Process for continuous production of octa -2,7-dien-1-ol

Claim 2

A process for continuous production of octa-2,7-­dien-1-ol which comprises reacting butadiene with water in a solvent which is capable of dissolving both reactants at least partially in the presence of a palladium catalyst with the mole ratio of butadiene to octa-2,7-dien-1-ol in the reaction mixture being maintained at 0.6 or more.

Claim 3

The process of Claim 1 wherein the mole ratio of butadiene to octa-2,7-dien-1-ol in the reaction mixture is within the range of 0.6 to 2.5.

Claim 4

The process of Claim 1 wherein the concentration of butadiene in the reaction mixture is 0.6 to 2.0 moles/liter.

Claim 5

The process of Claim 1 wherein said solvent is an aprotic polar solvent having a dielectric constant in the range of 39 to 100.

Claim 6

The process of Claim 4 wherein said polar solvent is sulfolane.

Claim 7

The process of Claim 1 wherein the carbonate and/or bicarbonate of a monodentate tertiary amine having a basicity constant (pKa) of 7 or more is added to the reaction system.

Claim 8

The process of Claim 6 wherein said tertiary amine is triethylamine.

Claim 9

The process of Claim 1 wherein the concentration of said palladium catalyst is 0.5 to 5 milligram atoms as palladium atom per liter of the reaction mixture.

Claim 10

The process of Claim 1 wherein a monodentate organophosphorus compound is present in the reaction system.

Claim 11

The process of Claim 9 wherein said monodentate organophosphorus compound is a hydrophilic monodentate organophosphorus compound.

Claim 12

The process of Claim 10 wherein a hydrophilic monodentate phosphine of the general formula wherein R¹ is an aliphatic, alicyclic or substituted or unsubstituted aromatic hydrocarbon group containing 1 to 8 carbon atoms; R² is a hydrogen atom, a methyl, nitro, cyano or methoxy group, or a halogen atom; n is an integer of 0 or 1; x is an integer of 0, 1 or 2; y and z are each an integer of 0, 1, 2 or 3 (provided that y and z are not concurrently equal to 0 and that x+y+z = 3); A is a carbonate or bicarbonate of or a carbonate or bicarbonate of B is -SO₃M, -COOM, or a carbonate or bicarbonate of (wherein R³ and R⁴ each represents a methyl, ethyl or n-propyl group; M is an alkali metal), is used as said hydrophilic monodentate organophosphorus compound.

Claim 13

The process of Claim 1 wherein said solvent is an aprotic polar solvent having a dielectric constant in the range of 39 to 100, the reaction is conducted in the reaction system to which the carbonate and/or bicarbonate of a monodentate tertiary amine having a basicity constant (pKa) of 7 or more and a hydrophilic monodentate organophosphorus compound are added, at least a part of the reaction mixture is extracted with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon to separate octa-2,7-dien-1-ol, and at least a part of the extraction residue containing the catalyst component is recycled to the above reaction system.

Claim 14

The process of Claim 12 wherein the level of addition of said carbonate and/or bicarbonate of monodentate tertiary amine to the reaction system is such that its concentration in the reaction mixture is in the range of 5 to 30 weight percent, the level of addition of said monodentate organophosphorus compound is at least 6 moles per gram atom of palladium, and the reaction is conducted in the homogeneous reaction mixture containing said aprotic polar solvent in an amount such that the weight ratio of water to the aprotic polar solvent in the reaction mixture is in the range of 70/30 through 30/70.

Claim 15

The process of Claim 13 wherein the extraction is performed in an atmosphere, the carbon dioxide partial pressure of which is higher than 3 kg/cm² (absolute pressure) and lower than 20 kg/cm² (absolute pressure) and at a temperature in the range of 0° to 40°C.

Claim 16

The process of Claim 14 wherein said monodentate tertiary amine is added to the extraction system in an amount equal to the amount of dissolution of the mono­dentate tertiary amine into the extract obtained by extraction.

Claim 17

The process of Claim 15 wherein said monodentate tertiary amine is triethylamine, the extractant is n-­hexane, the extract is subjected to distillation, and the mixture of n-hexane and triethylamine thus recovered is recycled to the extraction system.

Claim 18

A process for continuous production of octa-2,7-­dien-1-ol which comprises reacting butadiene with water in an aqueous solution of an aprotic polar solvent having a dielectric constant in the range of 39 to 100 containing the carbonate and/or bicarbonate of a mono­dentate tertiary amine having a basicity constant (pKa) of 7 or more in the presence of a palladium catalyst and a hydrophilic monodentate organophosphorus compound to synthesize octa-2,7-dien-1-ol, extracting at least a part of the resulting reaction mixture with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon to separate the octa-2,7-dien-1-­ol, and recycling at least a part of the extraction residue containing the catalyst components to said reaction for synthesis of octa-2,7-dien-1-ol, the above extraction being conducted in an atmosphere, the carbon dioxide partial pressure of which is higher than 3 kg/cm² (absolute pressure) and lower than 20 kg/cm² (absolute pressure) and at a temperature in the range of 0 to 40°C.

Claim 19

A process for continuous production of octa-2,7-­dien-1-ol which comprises reacting butadiene with water in an aqueous solution of an aprotic polar solvent having a dielectric constant in the range of 39 to 100 containing the carbonate and/or bicarbonate of a mono­dentate tertiary amine having a basicity constant (pKa) of 7 or more in the presence of a palladium catalyst and a hydrophilic monodentate organophosphorus compound to synthesize octa-2,7-dien-1-ol, extracting at least a part of the resulting reaction mixture with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon to separate the octa-2,7-dien-1-­ol, and recycling at least a part of the extraction residue containing the catalyst components to said reaction for synthesis of octa-2,7-dien-1-ol, the above extraction being conducted in an atmosphere, the carbon dioxide partial pressure of which is higher than 3 kg/cm² (absolute pressure) and lower than 20 kg/cm² (absolute pressure) and at a temperature in the range of 0 to 40°C.

Claim 20

The process of Claim 17 wherein said monodentate tertiary amine is added to the extraction system in an amount equal to the amount of dissolution of the monodentate tertiary amine into the extract obtained by the extraction.

Claim 21

The process of Claim 18 wherein said monodentate tertiary amine is triethylamine, the extractant is n-­hexane, the extract is subjected to distillation, and the mixture of n-hexane and triethylamine thus re­covered is recycled to the extraction system.