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Synthesis of alkali metal substituted borohydride reagents

A technology of borohydride and alkali metal, which is used in the synthesis field of replacing borohydride reagents, and can solve problems such as danger, intractability, and high temperature

Inactive Publication Date: 2001-07-11
巴斯夫公开股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Of course, since the potassium hydride reagent is extremely difficult to handle and dangerous, there is no industrial use of this reagent in synthetic routes
In addition, current methods for industrially synthesizing alkali metal hydride reagents require higher pressures and higher temperatures

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0061] Example 1: Potassium tri-sec-butyl borohydride in THF (two steps, single reactor)

[0062] 13.7 grams of metallic potassium, 241.7 grams of dry tetrahydrofuran, and 1.0 grams of phenanthrene were added to a Parr pressure reactor equipped with a back pressure regulator (set at 95 psig) and a bubbler system. The mixture was heated to about 65°C to melt the potassium metal, and then stirred to disperse the potassium metal in tetrahydrofuran. The temperature was then increased to 85°C.

[0063]Hydrogen pressure is applied to the reactor until the reactor pressure reaches 50 psig. The pressure is maintained for about 8 hours. The reactor was then cooled to 25°C and depressurized. Then 65.4 g of tri-sec-butylborane was added to keep the reaction temperature below 30°C. After the addition of tri-sec-butylborane, the reaction mixture was stirred for about 1 hour, and then filtered through a filter. The filtrate contains potassium tri-sec-butyl borohydride. The yield is almost quant...

Embodiment 2

[0064] Example 2: Potassium tri-sec-butyl borohydride in THF (two steps, single reactor)

[0065] 23.46 grams of metallic potassium, 136.64 grams of dry tetrahydrofuran and 1.71 grams of phenanthrene were added to a Parr pressure reactor equipped with a back pressure regulator (set at 95 psig) and a bubbling system. The mixture was heated to about 65°C to melt the potassium metal, and then stirred to disperse the potassium metal in tetrahydrofuran. Then the temperature was increased to 85°C.

[0066] Hydrogen pressure is applied to the reactor until the reactor pressure reaches 50 psig. The pressure is maintained for about 8 hours. The reactor was then cooled to 25°C and depressurized. Then, 111.48 grams of tri-sec-butylborane was added to keep the reaction temperature below 30°C. After the addition of tri-sec-butylborane, the reaction mixture was stirred for about 1 hour, and then filtered through a filter. The filtrate contains potassium tri-sec-butyl borohydride. The yield is a...

Embodiment 3

[0067] Example 3: Potassium tri-sec-butyl borohydride in THF (one step, single reactor)

[0068] 16.4 grams of metallic potassium, 265.0 grams of dry tetrahydrofuran and 64.4 grams of tri-sec-butylborane were added to a Parr pressure reactor equipped with a back pressure regulator (set at 95 psig) and a bubbling system. The mixture was heated to about 65°C to melt the potassium metal, and then stirred to disperse the potassium metal in tetrahydrofuran. Then the temperature was increased to 85°C.

[0069] Hydrogen pressure is applied to the reactor until the reactor pressure reaches 50 psig. The pressure is maintained overnight. The reactor was then cooled to 25°C and depressurized. Then filter the contents of the reactor with a filter. The filtrate contains potassium tri-sec-butyl borohydride. The yield was 95%.

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PUM

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Abstract

Synthetic routes for forming alkali metal substituted borohydride compounds include the step of reacting an alkali metal reagent, a hydrogen donor, and a substituted borane. The reactions proceed without the requirement of specialised handling of alkali metal hydrides associated with prior synthetic processes for the production of alkali metal trisubstituted borohydride compounds. A chemical composition comprises solid potassium tri-sec-butyl borohydride.

Description

Invention field [0001] The invention relates to a method for synthesizing a substituted borohydride reagent, in particular to a method for synthesizing an alkali metal trisubstituted borohydride reagent from an alkali metal, a hydrogen donor and a trisubstituted borane. Background of the invention [0002] Since the early 1970s, the alkali metal tri-substituted borohydride reagents have unique reactivity and synthetic uses in organic chemistry, so there has been great interest in the synthesis of this compound. Alkali metal trisubstituted borohydride reagents are mainly used as regioselective and stereoselective borohydride reducing agents in organic synthesis. So far, all preparation methods of alkali metal trisubstituted borohydride have focused on the reaction of alkali metal hydride or lithium aluminum reagent with trisubstituted borane to prepare the above-mentioned compounds. The most common preparation method of tri-substituted borohydride is through the reaction of alkali...

Claims

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Application Information

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IPC IPC(8): C07B61/00C07F5/02C07F19/00
CPCC07F5/027
Inventor J·A·科尔利亚二世D·H·埃伦伯格J·布吕宁
Owner 巴斯夫公开股份有限公司