CA1279873C - Perfluoroalkylation process - Google Patents
Perfluoroalkylation processInfo
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- CA1279873C CA1279873C CA000545649A CA545649A CA1279873C CA 1279873 C CA1279873 C CA 1279873C CA 000545649 A CA000545649 A CA 000545649A CA 545649 A CA545649 A CA 545649A CA 1279873 C CA1279873 C CA 1279873C
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Abstract
ABSTRACT
PERFLUOROALKYLATION PROCESS
Perfluoroalkylaromatic compounds containing at least two carbons in the perfluoroalkyl group are prepared by reacting an aromatic bromide or iodide with a potassium perfluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent.
PERFLUOROALKYLATION PROCESS
Perfluoroalkylaromatic compounds containing at least two carbons in the perfluoroalkyl group are prepared by reacting an aromatic bromide or iodide with a potassium perfluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent.
Description
Case 5542 PERFLUOROALKYLATION PROCESS
This invention relates to perfluoroalkylaromatic compounds and more particularly to a process for preparing them.
As disclosed in McLoughlin et al., Tetrahedron, Vol. 25, pp. 5921-5940, 1969, Kobayashi et al., Tetrahedron Letters, No. 42, pp~ 4071-4072, 1979, Gassman et al., Tetrahedron Letters, Vol. 26, No. 43, pp.
5243-5246, 1985, and U. S. Patents 3,408,411 (McLoughlin 10 et al.) and 4,439,617 (Sestanj et al.), it is known that perfluoroalkylaromatic compounds are apt to be useful as biologically-active compounds, surfactants, coatings, sealants, dyestuffs, and alkyd-type resins, and they can be prepared in various ways. Matsui et al., ChemistrY
15 Letters, 1981, pp. 1719-1720, teach that aromatic halides may be trifluoromethylated with sodium trifluoroacetate in the presence of cuprous iodide and a dipolar aprotic solvent. United States patent 4,590,010 (Ramachandran et al.) discloses the use of the technique of Matsui et al.
in trifluoromethylating 6-alkoxy-5-halo-1-cyanonaphtha-lenes and hydrocarbyl 6-alkoxy-5-halo-1-naphthoates.
An ob~ect of this invention is to provide a novel process for preparing perfluoroalkylaromatic compounds 7~7~
This invention relates to perfluoroalkylaromatic compounds and more particularly to a process for preparing them.
As disclosed in McLoughlin et al., Tetrahedron, Vol. 25, pp. 5921-5940, 1969, Kobayashi et al., Tetrahedron Letters, No. 42, pp~ 4071-4072, 1979, Gassman et al., Tetrahedron Letters, Vol. 26, No. 43, pp.
5243-5246, 1985, and U. S. Patents 3,408,411 (McLoughlin 10 et al.) and 4,439,617 (Sestanj et al.), it is known that perfluoroalkylaromatic compounds are apt to be useful as biologically-active compounds, surfactants, coatings, sealants, dyestuffs, and alkyd-type resins, and they can be prepared in various ways. Matsui et al., ChemistrY
15 Letters, 1981, pp. 1719-1720, teach that aromatic halides may be trifluoromethylated with sodium trifluoroacetate in the presence of cuprous iodide and a dipolar aprotic solvent. United States patent 4,590,010 (Ramachandran et al.) discloses the use of the technique of Matsui et al.
in trifluoromethylating 6-alkoxy-5-halo-1-cyanonaphtha-lenes and hydrocarbyl 6-alkoxy-5-halo-1-naphthoates.
An ob~ect of this invention is to provide a novel process for preparing perfluoroalkylaromatic compounds 7~7~
containing at least two carbons in the perfluoroalkyl group.
This and other objects are attained by (A~ reacting an aromatic bromide or iodide with at least about one 5 equivalent of a potassium perfluoroalkanoate corresponding to the formula:
KOOC(CF2)ncF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent and (B) if 10 desired, subjecting the product to one or more additional reactions to form a derivative.
Aromatic halides utilizable in the practice of the invention are substituted and unsubstituted aromatic iodides and bromides wherein any substituents are inert l5 substituents (i.e., substituents that do not prevent the reaction from occurring) such as alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, cyano, nitro, acylamino, alkyl-amino, tertiary amino, sulfonamido, sulfone, sulfonyl, phosphino, perfluoroalkyl, chloro, fluoro, ester, alde-20 hyde, ketone, acetal, and sulfono groups. The aromaticring may be a carbocyclic ring such as a benzene, naphthalene, or anthracene ring or a five- or six-membered heterocyclic ring having aromatic character, e.g., a pyridine, quinoline, isoquinoline, thiophene, 25 pyrrole, or furan ring. Exemplary of such compounds are iodobenzene, 3-iodotoluene, 4-chloroiodobenzene, 4-iodomethoxybenzene, l-iodonaphthalene, 3-iodoaniline, 7~7~
l-iodo-3-nitrobenzene, 2-iodothiophene, 4-iodoiso-quinoline, 2-iodopyridine, 3-iodoquinoline, and the corresponding bromides~
In a preferred embodiment of the invention, the 5 aromatic halide i5 a halonaphthalene corresponding to the formula:
Q
~1 X R' 10 wherein R and R' are independently selected from chloro, : fluoro, nitro, hydroxy, and alkyl and alkoxy substituents containing 1-6 carbons; Q is -CN or -COOR"7 R" is satu-rated hydrocarbyl; X is bromo or iodo; and m is 0 or 1.
The halocyanonaphthalenes and halonaphthoates 15 utilizable in the practice of the invention may be any compounds corresponding to the above halonaphthalene formula, but they are preferably compounds wherein m is o, X is in the 5-position, and R is an alkyl or alkoxy substituent in the 6-position. When the R and R' 20 substituents are alkyl or alkoxy, they are generally straight-chain groups of 1-3 carbons or branched-chain groups of three or four carbons, such as methyl, ethyl, propyl, l-methylethyl, butyl, 2-methylpropyl, l,1-dimethyl-ethyl, and the corresponding alkoxy groups, although, as 25 indicated above, larger groups such as hexyl and hexanoxy ~V~ 8~3 are also utilizable. When the halonaphthalene is an ester, Rl' may be any saturated hydrocarbyl group (i.e., a hydrocarbyl group that is free of aliphatic unsaturation) but i5 preferably an alkyl, cycloalky:L, aryl, alkaryl, or 5 aralkyl group containing 1-10 carbons/ e.g., methyl, ethyl, prapyl, cyclohexyl, phenyl, tolyl, and benzyl.
Particularly preferred halonaphthalenes are 6 alkoxy-5-bromo-1-cyanonaphthalenes, 6-alkoxy-5-iodo-1-cyano-naphthalenes, 6-alkoxy-5-bromo-1-naphthoates, and 10 6-alkoxy-5-iodo-1-naphthoates, especially those compounds wherein the alkoxy groups are methoxy.
The halonaphthoates are known compounds. The halocyanonaphthalenes are compounds that can be prepared by cyanating the appropriately substituted tetralone, 15 e.g., 6-methoxytetralone, to form the appropriately substituted 1-cyano-3,~-dihydronaphthalene, e.g., 6-methoxy-1-cyano-3,4-dihydronaphthalene, aromatizing the product in any suitable manner, and brominating or iodinating the resultant substituted l-cyanonaphthalene by 20 known techniques.
As already mentioned, the halonaphthalene or other aromatic halide is reacted with at least about one equivalent of a potassium perfluoroalkanoate to form the corresponding perfluoroalkylaromatic compound. Since 25 there does not appear to be any maximum to the number of CF2 groups that can desirably be incorporated into the aromatic molecule, the potassium perfluoroalkanoate employed in the reaction may be any compound corre~ponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one, and it is yenerally the salt which 5 contains the same number of CF2 groups as is desired in the product. However, because of cost and availability factors, as well as the fact that the reaction typically permits the formation of at least some perfluoroalkyl-aromatic compound containing more CF2 groups in the 10 substituent than are present in the perfluoroalkanoate, the preferred reactants are those containing 1 16 CF2 groups, such as potassium pentafluoropropionate, hepta-fluorobutyrate, nona~luorovalerate, tridecafluorohepta-noate, pentadecafluorooctanoate, heptadecafluorononanoate, 15 and nondecafluorodecanoate. There does not appear to be any maximum to the amount of salt that may be employed.
However, as a practical matter, the amount used is generally in the range of 1-20 equivalents, preferably at least 1.5 equivalents.
Dipolar aprotic solvents that may be utilized include, e.g., N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric triamide, and dimethylsulfoxide, but the particular solvent employed does not appear to be critical except in the sense that 25 it should have an appropriate boiling point for use at the reaction temperatures to be utilized. The solvent is used 87^3 in solvent amounts, e.g., an amount such as to provide an organic solids concentration of up to about 15%.
The cuprous iodide may be employed in any suit-able amount, generally an amount in the range of 0.5-5 5 equivalents.
The reaction is conducted by combining the in-gredients in any convenient order and heating them at a suitable temperature, conveniently reflux temperature, to accomplish the desired perfluoroalkylation Anhydrous con-10 ditions are preferably employed, and the temperature isgenerally in the range of 130-160C., preferably ~40-155C.
The perfluoroalkylnaphthalene products of the preferred reaction, like their trifluoromethyl homologs, 15 can be subjected to reactions such as those taught by Sestanj et al. Thus, e.g., (1~ a (perfluoroalkyl)cyano-naphthalene or perfluoroalkylnaphthoate prepared by the perfluoroalkylation reaction may be hydrolyzed to the corresponding acid in the presence of a base such as 20 sodium or pctassium hydroxide, (2) the acid can be halogenated, e.g., by reaction with thionyl chloride, to form the corresponding acid halide, t2) the acid halide may be reacted with a saturated hydrocarbyl ester of an acid corresponding to the formula ZNHCH2COOH ~e.g., 25 methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, or benzyl sarcosinate, the corresponding esters of amino-.3 acetic acids having other N-substituents (Z) containing 1-6 ~arbons, such as N-ethyl and N-propyl) to form an amide corresponding to the formula:
O=C~N~Z)-CH2COO~"
~/ "
(CF2)n R/m (3~ the amide may be saponified to form the corresponding salt, then hydrolyzed to the corresponding acid, and then - 10 thiated, e.g., with phosphorus pentasulfide or the like, to form a thioamide corresponding to the formula:
S=C-N(Z)-CH2COOH
R [~r ~ ' ~
( IF2)n R~m or (4) the thioamide may be prepared by thiating the amide and then subjecting the product to the saponification and hydrolysis steps.
The invention is advantageous in that it provides a 20 means of preparing perfluoroalkyl compounds useful in various applications, such as surfactants, coatings, sealants, resins, and dyestuffs, as well as biologically-active matarials or precursors therefor.
387'3 The following examples are given to illustrate the invention and are not intended as a limitation thereof.
EXAMPLE I
A suitable reaction vessel was charged with 8.1 g 5 of 6-methoxy-5-bromo-1-cyanonaphthalene, 11.8 g of CuI, 35 ml of toluene, and 55 ml of N,N-dimethylformamide. The reaction mixture was heated to 165C. with concurrent azeotropic removal of toluene/ water (25 ml) and then maintained at 155C. when 11.8 g of potassium pentafluoro-10 propionate was added. The reaction was monitored by VPC.After five hours no starting material was detected and the reaction mixture was poured into 150 ml of water and 125 ml of methylene chloride. The two phases were filtered, after which the organic layer was separated, washed with 15 brine, and concentrated in vacuo to provide a crude 6-methoxy-5-pentafluoroethyl-1-cyano-naphthalene (6-MPCN) having a purity of greater than 95%.
EXAMPLE II
The crude 6-MPCN product of Example I was dissolved 20 in 135 ml of methanol and 40 ml of a potassium hydroxide solution (4.5 g of KOH in 40 ml of water) and heatecl to 125C./70 psi for seven hours. The reaction mixture was then worked up and acidified to yield 6.6 g of 6-methoxy-5-pentafluoroethyl-1-naphthoic acid.
This and other objects are attained by (A~ reacting an aromatic bromide or iodide with at least about one 5 equivalent of a potassium perfluoroalkanoate corresponding to the formula:
KOOC(CF2)ncF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent and (B) if 10 desired, subjecting the product to one or more additional reactions to form a derivative.
Aromatic halides utilizable in the practice of the invention are substituted and unsubstituted aromatic iodides and bromides wherein any substituents are inert l5 substituents (i.e., substituents that do not prevent the reaction from occurring) such as alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, cyano, nitro, acylamino, alkyl-amino, tertiary amino, sulfonamido, sulfone, sulfonyl, phosphino, perfluoroalkyl, chloro, fluoro, ester, alde-20 hyde, ketone, acetal, and sulfono groups. The aromaticring may be a carbocyclic ring such as a benzene, naphthalene, or anthracene ring or a five- or six-membered heterocyclic ring having aromatic character, e.g., a pyridine, quinoline, isoquinoline, thiophene, 25 pyrrole, or furan ring. Exemplary of such compounds are iodobenzene, 3-iodotoluene, 4-chloroiodobenzene, 4-iodomethoxybenzene, l-iodonaphthalene, 3-iodoaniline, 7~7~
l-iodo-3-nitrobenzene, 2-iodothiophene, 4-iodoiso-quinoline, 2-iodopyridine, 3-iodoquinoline, and the corresponding bromides~
In a preferred embodiment of the invention, the 5 aromatic halide i5 a halonaphthalene corresponding to the formula:
Q
~1 X R' 10 wherein R and R' are independently selected from chloro, : fluoro, nitro, hydroxy, and alkyl and alkoxy substituents containing 1-6 carbons; Q is -CN or -COOR"7 R" is satu-rated hydrocarbyl; X is bromo or iodo; and m is 0 or 1.
The halocyanonaphthalenes and halonaphthoates 15 utilizable in the practice of the invention may be any compounds corresponding to the above halonaphthalene formula, but they are preferably compounds wherein m is o, X is in the 5-position, and R is an alkyl or alkoxy substituent in the 6-position. When the R and R' 20 substituents are alkyl or alkoxy, they are generally straight-chain groups of 1-3 carbons or branched-chain groups of three or four carbons, such as methyl, ethyl, propyl, l-methylethyl, butyl, 2-methylpropyl, l,1-dimethyl-ethyl, and the corresponding alkoxy groups, although, as 25 indicated above, larger groups such as hexyl and hexanoxy ~V~ 8~3 are also utilizable. When the halonaphthalene is an ester, Rl' may be any saturated hydrocarbyl group (i.e., a hydrocarbyl group that is free of aliphatic unsaturation) but i5 preferably an alkyl, cycloalky:L, aryl, alkaryl, or 5 aralkyl group containing 1-10 carbons/ e.g., methyl, ethyl, prapyl, cyclohexyl, phenyl, tolyl, and benzyl.
Particularly preferred halonaphthalenes are 6 alkoxy-5-bromo-1-cyanonaphthalenes, 6-alkoxy-5-iodo-1-cyano-naphthalenes, 6-alkoxy-5-bromo-1-naphthoates, and 10 6-alkoxy-5-iodo-1-naphthoates, especially those compounds wherein the alkoxy groups are methoxy.
The halonaphthoates are known compounds. The halocyanonaphthalenes are compounds that can be prepared by cyanating the appropriately substituted tetralone, 15 e.g., 6-methoxytetralone, to form the appropriately substituted 1-cyano-3,~-dihydronaphthalene, e.g., 6-methoxy-1-cyano-3,4-dihydronaphthalene, aromatizing the product in any suitable manner, and brominating or iodinating the resultant substituted l-cyanonaphthalene by 20 known techniques.
As already mentioned, the halonaphthalene or other aromatic halide is reacted with at least about one equivalent of a potassium perfluoroalkanoate to form the corresponding perfluoroalkylaromatic compound. Since 25 there does not appear to be any maximum to the number of CF2 groups that can desirably be incorporated into the aromatic molecule, the potassium perfluoroalkanoate employed in the reaction may be any compound corre~ponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one, and it is yenerally the salt which 5 contains the same number of CF2 groups as is desired in the product. However, because of cost and availability factors, as well as the fact that the reaction typically permits the formation of at least some perfluoroalkyl-aromatic compound containing more CF2 groups in the 10 substituent than are present in the perfluoroalkanoate, the preferred reactants are those containing 1 16 CF2 groups, such as potassium pentafluoropropionate, hepta-fluorobutyrate, nona~luorovalerate, tridecafluorohepta-noate, pentadecafluorooctanoate, heptadecafluorononanoate, 15 and nondecafluorodecanoate. There does not appear to be any maximum to the amount of salt that may be employed.
However, as a practical matter, the amount used is generally in the range of 1-20 equivalents, preferably at least 1.5 equivalents.
Dipolar aprotic solvents that may be utilized include, e.g., N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoric triamide, and dimethylsulfoxide, but the particular solvent employed does not appear to be critical except in the sense that 25 it should have an appropriate boiling point for use at the reaction temperatures to be utilized. The solvent is used 87^3 in solvent amounts, e.g., an amount such as to provide an organic solids concentration of up to about 15%.
The cuprous iodide may be employed in any suit-able amount, generally an amount in the range of 0.5-5 5 equivalents.
The reaction is conducted by combining the in-gredients in any convenient order and heating them at a suitable temperature, conveniently reflux temperature, to accomplish the desired perfluoroalkylation Anhydrous con-10 ditions are preferably employed, and the temperature isgenerally in the range of 130-160C., preferably ~40-155C.
The perfluoroalkylnaphthalene products of the preferred reaction, like their trifluoromethyl homologs, 15 can be subjected to reactions such as those taught by Sestanj et al. Thus, e.g., (1~ a (perfluoroalkyl)cyano-naphthalene or perfluoroalkylnaphthoate prepared by the perfluoroalkylation reaction may be hydrolyzed to the corresponding acid in the presence of a base such as 20 sodium or pctassium hydroxide, (2) the acid can be halogenated, e.g., by reaction with thionyl chloride, to form the corresponding acid halide, t2) the acid halide may be reacted with a saturated hydrocarbyl ester of an acid corresponding to the formula ZNHCH2COOH ~e.g., 25 methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, or benzyl sarcosinate, the corresponding esters of amino-.3 acetic acids having other N-substituents (Z) containing 1-6 ~arbons, such as N-ethyl and N-propyl) to form an amide corresponding to the formula:
O=C~N~Z)-CH2COO~"
~/ "
(CF2)n R/m (3~ the amide may be saponified to form the corresponding salt, then hydrolyzed to the corresponding acid, and then - 10 thiated, e.g., with phosphorus pentasulfide or the like, to form a thioamide corresponding to the formula:
S=C-N(Z)-CH2COOH
R [~r ~ ' ~
( IF2)n R~m or (4) the thioamide may be prepared by thiating the amide and then subjecting the product to the saponification and hydrolysis steps.
The invention is advantageous in that it provides a 20 means of preparing perfluoroalkyl compounds useful in various applications, such as surfactants, coatings, sealants, resins, and dyestuffs, as well as biologically-active matarials or precursors therefor.
387'3 The following examples are given to illustrate the invention and are not intended as a limitation thereof.
EXAMPLE I
A suitable reaction vessel was charged with 8.1 g 5 of 6-methoxy-5-bromo-1-cyanonaphthalene, 11.8 g of CuI, 35 ml of toluene, and 55 ml of N,N-dimethylformamide. The reaction mixture was heated to 165C. with concurrent azeotropic removal of toluene/ water (25 ml) and then maintained at 155C. when 11.8 g of potassium pentafluoro-10 propionate was added. The reaction was monitored by VPC.After five hours no starting material was detected and the reaction mixture was poured into 150 ml of water and 125 ml of methylene chloride. The two phases were filtered, after which the organic layer was separated, washed with 15 brine, and concentrated in vacuo to provide a crude 6-methoxy-5-pentafluoroethyl-1-cyano-naphthalene (6-MPCN) having a purity of greater than 95%.
EXAMPLE II
The crude 6-MPCN product of Example I was dissolved 20 in 135 ml of methanol and 40 ml of a potassium hydroxide solution (4.5 g of KOH in 40 ml of water) and heatecl to 125C./70 psi for seven hours. The reaction mixture was then worked up and acidified to yield 6.6 g of 6-methoxy-5-pentafluoroethyl-1-naphthoic acid.
3~.3 It is obvious that many variations may be made in the products and processes set forth above without departing from the spirit and scope of this invention.
Claims (19)
1. A process which comprises reacting an aromatic bromide or iodide with at least one equivalent of a potassium perfluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent.
2. A process which comprises reacting a halo-naphthalene corresponding to the formula:
with at least about one equivalent of a potassium per-fluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent so as to form a perfluoroalkylnaphthalene corresponding to the formula:
in which substituted naphthalene formulas R and R' are independently selected from chloro, fluoro, nitro, hydroxy, and alkyl andalkoxy substituents containing 1-6 carbons; Q is -CN or -COOR"; R" is saturated hydrocarbyl; X
is bromo or iodo; m is 0 or 1; and n is an integer of at least one.
with at least about one equivalent of a potassium per-fluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 wherein n is an integer of at least one in the presence of cuprous iodide and a dipolar aprotic solvent so as to form a perfluoroalkylnaphthalene corresponding to the formula:
in which substituted naphthalene formulas R and R' are independently selected from chloro, fluoro, nitro, hydroxy, and alkyl andalkoxy substituents containing 1-6 carbons; Q is -CN or -COOR"; R" is saturated hydrocarbyl; X
is bromo or iodo; m is 0 or 1; and n is an integer of at least one.
3. The process as claimed in 2 in which Q is -CN.
4. The process as claimed in 2 in which Q is -COOR".
5. The process as claimed in 2 in which the halonaphthalene is 6-methoxy-5-bromo-1-cyanonaphthalene.
6. The process as claimed in 2 in which the halonaphthalene is 6-methoxy-5-iodo-1-cyanonaphthalene.
7. The process as claimed in 2 in which the amount of potassium perfluoroalkanoate used is 1-20 equivalents.
8. The process as claimed in 2 in which a 6-alkoxy-5-bromo-1-cyanonaphthalene is reacted with 1-20 equivalents of potassium perfluoroalkanoate.
9. The process as claimed in 8 in which the alkoxy group is methoxy.
10. The process as claimed in 2 in which a 6-alkoxy-5-iodo-1-cyanonaphthalene is reacted with 1-20 equivalents of potassium perfluoroalkanoate.
11. The process as claimed in 10 in which the alkoxy group is methoxy.
12. The process as claimed in 2 in which the amount of cuprous iodide used is 0.5-5 equivalents.
13. The process as claimed in 2 in which the reaction temperature is 130-160°C.
14. The process as claimed in 13 in which the reaction temperature is 140-155°C.
15. In a process for preparing a thioamide by (A) reacting a halocyanonaphthalene corresponding to the formula:
with a perfluoroalkanoate to replace the X with a per-fluoroalkyl group, (B) hydrolyzing the perfluoroalkylated nitrile to the corresponding acid, (C) halogenating the acid to the corresponding acid halide, (C) reacting the acid halide with a saturated hydrocarbyl ester of an acid corresponding to the formula ZNHCH2COOH to form an amide-ester, (D) thiating the amide-ester, and (E) sub-jecting the product to saponification and hydrolysis to form a thioamide-acid, the improvement which comprises conducting the perfluoroalkylation by reacting the halocyanonaphthalene with at least about one equivalent of a potassium perfluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 in whichn is an integer of at least one at 130-160°C. in the presence of 0.5-5 equivalents of cuprous iodide in a dipolar aprotic solvent so as to form a perfluoroalkylnaphthalene corresponding to the formula:
in which substituted naphthalene formulas R and R' are independently selected from chloro, fluoro, nitro, hydroxy, and alkyl and alkoxy substituents containing 1-6 carbons; X is bromo or iodo; Z is an alkyl group contain-ing 1-6 carbons; m is 0 or 1; and n is an integer of at least one.
with a perfluoroalkanoate to replace the X with a per-fluoroalkyl group, (B) hydrolyzing the perfluoroalkylated nitrile to the corresponding acid, (C) halogenating the acid to the corresponding acid halide, (C) reacting the acid halide with a saturated hydrocarbyl ester of an acid corresponding to the formula ZNHCH2COOH to form an amide-ester, (D) thiating the amide-ester, and (E) sub-jecting the product to saponification and hydrolysis to form a thioamide-acid, the improvement which comprises conducting the perfluoroalkylation by reacting the halocyanonaphthalene with at least about one equivalent of a potassium perfluoroalkanoate corresponding to the formula KOOC(CF2)nCF3 in whichn is an integer of at least one at 130-160°C. in the presence of 0.5-5 equivalents of cuprous iodide in a dipolar aprotic solvent so as to form a perfluoroalkylnaphthalene corresponding to the formula:
in which substituted naphthalene formulas R and R' are independently selected from chloro, fluoro, nitro, hydroxy, and alkyl and alkoxy substituents containing 1-6 carbons; X is bromo or iodo; Z is an alkyl group contain-ing 1-6 carbons; m is 0 or 1; and n is an integer of at least one.
16. The process as claimed in 15 in which the halocyanonaphthalene is a 6-alkoxy-5-bromo-1-cyano-naphthalene.
17. The process as claimed in 16 in which the alkoxy group is methoxy.
18. The process as claimed in 15 in which the halocyanonaphthalene is a 6-alkoxy-5-iodo-1-cyano-naphthalene.
19. The process as claimed in 18 in which the alkoxy group is methoxy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000545649A CA1279873C (en) | 1987-08-28 | 1987-08-28 | Perfluoroalkylation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000545649A CA1279873C (en) | 1987-08-28 | 1987-08-28 | Perfluoroalkylation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1279873C true CA1279873C (en) | 1991-02-05 |
Family
ID=4136357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545649A Expired - Fee Related CA1279873C (en) | 1987-08-28 | 1987-08-28 | Perfluoroalkylation process |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1279873C (en) |
-
1987
- 1987-08-28 CA CA000545649A patent/CA1279873C/en not_active Expired - Fee Related
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