CN101031504B - B10h102-铵盐的制造方法以及b18h22的制造方法 - Google Patents
B10h102-铵盐的制造方法以及b18h22的制造方法 Download PDFInfo
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- CN101031504B CN101031504B CN2005800120708A CN200580012070A CN101031504B CN 101031504 B CN101031504 B CN 101031504B CN 2005800120708 A CN2005800120708 A CN 2005800120708A CN 200580012070 A CN200580012070 A CN 200580012070A CN 101031504 B CN101031504 B CN 101031504B
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/11—Preparation from boron or inorganic compounds containing boron and oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
- H01L21/2658—Bombardment with radiation with high-energy radiation producing ion implantation of a molecular ion, e.g. decaborane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供合成B9H9 -、B10H10 2-、B11H14 -及B12H12 2-盐类的新方法,特别是B9H9 -、B10H10 2-、B11H14 -及B12H12 2-的烷基铵盐。更特别地,本发明提供藉由在控制条件热裂解四烷基硼氢化铵制备B9H9 -、B10H10 2-、B11H14 -及B12H12 2-四烷基铵盐的方法。本发明更提供,在原子有效方法,从本发明的四烷基铵盐制备十八硼烷的方法。本发明的较佳方法适合制备富含同位素硼烷,特别是10B18H22和11B18H22。
Description
【发明所属的技术领域】
本发明提供合成硼烷化合物的方法,包括在控制热条件下热裂解(pyrolysis)硼氢化铵化合物。本发明复提供藉由前述方法合成富含同位素硼化合物。在一些态样中,本发明是关于制备富含10B与11B的B18H22 及制备B9H9 -、B10H10 2-、B11H14 -及B12H12 2-的方法。
【先前技术】
大量的氢化硼化合物成为重要的进料原料,以作为在半导体制造中的硼掺杂P型不纯物区。特别地,高分子量氢化硼化合物,例如氢化硼化合物包括至少5个硼原子的团簇(cluster),为较佳用于硼原子植入(implantation)的硼原子进料原料。
现今半导体科技的重要方向为持续发展更小且更快的装置。此过程称为微缩(scaling)。微缩是藉由持续发展的微影技术驱动,其允许在包括集成电路的基材上定义越来越小的特征。普遍接受的微缩理论已同时发展,以导引芯片制造者同时在半导体装置设计的所有方向中合适地调整芯片大小,即在每一技术或微缩的节点。微缩对离子植入技术的最大冲击是接面深度的微缩,其为当装置尺寸缩小时需要增加浅接面。此依集成电路微缩的增加浅接面要求,可以下列要求表达:离子植入能量在每一微缩步骤必需降低。极度浅接面,在现今次0.13微米装置称为“超浅接面”(Ultra-Shallow Junctions)或USJs。
制造硼掺杂P型接面的方法由于在离子植入制程使用硼的困难所阻碍。硼原子,质轻(平均原子量为10.8),在退火(annealing)或其它升温制程中可穿透至硅基材更深处且快速扩散通过基材的晶格。
硼团簇或笼(cage),例如硼烷类已经研究作为传递硼到半导体基材的进料原料且降低穿透。例如,在2003年6月26日申请的国际专利申请案PCT/US03/20197中所述,硼离子可藉由分子式为BnHm(其中100>n>5且m≤n+8)的离子化氢化硼分子植入基材,以及用于该植入方法的离子源。一些较佳用于硼离子植入方法的化合物包括十硼烷 (B10H14)和十八硼烷(B18H22)。
通常B18H22的典型分子离子束含有广范围质量的离子,因为分子离子损失多种不同数目的氢,以及因为两种天然产生同位素的多种质量。因为质量选择在半导体制造的植入装置是可能的,在B18H22使用富含同位素硼可大量降低质量分布,藉此提供增加所需植入物种束的流量。因此,B-11和B-10富含同位素B18H22亦引起极大兴趣。
B18H22可藉由氧化B10H10二阴离子(dianion)的烷基铵盐制备。制备此二阴离子可由十硼烷以高产率完成(M.F.Hawthorne及A.R.Pitochelli,J.Am.Chem.Soc.81,5519,1959)。然而,十硼烷为毒性、昂贵且难以经报导的合成制法制备(见美国专利4,115,521,由Dunks等人提出)。更甚者,Dunks的合成十硼烷方法使用成本高的溶剂及反应剂,花费时间的反应条件,及时常在制法中需人力工作。因此,从硼氢化钠开始到十烷硼以制备B10H10二阴离子盐类的整体产率通常低于30%。
制备富含B-10和B11的B10H10二阴离子盐类及由B10H10二阴离子盐类(如B18H22)制备大的氢化硼,其经由富含十硼烷在某程度上为特别昂贵制法,因为从硼氢化钠制备富含B-10和B11的实质产量会转向副产物而非富含十硼烷与富含B10H10 2-二阴离子。
国际专利申请案WO 03/044837(应用材料公司,Santa Clara,CA)描述离子植入方法,其中包括富含11B化合物的富含同位素硼化合物离子化,且接着植入基材。该’837公开案描述制备富含同位素硼烷是藉由美国专利6,086,837(Cowan等人)描述的方法,该方法为现今制备富含同位素10B或11B硼烷的工业制法。
Cowan(美国专利6,086,837)描述由富含B-10硼酸开始制备富含B-10十硼烷的方法。Cowan制备富含B-10或B-11氢化硼的方法从硼酸开始且需要许多合成和纯化步骤。更重要地,Cowan方法转换硼酸为硼氢碱金属需要许多花费时间步骤且导致有价值的富含B-10氢化硼的相对低产率,其需要经过近一步反应来获得最终产物。
因此,Cowan方法使用共沸蒸馏法从硼酸和甲醇开始制备B-10硼酸甲酯。藉由三个一步方法的冷冻再结晶让硼酸甲酯从剩下甲醇分离以产生80%产率的硼酸三甲酯。硼酸三甲酯接着加入在220℃至250℃的氢化钠无机油悬浮物,且加热12小时。为了安全,需要金属 回流冷凝器。单离所形成氢化硼需特别注意,首先,过量氢化钠藉由将无机油混合物倒入冰水混合物破坏,为相当的放热步骤(exothermicprocess)且释放氢气。接着,藉由倾析或分液漏斗将硼化氢水溶液与无机油分离。氢化硼水溶液必需以甲醇清洗,藉由加热至60℃及氮气流清洗或藉由减压下移除。所得的水溶液包括氢氧化钠及富含B-10的氢化硼。以气泡方式使二氧化碳气体打入溶液使氢氧化钠转换为碳酸钠。所得浆状物接着以正丙基胺萃取,以及蒸发正丙基胺产生最终产物。硼氢化钠在正丙基胺的溶解度有限且挥发性溶剂需要适当的体积。通常可获得产率为45至65%。总共需要十个花费时间步骤来经由Cowan所描述的方法制备富含同位素的硼氢化钠。
一些文献文件描述关于从硼氢化四烷基铵盐制备B10H10 2-阴离子盐的分歧的合成报告。文献描述在多种反应器、溶剂存在或不存在及在多种反应条件下热裂解。参照例如(1)W.E.Hill等人,“BoronChemistry”,Pergamon Press,Oxford 1979,第33页;(2)Mongeot等人,Bull.Soc.Chim.Fr.385,196;及(3)美国专利4,150,057和4,391,993,Sayles提出。已发表制程没有提供用于B10H10 2-阴离子的工业上量产方法,没有教导可预测及前后一致的转换至产物,以及纯化技术不适合于欲使用的用途。
一些报告己描述从硼氢化钠制备天然丰富的硼氢化四烷基铵化合物制法。然而,文献方法并不适合于制备富含同位素硼氢化胺,部分是因为在阳离子交换时会牺牲大量的氢化硼。例如,Gibson和Shore分别描述两当量的硼氢化钠与氢氧化四乙基铵和氢氧化钠于甲醇中的混合物接触,以产生一当量的硼氢化四乙基铵,其可为氢氧化钠污染(D.Gibson等人,J.Organomet.Chem.218,325,1981;S.Shore等人,Inorg.Synth.17,21,1977)。因为硼的化学计量流失,这些方法并不适合用于制备富含B-10或B-11的硼氢化四烷基铵盐。
等人描述由硫酸氢四烷基盐以及10%过量的硼氢化钠合成含有12个或更多个碳原子的硼氢四烷基铵盐化合物方法(等人,Tet.Lett.31,3173,1972)。尽管所需产生溶液有定量转换,申请人想要从溶液分离产物硼氢化四烷基铵却是麻烦的,因为不满意的分离产率且产生难以藉由下列方式结晶和纯化的黏性“油”。
因此需要具有可再现性、原子效能、高产率的方法以从氢化硼前驱物制备高纯度B10H10 2-二阴离子盐。更特别地,需要制备高纯度天然丰富的、富含B-10或富含B-11的B10H10 2-盐,该方法具有降低数目的合成步骤。
我们已发现合成B10H10二阴离子烷基铵盐新方法。更特别地,我们发现原子有效且高产率合成B10H10 2-烷基铵盐的方法,该方法不包括形成十硼烷为中间产物。本发明方法通常包括从硼氢化钠制备硼氢化四烷基铵且热裂解硼氢化烷基铵产生B10H10 2-烷基铵盐。本发明的方法适合用于制备天然丰富的、富含B-10或富含B-11的B10H10 2-二阴离子烷基铵盐。
在一态样中,本发明提供一种制备B10H10二阴离子烷基铵盐的方法,包括下列步骤:
(a)在足以形成硼酸酯的条件下使硼酸和伯、仲或叔醇接触;
(b)以NaAlH4或NaH还原所述硼酸酯以形成NaBH4;
(c)在足以在原位(in situ)或分离而产生R4NBH4的条件下,以NaBH4与分子式为R4NX的烷基铵盐接触,其中R为直链或支链烷基或芳烷基;
(d)在约185℃热裂解固体R4NBH4以形成B10H10 2-的铵盐。
在另一态样中,本发明提供制备B18H22的方法,包括下列步骤:
(a)在足以形成硼酸酯的条件下使硼酸和伯、仲或叔醇接触;
(b)以金属氢化物或金属氢化物盐还原该硼酸酯以获得金属硼氢化物;
(c)以金属硼氢化物与分子式为R4NX盐类接触,其中R为烃基且X为阴离子以获得R4NBH4;
(d)于足以在热裂解时选择性形成B10H10 2-阴离子盐的温度加热固体R4NBH4;
(e)在足以形成B20H18 2-盐的条件下,让B10H10 2-阴离子盐与氧化剂接触;
(f)在足以形成B20H18 2-盐的共轭酸的条件下,将游离形式的B20H18 2-盐在至少一非水性溶剂的浆状物、水性溶液或至少一非水性溶 剂的溶液,与酸接触;
(g)在足以降解部分B20H18 2-盐的共轭酸的条件下,移除包含B20H18 2-盐的共轭酸溶液的挥发成分;
(h)以己烷类或其它不溶解硼酸副产物的适合烃类溶剂萃取残余物;
(i)重复步骤(g)和(h),直到没有进一步的B18H22产生;
(j)残余物与溶剂接触以溶解任何含B20H18 2-盐;
(k)重复步骤(f)至(j)至少一次;
(l)浓缩合并的烃类溶液以获得B18H22。
在另一态样中,本发明提供制备富含11B的B18H22的方法,包括下列步骤:
(a)在足以形成硼酸酯的条件下使硼酸和伯、仲或叔醇接触;
(b)以金属氢化物或金属氢化物盐还原该硼酸酯以获得金属硼氢化物;
(c)以金属硼氢化物与分子式为R4NX盐类接触,其中R为烃基且X为阴离子以获得R4NBH4;
(d)于足以在热裂解时选择性形成B10H10 2-阴离子盐的温度加热固体R4NBH4;
(e)在足以形成B20H18 2-盐的条件下,使B10H10 2-阴离子与氧化剂接触;
(f)在足以形成B20H18 2-盐的共轭酸的条件下,将游离形式的B20H18 2-盐在至少一非水性溶剂的浆状物、水性溶液或至少一非水性溶剂的溶液,与酸接触;
(g)在足以降解部分B20H18 2-盐的共轭酸的条件下,移除包含B20H18 2-盐的共轭酸的溶液的挥发成分;
(h)以己烷类或其它不溶解硼酸副产物的适合烃类溶剂萃取残余物;
(i)重复步骤(g)和(h),直到没有进一步的B18H22产生;
(j)残余物与溶剂接触以溶解任何含B20H18 2-盐;
(k)重复步骤(f)至(j)至少一次;
(l)浓缩合并的烃类溶液以获得B18H22。
在另一态样中,本发明提供制备富含10B的B18H22的方法,包括下列步骤:
(a)在足以形成硼酸酯的条件下使硼酸和伯、仲或叔醇接触;
(b)以金属氢化物或金属氢化物盐还原该硼酸酯以获得金属硼氢化物;
(c)以金属硼氢化物与分子式为R4NX盐类接触,其中R为烃基且X为阴离子以获得R4NBH4;
(d)于足以在热裂解时选择性形成B10H10 2-铵盐的温度加热固体R4NBH4;
(e)在足以形成B20H18 2-盐条件,使B10H10 2-阴离子与氧化剂接触;
(f)在足以形成B20H18 2-盐的共轭酸的条件下,将游离形式的B20H18 2-盐在至少一非水性溶剂的浆状物、水性溶液或至少一非水性溶剂的溶液,与酸接触;
(g)在足以降解部分B20H18 2-盐的共轭酸的条件下,移除包含B20H18 2-盐的共轭酸的溶液的挥发成分;
(h)以己烷类或其它不溶解硼酸副产物的适合烃类溶剂萃取残余物;
(i)重复步骤(g)和(h),直到没有进一步的B18H22产生;
(j)将残余物与溶剂接触以溶解任何含B20H18 2-盐;
(k)重复步骤(f)至(j)至少一次;
(l)浓缩合并的烃类溶液以获得B18H22。
本发明其它态样如下讨论。
【实施方式】
显著地,我们已发现从多种硼氢铵盐制备具有9至12个硼原子的硼氢阴离子铵盐新方法。我们亦已发现制备氢化硼包括B18H22及相关的大的氢化硼化合物新方法,其可用于藉由分子离子植入的硼离子植入基材方法的进料原料。
现在参考第1图,本发明提供一些合成B18H22较佳方法是描述于路径A。相反的,一些制作B18H22合成流程是使用路径B的Duncks流程制作十硼烷铵盐。
富含硼氢化四烷基铵盐可藉由下述步骤制备富含氢化硼获得:
(a)富含B-11或B-10硼酸转换至有机酯,其可制备自多种醇、二醇及酚。参照例如Steinberg and Hunter,J.of Industrial and EngineeringChemistry,Vol 49,174-181。通常,醇、二醇及酚的选择是根据成本和可用的酯化剂和制备容易性而定。一些适合醇及二醇的非限制例子包括正丁醇和2-甲基-2,4-戊二醇。通常二醇产生高产率的二硼酸三(二醇酯)结构,例如二硼酸三(2-甲基-2,4-戊二醇酯)可在实质上计量产率制备。
(b)硼酸酯使用如铝氢化钠的氢化碱金属直接还原成富含B-11或B-10硼氢化碱金属。较佳使用铝氢化钠于四氢呋喃(THF)及/或二乙醚,其可复包括甲苯为共溶剂。添加甲苯为共溶剂在一些实施例可为需要的,部分因为使用甲苯降低使用醚类溶剂相关风险。
(c)步骤(b)制备的富含B-11或B-10硼氢化金属盐为足够纯度用于产生富含的硼氢化四烷基铵。
硼氢化四烷基铵盐(R4N+BH4-)藉由在水或醇溶液中使硼氢化钠与一或多当量如硫酸氢四烷基铵等四烷基铵盐接触而制备。氢氧化钠等接着加入反应混合物以产生碱性反应混合物。当使用水溶液介质,水溶液以二氯甲烷于二相萃取来萃取。或者,当使用醇溶液,蒸发醇且残余物以二氯甲烷萃取。干燥的后浓缩二氯甲烷溶液以获得黏性溶液。添加二乙醚至浓缩二氯甲烷溶液产生高产率的氢化硼盐沉淀。或者,当完全移除二氯甲烷且粗固体以低分离产率自乙酸乙酯再结晶。
本发明提供藉由热裂解至少一种硼氢化四烷基铵盐制造B10H10 2-二阴离子的四烷基铵盐的方法。一些本发明的较佳热裂解方法为可放大用于大量合成B10H10 2-的四烷基铵盐。热裂解反应可使用固体硼氢化四烷基铵或于具有至少100℃沸点的烃类溶剂的硼氢化四烷基铵浆状物施行。一些较佳烃类溶剂包括具有8至18个碳原子的烷类溶剂。
本发明的热裂解反应较佳是在反应装置进行,该反应装置具有接口以允许反应瓶可排空及/或允许导入惰性大气(例如氮、氩等)。此外,较佳热裂解反应装置包括排气孔以传送气体副产物至适当洗涤器。
在热裂解时小心控制反应混合物的温度增进组成物与产物混合物纯度的控制。因此,较佳反应器允许精确温度控制。更佳地,装置包括热墙等以精确读取内部温度,外部火炉或其它热源传递均匀热量 至反应,冷却反应混合物的方法避免在温度控制最大化时过热,以及温度控制单元其可保持包括多个“爆升(ramp)”与“浸泡(soak)”事件的温度程序。在此反应瓶中硼氢化四烷基铵盐的热裂解藉由在热裂解时调控反应瓶的温度曲线提供B10H10 2-、B9H9 -、B11H14 -、B12H12 2-的四烷基铵盐佳及高的产率。
反应装置复允许并用额外反应剂(如三烷基胺硼烷加成物)及/或溶剂以达到特定氢化硼阴离子(如B10H10 2-、B9H9 -、B11H14 -、B12H12 2-)的最佳产率。B10H10 2-或B12H12 2-的大于90%产率已藉由本发明的方法达成。从NaBH4,B10H10 2-的四烷基铵盐整体产率可大于80%,其实质上大于藉由使用十硼烷为中间产物的合成流程所获得产率(即藉由Dunks方法其提供整体产率少于30%)。
在一些制备B10H10 2-、B9H9 -、B11H14 -及/或B12H12 2-盐类的较佳方法中,将R4NBH4溶解、悬浮或混合于具有沸点至少约100℃的溶剂中。一些较佳溶剂包括C8-18烷类及C8-18烷类的混合物,更佳地,较佳溶剂包括正十二烷、50至70体积%的正十烷与50至30体积%的正十二烷混合物。
在一些制备B10H10 2-、B9H9 -、B11H14 -及/或B12H12 2-盐类的其它较佳方法,热裂解R4NBH4及三烷基胺硼烷加成物的混合物。较佳硼氢化铵及三烷基胺硼烷莫耳比为介于约1∶3至3∶1间,特佳为硼氢化铵及三烷基胺硼烷为等莫耳比。在一些较佳方法,其中需要B10H10 2-、B9H9 -、B11H14 -及/或B12H12 2-的富含同位素盐,R4NBH4及三烷基胺硼烷加成物为富含同位素10B或11B。
藉由本发明的热裂解方法提供四烷基铵盐,包括B10H10 2-、B9H9 -、B11H14 -及B12H12 2-阴离子盐,适合用于合成多种具有多于12个硼原子的大的氢化硼化合物的起始材料。例如,使用如三氯化铁(III)的适当氧化剂在水溶液中氧化B10H10 2-的四烷基铵盐产生B20H18 2-盐类。B20H18 2-盐类接着与酸交换树脂接触及游离酸分解藉由下列方法产生B18H22:
(a)提供(B20H18)2-盐类;
(b)在足以形成酸共轭(B20H18)2-盐的共轭酸的条件下,将游离形式的(B20H18)2-在至少一非水性溶剂的浆状物、水性溶液或至少一非水性溶剂的溶液,与酸接触;
(c)在足以降解部分(B20H18)2-盐的共轭酸的条件下,移除包含(B20H18)2-盐的共轭酸溶液的挥发成分;
(d)以己烷类或其它不溶解硼酸副产物的适合烃类溶剂萃取残余物;
(e)重复步骤(c)和(d),直到没有进一步的B18H22产生;
(f)残余物与乙腈接触以溶解任何含B20H18 2-盐;
(g)重复步骤(b)至(f)至少一次;
(h)浓缩合并的烃类溶液以获得B18H22。
在一些本发明提供制备十八硼烷(如B18H22)较佳实施例中,硼酸为富含同位素。亦即,硼酸为富含B-10硼酸或富含B-11硼酸。
一些本发明提供制备十八硼烷(如B18H22)其它较佳方法中,制备R4NBH4的步骤包括使约等当量的硼氢化钠与R4BX接触。在一些较佳方法中,硼氢化钠为富含同位素。亦即硼氢化钠为富含B-10硼氢化钠或富含B-11硼氢化钠。在一些其它较佳方法中,硼氢化钠是制备且在原处使用。在一非限制性预期用于立即方法的制备硼氢化钠方法中,包括在醚类溶剂于约65℃至约135℃温度使硼酸酯与NaAlH4接触。较佳醚类溶剂包括四氢呋喃、二乙醚或四氢呋喃与甲苯的混合物。
一些本发明提供制备十八硼烷(如B18H22)其它较佳方法中,非水性溶剂为腈、醇、醚或其组合。一些特佳非水性溶剂包括乙腈或乙醇。
一些本发明提供制备十八硼烷(如B18H22)其它较佳方法中,萃取用烃类为C5-12烷类、C5-10环烷类、苯、或烷化苯。特佳萃取用烃类为选自于己烷类、环己烷、苯、甲苯或二甲苯。
下述非限制性实施例是描述本发明。所有在此所提文件合并为参考。
实施例1制备10B硼酸三丁酯
具有Dean-Stark接收器与回流冷凝器附着的一颈500毫升圆底烧瓶装有10B硼酸(40克)、正丁醇(200克)及甲苯(约100毫升)。混合物加热至回流且水藉由甲苯-水共沸蒸馏从混合物移除。移除Dean-Stark接收器后,产物混合物分馏。10B硼酸三丁酯在常压下于226至228℃分馏沸点获得(195克,87%分离产率)。
实施例2制备富含11B硼酸三丁酯
以富含11B硼酸开始,11B硼酸三丁酯根据实施例1描述流程制备。
实施例3制备富含10B二硼酸三(2-甲基-2,4-戊二醇酯)
富含10B硼酸、2-甲基-2,4-戊二醇及甲苯混合物以1∶1.5∶1莫耳比混合于具有Dean-Stark接收器与回流冷凝器附着的反应器。反应混合物加热至回流且缩合反应产生的水藉由甲苯-水共沸蒸馏从混合物移除。混合物加热至三莫耳当量的水收集于Dean-Stark捕捉器。反应混合物包括产物实质上计量产率的富含10B二硼酸三(2-甲基-2,4-戊二醇酯)及甲苯。混合物可于下一合成硼氢化金属步骤直接接触铝氢化金属。或者,富含10B二硼酸三(2-甲基-2,4-戊二醇酯)可藉由减压移除甲苯纯化。
实施例4制备富含11B二硼酸三(2-甲基-2,4-戊二醇酯)
富含11B二硼酸三(2-甲基-2,4-戊二醇酯)藉由实施例3的方法制备,其中使用富含11B硼酸取代富含10B硼酸。
实施例5制备富含11B硼氢化钠
装配有高架搅拌子及回流冷凝器的5升三颈烧瓶在氩气下装有无水四氢呋喃(1升)及无水二乙醚(700毫升)。铝氢化钠(105克约纯度86%,1.77莫耳)加入反应烧瓶且等压添加漏斗装有实施例2制备的富含11B硼酸三丁酯(427毫升,1.57莫耳),硼酸酯逐滴加入搅拌混合物且反应混合物逐渐加热至回流且维持回流数小时。冷却之后,粗固体富含11B硼氢化钠在氩气正压下过滤,固体以无水甲苯洗涤以移除丁氧化铝副产物,且甲苯藉由氩气正压下过滤移除。甲苯过滤流程重复需要次数以移除残余丁氧化铝副产物。产率:55.5克、1.46莫耳、93.1%。 11B核磁共振光谱仪只观察到一种硼相对于11BH4(1∶4∶6∶4∶1五重峰且中心在-37ppm)。视需要,富含11B的Na11BH4可藉由二甘醇二甲醚(diglyme)再结晶或以液体氨萃取做进一步纯化。该所得产物保留起始富含11B的 11B(OH)3及富含11B的硼酸三丁酯的同位素纯度。此制法已成功放大至数公斤计量且不流失产物品质。
实施例7制备硼氢化四乙基铵
NaBH4(261.4克,6.9莫耳)置入4升锥形瓶且溶解于2.3升的制备碱性甲醇溶液。600毫升碱性甲醇是用于溶解Et4NBr(1452.5克,6.9莫耳)于2升锥形瓶。在此溶液中加入无水MgSO4(158.4克,1.3莫耳)。快速搅拌Et4NBr溶液,缓慢加入NaBH4溶液以产生立即的NaBr白色沉淀。此溶液在室温搅拌3小时。任何仍留存固体藉由真空过滤移除且收集滤液,而移除甲醇获得白色固体。在真空移除任何留存甲醇后,固体以CH2Cl2(2x1.7升)萃取。合并CH2Cl2萃取液,MgSO4干燥且过滤。收集滤液且在旋转蒸发器移除直到移除大部分CH2Cl2且开始形成白色固体。重新获得的CH2Cl2存于容纳球状瓶以备未来使用。二乙醚(1.4升)加入CH2Cl2溶液以沉淀Et4NBH4为白色为结晶粉末。冷却到0℃后,Et4NBH4藉由过滤分离并在真空下干燥。产率:910.2克、6.3莫耳、90.9%。此制法已成功用于合成富含11B或10B产物。
实施例8制备十硼十氢化四乙基铵盐
Et4NBH4(1000.0克,6.9莫耳)置入烧杯接着传送至使用粉体漏斗的5升三颈圆底烧瓶。烧瓶设于5升加热包中。正十烷:正十二烷的60∶40混合物(2.5升)经由漏斗加入烧瓶。烧瓶的中央颈装配有 玻璃轴承及具有24公厘x130公厘叶片的玻璃搅拌棒。搅拌棒插入高架混合器,一边的颈加上Claisen温度计接合器以符合温度计及具有阀门的活塞作为氩气入口。第三颈加上配置有管接合器的冷凝器。管接合器附着至两异丙醇发泡器。入口附着氩气软管,及整个装置充满氩气。充入氩气之后入口阀门关闭后,反应混合物搅拌加热至回流(185℃)。回流维持16小时。16小时之后关掉加热包混合物在氩气下冷却且真空滤出白色混合物。任何在粗固体中残留的反应溶剂经由己烷洗涤移除。粗固体溶解于乙腈(1升),溶液加热至40℃且由空气发泡30分钟。溶液冷却且滤除沉淀。移除乙腈且残余物从水-异丙醇混合物中再结晶。(Et4N)2B10H10产率:124.9克、0.33莫耳、48.1%。
实施例9制备十八硼烷
(NEt4)2B20H18(10.8克,21.8毫莫耳)溶解至含有40毫升乙腈与5 毫升水的溶液且接着在54.0克酸性交换树脂上搅拌经约24小时。滤除树脂且以乙腈完全洗涤。结合滤液与洗液并浓缩至黄色油。油放置在真空下直到硬固体形成(约五天)接着以100毫升己烷萃取。移除己烷留下浅黄色B18H22(2.0克,0.92毫莫耳)。从已烷萃取留下的残余物暴露于真空下并经第二次萃取以移除更多B18H22。总产率:2.8克、12.9毫莫耳、59.2%。
实施例10制备富含11B十八硼烷
富含11B的(NEt3H)2B20H18(17.4克,35.2毫莫耳)溶解于50毫升乙腈与5毫升H2O。溶液置于含有500克酸性交换树脂管柱且容许置放18小时。溶液自管柱及树脂溶洗并以乙腈完全冲洗。结合溶洗液与洗液并通过第二支管柱经2小时。移除乙腈形成黏稠浆状物含有黄色H2B20H18·xH2O结晶。浆状物放置在真空下超过10天产生黄色固体。加入100毫升水及100毫升己烷至固体且搅拌混合物3小时。己烷层自水层分离,以K2CO3干燥并滤除。移除己烷留下淡黄色粉末的富含 11B的B18H22(3.5克,16.1毫莫耳,45.9%)。11B富含量以起始硼酸(>98.6%的11B同位素富含量)决定。
本发明藉由参考其较佳实施例详细描述。然而,为在相关技术领域具有通常知识者了解,根据相关揭露,许多修改与改良可在本发明的申请专利范围下进行。
本文所引用的所有专利及公开资料合并于此做参考。
在相关领域具有通常知识者可了解或可以清楚不需使用超过例行的实验,有许多在此描述的本发明的特定实施例的均等物。该均等物包括于下述申请专利范围之中。
【图式简单说明】
我们首先简要描述本发明较佳实施例的图式。
第1图为流程图,藉由本发明的方法制备B18H22(路径A)与藉由Dunks方法制备(NR4)2B10H10(路径B)来制备B18H22。
【主要组件符号说明】
A路径
B路径
Claims (10)
1.一种从硼酸制备B18H22的方法,包括下列步骤:
(a)从硼酸和伯、仲或叔醇制备硼酸酯;
(b)以NaAlH4或NaH在醚溶剂中还原所述硼酸酯以形成NaBH4;
(c)在原位或将NaBH4分离后,从NaBH4及R4NX制备R4NBH4,其中R为烃类且X为阴离子以获得R4NBH4;
(d)在185℃热裂解固体R4NBH4以形成B10H10 2-;
(e)氧化B10H10 2-以获得B20H18 2-;
(f)将B20H18 2-溶液与酸性阳离子交换树脂接触;
(g)分解所得酸以获得B18H22;
(h)以己烷类或其它不溶解硼酸副产物的适合烃类溶剂萃取残余物;
(i)重复步骤(g)和(h),直到没有进一步的B18H22产生;
(j)将残余物与非水性溶剂接触以溶解任何含B20H18 2-的盐,其中所述非水性溶剂为腈、醇、醚或其组合;
(k)重复步骤(f)至(j)至少一次;
(l)浓缩合并的烃类溶液以提供B18H22。
2.如权利要求1所述的方法,其中所述硼酸为富含B10的硼酸或富含B11的硼酸。
3.如权利要求1所述的方法,其中制备R4NBH4的步骤包括使等摩尔量的硼氢化钠与R4NX接触。
4.如权利要求3所述的方法,其中硼氢化钠为富含B10的硼氢化钠或富含B11的硼氢化钠。
5.如权利要求3或4中述的方法,其中在步骤(b)中制备的硼氢化钠为原位使用。
6.如权利要求1所述的方法,其中硼酸酯为富含B10的硼酸酯或富含B11的硼酸酯。
7.如权利要求6所述的方法,其中所述醚溶剂为四氢呋喃或四氢呋喃与甲苯的混合物。
8.如权利要求1所述的方法,其中萃取用烃类为C5-C12烷类、C5-C10环烷类、苯或烷基化苯。
9.一种制备B10H10二价阴离子的烷基铵盐的方法,包括下列步骤:
(a)在足以形成硼酸酯的条件下使硼酸与伯、仲或叔醇接触;
(b)以NaAlH4或NaH还原所述硼酸酯以形成NaBH4;
(c)在足以在原位或分离而产生R4NBH4的条件下,以NaBH4与分子式为R4NX的烷基铵盐接触,其中R为直链或支链烷基或芳烷基且X为阴离子;
(d)在185℃热裂解固体R4NBH4以形成B10H10 2-的烷基铵盐。
10.如权利要求9所述的方法,其中硼酸为富含B10的硼酸或富含B11的硼酸。
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DE102008004530A1 (de) | 2008-01-15 | 2009-07-16 | Bergische Universität Wuppertal | Verfahren zur Herstellung von closo-Boranaten |
US9598352B2 (en) * | 2011-11-18 | 2017-03-21 | The Curators Of The University Of Missouri | Process and device for the production of polyhedral boranes |
KR102225854B1 (ko) | 2013-03-15 | 2021-03-12 | 세라딘, 인크. | 다면체 수소화붕소 또는 카르보란 음이온을 포함하는 원자로 및 원자로의 냉각 방법 |
CN103288097B (zh) * | 2013-05-13 | 2014-10-15 | 西安近代化学研究所 | 一种十氢十硼酸铯的制备方法 |
EP3102586B1 (en) | 2014-02-03 | 2020-09-02 | The Curators Of The University Of Missouri | Synthesis of amine boranes and polyhedral boranes |
US10059599B2 (en) | 2014-02-03 | 2018-08-28 | The Curators Of The University Of Missouri | Synthesis of borane compounds |
CN106463190B (zh) * | 2014-04-25 | 2019-02-15 | 赛瑞丹公司 | 包含多面体硼烷阴离子或碳硼烷阴离子的水性溶液的池及其使用方法 |
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- 2005-02-02 CN CN2005800120708A patent/CN101031504B/zh not_active Expired - Fee Related
- 2005-02-02 TW TW094103167A patent/TWI391325B/zh not_active IP Right Cessation
- 2005-02-02 JP JP2008501102A patent/JP5025633B2/ja not_active Expired - Fee Related
- 2005-02-02 WO PCT/US2005/002981 patent/WO2005074586A2/en active Application Filing
- 2005-02-02 KR KR1020067017016A patent/KR101196068B1/ko active IP Right Grant
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Publication number | Publication date |
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EP1758816A2 (en) | 2007-03-07 |
WO2005074586A3 (en) | 2007-05-24 |
US20050169828A1 (en) | 2005-08-04 |
JP2008525310A (ja) | 2008-07-17 |
CN101031504A (zh) | 2007-09-05 |
EP1758816B1 (en) | 2015-05-13 |
WO2005074586A2 (en) | 2005-08-18 |
TWI391325B (zh) | 2013-04-01 |
JP5025633B2 (ja) | 2012-09-12 |
EP1758816A4 (en) | 2010-04-28 |
KR101196068B1 (ko) | 2012-11-01 |
TW200538391A (en) | 2005-12-01 |
US7524477B2 (en) | 2009-04-28 |
KR20070085067A (ko) | 2007-08-27 |
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