公开(公告)号：US06723874B1

公开(公告)日：2004-04-20

申请号：US09856909

申请日：2001-05-30

Applicant: Max Braun ,  Matthias Rieland ,  Francine Janssens ,  Kerstin Eichholz ,  Stefan Palsherm

Inventor： Max Braun ,  Matthias Rieland ,  Francine Janssens ,  Kerstin Eichholz ,  Stefan Palsherm

IPC: C07C5158

CPC classification number: C01B17/4576 ,  C01B17/4561 ,  C07C51/58

Abstract: Acid fluorides, for example carboxylic acid fluorides and sulfuryl fluoride are produced by reacting the corresponding acid chlorides with hydrogen fluoride adducts of ammonium fluoride or amine hydrofluorides (which act as a catalyst or as a fluorination agent). Consumed HF adducts may be regenerated with HF.

Abstract translation: 酸性氟化物，例如羧酸氟化物和硫酰氟通过使相应的酰氯与氟化铵或胺氢氟酸（其充当催化剂或氟化剂）的氟化氢加合物反应来制备。 消耗的HF加合物可以用HF再生。

公开(公告)号：US06525213B1

公开(公告)日：2003-02-25

申请号：US10104059

申请日：2002-03-25

Applicant: Max Braun ,  Kerstin Eichholz

Inventor： Max Braun ,  Kerstin Eichholz

IPC: C07C6976

CPC classification number: C07D487/04 ,  C07C67/14 ,  C07C69/63

Abstract: An improved process for preparing carboxylic acid esters from acid chlorides, acid bromides or acids and alcohols provides for performing the esterification in the presence of the adduct (onium salt) of the corresponding carboxylic acid and 1,5-diazabicyclo[4.3.0]-non-2-ene or 1,8-diazabicyclo[5.4.0]-undec-7-ene. Alternatively, it is possible to operate in the presence of the corresponding carboxylic acid and an onium salt of the corresponding carboxylic acid.

Abstract translation: 由酰氯，酸溴化物或酸和醇制备羧酸酯的改进方法提供了在相应羧酸的加合物（鎓盐）和1,5-二氮杂双环[4.3.0] - 酮的存在下进行酯化反应。 壬-2-烯或1,8-二氮杂双环[5.4.0]十一碳-7-烯。 或者，可以在相应的羧酸和相应的羧酸的鎓盐存在下操作。

公开(公告)号：US06489510B1

公开(公告)日：2002-12-03

申请号：US09319451

申请日：1999-07-29

Applicant: Max Braun ,  Kerstin Eichholz ,  Werner Rudolph

Inventor： Max Braun ,  Kerstin Eichholz ,  Werner Rudolph

IPC: C07C5338

CPC classification number: C07C51/60 ,  B01J19/02 ,  B01J19/123 ,  B01J2219/00078 ,  B01J2219/0245 ,  B01J2219/0254 ,  B01J2219/0875 ,  C07C51/58 ,  C07C53/50 ,  C07C53/48 ,  C07C53/46

Abstract: A method for producing carboxylic acid fluorides of the formula RCFXC(O)F, where X represents fluorine or chlorine, in good yields and with good selectivity for the carboxylic acid fluorides by reacting compounds of the formula RCFXCHFCl with oxygen by photochemical oxidation in the gaseous phase, preferably under sensitization with chlorine and using light having a wavelength &lgr;≧280 nm, which conditions make it possible to work without the use of pressure. Glass apparatus may be covered with a protective coating so as to protect it against traces of hydrogen fluoride. To this end, for example, heat-shrinkable sleeves made of light-permeable hydrogen fluoride-resistant material may be used. Polytetrafluoroethylene, polyfluoropropylene or a mixture thereof are especially suitable for this purpose. This type of protection is also suitable for other reactions such as photo-induced fluoro-dediazonation in hydrogen fluoride/pyridine for the production of aromatic compounds fluorinated in the nucleus or the oxidation of CHCl2 groups for the production of carboxylic acid chlorides.

Abstract translation: 通过使式RCFXCHFCl的化合物与氧通过光化学氧化反应生成式RCFXC（O）F的羧酸氟化物的方法，其中X表示氟或氯，以良好的产率和对羧酸氟化物具有良好的选择性 相，优选用氯敏感并使用波长λ= 280nm的光，该条件使得可以在不使用压力的情况下工作。 玻璃装置可以用保护涂层覆盖，以保护其免受痕量的氟化氢。 为此，例如，可以使用由透光耐氟化氢材料制成的热收缩套筒。 聚四氟乙烯，聚氟丙烯或其混合物特别适用于此目的。 这种类型的保护也适用于其它反应，例如在氟化氢/吡啶中用于生产在核中氟化的芳族化合物的光引发的氟 - 重氮化或用于生产羧酸氯化物的CHCl 2基团的氧化。

公开(公告)号：US06423866B1

公开(公告)日：2002-07-23

申请号：US09530909

申请日：2000-05-08

Applicant: Max Braun ,  Francine Jannssens ,  Werner Rudolph ,  Kerstin Eichholz

Inventor： Max Braun ,  Francine Jannssens ,  Werner Rudolph ,  Kerstin Eichholz

IPC: C07C22900

CPC classification number: C07C227/08 ,  C07C229/30

Abstract: Lower alkyl esters of 3-amino crotonates substituted by halogen in the C-4 position, e.g. ethyl 3-amino-4,4,4-trifluoro-crotonate, in which the amino group optionally may be substituted by one or two C1 to C3 alkyl groups or by one or two aryl groups, e.g. phenyl, are synthesized by thermolysis of ammonium salts of corresponding lower alkyl esters of acetoacetic acid substituted in the C-4 position by halogen, and removal of the resulting water of reaction. The water of reaction may be removed by an entraining agent, which preferably has a specific gravity heavier than that of the aqueous phase which forms in the reaction. This minimizes yield losses due to the ammonium salt becoming dissolved in the aqueous phase and results in especially high yields. Formation of the ammonium salt and thermolysis can be carried out simultaneously. Alternatively, it is possible to start from a molten ammonium salt of the halogencrotonate, e.g. the salt of the lower alkyl ester of 4,4,4-trifluoroacetoacetic acid, or to produce the salt in situ, and to pass an inert gas through the molten salt under thermolytic conditions and in the absence of a solvent. In this way the desired product can be produced in high yield and in high purity. This alternative can be implemented as a continuous process.

Abstract translation: C-4位被卤素取代的3-氨基巴豆酸酯的低级烷基酯，例如 3-氨基-4,4,4-三氟巴豆酸乙酯，其中氨基可任意地被一个或两个C 1至C 3烷基取代，或被一个或两个芳基取代。 苯基，通过用卤素热解在C-4位置取代的乙酰乙酸的相应低级烷基酯的铵盐，除去所得的反应水来合成。 反应水可以通过夹带剂除去，该夹带剂优选具有比在反应中形成的水​​相重的比重。 这使得由于铵盐溶解在水相中导致的产量损失最小化并导致特别高的产率。 铵盐的形成和热解可以同时进行。 或者，可以从卤代克酸内酯的熔融铵盐开始，例如， 4,4,4-三氟乙酰乙酸的低级烷基酯的盐，或者在原位产生盐，并在惰性溶解条件下和不溶于溶剂的条件下使惰性气体通过熔融盐。 以这种方式，可以以高产率和高纯度生产所需的产物。 这种替代方案可以被实现为连续过程。

公开(公告)号：US5919341A

公开(公告)日：1999-07-06

申请号：US981423

申请日：1997-12-23

Applicant: Max Braun ,  Werner Rudolph ,  Kerstin Eichholz

Inventor： Max Braun ,  Werner Rudolph ,  Kerstin Eichholz

IPC: C07C51/58 ,  C07C53/48 ,  C07C51/00

CPC classification number: C07C51/58

Abstract: A process for preparing chlorodifluoroacetyl chloride from 1,1-difluoro-2,2-dichloroethylene and dichloroacetyl chloride from trichloroethylene or 1,1,2,2-tetrachloroethane, in which the starting compounds are continuously reacted in the gaseous phase with oxygen to obtain a photochemical oxidation reaction, chlorine being added as a sensitizer, the reaction mixture being irradiated with light having a wavelength .lambda..gtoreq.280 nm, the reaction preferably being carried out unpressurized. Particularly high yields with height selectivity are achieved by using doped high pressure mercury vapor lamps to irradiate the reaction mixture.

Abstract translation: PCT No.PCT / EP96 / 02596 371 1997年12月23日第 102（e）1997年12月23日PCT PCT 1997年6月17日PCT公布。 出版物WO97 / 00847 日本1997年1月9日由三氯乙烯或1,1,2,2-四氯乙烷从1,1-二氟-2,2-二氯乙烯和二氯乙酰氯制备氯二氟乙酰氯的方法，其中起始化合物在气态 与氧气相进行光化学氧化反应，加入氯作为敏化剂，反应混合物用波长λ= 280nm的光照射，反应优选进行无压力的处理。 通过使用掺杂的高压汞蒸汽灯来照射反应混合物，实现了具有高度选择性的特别高产率。

公开(公告)号：US5569782A

公开(公告)日：1996-10-29

申请号：US360026

申请日：1994-12-20

Applicant: Max Braun ,  Werner Rudolph ,  Kerstin Eichholz

Inventor： Max Braun ,  Werner Rudolph ,  Kerstin Eichholz

IPC: B01J19/08 ,  C07B61/00 ,  C07C51/58 ,  C07C53/46

CPC classification number: C07C51/58

Abstract: A process for preparing polyfluorochloro- and perfluorocarbonyl chlorides, for example for preparing perfluoropropionyl chloride, chlorodifluoroacetyl chloride or trifluoroacetyl chloride, in which starting materials are employed which have a CHCl.sub.2 group which is converted to a C(O)Cl group by photochemical oxidation with oxygen in the presence of added elemental chlorine and under exposure to activating irradiation by light having a wavelength .lambda..gtoreq.290 nm. The procedure is preferably unpressurized. Outstanding conversions with high selectivity are achieved using doped Hg light sources.

Abstract translation: 制备全氟氯代全氟羰基氯的方法，例如用于制备全氟丙酰氯，氯二氟乙酰氯或三氟乙酰氯，其中使用具有CHCl 2基团的起始原料，其通过用氧化物进行光化学氧化转化成C（O）Cl基团 在添加的元素氯的存在下，并且在通过波长λ> 290nm的光的激活照射下曝光。 该方法优选不加压。 使用掺杂的Hg光源实现了高选择性的卓越转化。