WO2014173804A1 - Process for the preparation of 2-phenylphenol and its sodium salt - Google Patents
Process for the preparation of 2-phenylphenol and its sodium salt Download PDFInfo
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- WO2014173804A1 WO2014173804A1 PCT/EP2014/057878 EP2014057878W WO2014173804A1 WO 2014173804 A1 WO2014173804 A1 WO 2014173804A1 EP 2014057878 W EP2014057878 W EP 2014057878W WO 2014173804 A1 WO2014173804 A1 WO 2014173804A1
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- phenylphenol
- dibenzofuran
- sodium salt
- sodium
- reaction
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/65719—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
Definitions
- the present invention relates to a process for the preparation of 2-phenylphenol or its sodium salt, wherein dibenzofuran is reacted with metallic sodium in presence of a complexing agent, as well as to the use of 2-phenylphenol or its sodium salt obtained according to the inventive process as biocides or as precursors for specific flame re- tardants.
- 2-phenylphenol and its sodium salt are useful as biocides, especially as agricultural fungicides and as surface disinfect- ants for use in households, hospitals, nursing homes, laundries and food processing plants. Furthermore, 2-phenylphenol and its sodium salt are useful as precursors for the preparation of specific flame retardants.
- 2-Phenylphenol in an industrial scale is presently obtained, for example, by autocon- densation of cyclohexanone to form 2-cyclohexenylcyclohexanone, which reaction is catalyzed by various catalysts, for example by acidic ion exchangers or by metal salts of higher aliphatic carboxylic acids.
- the resulting 2-cyclohexenylcyclohexanone is subsequently dehydrogenated with transition metal catalysts.
- the present invention relates to a process for the preparation of 2-phenylphenol or its sodium salt, wherein dibenzofuran is reacted with metallic sodium in pres- ence of a complexing agent, which is selected from the group consisting of aliphatic ethers, cycloaliphatic ethers, oligomeric aliphatic ethers, polymeric aliphatic ethers and thio ethers, and wherein the molar ratio of metallic sodium to dibenzofuran is less than 5:1 .
- a complexing agent which is selected from the group consisting of aliphatic ethers, cycloaliphatic ethers, oligomeric aliphatic ethers, polymeric aliphatic ethers and thio ethers, and wherein the molar ratio of metallic sodium to dibenzofuran is less than 5:1 .
- Aliphatic ethers are preferably C 4 -C 50 o aliphatic ethers having 1 to 200 oxygen atoms, especially C 4 -C 50 aliphatic ethers having 1 to 20 oxygen atoms. Most preferred are C 4 - C 2 o aliphatic ethers having 1 to 15 oxygen atoms. Highly preferred aliphatic ethers are those having a terminal methoxy group, as well as those having at least two oxygen atoms. Preference is given to ethylene glycol dimethyl ether.
- Cycloaliphatic ethers are preferably C 4 -C 2 o cycloaliphatic ethers having 1 to 18 oxygen atoms, especially C 4 -Ci 0 cycloaliphatic ethers having 1 to 9 oxygen atoms. Also into consideration come crown ethers, like 12-crown-4, 15-crown-5 and 18-crown-6. Preference is given to 1 ,4-dioxane.
- Preferred oligomeric aliphatic ethers are diethylene glycol dimethyl ether and triethy- lene glycol dimethyl ether.
- Preferred polymeric aliphatic ethers are polyethylene glycol ethers, especially those of formula (1 )
- n is a number ranging from 4 to 2000, preferably from 4 to 500, and
- Ri and R 2 independently from each other, are C C 4 alkyl, especially methyl.
- Preferred thioethers are those of formula (2)
- R 3 -S-R 4 (2) wherein R 3 and R 4 , independently from each other, are C 1 -C 1 0 alkyl, especially methyl.
- Preferred complexing agents are 1 ,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and polyethylene glycol dimethyl ether, especially ethylene glycol dimethyl ether.
- the complexing agent may, for example, be used in a molar ratio of complexing agent to dibenzofuran of 1 :1 to 20:1 , especially 1 :1 to 10:1. Highly preferred is a molar ratio of 2:1 to 10:1 .
- the process can be carried out in presence of a solvent, which is used in addition to the complexing agent.
- such solvent is selected from the group consisting of alkylated benzenes and aliphatic or cycloaliphatic hydrocarbons.
- Preferred alkylated benzenes are C Ci 2 alkylated benzenes, especially Ci-C 6 alkylated benzenes, like toluene or xylene.
- Preferred aliphatic hydrocarbons are C 6 -C 20 aliphatic hydrocarbons, like hexane and heptane.
- Preferred cycloaliphatic hydrocarbons are C 6 -C 20 cycloaliphatic hydrocarbons, like cy- clohexane.
- the molar ratio of metallic sodium to dibenzofuran is preferably 1 :1 to 4:1 , more preferably 1 :1 to 3:1 , especially 1.5:1 to 3:1. Highly preferred is a ratio of about 2:1.
- the reaction of dibenzofuran with metallic sodium is preferably carried out at a temperature of 50°C to 250°C, especially 70°C to 160°C. Highly preferred is a temperature of 70°C to 100°C.
- reaction of dibenzofuran with metallic sodium is preferably carried out in only one step.
- the reaction product 2-phenylphenol is, as a rule, obtained in the form of the sodium salt (sodium 2-phenylphenate).
- the corresponding sodium salt may be hydrolysed to obtain 2-phenylphenol, for example by addition of water or an alcohol (e.g. methanol, ethanol, isopropanol), preferably by addition of water.
- an alcohol e.g. methanol, ethanol, isopropanol
- ambient temperature is preferred.
- the reaction mixture can be neutralized, for example by addition of an aqueous solution of hydrogen chloride.
- Purification of the reaction product may be effected by conventional methods, for example by solvent extraction, distillation or crystallization.
- purification is carried out by solvent extraction, followed by distillation and optionally followed by crystallization.
- purification is carried out by distillation, especially fractional distillation, optionally followed by crystallization.
- crystallization of the reaction product can occur directly after the isolation thereof. But crystallization can, for example, also be effected by crystallization from aliphatic or aromatic hydrocarbons, or by crystallization from the melt.
- the process according to the present invention allows to be carried out in only one step, results in high yields of 2-phenylphenol or its sodium salt and only a short reaction time is required.
- the process overcomes encountered difficulties in the purification of the reaction product. This is mainly due to the effect, that the formation of major amounts of by-products is avoided.
- the inventive process there is no specific need for the inventive process to be carried out under a hydrogen atmosphere, like under hydrogen pressure.
- the 2-phenylphenol and its sodium salt obtained according to the process of the pre- sent invention may be used as biocides, especially as agricultural fungicides, or as surface disinfectants, especially for use in households, hospitals, nursing homes, laundries, treatment of citrus fruits and food processing plants.
- 2-phenylphenol and its sodium salt obtained according to the process of the present invention may be used as precursors for the preparation of flame retard- ants corresponding to the compound of formula (3)
- Compounds of formula (3) can, for example, be obtained by reaction of 2-phenylphenol with phosphorus trichloride (PCI 3 ) in presence of a catalyst, like ZnCI 2 , by heating first to a temperature of about 30 to 80°C and in a second step to a temperature of 150 to 200°C.
- PCI 3 phosphorus trichloride
- Compounds of formula (4) can, for example, be obtained by hydrolysis of the compound of formula (3).
- the compounds of formulae (3) and (4) can each be used as such as a flame retard- ant, or can be further derivatized to form other suitable flame retardants.
- Such flame retardants are added to polymeric materials, like thermoplasts and du- roplasts, to enhance the flame retardant properties of the polymers.
- the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively.
- the combined tert-butyl methyl ether extracts are washed with 50 ml of water and subsequently with a saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated in vacuo.
- the residue is subjected to fractional distillation at 0.1 mbar, resulting in 40.1 g (99% of theory) of a colourless oil, which crystallizes on standing after a short time.
- the reaction mixture is three times extracted with 20 ml tert-butyl methyl ether, respectively.
- the combined tert-butyl methyl ether extracts are washed with water (20 ml, 3 x) and once with 20 ml of a saturated sodium chloride solution, dried over sodium sulphate and evaporated in vacuo. 10.7 g (99.5% of theory) of an oil are obtained, which, on standing, crystallizes after some time.
- the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively.
- the combined tert-butyl methyl ether extracts are washed three times with 50 ml of water, respectively, and once with a saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated in vacuo. After purification by distillation, 40.2 g (99% of theory) of 2-phenylphenol are obtained in the form of colourless needles.
- the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively.
- the combined tert-butyl methyl ether extracts are washed five times with 50 ml of water, respectively, and once with a saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated in vacuo. 9.9 g (99% of theory) of an oil are obtained which, after some time, crystallizes.
- the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively.
- the combined tert-butyl methyl ether extracts are washed three times with water (3 x 20ml), and brine (20 ml), dried over sodium sulphate, filtered and evaporated in vacuo. 9.8 g (98% of theory) of an oil are obtained which crystallizes after some time.
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Abstract
The present invention relates to a process for the preparation of 2-phenylphenol or its sodium salt, wherein dibenzofuran is reacted with metallic sodium in presence of a complexing agent, which is selected from the group consisting of aliphatic ethers, cycloaliphatic ethers, oligomeric aliphatic ethers, polymeric aliphatic ethers and thio ethers, and wherein the molar ratio of metallic sodium to dibenzofuran is less than 5:1.
Description
Process for the preparation of 2-phenylphenol and its sodium salt
Description
The present invention relates to a process for the preparation of 2-phenylphenol or its sodium salt, wherein dibenzofuran is reacted with metallic sodium in presence of a complexing agent, as well as to the use of 2-phenylphenol or its sodium salt obtained according to the inventive process as biocides or as precursors for specific flame re- tardants.
There is a demand for 2-phenylphenol and its sodium salt because these have been found useful as biocides, especially as agricultural fungicides and as surface disinfect- ants for use in households, hospitals, nursing homes, laundries and food processing plants. Furthermore, 2-phenylphenol and its sodium salt are useful as precursors for the preparation of specific flame retardants.
2-Phenylphenol in an industrial scale is presently obtained, for example, by autocon- densation of cyclohexanone to form 2-cyclohexenylcyclohexanone, which reaction is catalyzed by various catalysts, for example by acidic ion exchangers or by metal salts of higher aliphatic carboxylic acids. The resulting 2-cyclohexenylcyclohexanone is subsequently dehydrogenated with transition metal catalysts.
Such processes do not meet all present demands with respect to yield, selectivity and reaction time. Furthermore, purification of the reaction product cannot be easily han- died.
It has now been found that 2-phenylphenol and its sodium salt may be produced economically in a process wherein dibenzofuran is reacted with metallic sodium in presence of a complexing agent.
It is an advantage of the present invention that the process allows to be carried out in only one step, resulting in high yields of 2-phenlyphenol and its sodium salt in a short reaction time, and that the process also overcomes encountered difficulties in the purification of the reaction product.
Therefore, the present invention relates to a process for the preparation of 2-phenylphenol or its sodium salt, wherein dibenzofuran is reacted with metallic sodium in pres- ence of a complexing agent, which is selected from the group consisting of aliphatic ethers, cycloaliphatic ethers, oligomeric aliphatic ethers, polymeric aliphatic ethers and thio ethers, and wherein the molar ratio of metallic sodium to dibenzofuran is less than 5:1 .
In the course of the reaction sodium cations as well as dibenzofuran anions are formed. These are separated by the complexing agent, due to solvation, which surprisingly leads to the activation of the reaction.
Aliphatic ethers are preferably C4-C50o aliphatic ethers having 1 to 200 oxygen atoms, especially C4-C50 aliphatic ethers having 1 to 20 oxygen atoms. Most preferred are C4- C2o aliphatic ethers having 1 to 15 oxygen atoms. Highly preferred aliphatic ethers are those having a terminal methoxy group, as well as those having at least two oxygen atoms. Preference is given to ethylene glycol dimethyl ether.
Cycloaliphatic ethers are preferably C4-C2o cycloaliphatic ethers having 1 to 18 oxygen atoms, especially C4-Ci0 cycloaliphatic ethers having 1 to 9 oxygen atoms. Also into consideration come crown ethers, like 12-crown-4, 15-crown-5 and 18-crown-6. Preference is given to 1 ,4-dioxane.
Preferred oligomeric aliphatic ethers are diethylene glycol dimethyl ether and triethy- lene glycol dimethyl ether.
Preferred polymeric aliphatic ethers are polyethylene glycol ethers, especially those of formula (1 )
Rr(0-CH2-CH2)n-0-R2 (1 ), wherein n is a number ranging from 4 to 2000, preferably from 4 to 500, and
Ri and R2, independently from each other, are C C4 alkyl, especially methyl.
Preferred thioethers are those of formula (2)
R3-S-R4 (2), wherein R3 and R4, independently from each other, are C1-C10 alkyl, especially methyl. Preferred complexing agents are 1 ,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and polyethylene glycol dimethyl ether, especially ethylene glycol dimethyl ether.
The complexing agent may, for example, be used in a molar ratio of complexing agent to dibenzofuran of 1 :1 to 20:1 , especially 1 :1 to 10:1. Highly preferred is a molar ratio of 2:1 to 10:1 .
Optinonally, the process can be carried out in presence of a solvent, which is used in addition to the complexing agent.
Preferably, such solvent is selected from the group consisting of alkylated benzenes and aliphatic or cycloaliphatic hydrocarbons.
Preferred alkylated benzenes are C Ci2 alkylated benzenes, especially Ci-C6 alkylated benzenes, like toluene or xylene.
Preferred aliphatic hydrocarbons are C6-C20 aliphatic hydrocarbons, like hexane and heptane.
Preferred cycloaliphatic hydrocarbons are C6-C20 cycloaliphatic hydrocarbons, like cy- clohexane.
The molar ratio of metallic sodium to dibenzofuran is preferably 1 :1 to 4:1 , more preferably 1 :1 to 3:1 , especially 1.5:1 to 3:1. Highly preferred is a ratio of about 2:1.
The reaction of dibenzofuran with metallic sodium is preferably carried out at a temperature of 50°C to 250°C, especially 70°C to 160°C. Highly preferred is a temperature of 70°C to 100°C.
The reaction of dibenzofuran with metallic sodium is preferably carried out in only one step.
According to the process of the present invention the reaction product 2-phenylphenol is, as a rule, obtained in the form of the sodium salt (sodium 2-phenylphenate). If de- sired, the corresponding sodium salt may be hydrolysed to obtain 2-phenylphenol, for example by addition of water or an alcohol (e.g. methanol, ethanol, isopropanol), preferably by addition of water. For this step ambient temperature is preferred. Subsequently, the reaction mixture can be neutralized, for example by addition of an aqueous solution of hydrogen chloride.
Purification of the reaction product may be effected by conventional methods, for example by solvent extraction, distillation or crystallization.
According to one preferred embodiment of the present invention purification is carried out by solvent extraction, followed by distillation and optionally followed by crystallization.
According to a further preferred embodiment of the present invention purification is carried out by distillation, especially fractional distillation, optionally followed by crystallization.
It is preferred to carry out a crystallization step. In some cases crystallization of the reaction product can occur directly after the isolation thereof. But crystallization can, for example, also be effected by crystallization from aliphatic or aromatic hydrocarbons, or by crystallization from the melt.
The process according to the present invention allows to be carried out in only one step, results in high yields of 2-phenylphenol or its sodium salt and only a short reaction time is required. In addition, the process overcomes encountered difficulties in the purification of the reaction product. This is mainly due to the effect, that the formation of major amounts of by-products is avoided. Furthermore, there is no specific need for the inventive process to be carried out under a hydrogen atmosphere, like under hydrogen pressure.
The 2-phenylphenol and its sodium salt obtained according to the process of the pre- sent invention may be used as biocides, especially as agricultural fungicides, or as
surface disinfectants, especially for use in households, hospitals, nursing homes, laundries, treatment of citrus fruits and food processing plants.
Furthermore, the 2-phenylphenol and its sodium salt obtained according to the process of the present invention may be used as precursors for the preparation of flame retard- ants corresponding to the compound of formula (3)
The preparation of the compounds of formulae (3) and (4) starting from 2-phenylphenol is known and can be carried out according to conventional methods.
Compounds of formula (3) can, for example, be obtained by reaction of 2-phenylphenol with phosphorus trichloride (PCI3) in presence of a catalyst, like ZnCI2, by heating first to a temperature of about 30 to 80°C and in a second step to a temperature of 150 to 200°C.
Compounds of formula (4) can, for example, be obtained by hydrolysis of the compound of formula (3).
The compounds of formulae (3) and (4) can each be used as such as a flame retard- ant, or can be further derivatized to form other suitable flame retardants.
Such flame retardants are added to polymeric materials, like thermoplasts and du- roplasts, to enhance the flame retardant properties of the polymers.
The following examples illustrate the invention:
Example 1
40.0 g (0.238 moles) of dibenzofuran are dissolved in 188 g of diethylene glycol dimethyl ether. Under argon atmosphere, 1 1.48 g of small pieces of metallic sodium are added. With stirring, the reaction mixture is heated to a temperature of 156°C (reflux), whereby the colour of the mixture changes from blue to red. With stirring, the mixture is refluxed for two hours; thereafter no educts are detectable by gas chromatography. The reaction mixture is cooled to ambient temperature and about 135 ml of the solvent are distilled off at 100 mbar. To the residue, 50 ml of deionized water are added drop- wise. Subsequently, the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively. The combined tert-butyl methyl ether extracts are washed with 50 ml of water and subsequently with a saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated in vacuo. The residue is subjected to fractional distillation at 0.1 mbar, resulting in 40.1 g (99% of theory) of a colourless oil, which crystallizes on standing after a short time.
Example 2
10.0 g (0.059 moles) of dibenzofuran are dissolved in 50 ml of dry triethylene glycol dimethyl ether. At ambient temperature, 2.87 g of small pieces of metallic sodium are added. The reaction mixture is slowly heated to a temperature of 100°C. The sodium melts and an exothermic reaction starts, letting the temperature rise to 130°C. Thereby, the colour of the mixture changes from blue to red. With stirring, the mixture is held at a temperature of 130°C for 1 .5 hours. The reaction mixture is cooled to ambient temperature and 10 ml of water are added dropwise. Subsequently, the mixture is adjusted to a pH value of 3 to 4 by use of an aqueous 1 molar solution of hydrogen chloride. The reaction mixture is three times extracted with 20 ml tert-butyl methyl ether, respectively.
The combined tert-butyl methyl ether extracts are washed with water (20 ml, 3 x) and once with 20 ml of a saturated sodium chloride solution, dried over sodium sulphate and evaporated in vacuo. 10.7 g (99.5% of theory) of an oil are obtained, which, on standing, crystallizes after some time.
Example 3
Example 4
10.0 g (0.059 moles) of dibenzofuran are dissolved in 30 ml of an isomeric mixture of xylenes, and under argon atmosphere 26.49 g of triethylene glycol dimethyl ether and 2.87 g of small pieces of metallic sodium are added. With stirring, the reaction mixture is heated to a temperature of 147°C (reflux), whereby the colour of the mixture changes from blue to red. With stirring, the mixture is refluxed for five hours. The reaction mixture is cooled to ambient temperature and 20 ml of deionized water are added drop- wise. Subsequently, the mixture is adjusted to a pH value of 6 to 7 by addition of an
aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively. The combined tert-butyl methyl ether extracts are washed five times with 50 ml of water, respectively, and once with a saturated sodium chloride solution, dried over sodium sulphate, filtered and evaporated in vacuo. 9.9 g (99% of theory) of an oil are obtained which, after some time, crystallizes.
Example 5
Xylenes, 147°C
10.0 g (0.059 moles) of dibenzofuran are dissolved in 30 ml of an isomeric mixture of xylenes, and under argon atmosphere 16.75 g of diethylene glycol dimethyl ether and 2.87 g of small pieces of metallic sodium are added. With stirring, the reaction mixture is heated to a temperature of 147°C (reflux), whereby the colour of the mixture changes from blue to red. With stirring, the mixture is refluxed for six hours. The reaction mixture is cooled to ambient temperature and 20 ml of deionized water are added dropwise. Subsequently, the mixture is adjusted to a pH value of 6 to 7 by addition of an aqueous solution of hydrogen chloride and three times extracted with 30 ml tert-butyl methyl ether, respectively. The combined tert-butyl methyl ether extracts are washed three times with water (3 x 20ml), and brine (20 ml), dried over sodium sulphate, filtered and evaporated in vacuo. 9.8 g (98% of theory) of an oil are obtained which crystallizes after some time.
Claims
1 . Process for the preparation of 2-phenylphenol or its sodium salt, wherein
dibenzofuran is reacted with metallic sodium in presence of a complexing agent, which is selected from the group consisting of 1 ,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and polyethylene glycol dimethyl ether and wherein the molar ratio of metallic sodium to dibenzofuran is less than 5:1 .
Process according to claim 1 , wherein the molar ratio of metallic sodium to dibenzofuran is 1 :1 to 4:1.
Process according to claims 1 or 2, wherein the reaction is carried out in presence of a solvent selected from the group consisting of alkylated benzenes and aliphatic or cycloaliphatic hydrocarbons.
4. Process according to any of claims 1 to 3, wherein the reaction of dibenzofuran with metallic sodium is carried out at a temperature of 50°C to 250°C.
Process according to any of claims 1 to 4, wherein the reaction of dibenzofuran with metallic sodium is carried out at a temperature of 70°C to 160°C.
Process according to any of claims 1 to 5, wherein 2-phenylphenol sodium salt obtained as the reaction product is subsequently subjected to hydrolysis by addition of water or an alcohol.
7. Process according to any of claims 1 to 6, wherein 2-phenylphenol or its sodium salt obtained as reaction products are purified by distillation, optionally followed by crystallization.
8. Use of 2-phenylphenol or its sodium salt obtained according to any of claims 1 to 7 as biocides.
9. Use of 2-phenylphenol or its sodium salt obtained according to any of claims 1 to 7 as precursors for the preparation of flame retardants corresponding to the compound of formula (3)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018127807A1 (en) * | 2017-01-07 | 2018-07-12 | Decco Worldwide Post-Harvest Holdings B.V. | A fungicidal treatment for black sigatoka |
| CN113429267A (en) * | 2021-04-30 | 2021-09-24 | 沧州临港丰亚化工有限公司 | Novel continuous process and device for preparing o-phenylphenol |
| CN115772069A (en) * | 2022-11-29 | 2023-03-10 | 沧州临港丰亚化工有限公司 | Synthesis method of vinyl methyl ether |
| CN116199566A (en) * | 2023-02-22 | 2023-06-02 | 中化国际新材料(河北)有限公司 | Method for producing o-phenylphenol compound |
| CN116375563A (en) * | 2023-02-22 | 2023-07-04 | 中化国际新材料(河北)有限公司 | A kind of production method of o-phenylphenol compound |
| CN116514638A (en) * | 2023-05-09 | 2023-08-01 | 信诺立兴(沧州渤海新区)化工有限公司 | Separation method of byproduct sodium methoxide |
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| DE492064C (en) * | 1927-03-19 | 1930-02-17 | Hermine Weissgerber Geb Marsch | Process for the preparation of o-oxydiphenyl |
| US2862035A (en) * | 1955-01-28 | 1958-11-25 | Bayer Ag | Process for the fission of ethers |
| US4000203A (en) * | 1975-08-08 | 1976-12-28 | Monsanto Company | Production of orthophenylphenols |
| US6245880B1 (en) * | 1999-10-08 | 2001-06-12 | Toyo Boseki Kabushiki Kaisha | Organophosphorous composition, method of producing organophosphorous compound, polyester composition and method of producing the same |
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| CN116199566A (en) * | 2023-02-22 | 2023-06-02 | 中化国际新材料(河北)有限公司 | Method for producing o-phenylphenol compound |
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