A method for synthesizing 4a, 8a-borazyridine and derivatives thereof

A technology of derivatives and heteronaphthalene, which is applied in the field of synthesizing 4a,8a-borazanaphthalene and its derivatives, can solve the problems of inability to effectively prepare large quantities of target products, limit research on the properties of heteronaphthalene compounds, and low overall yields , to achieve great scientific research value and commercial application prospects, simple and efficient post-processing process, and simple steps

Inactive Publication Date: 2016-08-24
TONGJI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Compared with Dewar's work, this method has greatly improved the utilization rate of materials, but due to the cumbersome steps of the method, the overall yield of the reaction is maintained at a low level, and it cannot effectively prepare a large amount of target products. Further research on this type of compound limits the research on the properties of this heteronaphthalene compound

Method used

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  • A method for synthesizing 4a, 8a-borazyridine and derivatives thereof
  • A method for synthesizing 4a, 8a-borazyridine and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] synthesis

[0036] Take a 500mL Schlenk bottle, under a nitrogen atmosphere, at -35°C, add diallylamine (25.2g, 520mmol) dropwise to boron trichloride (16.4g, 140mmol) in dichloromethane as a solvent, a total of 200mL, at room temperature Stir overnight. Atmospheric pressure distills out dichloromethane, pentane extracts the residue, normal pressure steams off pentane, and then vacuum distillation obtains the product diallylamine boron dichloride as (10.4g, 45%) colorless flammable liquid , boiling point 25°C (1Torr). 1 HNMR (400MHz, C 6 D. 6 ): δ5.42-5.32 (m, 2H), 4.88 (d, J = 7, 6Hz, 2H), 4.84 (d, J = 17, 6Hz, 2H), 3.53 (d, J = 4.7Hz, 4H) . 13 CNMR (100Hz, C 6 D. 6 ): δ133.9, 117.1, 51.6. 11 BNMR (128MHz, C 6 D. 6 ): δ31.5.

Embodiment 2

[0038] synthesis

[0039]Take 20g of magnesium chips, 5mL of allyl chloride, a few grains of elemental iodine, and 60mL of tetrahydrofuran as a solvent and place them in a three-necked flask. After triggering, the remaining allyl chloride in tetrahydrofuran solution is about 180mL. The prepared allylmagnesium chloride is the Grignard reagent with a concentration of 0.8-1.2 mol / L. Take 18g of diallylamino boron dichloride and 100ml of tetrahydrofuran as a solvent in the glove box, add 200mL of Grignard reagent with a concentration of 1.05mol / L with an injection needle at low temperature, and stir overnight at room temperature. First distill off most of THF, then add hexane for multiple extractions, discard the white precipitate, transfer the extract to another flask, first distill off the solvent hexane, then distill under reduced pressure to obtain (13.8g, 70%) colorless Liquid, boiling point 50°C (0.133KPa). 1 HNMR (400MHz,C 6 D. 6 ):δ6.02-5.92(m,2H),5.59-5.50(m,2H),5.0...

Embodiment 3

[0041] synthesis

[0042] Take diallylaminodiallyl borane (8.20 g, 43 mmol) from the glove box, add 80 mL of dichloromethane, and put it in a -35°C environment. Take (0.28g, 0.34mmol, 0.8% catalytic amount) first-generation Grubbs catalyst and add 40mL of dichloromethane to dissolve it. The catalyst was introduced into the reaction bottle, and the reaction was continued at low temperature for 1 hour, then slowly raised to room temperature, and stirred overnight. The dichloromethane was distilled off under normal pressure, and distilled under reduced pressure to obtain (5.13 g, 90%), a colorless and easily crystalline liquid with a boiling point of 20°C (1 Torr). 1 HNMR (400MHz,C 6 D. 6 ): δ5.48, (d, J=10Hz, 2H), 3.15(m, 4H), 1.42(d, J=4.6Hz, 4H). 13 CNMR (100Hz, C 6 D. 6 ): δ126.1, 124.5, 50.2, 16.6(bs). 11 BNMR (128MHz, CDCl 3 ):δ41.3.HRMS(ESI-TOF)m / z calcd.For C 8 h 13 BN[M+H]: 134.1137, found: 134.1163.

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Abstract

The present invention relates to a kind of novel synthetic method of 4a, 8a borazine and derivatives thereof, and its synthetic steps comprise: (1) diallylamine reacts with boron trichloride at low temperature, generates diallyl Amino boron dichloride; (2) diallylamino boron dichloride reacts with allyl Grignard reagent at low temperature to generate diallylamino diallyl borane; (3) diallyl Aminodiallylborane uses Grubbs first-generation catalyst to trigger olefin metathesis into ring reaction; (4) the ring-forming product and dichlorodicyanobenzoquinone undergo dehydroaromatization reaction to generate 4a, 8a-borazepine Naphthalene; (5) 4a, 8a-borazine and halogenated succinimide undergo a halogenation reaction under Lewis acid catalysis to generate 4a, 8a-borazine derivatives substituted by halogen at the 4 / 5 position. The invention has simple steps, cheap and easy-to-obtain raw material sources, mild reaction conditions, less side reactions, and simple and efficient post-treatment process.

Description

technical field [0001] The invention relates to the field of synthesis of borazine-condensed polycyclic compounds, in particular to a method for synthesizing 4a, 8a-borazyridine and derivatives thereof. Background technique [0002] In the coexistence with nature, people are constantly exploring new fields, trying to find ways to change the human living environment. Organic compounds are the material basis of life, and the formation of this material basis is due to the strong covalent bonds that can be formed between carbon atoms. Boron and nitrogen are listed on the left and right sides of carbon in the periodic table of elements. Boron atoms have one extranuclear electron less than carbon, and their electronegativity is weaker than carbon. Nitrogen atoms have one more extranuclear electron than carbon, and have more Atoms have strong electronegativity. If the bond of two carbon atoms is replaced by the bond of boron and nitrogen, then the two are isoelectronics to each o...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
Inventor 方向东吕莉莉
Owner TONGJI UNIV
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