2-Methylbenzenesulfonic acid hydrate → HCID 21242435, compound

A reaction vessel was charged with 144.5 grams of aluminum chloride, 300 milliliters of toluene. A solution of 100.1 grams of isophthaloyol dichloride dissolved in 150 milliliters of toluene was added over a one hour period while the vessel and contents were maintained at a temperature below about 40° C. The reaction mixture was stirred for 30 minutes after completion of the addition of the dichloride-toluene solution. The reactor and contents were then heated to 90° C. over a period of 30 minutes and maintained at that temperature for an additional 60 minutes. The flask and contents were then cooled at ambient temperature for an additional 30 minutes. At the end of this period, the mixture was poured over one kilogram of ice, and chloroform was added to the reaction mixture to dissolve solids which formed on cooling. A water layer and an organic layer were present when the ice had melted. The organic layer was separated and washed with one liter of water. The aqueous layer and the water wash from the organic layer were combined and the combination was extracted twice with 100 milliliter portions of chloroform and the chloroform extract combined with the organic layer and washed with one liter of saturated aqueous sodium chloride. The organic layer was separated and dried over anhydrous magnesium sulfate. The organic layer was filtered to remove the magnesium sulfate and solvent removed from the organic layer in a rotary evaporator to yield solid 1,3-di(4-methylbenzoyl)benzene which was recrystallized twice from absolute ethanol. A Grignard reagent solution was prepared in the following manner: 118 milliliters of a 1 to 1 by volume mixture of iodomethane and diethyl ether were added to 23.2 grams of magnesium turnings in 150 milliliters of diethyl ether. The mixture was stirred for one hour. A solution was prepared of 50 grams of 1,3-di(4-methylbenzoyl)benzene in 500 milliliters of toluene. The Grignard reagent solution was added to the 500 milliliter toluene solution over a period of 1/4 hour. The resultant mixture was refluxed for one and one-half hours and allowed to stand and cool to room temperature. The cooled mixture was then poured over one kilogram of ice. When the ice had melted, the aqueous layer was acidified with a 15 percent aqueous hydrochloric acid solution to dissolve solids present and the aqueous and organic layers separated. The aqueous solution was extracted twice with 100 milliliter portions of toluene. The toluene was combined with the organic layer and the resultant organic phase was washed with 500 milliliters of saturated aqueous sodium chloride. The organic phase was then separated and dried with anhydrous magnesium sulfate to provide a solution of 1,3-di[1-(4-methylphenyl)1-hydroxyethyl]benzene in toluene. The solution of 1,3-di[1-(4-methylphenyl)1-hydroxyethyl]benzene was mixed with 0.25 gram of toluene sulfonic acid monohydrate and the solution refluxed for 45 minutes in a Dean-Stark assembly. After 200 milliliters of solvent had distilled, the mixture was maintained under total reflux for an additional 45 minutes. The reaction mixture was then washed once with 500 milliliters of aqueous sodium bicarbonate, once with 500 milliliters of water and once with 500 milliliters of saturated aqueous sodium chloride. The organic phase was separated from the sodium chloride solution and dried over anhydrous magnesium sulfate. The organic phase was filtered and the solvent removed in a rotary evaporator to leave a yellow oil which solidified on standing. The reaction product was purified by twice recrystallizing from absolute ethanol to provide a white crystalline solid 1,3-di[1-(4-methylphenyl)ethenyl]benzene. ##STR7## The melting point range was 65° to 66° C. The material distills at 177° C. at about 0.13 millimeter of mercury. A nitrogen-purged flask was provided which contained 15 milliliters of toluene having 0.668 millimole of 1,3-di[1-(4-methylphenyl)ethenyl]benzene. A solution of 1.340 milliequivalents of secondary butyllithium in cyclohexane was added to the toluene solution. After three hours at room temperature, the diethenyl compound was converted to 1,3-phenylene-bis(3-methyl-1,[4-methylphenyl]pentylidene)bis(lithium). ##STR8## The compound is soluble in normal hexane and can be prepared in normal hexane instead of toluene. A 1-liter nitrogen filled reaction flask had charged therein 39 grams of butadiene dissolved in 450 milliliters of toluene which had previously been treated with 0.275 milliequivalents of secondary butyllithium to destroy active impurities therein. The toluene solution of the dilithium initiator was added to the 1-liter reaction flask and the flask heated with a water bath maintained at about 50° C. After a period of about 80 minutes, the polymerization of the butadiene was for practical purposes complete. At this time, two milliliters of distilled tetrahydrofuran and 23 milliliters of purified styrene monomer were added. Polymerization of styrene continued for a period of about 40 minutes without heating. At the end of this period, one milliliter of methanol was added to the reaction mixture to terminate or kill any anions present. The reaction mixture was recovered by precipitation in methanol. When dried, the polymer weighed 65 grams and had a molecular weight as determined by gel permeation chromatography of 114,000. A portion of the polymer was molded and determined to have a tensile strength at break of 3160 pounds per square inch and an elongation of 790 percent.

1. temperaturethe solution refluxed for 45 minutes in a Dean-Stark assembly
2. distillationAfter 200 milliliters of solvent had distilled
3. temperaturethe mixture was maintained
4. temperatureunder total reflux for an additional 45 minutes
5. washThe reaction mixture was then washed once with 500 milliliters of aqueous sodium bicarbonate, once with 500 milliliters of water and once with 500 milliliters of saturated aqueous sodium chloride
6. customThe organic phase was separated from the sodium chloride solution
7. dry with materialdried over anhydrous magnesium sulfate
8. filtrationThe organic phase was filtered
9. customthe solvent removed in a rotary evaporator
10. customto leave a yellow oil which
11. customThe reaction product was purified
12. customby twice recrystallizing from absolute ethanol

ORD record

ord-6b1dd082321d4fc883400ee8d2d6add0

Source dataset

uspto-grants-1979_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04172190