Method for producing alkoxycarbonylfluoroalkanesulfonic acid salt

摘要

In the present invention, a target alkoxycarbonylfluoroalkanesulfonic acid salt is obtained by using a halofluoroalkanoic acid ester as a starting raw material, sulfinating the halofluoroalkanoic acid ester in the presence of an amine (as a first step), and then, oxidizing the resulting sulfination product (as a second step). Further, an alkoxycarbonylfluoroalkanesulfinic acid onium salt, which is useful as a photoacid generator, is obtained by salt exchange reaction of the alkoxycarbonylfluoroalkanesulfonic acid salt.

主权项

1. A method for producing an alkoxycarbonylfluoroalkanesulfonic acid salt, comprising the following steps:
(1) reacting a halofluoroalkanoic acid ester of the general formula [2] with a sulfinating agent in the presence of tert-butylamine or tert-butylammonium chloride to form an alkoxycarbonylfluoroalkanesulfinic acid ammonium salt of the general formula [3]; (2) purifying the alkoxycarbonylfluoroalkanesulfinic acid ammonium salt by extracting with an organic solvent a crude product of the alkoxycarbonylfluoroalkanesulfinic acid ammonium salt, and then, washing a layer of the organic solvent with either one of water, an aqueous metal thiosulfate solution, and an aqueous metal sulfite solution; (3) reacting the alkoxycarbonylfluoroalkanesulfinic acid ammonium salt of the general formula [3] with an oxidizing agent, thereby obtaining an alkoxycarbonylfluoroalkanesulfonic acid ammonium salt of the general formula [1]; (4) purifying the alkoxycarbonylfluoroalkanesulfonic acid ammonium salt by recrystallization with an organic solvent; and (5) performing a salt exchange reaction of the alkoxycarbonylfluoroalkanesulfonic acid ammonium salt of the general formula [1] with a monovalent onium salt of the general formula [5], thereby obtaining an alkoxycarbonylfluoroalkanesulfonic acid onium salt of the general formula [4] as the alkoxycarbonylfluoroalkanesulfonic acid salt,
Q+X′−  [5]; wherein, in the general formula [1], R represents a C1-C10 straight or branched alkyl group, a C1-C10 straight or branched alkenyl group having at least at an end thereof a polymerizable double bond, a C3-C20 alicyclic organic group, an organic group formed of a C3-C20 alicyclic organic group and a straight alkylene group, a C3-C30 monocyclic or polycyclic lactone group, or a C6-C20 aryl group; a part or all of hydrogen atoms of the alkyl group, the alkenyl group, the alicyclic organic group, the organic group formed of the alicyclic organic group and the straight alkylene group, the monocyclic or polycyclic lactone group and the aryl group may be substituted with a fluorine atom, a hydroxyl group, a hydroxycarbonyl group or a C1-C6 straight, branched or cyclic alkoxy group; two hydrogen atoms on the same carbon atom of the alkyl group, the alkenyl group, the alicyclic organic group or the organic group formed of the alicyclic organic group and the straight alkylene group may be replaced with a single oxygen atom to form a keto group; and one of hydrogen atoms of the alkyl group may be substituted with a 2-acryloyloxy group, 2-methacryloyloxy group or 2-trifluoromethacryloyloxy group; R1 and R2 each independently represent a fluorine atom or a C1-C6 straight, branched or cyclic perfluoroalkyl group; and A+ represents tert-butylammonium ion; wherein, in the general formula [2], X represents a chlorine atom, a bromine atom or an iodine atom; and R, R1 and R2 have the same definitions as in the general formula [1]; wherein, in the general formula [3], R, R1, R2 and A+ have the same definitions as in the general formula [1] wherein, in the general formula [4], R, R1 and R2 have the same definitions as in the general formula [1]; and Q+ represents a sulfonium cation of the following general formula (a) or the following general formula (b) or an iodonium cation of the following general formula (c); and wherein, in the general formula [5], X′ represent a monovalent anion wherein, in the general formula (a), R3, R4 and R5 each independently represent a substituted or unsubstituted C1-C10 straight or branched alkyl, alkenyl or oxoalkyl group, or a substituted or unsubstituted C6-C18 aryl, aralkyl or aryloxoalkyl group; and two or more of R3, R4 and R5 may be bonded to each other to form a ring with a sulfur atom in the formula; wherein, in the general formula (b), R6 represents a substituted or unsubstituted C1-C20 straight, branched or cyclic alkyl or alkenyl group, or a substituted or unsubstituted C6-C14 aryl group; m represents an integer of 1 to 5; and n represents 0 or 1; wherein, in the general formula (c), R6 represents a substituted or unsubstituted C1-C20 straight, branched or cyclic alkyl or alkenyl group, or a substituted or unsubstituted C6-C14 aryl group; q represents an integer of 0 to 5; and n represents 0 or 1; wherein the sulfinating agent is sodium dithionite.