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    • 24. 发明授权
    • Preparation of .epsilon.-caprolactone
    • ε-己内酯的制备
    • US4341709A
    • 1982-07-27
    • US150260
    • 1980-05-15
    • Willi HofenHerbert KlenkGerd SchreyerOtto WeibergHelmut WaldmannHermann SeifertKarl-Hermann ReissingerWolfgang Swodenk
    • Willi HofenHerbert KlenkGerd SchreyerOtto WeibergHelmut WaldmannHermann SeifertKarl-Hermann ReissingerWolfgang Swodenk
    • C07D313/04C07D315/00C07D313/02
    • C07D315/00
    • A process for the preparation of .epsilon.-caprolactone comprising:(a) reacting cyclohexanone with a solution of perpropionic acid in an organic solvent at a molar ratio of cyclohexanone;perpropionic acid of about 1.1-5:1 at a temperature of about 10.degree. to 80.degree. C. to form a reaction mixture consisting essentially of .epsilon.-caprolactone, propionic acid and organic solvent,(b) distilling the reaction mixture from (a) in a first distillation unit to obtain a distillate comprising the organic solvent and a distillation residue,(c) introducing the distillation residue from (b) at a point into a second distillation unit to obtain a distillate comprising propionic acid and unreacted cyclohexanone, removing from the second distillation unit, separately from one another and at a point below the point of introduction into the second distillation unit, .epsilon.-caprolactone and any high-boiling constituents, and,(d) distilling in a third distillation unit the distillate from (c) to obtain a distillate consisting essentially of propionic acid and a distillation residue comprising a mixture of propionic acid and cyclohexanone.
    • 一种制备ε-己内酯的方法,包括:(a)使环己酮与过丙酸在有机溶剂中的溶液以环己酮的摩尔比约1.1-5:1的约0.1〜5:1的摩尔比在约10℃〜 形成基本上由ε-己内酯,丙酸和有机溶剂组成的反应混合物,(b)在第一蒸馏单元中将反应混合物从(a)中蒸馏,得到包含有机溶剂和蒸馏残余物的馏出物 (c)在一点将来自(b)的蒸馏残余物引入第二蒸馏单元以获得包含丙酸和未反应的环己酮的馏出物,从第二蒸馏单元彼此分离并在低于 引入第二蒸馏装置,ε-己内酯和任何高沸点组分,和(d)在第三蒸馏装置中蒸馏出馏出物(c)得到 基本上由丙酸组成的馏出物和包含丙酸和环己酮的混合物的蒸馏残渣。
    • 27. 发明授权
    • Process for the production of 1,2,4-triazin-5-one derivatives
    • 制备1,2,4-三嗪-5-酮衍生物的方法
    • US4175188A
    • 1979-11-20
    • US924062
    • 1978-07-12
    • Herbert KlenkWerner SchwarzeWolfgang Leuchtenberger
    • Herbert KlenkWerner SchwarzeWolfgang Leuchtenberger
    • C07D253/06A01N43/707C07D253/075
    • C07D253/075A01N43/707
    • 1,2,4-triazin-5-one compounds of the general formula (I) ##STR1## where R is ##STR2## are prepared by reacting a compound of general formula (II) ##STR3## in which R is defined above with either (a) a tertiary alcohol of general formula (III)HO--R' (III) in which R' is a t-alkyl group having 4 to 18 carbon atoms, especially t-amyl or t-octyl or preferably t-butyl or(b) an alkene of general formula (IV) ##STR4## in which R.sub.1 and R.sub.2 are the same or different and are hydrogen or an alkyl group and R.sub.3 and R.sub.4 are the same or different and wherein the alkyl groups in each case can be 1 to 15 carbon atoms and wherein preferably R.sub.1 and R.sub.2 are hydrogen and R.sub.3 and R.sub.4 each are methyl to form an .alpha.-ketocarboxylic acid amide of general formula (V) ##STR5## and this, in a given case after previous saponification to the free acid, condensed with thiocarbohydrazide ##STR6## to form a 1,2,4-triazin-5-one compound of general formula (VI) ##STR7## and then the mercapto group is methylated.
    • 通式(I)的化合物通过使通式(II)的化合物(II)的化合物在 其中R定义如上:(a)通式(III)的叔醇HO-R'(III),其中R'是具有4至18个碳原子的叔烷基,特别是叔戊基或t- 辛基或优选叔丁基或(b)通式(IV)的烯烃其中R 1和R 2相同或不同,为氢或烷基,且R 3和R 4相同或不同 并且其中每种情况下的烷基可以是1至15个碳原子,并且其中优选地,R 1和R 2是氢,并且R 3和R 4各自是甲基,形成通式(V)的α-酮羧酸酰胺。 并且在给定情况下,在先前皂化成游离酸后,与硫代碳酰肼“IMAGE”缩合形成通式(VI)的化合物VI(VI),然后 巯基是甲基 ted。
    • 29. 发明授权
    • Substituted cyclopropyl glyoxylnitriles
    • 取代的环丙基乙醛腈
    • US4122116A
    • 1978-10-24
    • US880483
    • 1978-02-23
    • Herbert KlenkHeribert OffermannsWerner Schwarze
    • Herbert KlenkHeribert OffermannsWerner Schwarze
    • C07C255/45C07C255/56C07D307/54C07C61/00C07C51/00C07C121/46
    • C07C253/14C07D307/54
    • There are prepared acyl cyanides of the formula ##STR1## where R is a straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and which also can be substituted by one or more phenyl groups or halogen atoms, preferably chlorine, or R is preferably a cycloalkyl group having 3 to 8 carbon atoms, preferably cyclopropyl, which can have one or more 1 to 3 carbon atoms alkyl or halogen, preferably chlorine, substituents wherein in all of the above set forth substitutions the halogen atoms and the phenyl groups are not on the carbon atom adjacent to the carbonyl group or R is a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a five membered heterocyclic group, e.g., furyl, thienyl or alkyl substituted thienyl wherein the substituents on the phenyl or naphthyl are halogen atoms, nitro groups or alkyl or alkoxy groups having 1 to 5 carbon atoms. The process comprises reacting and acyl halide of the formulaR--CO--Hal (II)in which R is as defined above and Hal is a chlorine or bromine atoms, with CuCN at a temperature of about 50.degree. to 180.degree. C in the presence of a carboxylic acid nitrile inert under the reaction conditions, there being employed about 1 to 10 parts by weight of the carboxylic acid nitrile and about 0.5 to 20 parts by weight of at least one organic solvent which is inert under the reaction conditions. Certain of the compounds are novel per se.
    • 制备式(I)的酰基氰化物,其中R是具有1至18个碳原子,优选1至10个碳原子的直链或支链烷基,并且也可被一个或多个苯基取代 或卤素原子,优选氯,或R优选为具有3至8个碳原子的环烷基,优选环丙基,其可以具有一个或多个1至3个碳原子的烷基或卤素,优选氯,取代基,其中在所有上述定义 卤素原子和苯基不在与羰基相邻的碳原子上,或者R是取代的苯基,萘基,取代的萘基或五元杂环基,例如呋喃基,噻吩基或烷基 取代的噻吩基,其中苯基或萘基上的取代基是卤素原子,硝基或具有1至5个碳原子的烷基或烷氧基。 该方法包括在存在下将式R-CO-Hal(II)的酰卤与其中R定义如上和Hal为氯或溴原子的酰卤与CuCN在约50-180℃的温度下反应, 的在反应条件下为惰性的羧酸腈,使用约1-10重量份的羧酸腈和约0.5-20重量份的至少一种在反应条件下为惰性的有机溶剂。 某些化合物本身是新颖的。
    • 30. 发明授权
    • Process for the production of acyl cyanides (A)
    • 酰基氰的制备方法(A)
    • US4108877A
    • 1978-08-22
    • US802944
    • 1977-06-02
    • Herbert KlenkHeribert OffermannsWerner Schwarze
    • Herbert KlenkHeribert OffermannsWerner Schwarze
    • C07C67/00C07C253/00C07C253/14C07C255/16C07C255/17C07C255/18C07C255/31C07C255/40C07C255/45C07C255/53C07C255/56C07D307/06C07D307/38C07D307/46C07D307/54C07D307/56C07D333/16F28F3/00C07D307/36C07C57/00C07C63/06
    • C07C255/00C07C253/14C07D307/54
    • There are prepared acyl cyanides of the formula ##STR1## where R is a straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and which also can be substituted by one or more phenyl groups or halogen atoms, preferably chlorine, or R is preferably a cycloalkyl group having 3 to 8 carbon atoms, preferably cyclopropyl, which can have one or more 1 to 3 carbon atom alkyl or halogen, preferably chlorine, substituents wherein in all of the above set forth substitutions the halogen atoms and the phenyl groups are not on the carbon atom adjacent to the carbonyl group or R is a substituted phenyl group, a naphthyl group, a substituted naphthyl group or a five membered heterocyclic group, e.g., furyl, thienyl or alkyl substituted thienyl, wherein the substituents on the phenyl or naphthyl are halogen atoms, nitro groups or alkyl or alkoxy groups having 1 to 5 carbon atoms. The process comprises reacting an acyl halide of the formulaR -- Co -- Hal (II)in which R is as defined above and Hal is a chlorine or bromine atom, with CuCN at a temperature of about 50.degree. to 180.degree. C in the presence of a carboxylic acid nitrile inert under the reaction conditions, there being employed about 1 to 10 parts by weight of the carboxylic acid nitrile and about 0.5 to 20 parts by weight of at least one organic solvent which is inert under the reaction conditions. Certain of the compounds are novel per se.
    • 制备式(I)的酰基氰化物,其中R是具有1至18个碳原子,优选1至10个碳原子的直链或支链烷基,并且也可被一个或多个苯基取代 或卤素原子,优选氯,或R优选为具有3至8个碳原子的环烷基,优选环丙基,其可以具有一个或多个1至3个碳原子的烷基或卤素,优选氯,取代基,其中在上述所有 卤素原子和苯基不在与羰基相邻的碳原子上,或者R是取代的苯基,萘基,取代的萘基或五元杂环基,例如呋喃基,噻吩基或烷基 取代的噻吩基,其中苯基或萘基上的取代基是卤素原子,硝基或具有1-5个碳原子的烷基或烷氧基。 该方法包括使式R-Co-Hal(II)的酰卤,其中R如上所定义,Hal是氯或溴原子,与CuCN在约50-180℃的温度下反应, 的在反应条件下为惰性的羧酸腈,使用约1-10重量份的羧酸腈和约0.5-20重量份的至少一种在反应条件下为惰性的有机溶剂。 某些化合物本身是新颖的。