Process for producing fluorine-containing organic compound

Claim 2

A process for producing fluorine-containing organic compounds characterized in that fluorine-containing compounds which are at least one member selected from the group consisting of aliphatic iodides of R f I, R f ZnI, and R f SnX 2 I (where R f indicates a fluorine-containing aliphatic group; and X indicates halogen), and fluoroesters of R f COOR' (where R f indicates a fluorine-containing aliphatic group; and R' indicates an aliphatic hydrocarbon group or aromatic hydrocarbon group) are reacted with organic compounds in the presence of ultrasonic wave action, whereby the R f group or the R f CO group is introduced into the said organic compounds.

Claim 3

A process according to claim 1, wherein a carbonyl compound which is represented by the Formula: RCOR' (where R and R' represent similar or dissimilar atoms or groups which are selected from the group consisting of hydrogen atom, aliphatic group, and aromatic group, and where both of them are of the same aliphatic group, they are capable of forming rings jointly) is used as said organic compound, and is caused to react with said fluorine-containing aliphatic iodide in the presence of at least either zinc powder and halogenated tin powder which is represented by SnX 2 (where X represents halogen).

Claim 4

A process according to claim 1, wherein said fluorine-containing aliphatic iodide is caused to react with a halogen-substituted unsaturated compound having multiple bonds between carbon atoms, or a halogen-substituted aromatic compound in the presence of the action of ultrasonic waves and in the presence of zinc powder and palladium compound catalyst, whereby said R f is introduced into said multiple bond or aromatic nucleus, and whereby an unsaturated compound or an aromatic compound from which halogen is eliminated is obtained.

Claim 5

A process according to claim 3, wherein said halogen-substituted unsaturated compound is represented by the Formula: ##STR75## (where R, R' and R" represent a hydrogen atom, an alkyl group or alkenyl group, having carbon atom numbers of 10 or less than 10, aromatic group or aromatic group substituted with a substituent and X represents halogen), or is represented by the Formula: ##STR76## (where R, R' and R" are the same as those described above, and X represents halogen); and as said halogen-substituted aromatic compound, a halogenated aryl compound or its derivative which is represented by the Formula: ##STR77## (where X represents halogen; and Y represents at least one type of a hydrogen atom or substituents which are selected from the group consisting of an alkyl group or alkenyl group having carbon atom numbers of 5 or less than 5, cyano group, nitro group, ester group and aryl group) is used.

Claim 6

A process according to claim 3 or claim 4, wherein the palladium compound catalyst is a divalent compound or Pd(O)Ln.

Claim 7

A process according to claim 3, wherein said halogen-substituted unsaturated compound is represented by the Formula: ##STR78## (where R, R' and R" represent a hydrogen atom, an alkyl group or alkenyl group, having varbon atom numbers of 10 or less than 10, or aromatic group or aromatic group which is substituted with a substituent; and X represents halogen, or is represented by the Formula: ##STR79## (wherein R, R' and R" are the same as those described before; and X represents halogen), and as said halogen-substituted aromatic compound, a halogenated aryl compound or its derivative which is represented by the Formula: ##STR80## (where X represents halogens; and Y represents a hydrogen atom or at least one of substituents which is selected from the group consisting of an alkyl group or alkenyl group, having carbon atom numbers of 5 or less than 5, cyano gruop, nitro group, ester group and aryl group is used.

Claim 8

A process according to claim 6, wherein, the palladium compound catalyst is a divalent compound or Pd(O)Ln.

Claim 9

A process according to claim 1; wherein R f is a fluorine-containing alkyl group or alkenyl group having carbon atoms in the number of 10 or less.

Claim 10

A process according to claim 2 or claim 8, wherein R and R' are an alkyl group or alkenyl group having carbon atoms in the number of 15 or less.

Claim 11

A process according to claim 1 wherein zinc powder and/or halogenated tin powder are used within a range of one to three times R f I, in the number of moles.

Claim 12

A process according to claim 1 wherein fluorine-containing aliphatic iodide and a carbonyl compound or a halogen-substituted aliphatic or aromatic compound are caused to react under the use of an aprotic polar solvent.

Claim 13

A process according to claim 1, wherein the reaction is caused under ambient temperature and atmospheric pressure.

Claim 14

A process according to claim 1, wherein fluorine-containing aliphatic iodide which is represented by the Formula: R.sub.f ZnI or R.sub.f SnX.sub.2 I (where R f represents fluorine-containing aliphatic group; and X represents halogen) is caused to react with a carbonyl compound which is represented by the formula: RCOR' (where R and R' represent similar or dissimilar atoms or groups which are selected from the group consisting of hydrogen atom, aliphatic group and aromatic group, and where both of them are of aliphatic groups, they are capable of forming rings jointly).

Claim 15

A process according to claim 13, wherein R f represents a fluorine-containing alkyl group or fluorine-containing alkenyl group having carbon atoms in the number of 10 or less.

Claim 16

A process according to claim 13 or claim 14, wherein R and R' are to be an alkyl group or alkenyl group having carbon atoms in the number of 15 or less.

Claim 17

A process according to claim 13, wherein the reaction is caused under ambient temperature and atomospheric pressure.

Claim 18

A process according to claim 13, wherein fluorine-containing aliphatic iodide which is represented by the Formula: R.sub.f I (where R f represents a fluorine-containing aliphatic group) is caused to react with zinc powder and/or halogenated tin powder which is represented by SnX 2 (where X presents halogens) under heating, whereby R f ZnI and/or R f SnX 2 I is generated, and the product is used for the reaction.

Claim 19

A process according to claim 17, wherein zinc powder is used within a range of one to three times that of R f I in the number of moles.

Claim 20

A process according to claim 1, (1) wherein halogenated ketone which is represented by the Formula; ##STR81## (where R represents an aliphatic hydrocarbon-oxy group, aliphatic hydrocarbon group or fluoro aliphatic hydrocarbon group, and includes those which are forming rings between carbon atoms being bonded with X; X represents halogen; and Y represents hydrogen atoms or fluorine atom) is caused to react with a metal (M) comprising zinc or magnesium, whereby a metallic halogenated ketone is generated which is represented by the Formula: ##STR82## (where R, X and Y are the same as those described before; and M represents zinc or magnesium); and (2) wherein the metallic halogenated ketone thus generated is caused to react with a fluoroester which is represented by the Formula: R.sub.f COOR' (where R f represents a fluoroaliphatic hydrocarbon group, and includes those having ether bonds in their chains; R' represents an aliphatic hydrocarbon group or aromatic hydrocarbon group) in the presence of ultrasonic waves, whereby a fluorine-containing diketone is generated which is represented by the Formula: ##STR83## (where R, Y and R f are the same as those described before.)

Claim 21

A process according to claim 19, wherein a halogenated ketone is caused to react with a fluoroalkylester under the action of ultrasonic waves in the presence of zinc or magnesium.

Claim 22

A process according to claim 19; wherein a halogenated ketone is caused to react with zinc or magnesium in the presence of ultrasonic waves to generate metallic halogenated ketone, and further this metallic halogenated ketone is caused to react with fluoroalkylester in the presence of ultrasonic waves.

Claim 23

A process according to claim 19, wherein metallic halogenated ketone is generated by making halogenated ketone and zinc or magnesium to react under heating, and further this metallic halogenated ketone is subjected to reaction with fluoroalkyl ester under the action of ultrasonic waves.

Claim 24

A process according to any one of claim 19 through claim 22, wherein, in at least one of aprotic polar solvents which is selected from the group consisting of tetrahydrofuran, dimethylformamide, acetonitrile, dimethlsulfoxide, dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoamide, the reaction is caused to take place.

Claim 25

A process according to claim 19, wherein the number of carbon atoms of R is limited to 10 or less.

Claim 26

A process according to claim 24, wherein, as halogenated ketone, d-3-halogenated camphor is used.

Claim 27

A process according to claim 19, wherein X is to be of bromine atoms or iodine atoms.

Claim 28

A process according to claim 19, wherein R f is to be of a fluoroalkyl group or alkenyl group, or fluoroalkyl group or alkenyl group which is substituted and introduced with other halogens, all of which having carbon atoms in the number of 15 or less.

Claim 29

A process according to claim 19, wherein R f is to be of a fluoroalkylether group which is represented by the Formula: ##STR84## (where n=0˜3; and C* represents asymmetric carbon.)

Claim 30

A process according to claim 19, wherein R' is to be an alkyl group or alkenyl group having carbon atoms in the number of 10 or less.