CN104059094B - The dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane - Google Patents
The dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane Download PDFInfo
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- CN104059094B CN104059094B CN201410215370.7A CN201410215370A CN104059094B CN 104059094 B CN104059094 B CN 104059094B CN 201410215370 A CN201410215370 A CN 201410215370A CN 104059094 B CN104059094 B CN 104059094B
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Abstract
The present invention relates to a kind of 9 borabi cyclo [3.3.1] dimeric synthetic method of nonane; under inert gas shielding; the present invention is with boron hydride; oxidant; 1,5 cyclo-octadiene is raw material, with ethers; aromatic hydrocarbons or aliphatic hydrocarbon etc. are solvent, synthesize 9 borabi cyclo [3.3.1] nonane dimer by hydroboration.Synthetic method of the present invention is easy and simple to handle, mild condition, with low cost, product yield and purity high, is suitable for certain scale industrialized production.
Description
Technical field
The present invention relates to a kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, belong to organic chemical synthesis field.
Background technology
Borine can carry out various new chemical reaction, it has also become the reagent of organic synthesis, is widely used in the formation of C-H bond, carbon-oxygen bond, carbonnitrogen bond, carbon-carbon bond.9-borabi cyclo [3.3.1] nonane dimer is typically presented in crystal or solution.
Soderquist(Simple, remarkably efficient route to
high purity, crystalline 9-borabicyclo[3.3.1]nonane
(9-BBN) dimer. J.Org.chem.1981,46,4599-4600.) under nitrogen atmosphere, in the ethylene glycol dimethyl ether solution of dimethyl sulphide borine, it is added dropwise over 1,5-cyclo-octadiene, 50-60 DEG C of reaction 1h, then at 83-85 DEG C, vacuum distilling removes dimethyl sulphide, just can obtain 9-borabi cyclo [3.3.1] nonane dimer at 0 DEG C；(the Cyclic Hydrocarbon of such as Knights
1,5-Cyclooctadine. A Simple Synthesis of 9-Borabicyclo[3.3.1]nonane, an Unusually Stable Dialkylborane.
J.Am.Chem.Soc. 1968,90,5280-5281.) under conditions of ice bath, by 1, the tetrahydrofuran solution of 5-cyclo-octadiene is added drop-wise in borine tetrahydrofuran complex；Then reheating backflow 1h, ice bath cools down, and filters and prepare 9-borabi cyclo [3.3.1] nonane dimer under blanket of nitrogen.Above synthetic method, raw materials used price is higher, need cryopreservation；And dimethyl sulphide has foul odour, environmental pollution is bigger；The loaded down with trivial details harshness of reaction condition, operation inconvenience, it is unfavorable for industrialized production.
Summary of the invention
It is an object of the invention to provide a kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, raw material is cheap, and reaction condition is gentle, easy, safety.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) in molar ratio for 1:(0.3-3) weigh boron hydride and liquid oxidizer, or weigh boron hydride and solid oxidizer；Dissolve boron hydride with solvent, or dissolve boron hydride and solid oxidizer with solvent respectively；Oxidizing agent solution being added dropwise in borohydride solution, under inert gas shielding, reacts under the conditions of room-temperature water bath, oxidizing agent solution drips off and terminates reaction simultaneously, collects the diborane gas that reaction generates；
(2) diborane that step (1) generates is slowly introducing 1; in the ethers mixed solution of 5-cyclo-octadiene and lewis base; under inert gas shielding; ventilating complete, 40-50 DEG C is continued reacting by heating 1-5 h, terminates reaction; being cooled to room temperature has white needle-like crystals to separate out; filter, vacuum drying, obtain 9-borabi cyclo [3.3.1] nonane dimer product.
Boron hydride described in step (1) is sodium borohydride, potassium borohydride or lithium borohydride；Liquid oxidizer is boron trifluoride etherate or phosphoric acid；Solid oxidizer is calomel or iodine；Boron hydride is 1:(1.0-3.0 with the mol ratio of boron trifluoride etherate), boron hydride is 1:(1.0-3.0 with the mol ratio of phosphoric acid), the mol ratio of boron hydride and calomel is 1:(0.3-0.6), boron hydride and iodine and mol ratio be 1:(0.3-2.0).
Boron hydride solvent or solid oxidizer solvent described in step (1) are oxolane, glycol dimethyl ether, diglycol dimethyl ether, diglycol ethylene dimethyl ether, normal hexane, benzene or toluene；The boron hydride solvent 0.09-0.5 mL of 1 mmol boron hydride described in step (1) dissolves, and 1 mmol solid-oxide 0.2-1.0 mL solid-oxide solvent dissolves.
Step (1) described oxidant drips off time 2-6 h used.
1,5-cyclo-octadiene is (0.4-1.3) with the mol ratio of boron hydride: 1.
Lewis base described in step (2) is DMA, N, N-diethylaniline, oxolane, morpholine or pyridine；1 mmol 1,5-cyclo-octadiene need to add 0.03-0.25 mL lewis base.
Ethers described in step (2) is oxolane, glycol dimethyl ether, diglycol dimethyl ether or diglycol ethylene dimethyl ether；1 mmol 1,5-cyclo-octadiene need to add 0.3-1.5 mL ethers solution.
Step (2) vacuum drying condition is 50-60 DEG C of vacuum drying 10-15 h.
Step (1) and (2) described noble gas are nitrogen or argon, and step (1) and (2) described solvent, by decompression Distillation recovery, recycle.
The positive beneficial effect of the present invention:
1.
Low in raw material price of the present invention, production cost is low；
2.
The present invention use diborane to generate after the technology of transient absorption and technique, improve the safety of production technology, be suitable for the industrialized production of certain scale；
3.
Solvent for use of the present invention is by recovery, cycling and reutilization, it is achieved that the synthesis technique of environmental protection and technology.
Accompanying drawing explanation
Fig. 1 is that 9-borabi cyclo [3.3.1] nonane that embodiment 1 obtains is dimeric11B NMR schemes；
Fig. 2 is that 9-borabi cyclo [3.3.1] nonane that embodiment 1 obtains is dimeric13C NMR schemes；
Fig. 3 is that 9-borabi cyclo [3.3.1] nonane that embodiment 1 obtains is dimeric1H NMR schemes.
Detailed description of the invention
Below in conjunction with some specific embodiments, the present invention is further described.
Embodiment 1
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) it is that 1:1.5 takes sodium borohydride 2.84 g (75mmol) and boron trifluoride etherate 14 mL(113 mmol according to sodium borohydride and boron trifluoride etherate mol ratio); dissolve with 7 mL diglycol ethylene dimethyl ether; under water-bath, boron trifluoride etherate is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 5 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 6 mL
(50 mmol) 1,5-cyclo-octadiene, 5 mL(40 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in; under nitrogen protection; ventilating complete, 50 DEG C are continued reacting by heating 3 h, terminate reaction; being cooled to room temperature has white needle-like crystals to separate out; filter, 50 DEG C of vacuum drying 12 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 5.0 g; productivity is 82%, and testing result sees Fig. 1-3.
Embodiment 2
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) it is that 1:2.0 takes sodium borohydride 2.84 g (75 mmol) and boron trifluoride etherate 19 mL(150 mmol according to sodium borohydride and boron trifluoride etherate mol ratio); dissolve with 9 mL diglycol ethylene dimethyl ether; under water-bath, boron trifluoride etherate is added dropwise in sodium borohydride reaction bulb; under argon shield; room temperature 4 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 6 mL
(50 mmol) 1; 5-cyclo-octadiene, 5 mL(40 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in, under argon shield; ventilate complete; 50 DEG C are continued reacting by heating 5 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 60 DEG C of vacuum drying 10 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 4.9 g, and productivity is 80.3%.
Embodiment 3
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) it is that 1:1.5 takes sodium borohydride 2.84 g (75mmol) and boron trifluoride etherate 14 mL(113mmol according to sodium borohydride and boron trifluoride etherate mol ratio); dissolve with 9 mL glycol dimethyl ethers; under water-bath, boron trifluoride etherate is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 6 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 6 mL
(50 mmol) 1; 5-cyclo-octadiene, 5 mL(40 mmol) DMA and 30 mL glycol dimethyl ethers mixed solution in, under nitrogen protection; ventilate complete; 45 DEG C are continued reacting by heating 4 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 55 DEG C of vacuum drying 11 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 5.1 g, and productivity is 83.6%.
Embodiment 4
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) it is that 1:3 takes sodium borohydride 2.84 g (75 mmol) and boron trifluoride etherate 28 mL(225 mmol according to sodium borohydride and boron trifluoride etherate mol ratio); dissolve with 7 mL diglycol ethylene dimethyl ether; under water-bath, boron trifluoride etherate is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 5 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 9 mL (75
Mmol) 1; 5-cyclo-octadiene, 3.5 mL(40 mmol) morpholine and 35 mL diglycol ethylene dimethyl ether mixed solution in; under nitrogen protection, ventilating complete, 50 DEG C are continued reacting by heating 3 h; terminate reaction; being cooled to room temperature has white needle-like crystals to separate out, and filters, 50 DEG C of vacuum drying 12 h; obtaining 9-borabi cyclo [3.3.1] nonane dimer 7.4g, productivity is 85.2%.
Embodiment 5
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) it is that 1:1 takes sodium borohydride 2.84 g (75 mmol) and boron trifluoride etherate 9 mL(75 mmol according to sodium borohydride and boron trifluoride etherate mol ratio); dissolve with 7 mL diglycol ethylene dimethyl ether; under water-bath, boron trifluoride etherate is added dropwise in sodium borohydride reaction bulb; under argon shield; room temperature 5 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 12 mL (97.5
Mmol) 1; 5-cyclo-octadiene, 3.2 mL(40 mmol) pyridine and 30 mL diglycol ethylene dimethyl ether mixed solution in; under argon shield, ventilating complete, 50 DEG C are continued reacting by heating 3 h; terminate reaction; being cooled to room temperature has white needle-like crystals to separate out, and filters, 50 DEG C of vacuum drying 12 h; obtaining 9-borabi cyclo [3.3.1] nonane dimer 7.2 g, productivity is 78.7%.
Embodiment 6
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) sodium borohydride 1.55 g (41 mmol) and iodine 15.6 g (61.5 mmol) are taken according to the ratio that mol ratio is 1:1.5; dissolve with 15 mL diglycol ethylene dimethyl ether respectively; lower iodine liquid of water-bath is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 3 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 2.5 mL (20.1
Mmol) 1; 5-cyclo-octadiene, 4.2 mL(33 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in, under nitrogen protection; ventilate complete; 45 DEG C are continued reacting by heating 2 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 55 DEG C of vacuum drying 12 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 1.5 g, and productivity is 61.2%.
Embodiment 7
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) sodium borohydride 1.55 g (41 mmol) and iodine 10.4 g (41 mmol) are weighed according to the ratio that mol ratio is 1:1; dissolve with 20 mL diglycol ethylene dimethyl ether respectively; lower iodine liquid of water-bath is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 4 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 5 mL (41
Mmol) 1; 5-cyclo-octadiene, 4.2 mL(33 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in, under nitrogen protection; ventilate complete; 40 DEG C are continued to add reaction 4 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 50 DEG C of vacuum drying 15 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 3.2 g, and productivity is 64%.
Embodiment 8
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) sodium borohydride 1.55 g (41 mmol) and iodine 20.8 g (82 mmol) are weighed according to the ratio that mol ratio is 1:2; sodium borohydride is dissolved with 15 mL glycol dimethyl ethers; iodine is dissolved with 40 mL diglycol ethylene dimethyl ether; lower iodine liquid of water-bath is added dropwise in sodium borohydride reaction bulb; under argon shield; room temperature 5 h drips off, and terminates reaction simultaneously, collects the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 5 mL (41
Mmol) 1; 5-cyclo-octadiene, 4.2 mL(33 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in, under argon shield; ventilate complete; 50 DEG C are continued reacting by heating 1 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 60 DEG C of vacuum drying 10 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 2.9 g, and productivity is 58.5%.
Embodiment 9
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) potassium borohydride 3.1 g (82 mmol) and iodine 6.2 g (24.6 mmol) are weighed according to the ratio that mol ratio is 1:0.3; potassium borohydride is dissolved with 15 mL diglycol ethylene dimethyl ether; iodine is dissolved with 20 mL diglycol dimethyl ether; lower iodine liquid of water-bath is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 2 h drips off, and terminates reaction simultaneously, collects the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 5 mL (41
Mmol) 1; 5-cyclo-octadiene, 4.2 mL(33 mmol) DMA and 30 mL diglycol ethylene dimethyl ether mixed solution in, under nitrogen protection; ventilate complete; 45 DEG C are continued reacting by heating 2 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 55 DEG C of vacuum drying 12 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 3.2 g, and productivity is 64%.
Embodiment 10
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane, comprises the following steps:
(1) sodium borohydride 1.55 g (41 mmol) and iodine 10.4 g (41 mmol) are weighed according to the ratio that mol ratio is 1:1; dissolve with 15 mL oxolanes respectively; lower iodine liquid of water-bath is added dropwise in sodium borohydride reaction bulb; under nitrogen protection; room temperature 3 h drips off; terminate reaction simultaneously, collect the diborane gas that reaction generates；
(2) diborane that step (1) generates is passed through 5 mL (41
Mmol) 1; 5-cyclo-octadiene, 4.2 mL(33 mmol) DMA and 30 mL oxolanes mixed solution in, under nitrogen protection; ventilate complete; 45 DEG C are continued reacting by heating 2 h, terminate reaction, and being cooled to room temperature has white needle-like crystals to separate out; filter; 55 DEG C of vacuum drying 11 h, obtain 9-borabi cyclo [3.3.1] nonane dimer 2.8 g, and productivity is 56%.
Claims (7)
1. 9-borabi cyclo [3.3.1] the dimeric synthetic method of nonane, it is characterised in that comprise the following steps:
(1) in molar ratio for 1:(0.3-3) weigh boron hydride and liquid oxidizer, or weigh boron hydride and solid oxidizer；Dissolve boron hydride with solvent, or dissolve boron hydride and solid oxidizer with solvent respectively；Oxidizing agent solution being added dropwise in borohydride solution, under inert gas shielding, reacts under the conditions of room-temperature water bath, oxidizing agent solution drips off and terminates reaction simultaneously, collects the diborane gas that reaction generates；
(2) diborane that step (1) generates is slowly introducing 1; in the ethers mixed solution of 5-cyclo-octadiene and lewis base; under inert gas shielding; ventilating complete, 40-50 DEG C is continued reacting by heating 1-5 h, terminates reaction; being cooled to room temperature has white needle-like crystals to separate out; filter, vacuum drying, obtain 9-borabi cyclo [3.3.1] nonane dimer product；
Wherein, the boron hydride described in step (1) is sodium borohydride or potassium borohydride；Liquid oxidizer is boron trifluoride etherate；Solid oxidizer is iodine；The mol ratio of boron hydride and boron trifluoride etherate is 1:(1.0-3.0), boron hydride and iodine and mol ratio be 1:(0.3-2.0)；
Lewis base described in step (2) is DMA, N, N-diethylaniline, oxolane, morpholine or pyridine；1 mmol 1,5-cyclo-octadiene need to add 0.03-0.25 mL lewis base.
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterized in that, boron hydride solvent or solid oxidizer solvent described in step (1) are oxolane, glycol dimethyl ether, diglycol dimethyl ether, diglycol ethylene dimethyl ether, normal hexane, benzene or toluene；The boron hydride solvent 0.09-0.5 mL of 1 mmol boron hydride described in step (1) dissolves, and 1 mmol solid-oxide 0.2-1.0 mL solid-oxide solvent dissolves.
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterised in that step (1) described oxidant drips off time 2-6 h used.
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterised in that 1,5-cyclo-octadiene is (0.4-1.3) with the mol ratio of boron hydride: 1.
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterized in that, the ethers described in step (2) is oxolane, glycol dimethyl ether, diglycol dimethyl ether or diglycol ethylene dimethyl ether；1 mmol 1,5-cyclo-octadiene need to add 0.3-1.5 mL ethers solution.
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterised in that step (2) vacuum drying condition is 50-60 DEG C of vacuum drying 10-15
h。
A kind of dimeric synthetic method of 9-borabi cyclo [3.3.1] nonane the most according to claim 1, it is characterized in that, step (1) and (2) described noble gas are nitrogen or argon, and step (1) and (2) described solvent, by decompression Distillation recovery, recycle.
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