Process for synthesis of cyclic BINOL derivatives
A product and compound technology, applied in chemical instruments and methods, organic chemistry, liquid crystal materials, etc., can solve problems such as by-product formation and yield loss
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Embodiment 1
[0076] Example 1: 7,8-dihydro-6H-5,9-dioxanaphthyl-[a,c]-cyclononen (cyclononen)-7-ol (from 2,3-epoxy-1- propanol, Mitsunobu variant)
[0077]
[0078] 260 g of (S)-(-)-1,1'-binaphthyl-2,2'-diol and 274 g of triphenylphosphine were dissolved in 3146 g of THF, and the solution was warmed to an internal temperature of 65°C.
[0079] Then, first 80 g of 2,3-epoxy-1-propanol were added, and then 225 g of diisopropyl azodicarboxylate were added dropwise within about 40 minutes. After a reaction time of 20 minutes, HPLC check showed virtually complete reaction.
[0080] 1567 g of tetrahydrofuran were distilled over the course of 2.5 hours. At an internal temperature of 64° C., 192 g of 7.5% sodium hydroxide solution were metered in over the course of 5 minutes. After a reaction time of 1.5 hours, HPLC checks showed virtually complete crystallization of the desired product.
[0081] Separation and purification:
[0082] Distilled tetrahydrofuran and 16 g of ethylenediamine we...
Embodiment 2
[0093] Example 2: 7,8-Dihydro-6H-5,9-dioxanaphthyl-[a,c]-cyclononan-7-ol (DIAD variant)
[0094] 260 g of (S)-(-)-1,1'-binaphthyl-2,2'-diol and 274 g of triphenylphosphine were dissolved in 3120 g of THF, and the solution was warmed to 60° C. over the course of 50 minutes internal temperature.
[0095] Then 80 g of 2,3-epoxy-1-propanol were added, and after stirring the mixture for 10 minutes, 225 g of DIAD were metered in over the course of about 30 minutes. After a reaction time of 20 minutes, HPLC check showed virtually complete reaction (1.8% starting material).
[0096]2.6 kg of THF were distilled off from the reaction, the concentrate was taken up in 1343 g of toluene, the solution was warmed to 40° C., and 546 g of n-heptane were added. After stirring the mixture for 30 minutes, 1054 g of water were added. Most of the aqueous phase was drained and the remaining biphasic mixture was filtered through a layer filter covered with 30 g of diatomaceous earth. The remainin...
Embodiment 3
[0105] Example 3: 7,8-Dihydro-6H-5,9-dioxanaphthyl-[a,c]-cyclononan-7-ol (from epichlorohydrin)
[0106] 500 g of (S)-binaphthol were suspended in 1.25 l of acetonitrile, 715 ml of triethylamine and 335 ml of epichlorohydrin were added, and the mixture was warmed to 76° C. over the course of 1 hour.
[0107] After a reaction time of 40 hours, the mixture was cooled to 35° C. and a mixture of 250 ml of water and 150 ml of 32% hydrochloric acid was added.
[0108] The mixture was stirred at 50°C for 18 hours to complete the reaction of excess epichlorohydrin.
[0109] The mixture was adjusted to pH 7.5 with 50% sodium hydroxide solution. Acetonitrile was essentially distilled off, and the residue was diluted with 31 of water.
[0110] The reaction product was extracted 3 times with 1.5 l of dichloromethane. The combined dichloromethane phases were sucked dry on 600 g of sodium sulfate, the filter was washed with 500 ml of dichloromethane, and the filtrate was filtered through...
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