SYNTHETIC METHOD OF 9,9-BIS[4-(2-HYDROXYETHOXY)PHENYL]FLUORENE

Abstract

A synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, belonging to the technical field of chemical synthesis. 9-fluorenone, phenoxyethanol, a catalyst and a cocatalyst are stiffed in an alkane solvent and heated until refluxing, the generated water is removed from the reaction solution via an azeotropic method while reacting, the reaction solution is diluted with water after the reaction is ended, uniformly stirred and cooled to separate out crystals and then filtered, a filter cake is rinsed and dried to obtain a 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene finished product; the filtered crystallization mother liquor is subjected to standing and layering, a water phase is removed, then an organic phase is distilled to recycle the alkane solvent, and the concentrate is rectified to recycle phenoxyethanol.

Claims

1. A synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, comprising the following steps: stirring and heating 9-fluorenone, phenoxyethanol, a catalyst and a cocatalyst in an alkane solvent until refluxing, and removing the generated water from the reaction solution via an azeotropic method while reacting to obtain a mixed solution containing 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene; wherein the catalyst is selected from one or two of concentrated sulfuric acid and methanesulfonic acid, and a mass ratio of the catalyst to 9-fluorenone is 0.001-0.2:1; the cocatalyst means a linear alkyl carboxylic acid and alkyl alcohol compound containing a mercapto group in a molecular structure, and is selected from one or more of mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, 5-mercaptovaleric acid, 6-mercaptohexanoic acid, 7-mercaptoheptanoic acid, 8-mercaptooctanoic acid, 9-mercaptononanoic acid, 10-mercaptodecanoic acid, ethylmercaptan, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, 7-mercaptoheptanol, 8-mercaptooctanol, 9-mercaptononanol and 10-mercaptodecane alcohol, and a mass ratio of cocatalyst to 9-fluorenone is 0.001-0.1:1; the alkane solvent is selected from one or more of n-hexane, n-heptane, n-octane, isooctane, nonane, decane, cyclohexane, methylcyclohexane and ethylcyclohexane; diluting the mixed solution containing 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with water, uniformly stirring and cooling to separate out crystals, filtering, rinsing a filter cake and drying to obtain a 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene finished product; and standing and layering the obtained crystallization mother liquor, removing a water phase, then distilling an organic phase to recycle the alkane solvent, and rectifying the concentrate to recycle phenoxyethanol.

2. The synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene according to claim 1, wherein a molar ratio of 9-fluorenone to phenoxyethanol is 1:2-6.

3-5. (canceled)

6. The synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene according to claim 1, wherein the amount of the alkane solvent is [[0.3-5]]0.1-10 times the mass of 9-fluorenone.

7. The synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene according to claim 1, wherein the amount of water for dilution is 0.1-3 times the mass of 9-fluorenone.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Example 1

[0032] 180 g of 9-fluorenone, 415 g of phenoxyethanol, 1.8 g of 3-mercaptopropionic acid and 540 g of cyclohexane were added into a 2 L reaction bottle. The above raw materials were stirred, and 27 g of concentrated sulfuric acid was dropwise added. After dropwise addition was ended, the temperature was raised until refluxing, refluxing and water division was conducted for 24 h while reacting, and the reaction was stopped. 360 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 2 h at 20-30° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 412.2 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 94.1% and a content of 99.2%.

[0033] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 492g of cyclohexane with a content of 99.7% and a recovery rate of 91.1%. The concentrated solution was rectified at reduced pressure to obtain 127.1 g of phenoxyethanol with a content of 99.2%. After the theoretical consumption was deducted, the recovery rate was 91.5%.

Example 2

[0034] 90 g of 9-fluorenone, 173 g of phenoxyethanol, 1.8 g of mercaptoacetic acid, 315 g of n-heptane and 9 g of methylsulphonic acid were added into a 1 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 18 h while reacting, and the reaction was stopped. 135 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 2 h at 0-10° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 203.2 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 92.8% and a content of 99.1%.

[0035] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 291.4 g of n-heptane with a content of 99.8% and a recovery rate of 92.5%. The concentrated solution was rectified at reduced pressure to obtain 31.6 g of phenoxyethanol with a content of 99.1%. After the theoretical consumption was deducted, the recovery rate was 90.4%.

Example 3

[0036] 135 g of 9-fluorenone, 465 g of phenoxyethanol, 0.7 g of 8-mercaptooctanol, 200 g of methyl cyclohexane and 7 g of concentrated sulfuric acid were added into a 2 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 20 h while reacting, and the reaction was stopped. 135 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 3 h at 10-15° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 310.1 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 94.4% and a content of 99.2%.

[0037] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 181.8 g of methyl cyclohexane with a content of 99.6% and a recovery rate of 90.9%. The concentrated solution was rectified at reduced pressure to obtain 242.7 g of phenoxyethanol with a content of 99.6%. After the theoretical consumption was deducted, the recovery rate was 94.1%.

Example 4

[0038] 100 g of 9-fluorenone, 300 g of phenoxyethanol, 3 g of 3-mercaptopropanol, 1 g of concentrated sulfuric acid and 200 g of isooctane were added into a 1 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 15 h while reacting, and the reaction was stopped. 50 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 1 h at 20-25° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 228.3 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 93.8% and a content of 99.4%.

[0039] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 184.6 g of isooctane with a content of 99.7% and a recovery rate of 92.3%. The concentrated solution was rectified at reduced pressure to obtain 136.8 g of phenoxyethanol with a content of 99.7%. After the theoretical consumption was deducted, the recovery rate was 93.3%.

Example 5

[0040] 150 g of 9-fluorenone, 400 g of phenoxyethanol, 7.5 g of ethylmercaptan, 375 g of ethyl cyclohexane and 4.5 g of concentrated sulfuric acid were added into a 2 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 12 h while reacting, and the reaction was stopped. 120 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 2 h at 0-5° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 344.9 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 94.5% and a content of 99.3%.

[0041] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 343.9 g of ethyl cyclohexane with a content of 99.5% and a recovery rate of 91.7%. The concentrated solution was rectified at reduced pressure to obtain 157.7 g of phenoxyethanol with a content of 99.4%. After the theoretical consumption was deducted, the recovery rate was 92.8%.

Example 6

[0042] 80 g of 9-fluorenone, 300 g of phenoxyethanol, 1.2 g of 6-mercaptohexanoic acid, 6.4 g of methanesulfonic acid and 80 g of n-octane were added into a 1 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 12 h while reacting, and the reaction was stopped. 100 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 3 h at 15-20° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 181.6 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 93.3% and a content of 99.5%.

[0043] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 72.4 g of n-octane with a content of 99.3% and a recovery rate of 90.5%. The concentrated solution was rectified at reduced pressure to obtain 166.5 g of phenoxyethanol with a content of 99.5%. After the theoretical consumption was deducted, the recovery rate was 93.9%.

Example 7

[0044] 120 g of 9-fluorenone, 320 g of recycled phenoxyethanol, 1.2 g of 3-mercaptopropionic acid, 150 g of recycled n-heptane and 6 g of concentrated sulfuric acid were added into a 1 L reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 20 h while reacting, and the reaction was stopped. 100 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 2 h at 10-15° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 273 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 93.5% and a content of 99.4%.

[0045] The crystallization mother liquor obtained after filtration was subjected to standing to remove a water phase, and an organic phase was distilled at normal pressure to obtain 138.3 g of n-octane with a content of 99.3% and a recovery rate of 92.2%. The concentrated solution was rectified at reduced pressure to obtain 126.6 g of phenoxyethanol with a content of 99.5%. After the theoretical consumption was deducted, the recovery rate was 93.1%.

Comparative Example

[0046] 60 g of 9-fluorenone, 140 g of phenoxyethanol, 1 g of 3-mercaptopropionic acid, 6 g of concentrated sulfuric acid and 150 g of n-heptane were added into a 500 mL reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 25 h while reacting, a sampling was conducted for HPLC detection, the content of the product was 97.9%, and the reaction was stopped. 60 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 3 h at 0-10° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 135 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 92.5% and a content of 99.2%.

[0047] 60 g of 9-fluorenone, 140 g of phenoxyethanol, 1 g of 3-mercaptopropionic acid, 6 g of concentrated sulfuric acid and 80 g of toluene were added into a 500 mL reaction bottle, stirred and heated until refluxing, refluxing and water division was conducted for 25 h while reacting, sampling was conducted for HPLC detection, the content of the product was 89.6%, and the reaction was stopped. 60 g of water was added, the temperature was reduced to separate out crystals, the above reaction solution was stirred for 3 h at 0-10° C. and filtered, a filter cake was rinsed with pure water until the pH of the rinsing solution was neutral, and the filter cake was dried to obtain 120.2 g of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene with a yield of 82.3% and a content of 94.9%.

[0048] 60 g of 9-fluorenone, 140 g of phenoxyethanol, 1 g of 3-mercaptopropionic acid and 6 g of concentrated sulfuric acid were added into a 500 mL reaction bottle, then stirred and heated to 110° C. to react for 25 h, sampling was conducted for HPLC detection, the content of the product 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene was 38.2%, and the reaction was stopped.