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Preparation method of 2,7-dimethyl-2,4,6-octa-triene-1,8-diethylester biphosphonate

A technology of diethyl diphosphonate and octatriene, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the difficulties in the recovery of the by-product triphenylphosphine oxide, Triphenylphosphine is highly toxic and difficult to control

Inactive Publication Date: 2011-05-25
ZHEJIANG MEDICINE CO LTD XINCHANG PHAMACEUTICAL FACTORY
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AI Technical Summary

Problems solved by technology

[0002] 2,7-Dimethyl-2,4,6-octatriene-1,8-bis(triphenylphosphine bromide) (US2,945,888) is generally used as a key intermediate in the synthesis of carotenoids, triphenyl Phosphine is highly toxic, and the recovery of the by-product triphenylphosphine oxide is very difficult. At present, only Roche company has solved the problem of its reduction and regeneration, and applied it to the synthesis of carotenoids (DE1934446)
However, the short-term reaction with 48% hydrobromic acid has the disadvantages of being difficult to control and many reaction by-products, and there is no halogenation report of the same compound III

Method used

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  • Preparation method of 2,7-dimethyl-2,4,6-octa-triene-1,8-diethylester biphosphonate
  • Preparation method of 2,7-dimethyl-2,4,6-octa-triene-1,8-diethylester biphosphonate
  • Preparation method of 2,7-dimethyl-2,4,6-octa-triene-1,8-diethylester biphosphonate

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Put 8.2g (0.05mol) of 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde (decadecandialdehyde) (II) and 100mL of isopropanol into a 500mL three-necked flask and stir Dissolve, control the temperature at 25-30°C, add 20.5g (0.1mol) of aluminum isopropoxide in batches, keep warm and reflux for 5h. After freezing again to 25-30°C, use 1N hydrochloric acid to adjust the pH to about 6, recover the solvent, add 200 mL of water and 100 mL of chloroform, dissolve the separated salt, separate the layers, extract the aqueous layer with 50 mL of chloroform, and combine the organic layers , recovered and dried to obtain 7.1 g of 2,7-dimethyl-2,4,6-octatriene-1,8-diol (III), with a yield of 84.5%.

[0034] 1 H NMR (CDCl 3 , 200MHz) δ: 6.51 (2H, m), 6.25 (2H, m), 4.20 (4H, m), 1.71 (2H, m).

Embodiment 2

[0036] Add 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde (8.2 g (0.05 mol) of decabisaldehyde (II) and 100 mL of dimethyltetrahydrofuran into a 500 mL three-necked flask and stir Dissolve, cool to -5°C in an ice-salt bath, control the reaction temperature at 0-5°C, add 6.5g (0.12mol) of potassium borohydride in batches, control the temperature at 25-30°C after the injection, and keep warm for 4h. Freeze again until After 0~-5°C, use glacial acetic acid to adjust the pH to about 6, recover dimethyltetrahydrofuran, add 200mL of water and 100mL of dichloromethane, dissolve the separated salt, separate the layers, extract the aqueous layer with 50mL of dichloromethane, and combine the organic layer, recovered and dried to obtain 7.0 g of 2,7-dimethyl-2,4,6-octatriene-1,8-diol (III), with a yield of 83.4%.

[0037] 1 H NMR (CDCl 3 , 200MHz) δ: 6.51 (2H, m), 6.25 (2H, m), 4.20 (4H, m), 1.7l (2H, m).

Embodiment 3

[0039]Drop into 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde (decadecandialdehyde (II) 8.2g (0.05mol) and ethanol 100mL in 500mL three-necked flask and stir to dissolve, ice Cool the salt bath to -5°C, control the reaction temperature at 0~-5°C, add 3.8g (0.1mol) of sodium borohydride in batches, control the temperature at 25~30°C after the injection, and keep it warm for 2~3h. Freeze again to 0 After ~-5°C, use glacial acetic acid to adjust the pH to about 6, recover ethanol, add 200 mL of water and 100 mL of dichloromethane to dissolve the separated salt, separate layers, extract the aqueous layer with 50 mL of dichloromethane, combine the organic layers, and recover to dryness. 7.5 g of 2,7-dimethyl-2,4,6-octatriene-1,8-diol III was obtained, with a yield of 89.3%.

[0040] 1 H NMR (CDCl 3 , 200MHz) δ: 6.51 (2H, m), 6.25 (2H, m), 4.20 (4H, m), 1.71 (2H, m).

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Abstract

The invention provides a preparation method of 2,7-dimethyl-2,4,6-octa-triene-1,8-diethylester biphosphonate, which comprises the following steps of: preparing 2,7-dimethyl-2,4,6-octa-triene-1,8-diol by using 2,7-dimethyl-2,4,6-octa-triene-1,8-dialdehyde as an initiative raw material, adopting methanol, ethanol, dimethyl-tetrahydrofuran or isopropanol as a solvent, and using aluminum isopropoxide, potassium borohydride or sodium borohydride as a reducing agent for reduction; preparing 2,7-dimethyl-2,4,6-octa-triene-1,8-dihalide by using phosphorus tri-halide or thionyl chloride for halogenation; and finally, heating the 2,7-dimethyl-2,4,6-octa-triene-1,8-dihalide together with triethyl phosphate to remove chloroethane or bromoethane to obtain the target compound. While achieving the aims of facilitating industrial application and making reaction easily controlled, the preparation method provided by the invention ensures that the yield of the reaction of each step exceeds 60 percent.

Description

technical field [0001] The invention relates to the field of biochemical industry, in particular to a method for preparing diethyl 2,7-dimethyl-2,4,6-octatriene-1,8-diphosphonate. Background technique [0002] 2,7-Dimethyl-2,4,6-octatriene-1,8-bis(triphenylphosphine bromide) (US2,945,888) is generally used as a key intermediate in the synthesis of carotenoids, triphenyl Phosphine radicals are highly toxic, and the recovery of the by-product triphenylphosphine oxide is very difficult. At present, only Roche company has solved the problem of its reduction and regeneration, and has applied it to the synthesis of carotenoids (DE1934446). 2,7-Dimethyl-2,4,6-octatriene-1,8-diethyl diphosphonate has the advantages of easy separation and recovery due to the participation of phosphate, and it is more and more widely used to replace triphenyl Phosphine bromide is used in Wittig reaction, and Xinchang Pharmaceutical Factory has used it to replace 2,7-dimethyl-2,4,6-octatriene-1,8-bis(...

Claims

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Application Information

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IPC IPC(8): C07F9/40
Inventor 陈建辉皮士卿
Owner ZHEJIANG MEDICINE CO LTD XINCHANG PHAMACEUTICAL FACTORY
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