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    • 62. 发明授权
    • Preparation of 1,1-dihalogeno-alkenes
    • 制备1,1-二卤代烯烃
    • US4424166A
    • 1984-01-03
    • US237005
    • 1981-02-23
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • C07C69/743C07C17/00C07C17/26C07C17/263C07C21/02C07C21/17C07C22/00C07C22/02C07C22/04C07C22/08C07C45/00C07C49/567C07C51/00C07C61/40C07C67/00C07C231/00C07C231/12C07C233/38C07C253/00C07C255/48C07C121/48C07C61/35C07C121/66
    • C07C17/263
    • In the preparation of a 1,1-dihalogenoalkene of the formula ##STR1## in which R.sup.1 is a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, and R.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, or R.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain, and X.sup.1 and X.sup.2 each independently is a halogen atom, wherein a carbonyl compound of the formula ##STR2## is reacted with a trihalogenoacetate of the formula ##STR3## in which X.sup.3 is a halogen atom, and M.sup..sym. is an alkali metal ion or one equivalent of an alkaline earth metal ion, in the presence of an approximately equimolar amount of a phosphorus-containing compound, the improvement which comprises employing as said phosphorus-containing compound a phosphorous acid trialkyl ester or a phosphorous acid triamide and effecting the reaction at a temperature between about 0.degree. and 200.degree. C. A preferred end product is ##STR4## and the preferred phosphorus-containing compound is trimethyl phosphite, triethyl phosphite, tripropyl phosphite or phosphorous acid tris-dimethyl-amide.
    • 在制备其中R 1为氢原子或任选取代的烷基,烯基,炔基,环烷基,芳烷基,芳烯基或芳基的式“IMAGE”的1,1-二卤代烯烃中,R 2为任选取代的烷基, 烯基,炔基,环烷基,芳烷基,芳烯基或芳基,或R 1和R 2一起形成任选支链和/或任选的苯并稠合烃链,并且X 1和X 2各自独立地为卤素原子,其中式 与式(X3)中的X为卤素原子的式(III)的三卤代乙酸酯反应,M(+)​​为碱金属离子或1当量碱土金属离子,在大约等摩尔量存在下 的含磷化合物,其改进包括使用磷酸三烷基酯或亚磷酸三酰胺作为所述含磷化合物,并在约0℃至200℃的温度下进行反应。 优选的最终产物是“IMAGE”,优选的含磷化合物是亚磷酸三甲酯,亚磷酸三乙酯,亚磷酸三丙酯或亚磷酸三 - 二甲基 - 酰胺。
    • 66. 发明授权
    • Process for the preparation of 1,1-dichloro-alkenes
    • 1,1-二氯 - 烯烃的制备方法
    • US4492800A
    • 1985-01-08
    • US468786
    • 1983-02-22
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • Fritz MaurerUwe PriesnitzHans-Jochem Riebel
    • C07C69/743C07C17/00C07C17/26C07C17/263C07C21/04C07C21/19C07C22/00C07C22/02C07C22/04C07C45/00C07C49/567C07C51/00C07C61/40C07C67/00C07C253/00C07C255/48C07C69/74C07C121/48C07C121/60
    • C07C17/2635C07C21/19
    • A process for the preparation of a 1,1-dichloro-alkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or together are alkanediyl,in the presence of at least an equimolar amount of magnesium. Advantageously,R.sup.1 is hydrogen,R.sup.2 is a C.sub.2 to C.sub.5 alkenyl radical or a radical of the formula ##STR4## Z is a cyano, acetal, carboxyl or C.sub.1 to C.sub.4 alkoxycarbonyl radical, or a radical of the formula COOM, andM is sodium or potassium,R.sup.3 each individually is a C.sub.1 to C.sub.4 alkyl or phenyl radical, or the two radicals R.sup.3 together are C.sub.2 to C.sub.5 alkanediyl,about 0.95 to 1.4 moles of the trichloromethanephosphonic acid ester and about 1.5 to 4 moles of magnesium are employed per mole of the carbonyl compound, and the reaction is carried out at a temperature between about 0.degree. and 150.degree. C. in a polar aprotic solvent. The products are known intermediates, especially for insecticides.
    • 制备其中R 1为氢或任选取代的烷基,烯基,炔基,环烷基,芳烷基,芳烯基或芳基的式“IMAGE”的1,1-二氯 - 烯烃的方法,R 2为任选地 取代的烷基,烯基,炔基,环烷基,芳烷基,芳烯基或芳基,或者R 1和R 2一起形成任选支链和/或任选的苯并稠合烃链,包括使式IMA的羰基化合物与三氯甲烷膦酸 酯,其中R 3各自独立地是烷基或苯基,或者在至少等摩尔量的镁的存在下一起是烷二基。 有利地,R 1是氢,R 2是C 2至C 5链烯基或下式的基团Z是氰基,缩醛,羧基或C 1至C 4烷氧基羰基,或式COOM的基团,M是钠 或钾,R 3各自独立地为C 1至C 4烷基或苯基,或两个基团R 3一起为C 2至C 5烷二基,每摩尔使用约0.95至1.4摩尔三氯甲烷膦酸酯和约1.5至4摩尔镁 的羰基化合物,并且反应在极性非质子溶剂中在约0℃至150℃的温度下进行。 该产品是已知的中间体,特别是杀虫剂。
    • 67. 发明授权
    • Alpha-hydroxy-phosphonic acid esters
    • α-羟基膦酸酯
    • US4420435A
    • 1983-12-13
    • US391092
    • 1982-06-22
    • Hellmut HoffmannFritz MaurerUwe PriesnitzHans-Jochem Riebel
    • Hellmut HoffmannFritz MaurerUwe PriesnitzHans-Jochem Riebel
    • C07C17/26C07C25/24C07C45/41C07C45/54C07C45/56C07C45/68C07C49/355C07C49/567C07C61/40C07F9/40
    • C07C17/2635C07C25/24C07C45/41C07C45/54C07C45/56C07C45/68C07C49/355C07C49/567C07C61/40C07F9/4018C07F9/4056C07F9/4065
    • Styryl-cyclopropane derivatives of the formula ##STR1## in which R.sup.9 represents independently of one another when n=2, halogen, cyano, nitro, or an optionally halogen-substituted alkyl, alkoxy, alkylthio or alkylenedioxy radical,n represents zero, 1, 2, 3, 4 or 5,R.sup.10 represents hydrogen or halogen, and,Y represents acetyl, cyano or carbamoyl, are produced by reacting a benzylphosphonic acid ester of the formula ##STR2## in which R.sup.4 each independently represents alkyl or phenyl or together represent alkylene,with a formylcyclopropane derivative of the formula ##STR3## or by reacting an .alpha.-hydroxyphosphonic acid ester of the formula ##STR4## with an olefinating agent of the formula ##STR5## in which Z' represents a phosphorus-containing radical ##STR6## or --P(R.sup.7).sub.3.sup..sym. X.sup..crclbar. whereinR.sup.5 and R.sup.6 are identical or different and individually represent alkyl, phenyl, alkoxy or phenoxy or R.sup.5 and R.sup.6 together represent alkanedioxy,R.sup.7 represents alkyl or phenyl andX represents halogen,in the presence of a base at a temperature between about -70 and +150.degree. C. Other olefins can be similarly prepared. Many intermediates are new and the end products are themselves intermediates for insecticides.
    • n = 2时,R 9彼此独立地表示卤素,氰基,硝基或任选卤素取代的烷基,烷氧基,烷硫基或亚烷基二氧基,其中R 1表示0, 2,3,4或5,R 10表示氢或卤素,Y表示乙酰基,氰基或氨基甲酰基,是通过使式“IMAGE”的苄基膦酸酯反应而得的,其中R4各自独立地表示烷基或苯基, 亚烷基与式IMAMA的甲酰基环丙烷衍生物反应,或通过使式“IMAGE”的α-羟基膦酸酯与式“IMAGE”的烯烃化剂反应,其中Z'代表含磷基团“IMAGE” 或-P(R 7)3(+)X( - )其中R 5和R 6相同或不同,并且各自表示烷基,苯基,烷氧基或苯氧基或R 5和R 6一起表示烷二氧基,R 7表示烷基或苯基,X表示卤素, 在presen ce在约-70至+ 150℃之间的温度下进行。其它烯烃可以类似地制备。 许多中间体是新的,最终产品本身是杀虫剂的中间体。
    • 69. 发明授权
    • Process for the preparation of 1,1-dichloro-alkenes
    • 1,1-二氯 - 烯烃的制备方法
    • US4350824A
    • 1982-09-21
    • US236484
    • 1981-02-23
    • Hans-Jochem RiebelFritz MaurerUwe Priesnitz
    • Hans-Jochem RiebelFritz MaurerUwe Priesnitz
    • C07C69/013C07C17/00C07C17/26C07C17/263C07C21/073C07C21/19C07C21/22C07C22/00C07C22/02C07C22/04C07C25/24C07C41/00C07C43/225C07C45/00C07C49/567C07C51/00C07C61/40C07C67/00C07C201/00C07C205/09C07C231/00C07C231/12C07C233/38C07C253/00C07C255/48C07C255/50C07C21/20C07C67/307
    • C07C21/19C07C17/2635
    • A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or the two radicals R.sup.3 together are alkanediyl,in the presence of at least an equimolar amount of a phosphorous acid triamide of the formulaP(NR.sup.4.sub.2).sub.3in whichR.sup.4 each independently is an alkyl radical, or the two radicals R.sup.4 together are alkanediyl.Advantageously,R.sup.1 is hydrogen,R.sup.2 a C.sub.2 to C.sub.5 alkenyl radical, or a radical of the formula ##STR4## Z is a cyano, acetyl, carboxyl or C.sub.1 to C.sub.4 alkoxycarbonyl radical, or a radical of the formula --COOM,M is sodium or potassium, andR.sup.3 each individually is a C.sub.1 to C.sub.4 alkyl or phenyl radical,or the two radicals R.sup.3 together are C.sub.2 to C.sub.5 alkandiyl, the phosphorous acid triamide is phosphorous acid tris-dimethylamide or tris-diethylamide, about 0.94 to 1.1 moles of each of trichloromethanephosphonic acid ester and of the phosphorous acid triamide are employed per mole of the carbonyl compound, and the reaction is effected at about 10.degree. to 100.degree. C. in a polar aprotic solvent.
    • 制备其中R 1为氢或任选取代的烷基,烯基,炔基,环烷基,芳烷基,芳烯基或芳基的式“IMAGE”的1,1-二氯烯的方法,R 2为任选取代的烷基 ,烯基,炔基,环烷基,芳烷基,芳烯基或芳基,或者R 1和R 2一起形成任选支链和/或任选的苯并稠合烃链,包括使下式的羰基化合物与下式的三氯甲烷膦酸酯 在其中R 3各自独立地为烷基或苯基,或两个基团R 3一起为烷二基的式“IMAGE”中,在至少等摩尔量的式P(NR42)3的亚磷酸三酰胺存在下,式 R4各自独立地是烷基,或者两个基团R4一起是烷二基。 有利地,R 1是氢,R 2是C 2至C 5链烯基,或下式的基团Z是氰基,乙酰基,羧基或C 1至C 4烷氧基羰基,或式-COOM基团,M是钠 或钾,R3各自为C1至C4烷基或苯基,或两个基团R3一起为C 2至C 5亚烷基,亚磷酸三酰胺为亚磷酸三 - 二甲基酰胺或三 - 二乙基酰胺,约0.94至1.1摩尔 每摩尔羰基化合物使用三氯甲烷膦酸酯和亚磷酸三酰胺中的每一种,并且在极性非质子溶剂中在约10℃至100℃下进行反应。