Agency of Industrial Science and Technology

Ministry of International Trade & Industry

Agency of Industrial Science and Technology Ministry of International

Japan as Represented by Director General of Agency of Industrial Science

Takashi Abe

Eiji Hayashi

Haruhiko Fukaya

Yoshio Hayakawa

Shunji Nagase

Taizo Ono

Masakazu Nishida

Hajime Baba

Mahito Soeda

Hiroshi Okazaki

Hiroshige Muramatsu

Vadim A Soloshonok

The present invention, which is aimed at providing a novel reaction for converting a fluorine-containing carbonyl compound to an asymmetric fluorine-containing primary amine, relates to a method in which a Schiff base obtained by the condensation of a fluorine-containing carbonyl compound and an asymmetric amine ((S)- or (R)-1-phenylethylamine) is treated in the presence of an appropriate organic base to hydrolyze a tautomeric imine obtained by asymmetrically performing an enzyme-like transamination reaction, yielding an asymmetric fluorine-containing amine.

Asymmetric fluorine-containing primary amines and their preparation

The object of the invention is to provide a novel process for epoxidation of perfluoro-olefins. This invention relates to a process for epoxidizing a perfluoro-olefin, characterized by employing a tertiary amine N-oxide represented by the general formula (I): ##STR1## (wherein R.sup.1, R.sup.2 and R.sup.3 each is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms, or an aromatic group which may have a nitro group or a cyano group as a substituent; provided that all of R.sup.1, R.sup.2 and R.sup.3 are selected from the above alkyl groups, R.sup.1, R.sup.2 and R.sup.3 may combine with one another directly or through oxygen atoms or nitrogen atoms to form a cyclic compound of 5-7 membered ring), or iodosobenzene. According to the present invention, perfluoro-olefins can be converted to corresponding perfluoroepoxides cheaply and in high yields. Epoxides produced by the process of this invention are utilized as intermediates for syntheses of surface active agents, lubricant oils, water repellents, oil repellents, polymers, and the like.

Epoxidizing agent

A method for extinguishing fire uses a gaseous fire-extinguishing agent having as an active component thereof a polyfluoro-tertiary amine represented by the following formula:

Method for extinguishing fire

A perfluoro-cyclic imine represented by the formula: ##STR1## is produced by a method which comprises placing in a reaction vessel a perfluoro compound represented by the formula: ##STR2## wherein X stands for one member selected from among CF.sub.2, CF(CF.sub.3), and oxygen atom, M for one member selected from among monovalent alkali metal ions and alkaline earth metal ions, and n for 0, 1, or 2 and heating the perfluoro compound to a temperature in the approximate range of 100.degree. C. to 500.degree. C.

Method for production of perfluoro-cyclic imine

A nitrogen-containing perfluoroalkyl bromide, a novel compound to the art, is represented by the formula, ##STR1## wherein Rf.sub.1 and Rf.sub.2 independently stand for a perfluoroalkyl group of one to five carbon atoms, provided that Rf.sub.1 and Rf.sub.2 are 1) separated from each other, 2) directly bonded to each other, 3) bonded to each other through the medium of an oxygen atom, or 4) bonded to each other through the medium of a nitrogen atom. This novel compound is produced by decarbonylating a nitrogen-containing perfluorocarboxylic acid bromide represented by the formula, ##STR2## by exposure to an ultraviolet light.

Nitrogen-containing perfluoroalkyl bromide and method for production

A nitrogen-containing perfluoroalkanoyl peroxide is provided which is represented by the formula: ##STR1## wherein Rf.sub.1 and Rf.sub.2 independently stand for an alkyl group of 1 to 5 carbon atoms, provided that Rf.sub.1 and Rf.sub.2 are joined to each other in one of the three patterns of union, 1) direct union, 2) union through the medium of an oxygen atom or 3) union through the medium of a nitrogen atom to form one of the three rings, i.e. five-membered ring, six-membered ring or seven-membered ring. The nitrogen-containing perfluoroalkanoyl peroxide is produced by a method which comprises oxidizing a compound represented by the following formula: ##STR2##

Nitrogen-containing perfluoroalkanoyl peroxide and method for production

A nitrogen-containing perfluoroalkanoyl peroxide is provided which is represented by the formula: ##STR1## wherein Rf.sub.1 and Rf.sub.2 independently stand for an alkyl group of 1 to 5 carbon atoms, provided that Rf.sub.1 and Rf.sub.2 are joined to each other in one of the three patterns of union, 1) direct union, 2) union through the medium of an oxygen atom or 3) union through the medium of a nitrogen atom to form one of the three rings, i.e. five membered ring, six-membered ring or seven-membered ring. The nitrogen-containing perfluoroalkanoyl peroxide is produced by a method which comprises oxidizing a compound represented by the following formula: ##STR2##

Nitrogen-containing perfluoralkanoyl peroxide and method for production

A perfluoroalkyl halogenide represented by the formula: ##STR1## wherein X stands for one element selected from the group consisting of iodine and bromine, R.sub.f for a perfluorohydrocarbon group, n for an integer in the range of 1 to 3, and m for an integer in the range of 1 to 3, provided that n and m satisfy the relationship, n.gtoreq.m, is produced by a method which consists essentially in subjecting a perfluorocarboxylic acid fluoride represented by the formula, ##STR2## wherein R.sub.f and n have the same meanings as defined above, to a thermal reaction with a lithium halogenide represented by XI, wherein X has the same meaning as defined above.

Method for direct conversion of fluorocarbonyl group into halogenides

Perfluorocarboxylic acid fluorides represented by the formula A-B, wherein A is either ##STR1## and B stands for a perfluoro-di-substituted amino group, and perfluoro(dialkylaminopropenes) represented by the formula A'-B', wherein A' stands for ##STR2## and B' has the same meaning as B defined above, are novel compounds. Methods for the production of these novel compounds are also disclosed.

Perfluoro(dialkylaminopropene) derivatives

A perfluoro-(N-vinylamine) compound containing a &gt;NCF.dbd.CF.sub.2 group is produced from a perfluoro-compound containing a group of the general formula: ##STR1## (wherein X stands for a fluorine atom or a --OM group having an alkali or alkaline earth metal ion for M) and having connected to the group of the general formula a perfluoro-alkyl group having a total of 2 to 6 carbon atoms contained in the main carbon chain thereof by heating the perfluoro-compound at a temperature in the range of 100.degree. C. to 500.degree. C. thereby effecting conversion of the group of the foregoing general formula into the aforementioned &gt;NCF.dbd.CF.sub.2 group.

Method for production of perfluoro-(N-vinylamine) compounds

A perfluoro compound containing a group of the general formula: ##STR1## wherein X stands for a fluorine atom, perfluoro-alkoxy groups, or --OM where M stands for an alkali metal ion or an alkaline earth earth ion and having connected to the aforementioned group a perfluoro-alkyl group possessing a total of 2 to 6 carbon atoms in the trunk carbon chain thereof is subjected to a temperature in the range of 100.degree. to 500.degree. C. to produce a perfluoro-(N-vinylamine) compound now containing the aforementioned group as converted into the formula:

Method for production of perfluoro N-(vinyl)amines

Perfluorobicyclolactam compounds represented by the general formula: ##STR1## wherein --A-- stands for ##STR2## l, m, and n respectively stand for 0 or 1, 3 or 4, and 1 or 2, and R.sub.f stands for a lower perfluoroalkyl group, are novel compounds. These compounds are useful as intermediates for the synthesis of, e.g., functional macromolecular membranes and lubricants. These compounds are produced by subjecting compounds of the general formula: ##STR3## and fuming sulfuric acid to a thermal reaction.

Growing community of inventors

Kasugai, Japan

Takashi Abe