本文選題：N-取代硼氮丁烷類似物 + 氨基乙硼烷��； 參考：《河南師范大學》2017年碩士論文

【摘要】：N-取代硼氮丁烷類似物作為胺硼烷儲氫材料的關(guān)鍵中間產(chǎn)物而受到大家的廣泛關(guān)注。環(huán)硼氮烷和胺硼烷化合物是其脫氫產(chǎn)物,可作為低壓合成氮化硼的前驅(qū)體,因此N-取代硼氮丁烷類似物也是合成氮化硼的潛在前驅(qū)體。已經(jīng)報道的少數(shù)N-取代硼氮丁烷類似物的制備需要在低溫條件下進行,反應(yīng)時間長,提純過程復(fù)雜,進而限制了對該類化合物性質(zhì)及應(yīng)用方面的研究,僅有初步對硼氮丁烷類似物熱分解和金屬催化重排機理的研究。故系統(tǒng)研究N-取代硼氮丁烷類似物的合成和性質(zhì),對于豐富硼氮丁烷類似物和挖掘其潛在的應(yīng)用具有重要的意義。本論文利用19種胺與氨基乙硼烷發(fā)生親核反應(yīng),合成了一系列N-取代硼氮丁烷類似物,采用核磁、紅外、單晶衍射、XRD等測試手段對產(chǎn)物進行表征,并系統(tǒng)研究N-取代硼氮丁烷類似物的穩(wěn)定性和熱分解性質(zhì)。研究結(jié)果表明:1)氨基乙硼烷與胺反應(yīng)可以在室溫下進行,且反應(yīng)迅速。氨基乙硼烷與胺的反應(yīng),可能取決于氮原子上取代基的大小和個數(shù)。2)N-取代硼氮丁烷類似物BH_2中B的化學位移相對NH_3BH_2NH_2BH_3向低場移動,而BH_3中B的化學位移無明顯變化。通過DFT理論計算發(fā)現(xiàn)端基和中間硼原子上自然電荷的變化與實際化學位移變化趨勢一致。N-取代硼氮丁烷類似物B1H中H的化學位移相對NH_3BH_2NH_2BH_3向高場移動,N1H中H的化學位移向低場移動,可能是由于端基氮原子上的氫被取代基取代引起的。3)N-取代硼氮丁烷類似物存在全反式和半反式兩種構(gòu)型及分子內(nèi)雙氫鍵和分子間雙氫鍵。多數(shù)該類化合物兩端的硼氮鍵鍵長相差不多,但均比中間硼氮鍵長要大。4)端基氮是一級、二級、三級胺的N-取代硼氮丁烷類似物穩(wěn)定性依次減小;由于雙氫鍵的作用,N-取代硼氮丁烷類似物的熔點與相應(yīng)烷烴等電子體化合物相比較高;通過對N-取代硼氮丁烷類似物在不同溶劑中熱分解產(chǎn)物分析,推測N-取代硼氮丁烷類似物在THF和CH_2Cl2中分解機理不同,但均形成氨基乙硼烷中間體,在THF中氨基乙硼烷進一步轉(zhuǎn)化形成H_3N·BH_3,R3N·BH_3,[NHBH]3和[NH_2BH_2]x,在CH_2Cl2中氨基乙硼烷進一步轉(zhuǎn)化形成R3N·BH_3,[NHBH]3和[NH_2BH_2]_x。
[Abstract]:N- substituted boronazobutane analogues as the key intermediate products of amine borane hydrogen storage materials have attracted wide attention. Cycloboronazane and amine borane compounds are the dehydrogenation products of boron nitride and can be used as precursors for the synthesis of boron nitride at low pressure, so N- substituted boron nitrogen butane analogues are also potential precursors for the synthesis of boron nitride. The preparation of a few N- substituted boron butane analogues has been reported to be carried out at low temperature, the reaction time is long and the purification process is complex, which limits the study on the properties and applications of these compounds. Only the mechanism of thermal decomposition and metal catalytic rearrangement of boron nitrogen butane analogue was studied. Therefore, it is of great significance to study the synthesis and properties of N-substituted borobutane analogues in order to enrich boron nitrogen butane analogues and exploit their potential applications. In this paper, a series of N-substituted borobutane analogues were synthesized by the nucleophilic reaction of 19 amines with aminoethylborane. The products were characterized by NMR, IR and XRD. The stability and thermal decomposition of N-substituted boron butane analogue were studied. The results show that the reaction of amino ethylborane with amine can be carried out at room temperature, and the reaction is rapid. The reaction of aminoethylborane with amine may depend on the size and number of substituents on nitrogen atoms. The chemical shift of B in BH_2, a boron N-butane analogue, moves to a lower field than that of NH_3BH_2NH_2BH_3, but the chemical shift of B in BH_3 has no obvious change. It is found by DFT theory that the change of natural charge on the terminal group and intermediate boron atom is consistent with the change trend of actual chemical shift. The chemical shift of H in B1H, a boronazobutane analogue, moves to a higher field with respect to NH_3BH_2NH_2BH_3. The displacement moves to the lower field, It may be due to the substitution of hydrogen on the terminal nitrogen atom that the analogue of boron N-butane has two configurations: all-trans and semi-trans, intramolecular double hydrogen bond and intermolecular double hydrogen bond. Most of these compounds have the same appearance of boron and nitrogen bond at both ends, but the length of boron and nitrogen bond is larger than that of intermediate boron nitrogen bond, and the stability of N-substituted N-butane analogue of second-order amine decreases in turn. The melting point of N-substituted boronazobutane analogues is higher than that of corresponding electron compounds such as alkanes because of the effect of dihydrogen bonds. The thermal decomposition products of N-substituted boronazobutane analogues in different solvents are analyzed. It is inferred that N-substituted boronazobutane analogues have different decomposition mechanisms in THF and CH_2Cl2, but they all form aminoethylborane intermediates. In THF, aminoethylborane is further transformed into H3N BH3N BH3, [NHBH] 3 and [NH_2BH_2] x in THF. In CH_2Cl2, aminoethylborane is further converted to R3N BH3, [NHBH] 3 and [NH_2BH_2] x.
【學位授予單位】：河南師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB34

【參考文獻】

相關(guān)期刊論文 前2條

1 Weidong Chen;Zhenguo Huang;Guotao Wu;Ping Chen;;New synthetic procedure for Na NH_2(BH_3)_2 and evaluation of its hydrogen storage properties[J];Science China(Chemistry);2015年01期

2 時蕾;劉迎迎;毛潤澤;張貴生;;氨基硼烷化合物的合成及應(yīng)用研究進展[J];化學研究與應(yīng)用;2012年07期

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本文編號：1818761