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    • 2. 发明授权
    • Preparation of phenoxy-azolyl-butanone derivatives
    • 苯氧基 - 唑基 - 丁酮衍生物的制备
    • US4388465A
    • 1983-06-14
    • US300071
    • 1981-09-08
    • Hans-Ludwig ElbeHermann AroldEckart KranzClaus Stolzer
    • Hans-Ludwig ElbeHermann AroldEckart KranzClaus Stolzer
    • A01N43/50A01N43/653C07D233/60C07D249/08C07D521/00
    • C07D231/12C07D233/56C07D249/08
    • In the preparation of a phenoxy-azolyl-butanone derivative of the formula ##STR1## in which X is a halogen atom,Y is a hydrogen or halogen atom, andAz is an imidazolyl radical or a 1,2,4-triazolyl radical,wherein dichloropinacolin of the formulaCl.sub.2 CH--CO--C(CH.sub.3).sub.3is reacted with an azole of the formulaAz--Hand a phenol of the formula ##STR2## in the presence of an acid-binding agent, the improvement which comprises carrying out the reaction in the presence of a water-immiscible organic solvent at a temperature between about 40.degree. and 150.degree. C., adding to the solvent at a temperature between about 0.degree. and +80.degree. C. a mineral acid, thereby to precipitate the mineral acid salt of the phenoxy-azolyl-butanone derivative, and separating such salt. Surprisingly the product does not hydrolyze when standing in contact with the mineral acid solution. The product is a known fungicide.
    • 在制备其中X是卤素原子的式“IMAGE”的苯氧基 - 唑基 - 丁酮衍生物的制备中,Y是氢或卤素原子,并且Az是咪唑基或1,2,4-三唑基, 其中式Cl2CH-CO-C(CH3)3的二氯青霉素与酸结合剂存在下与式为Az-H的唑和式“IMAGE”的苯酚反应,其改进包括进行 在与水不混溶的有机溶剂的存在下在约40℃至150℃的温度下反应,在约0℃至+ 80℃的温度下加入无机酸,从而沉淀出 苯氧基 - 唑基 - 丁酮衍生物的无机酸盐,并分离此盐。 令人惊讶的是,当与无机酸溶液接触时,产物不会水解。 该产品是已知的杀真菌剂。
    • 3. 发明授权
    • Preparation of dithiophosphoric acid diester halides
    • 二硫代磷酸二酯卤化物的制备
    • US4130607A
    • 1978-12-19
    • US830381
    • 1977-09-02
    • Hermann Arold
    • Hermann Arold
    • C07F9/20C07F9/206
    • C07F9/20C07F9/206
    • A process for the preparation of a dithiophosphoric acid diester halide of the formula ##STR1## IN WHICH R.sup.1 and R.sup.2 each independently is alkyl with 1 to 5 carbon atoms, andHal is halogen, comprising reacting an S-alkyl dihalide of the formula ##STR2## WITH AN ALCOHOL OF THE FORMULAR.sup.2 OHat a temperature of about -5.degree. to -90.degree. C in the presence of about a 5 to 200% molar excess of potassium hydroxide. Advantageously about a 10 to 600% molar excess of alcohol is employed, R.sup.1 is n-propyl, R.sup.2 is ethyl, Hal is chlorine, and the reaction is effected in an aliphatic or aromatic optionally chlorinated hydrocarbon or an ether.
    • 制备下式的二硫代磷酸二酯卤化物的方法其中R 1和R 2各自独立地为具有1至5个碳原子的烷基,Hal为卤素,包括使式IMA图案的S-烷基二卤化物 >在约5至约200摩尔过量的氢氧化钾的存在下,在约-5至-90℃的温度下加入式R 2 OH的醇。 有利地,使用约10至600%摩尔过量的醇,R 1为正丙基,R 2为乙基,Hal为氯,反应在脂族或芳族任选氯代烃或醚中进行。
    • 4. 发明授权
    • Preparation of alkylthiomethylphenols
    • 烷硫基甲基苯酚的制备
    • US4091037A
    • 1978-05-23
    • US783370
    • 1977-03-31
    • Hermann Arold
    • Hermann Arold
    • C07C323/16C07C20060101C07C67/00C07C313/00C07C149/32C07C149/34C07C149/36
    • C07C319/14
    • A process for the preparation of an alkylthiomethylphenol of the formula ##STR1## COMPRISING REACTING A DIALKYLAMINOMETHYLPHENOL OF THE FORMULA ##STR2## WITH A THIOCARBOXYLIC ACID S-ester of the formula ##STR3## in which R.sup.1 is optionally substituted alkyl with 1 to 12 carbon atoms or optionally substituted phenyl, R.sup.2 and R.sup.3 each independently is hydrogen, alkyl with 1 to 5 carbon atoms, halogen or nitro, or together form a benzene ring or cycloalkane ring with 3 to 5 carbon atoms which is fused to the phenyl ring,R.sup.4 and R.sup.5 each independently is alkyl with 1 to 6 carbon atoms, or together with the nitrogen atom form a five- or six-membered heterocyclic ring,R.sup.6 is hydrogen or alkyl with 1 to 6 carbon atoms, and n is 1, 2 or 3.The process may be carried out in a solvent, advantageously at a temperature from about 100.degree. to 150.degree. C, at about normal pressure using phenol as a catalyst with about 0.9 to 1.5 moles of thiocarboxylic acid S-ester per mole of dialkylaminomethylphenol.
    • 制备式(Ia)的烷基硫代甲基苯酚的方法包括用式“IMAGE”的硫代羧酸S-酯反应式II的二烷基氨基甲基苯酚的方法,其中R 1是具有1至12个碳原子的任选取代的烷基 或任选取代的苯基,R 2和R 3各自独立地为氢,具有1至5个碳原子的烷基,卤素或硝基,或一起形成具有3至5个碳原子的苯环或环烷烃环,其与苯环稠合,R4和 R5各自独立地为具有1至6个碳原子的烷基,或与氮原子一起形成五元或六元杂环,R 6为氢或具有1至6个碳原子的烷基,n为1,2或3。
    • 6. 发明授权
    • Preparation of dithiophosphoric acid diester-halides
    • 二硫代磷酸二酯 - 卤化物的制备
    • US4154780A
    • 1979-05-15
    • US783371
    • 1977-03-31
    • Reimer CollnHermann AroldVidyanatha A. Prasad
    • Reimer CollnHermann AroldVidyanatha A. Prasad
    • B01J31/00B32B27/00C07B61/00C07F9/20
    • C07F9/20B32B27/00
    • A process for the preparation of a dithiophosphoric acid diester-halide of the formula ##STR1## IN WHICH R.sup.1 is alkyl with 1 to 10 carbon atoms, aralkyl with 1 to 6 carbon atoms in the alkyl radical, or alkoxyalkyl or alkylthioalkyl with 1 to 5 carbon atoms in each alkyl radical,R.sup.2 is alkyl with 1 to 8 carbon atoms, andHal is halogen,Which comprises reacting an S-alkyl or S-aralkyl ester of a dithiophosphoric acid dihalide of the formula ##STR2## WITH ABOUT A 5 TO 300% MOLAR EXCESS OF AN ALCOHOL OF THE FORMULAR.sup.2 OHin the presence of about a 5 to 300% molar excess of a tertiary pyridine base or tertiary aralkyl-alkylamine at a temperature between about -10.degree. and +60.degree. C. Advantageously the tertiary base is pyridine, 2-, 3- or 4-methyl-pyridine, 4-ethyl-pyridine, 5-ethyl-2-methyl-pyridine, 2,4- or 2,6-dimethyl-pyridine, 2,4,6-trimethyl-pyridine, quinoline, isoquinoline, 2-, 4- or 6-methyl-quinoline, 6-chloro-2-methyl-quinoline, 2-chloro-4-methyl-quinoline, 8-chloro-2-methyl-quinoline or dimethylbenzylamine, the reaction is carried out at about 0.degree. to 30.degree. C., the alcohol is ethanol employed in about a 15 to 30% molar excess, about a 20 to 210% molar excess of the tertiary base is employed, R.sup.1 is alkyl with 1 to 8 carbon atoms, aralkyl with 1 to 3 carbon atoms in the alkyl radical, or alkoxyalkyl or alkylthioalkyl with 1 to 3 carbon atoms in each alkyl radical and Hal is chlorine.
    • 一种制备下式的二硫代磷酸二酯 - 卤化物的方法,其中R1是具有1-10个碳原子的烷基,在烷基中具有1-6个碳原子的芳烷基,或具有1-5个碳原子的烷氧基烷基或烷硫基烷基 每个烷基中的碳原子,R 2是具有1至8个碳原子的烷基,Hal是卤素,其包含反应式为“A”的二硫代磷酸二卤化物的S-烷基或S-芳烷基酯 在约5-10%摩尔过量的叔吡啶碱或叔芳烷基 - 烷基胺的存在下,在约-10℃和+ 60℃之间的温度下,在摩尔过量的情况下,300摩尔过量的式 碱是吡啶,2-,3-或4-甲基 - 吡啶,4-乙基 - 吡啶,5-乙基-2-甲基 - 吡啶,2,4-或2,6-二甲基 - 吡啶,2,4,6 - 三甲基 - 吡啶,喹啉,异喹啉,2-,4-或6-甲基 - 喹啉,6-氯-2-甲基 - 喹啉,2-氯-4-甲基 - 喹啉,8-氯-2-甲基 - 喹啉 e或二甲基苄胺,反应在约0℃至30℃进行,醇为约15至30摩尔过量的乙醇,约20至210摩尔过量的叔碱,R1 具有1至8个碳原子的烷基,在烷基中具有1至3个碳原子的芳烷基,或每个烷基中具有1至3个碳原子的烷氧基烷基或烷硫基烷基,Hal为氯。