US4694100A — Method for producing α-(p-isobutylphenyl)propioni…

Claim 1

Independent Claim 220 words

A method for producing α-(p-isobutylphenyl)-propionic acid or its alkyl esters which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis(p-isobutylphenyl) ethane under the conditions that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of said sulfuric acid and any water formed in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde; (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylstyrene and isobutylbenzene as main products; and (III) reacting said p-isobutylstyrene with carbon monoxide and water or alcohol at temperatures in the range of 40° to 150° C. at a carbon monoxide pressure in the range of 30 to 400 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylphenyl)-propionic acid or its alkyl ester.

Claim 2

Independent Claim 220 words

A method for producing α-(p-isobutylphenyl)-propionic acid or its alkyl esters which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis(p-isobutylphenyl) ethane under the conditions that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of said sulfuric acid and any water formed in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde; (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylstyrene and isobutylbenzene as main products; and (III) reacting said p-isobutylstyrene with carbon monoxide and water or alcohol at temperatures in the range of 40° to 150° C. at a carbon monoxide pressure in the range of 30 to 400 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylphenyl)-propionic acid or its alkyl ester.

Claim 3

Dependent Claim 28 words

The method according to claim 1, wherein at least a portion of said isobutylbenzene obtained in said step (II) is recycled to the reaction of said step (I).

Claim 4

Dependent Claim 31 words

The method according to claim 1, wherein said protonic acid in said step (II) is at least one member selected from the group consisting of inorganic acids and organic sulfonic acids.

Claim 5

Dependent Claim 28 words

The method according to claim 3, wherein said inorganic acid is at least one member selected from the group consisting of phosphoric acids, sulfuric acids and heteropoly acids.

Claim 6

Dependent Claim 27 words

The method according to claim 3, wherein said organic sulfonic acid is at least one member selected from the group consisting of naphthalenesulfonic acid and toluenesulfonic acid.

Claim 7

Dependent Claim 39 words

The method according to claim 1, wherein said solid acid in said step (II) is at least one member selected from the group consisting of clay type solid acids, synthetic silica-alumina type solid acids and zeolite type solids acids.

Claim 8

Dependent Claim 21 words

The method according to claim 1, wherein said protonic acid carrying-solid acid in said step (II) is phosphoric acid carrying-solid acid.

Claim 9

Dependent Claim 43 words

The method according to claim 1, wherein said metal of said metal complex carbonylation catalyst in said step (III) is at least one member selected from the group consisting of precious metals of Pd, Rh, Ir and Ru and Ni, Co and Fe.

Claim 10

Dependent Claim 63 words

The method according to claim 8, wherein said metal complex comprises a complex selected from the group consisting of bistriphenylphosphine dichlorocomplex, bistributylphosphine dichlorocomplex, bistricyclohexylphosphine dichlorocomplex, π-allyltriphenylphosphine dichlorocomplex, triphenylphosphine piperidine dichlorocomplex, bisbenzonitrile dichlorocomplex, biscyclohexyloxime dichlorocomplex, 1,5,9-cyclododecatriene dichlorocomplex, bistriphenylphosphine dicarbonyl complex, bistriphenylphosphine diacetate complex, bistriphenylphosphine dinitrate complex, bistriphenylphosphine sulfate complex, tetrakistriphenylphosphine complex, and complexes in which a part of the ligands therein comprise carbon monoxide.

Claim 11

Dependent Claim 39 words

The method according to claim 9 wherein said complexes in which a part of the ligands therein comprise carbon monoxide are selected from the group consisting of chlorocarbonyl bistriphenylphosphine complex, hydridocarbonyl tristriphenylphosphine complex, bischlorotetracrabonyl complex and dicarbonyl acetylacetonate complex.

Claim 12

Dependent Claim 26 words

The method according to claim 1, wherein the alcohol in said step (II) is selected from the group consisting of C 1 -C 4 aliphatic alcohols.

Claim 13

Dependent Claim 41 words

The method according to claim 1, wherein the quantity of a metal complex or a compound which produces a metal complex to be used in said step (II) as a catalyst is 0.0001 to 0.5 mole per mole of said p-isobutylstyrene.

Claim 14

Dependent Claim 19 words

The method according to claim 12, wherein said quantity is 0.001 to 0.1 mole per mole of said p-isobutylbenzene.

Claim 15

Dependent Claim 32 words

The method according to claim 1, wherein the quantity of alcohol or water used in said step (II) is 0.5 to 50 parts by weight per part by weight of said p-isobutylbenzene.

Claim 16

Dependent Claim 23 words

The method according to claim 14, wherein said quantity is 1 to 20 parts by weight per part by weight of said p-oisobutylbenzene.

Claim 17

Dependent Claim 37 words

The method according to claim 1, wherein said 1,1-bis (p-isobutylphenyl) ethane is cracked in a gaseous phase in the presence of a quantity of steam which is two times or more the weight of said 1,1-bis(p-isobutylphenyl) ethane.

Claim 18

Dependent Claim 33 words

The method according to claim 1, wherein after said step (II) in which p-isobutylethylbenzene is produced as a minor product, said p-isobutylstryene is recovered by distillation and is used in said step (III).

Claim 19

Dependent Claim 19 words

The method according to claim 1, wherein said ester is further subjected to hydrolysis to produce α-(p-isobutylphenyl) propionic acid.

Claim 20

Independent Claim 207 words

A method for producing α-(p-isobutylphenyl)-propionaldehyde which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis (p-isobutylphenyl) ethane under the condition that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of sulfuric acid and any water formed in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde; (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylstyrene and isobutylbenzene as main products; and (III) reacting said p-isobutylstyrene with carbon monoxide and hydrogen at temperatures in the range of 40° to 150° C. at a reaction pressure in the range of 5 to 500 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylphenyl)-propionaldehyde.

Claim 21

Independent Claim 207 words

A method for producing α-(p-isobutylphenyl)-propionaldehyde which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis (p-isobutylphenyl) ethane under the condition that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of sulfuric acid and any water formed in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde; (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylstyrene and isobutylbenzene as main products; and (III) reacting said p-isobutylstyrene with carbon monoxide and hydrogen at temperatures in the range of 40° to 150° C. at a reaction pressure in the range of 5 to 500 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylphenyl)-propionaldehyde.

Claim 22

Independent Claim 216 words

A method for producing α-(p-isobutylphenyl)propionic acid which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis(p-isobutylphenyl) ethane under the conditions that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of said sulfuric acid and any water in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde. (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylsytrene and isobutylbenzene as main products; (III) reacting said p-isobutylstyrene with carbon monoxide and hydrogen at temperatures in the range of 40° to 150° C. at a reaction pressure in the range of 5 to 500 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylpheneyl)-propionaldehyde; and (IV) oxidizing said α-(p-isobutylphenyl)propionaldehyde to produce α-(p-isobutylphenyl) propionic acid.

Claim 23

Independent Claim 216 words

A method for producing α-(p-isobutylphenyl)propionic acid which comprises the following steps of: (I) reacting isobutylbenzene and acetaldehyde in the presence of sulfuric acid to produce 1,1-bis(p-isobutylphenyl) ethane under the conditions that the concentration of said sulfuric acid in the reaction system is not lower than 75% by weight based on the sum of the weights of said sulfuric acid and any water in the reaction system, the concentration of said acetaldehyde in the reaction system is maintained at 1% by weight or lower, and said isobutylbenzene is added in excess relative to said acetaldehyde. (II) catalytically cracking said 1,1-bis(p-isobutylphenyl) ethane in a liquid phase at reaction temperatures in the range of 200° to 350° C. in the presence of a protonic acid catalyst or in a gaseous phase at reaction temperatures in the range of 300° to 650° C. in the presence of a solid acid catalyst or a protonic acid carrying-solid acid catalyst to produce p-isobutylsytrene and isobutylbenzene as main products; (III) reacting said p-isobutylstyrene with carbon monoxide and hydrogen at temperatures in the range of 40° to 150° C. at a reaction pressure in the range of 5 to 500 kg/cm 2 in the presence of a metal complex carbonylation catalyst to produce α-(p-isobutylpheneyl)-propionaldehyde; and (IV) oxidizing said α-(p-isobutylphenyl)propionaldehyde to produce α-(p-isobutylphenyl) propionic acid.

Claim 24

Dependent Claim 28 words

The method according to claim 20, wherein at least a part of said isobutylbenzene obtained in said step (II) is recycled to the reaction of said step (I).

Claim 25

Dependent Claim 31 words

The method according to claim 20, wherein said protonic acid in said step (II) is at least one member selected from the group consisting of inorganic acids and organic sulfonic acids.

Claim 26

Dependent Claim 28 words

The method according to claim 22, wherein said inorganic acid is at least one member selected from the group consisting of phosphoric acids, sulfuric acids and heteropoly acids.

Claim 27

Dependent Claim 27 words

The method according to claim 22, wherein said organic sulfonic acid is at least one member selected from the group consisting of naphthalenesulfonic acid and toluenesulfonic acid.

Claim 28

Dependent Claim 39 words

The method according to claim 20, wherein said solid acid in said step (II) is at least one member selected from the group consisting of clay type solid acids, synthetic silica-alumina type solid acids and zeolite type solid acids.

Claim 29

Dependent Claim 21 words

The method according to claim 20, wherein said protonic acid carrying-solid acid in said step (II) is phosphoric acid carrying-solid acid.

Claim 30

Dependent Claim 43 words

The method according to claim 20, wherein said metal of said metal complex carbonylation catalyst in said step (III) is at least one member selected from the group consisting of precious metals of Pd, Rh, Ir and Ru and Ni, Co and Fe.

Claim 31

Dependent Claim 63 words

The method according to claim 27, wherein said metal complex comprises a complex selected from the group consisting of bistriphenylphosphine dichlorocomplex, bistributylphosphine dichlorocomplex, bistricyclohexylphosphine dichlorocomplex, π-allyltriphenylphosphine dichlorocomplex, triphenylphosphine piperidine dichlorocomplex, bisbenzonitrile dichlorocomplex, biscyclohexyloxime dichlorocomplex, 1,5,9-cyclododecatriene dichlorocomplex, bistriphenylphosphine dicarbonyl complex, bistriphenylphosphine diacetate complex, bistriphenylphosphine dinitrate complex, bistriphenylphosphine sulfate complex, tetrakistriphenylphosphine complex, and complexes in which a part of the ligands therein comprise carbon monoxide.

Claim 32

Dependent Claim 39 words

The method according to claim 28 wherein said complexes in which a part of the ligands therein comprise carbon monoxide are selected from the group consisting of chlorocarbonyl bistriphenylphosphine complex, hydridocarbonyl tristriphenylphosphine complex, bischlorotetracarbonyl complex and dicarbonyl acetylacetonate complex.

Claim 33

Dependent Claim 21 words

The method according to claim 20, wherein said oxidization of said step (IV) is carried out by a mild oxidizing agent.

Claim 34

Dependent Claim 15 words

The method according to claim 30, wherein said oxidizing agent is a hypohalogenous acid salt.

Claim 35

Dependent Claim 34 words

The method according to claim 20, wherein said 1,1-bis(p-isobutylphenyl)ethane is cracked in a gaseous phase in the presence of a quantity of steam which is two times or more the weight of said 1,1-bis(p-isobutylphenyl)ethane.

Claim 36

Dependent Claim 33 words

The method according to claim 20, wherein, after said step (II) in which p-isobutylethylbenzene is produced as a minor product, said p-isobutylstyrene is recovered by distillation and is used in said step (III).

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1990-09-14	1991-03-16	1991-09-15	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1994-09-14	1995-03-16	1995-09-15	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1998-09-14	1999-03-16	1999-09-15	$7700.00	Window Closed / Lapsed

Method for producing α-(p-isobutylphenyl)propionic acid or its alkyl esters

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