苯基,R'为烷氧基、芳氧基、烷硫基、芳硫基、二烷基氨基、氮杂环基、苯基和甲基,R"为C_1-4烷基时,4的氯化反应也能顺利发生,并得到较高产率的预期产物.     

S-烯丙基-O-取代苯基硫代磷(膦)酸衍生物的合成及杀菌活性研究

O,O-二烯丙基硫代磷(膦)酸酯(6)与三氯氧磷发生异构化氯化反应得到S-烯丙基硫代磷(膦)酰氯7和O-烯丙基磷酰二氯酯(8).7在碱性溶液中与取代酚反应,合成了18个新的标题化合物,生物活性测试表明,这些化合物均有一定的杀菌活性,有些化合物还具有较好的杀菌活性或杀虫活性.     

有机硫代磷(膦)酸铵盐与三氯氧磷的氯化反应──合成硫(酮)代磷(膦)酰氯的一种新的简便方法

O,O二烷基硫代磷(膦)酸衍生物与二甲胺水溶液发生去烷基反应后,生成的硫代磷(膦)酸铵盐与三氯氧磷发生氯化反应,得到硫(酮)代磷(膦)酰氯.本文还讨论了该反应可能的机理.     

S-烷基-O-(2,6-二氯-4取代苯基)硫代磷(膦)酸酯的合成及杀菌活性的研究

O,O-二烷基硫酮代磷(膦)酸酯(3)与三氯氧磷发生异构化氨化反应得到S-烷基硫代磷(膦)酰氨(4),4与2,6-二氯-4-取代苯酚反应,合成了26种新的标题化合物.生物活性初步测定结果表明,这些化合物均有一定的杀菌活性.     

S-烷基-O-多氯苯基硫代磷(膦)酸衍生物的合成及杀菌活性研究

O,O-二烷基硫代磷(膦)酸酯与三氯氧磷发生异构化氯化反应生成S-烷基硫代磷(膦)酰氯,后者在缚酸剂存在下与多氯酚反应得到标题化合物。此类化合物也可以用传统方法,从S-烷基硫代磷酰二氯先后与多氯酚及其它亲核试剂反应得到。对所合成的28个新化合物的平碟试验表明,在0.005%浓度下对小麦赤霉等12种植物病菌均表现了明显的抑制活性。     

O,O-二烷基S-烷基(芳基)二硫代磷酸酯的异构化氯化反应——合成S-烷基S-烷基(芳基)二硫代磷酸衍生物的新方法

报道了合成S-烷基S-烷基(芳基)二硫代磷酸衍生物的一种便利的新方法。O,O-二烷基S-烷基(芳基)二硫代磷酸酯与三氯氧磷发生氯化反应的同时,伴随着P=S键异构成P-S键,生成S-烷基S-烷基(芳基)二硫代磷酰氯,在碱存在下进一步与各种亲核试剂反应,得到S-烷基S-烷基(芳基)二硫代磷酸衍生物。     

有机硫代磷（膦）酸铵盐与三氯氧磷的氯化反应

Ｏ,Ｏ－二烷基硫代磷（膦）酸衍生物与二甲胺水溶液发生去烷基反应后,生成的硫代磷（膦）酸铵盐与三氯氧磷发生氯化反应,得到硫（酮）代磷（膦）酰氯,本文还讨论了该反应可能的机理。     

O—烷基S—烷基（芳基）硫代磷（膦）酸衍生物与三氯氧磷的氯化反应

在研究Ｏ,Ｏ－二烷基Ｏ－芳基硫代磷酸酯（１）与三氯氧磷的异构化氯化反应机理时,发现１的异构化产物Ｏ,Ｓ－二烷基硫代磷酸酯（４）能顺利地与三氯氧磷反应,４中的烷氧基被氯原子取代,得到的产物Ｓ－烷基硫代磷酰氯酯（２）和Ｏ－烷基磷酰二氯酯３,当４中的Ｒ为烷基或苯基,Ｒ为烷氧基、芳氧基、烷硫基、芳硫基、１二烷基氨基、氮杂环基、苯基和甲基,Ｒ为Ｃ１－４烷基时,４的氯化反应也能顺利发生,并得到较高产率的预期产     

S-烷基O-芳基硫代磷酸衍生物的合成及其杀虫活性的研究

研究了O,O-二烷基O-芳基硫代磷酸酯与三氧氧磷的异构化氯化反应。由此生成的S-烷基O-芳基硫代磷酰再与亲核试剂(醇,酚,硫醇,硫酚,伯胺或氨)在缚酸剂存在下反应,合成了42种化合物,其中34种未见文献报道。本文还研究了这类化合物的杀虫活性。     

S—烷基—O—（2,6—二氯—4—取代苯基）硫代磷（膦）酸酯的合成及杀…

Ｏ，Ｏ－烷基硫酮代磷（膦）酸酯（３）与三氯氧磷发生异构化氯化反应得到Ｓ－烷基硫代磷（膦）酰氯（４），４与２，６－二氯－４－取代苯酚反应，合成了２６种新的标题化合物。生物活性初步测定结果表明，这些化合物均有一定的杀菌活性。     

The Chlorination of O-Alkyl S-Alkyl(aryl) Thiophosphoric(-nic) Acid Derivatives with Phosphorus Oxychloride——A New Convenient Method for Synthesis of Chiral S-Alkyl(aryl) Thiophosphoro(-no) Chloridates

In our laboratory, the isomerization/chlorination of a variety of O,O-dialkyl phosphoro(-no)thionates 1 with phosphorus oxychloride have been systematically studied. It was found that when R' equals aryloxy^[1], alkylthio^[2], arylthio^[2], dialkylamino^[3], phenyl^[4], methyl^[5],and nitrogen heterocyclic group^[6] in 1,respectively, this reaction can proceed smoothly and gives the desired products ² and ³. Hence, it provides a general synthitic method for S-alkyl thiophosphoro(-no)chloridates, especially for the asymmetric ones.     

The Isomerization/Chlorination of O,O-Diallyl Thiophosphoric (-nic) Acid Esters with Phosphorus Oxychloride─A New Convenient Method for Synthesis of S-Alkyl Thiophosphoric(-nic) Acid Derivatives

In1991wefoundthattheisomerizationlchlorinationofO,O-dialbyIO-arylthiophosphates1(R'=ArO)withphosphorusoxychloridecantakeplaceandgivesSalkylO-arylthiophosphoridates2(R'=ArO)andO-alkylphosphorodichloridates31.Inthereaction,when1ischlorinatedwithphosphorusoxychloride,theisomerizationoftheP=StotheP-Soccurssimultaneously.Additionallythisisomerizationlchlorinationcanconvertanachiralphosphorusatomintoachiralphosphorusatomtogive2.LaterinvestigationsindicatedthatwhenR'equalsalkylthio',arylthio',…     

A NEW CONVENIENT SYNTHESIS OF S-ALKYL N,N-DIALKYL THIOPHOSPHORAMIDIC ACID DERIVATIVES

The chlorination of O,O-dialkyl N,N-dialkyl thiophosphoramidateswith phosphorus oxychloride proceeds with isomerization to give S-alkylN,N-dialkyl thiophosphoramidochloridates,which react further with variousnucleophiles in the presence of base to give the title compounds.     

The isomerization/chlorination of nitrogen heterocyclic O,O-dialkyl thiophosphoramidates with phosphorus oxychloride—A convenient synthesis of nitrogen heterocyclic S-alkyl thiophosphoramidic acid derivatives

In this article, it is reported that the isomerization/chlorination reactions of nitrogen heterocyclic O,O-dialkyl thiophosphoramidates 5 with equivalent amounts of phosphorus oxychloride give nitrogen heterocyclic S-alkyl thiophosphorochloridates 6 and O-alkyl phosphorodichloridates 3. After removal of the by-products 3 under reduced pressure, the crude products 6 are directly reacted with various nucleophiles, NuH, in the presence of triethylamine to give nitrogen heterocyclic S-alkyl thiophosphoramidic acid derivatives 7. Thus, a new convenient method has been provided for the synthesis of the title compounds. © 1996 John Wiley & Sons, Inc.     

The isomerization/chlorination of 0,0-dialkyl methylthiophosphonates with phosphorus oxychloride—a new convenient synthesis of S-alkyl methylthiophosphonic acid derivatives

A new method for the synthesis of S-alkyl methylthiophosphonic acid derivatives is reported. The chlorination of 0,0-dialkyl methylthiophosphonates 8 with phosphorus oxychloride proceeds with isomerization of the P=S to the P–S bond to give S-alkyl methylthiophosphonochloridates 9 , which react further with various nucleophiles in the presence of triethylamine to afford S-alkyl methylthiophosphonic acid derivatives 10 . Among them, several compounds 10 show excellent fungicidal or insecticidal activities. © 1995 John Wiley & Sons, Inc.