CN108235705B - 氢化硅杂吡咯、氢化硅杂氮杂吡咯、硫代硅杂环戊烷，其制备方法和获得的反应产物 - Google Patents
氢化硅杂吡咯、氢化硅杂氮杂吡咯、硫代硅杂环戊烷，其制备方法和获得的反应产物 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007795 chemical reaction product Substances 0.000 title description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- -1 N-tert-butoxycarbonyl-2-sila-5-aza-pyrrole Chemical compound 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- SMDVDXOWTRMZKF-UHFFFAOYSA-N C1C[SiH2]SC1 Chemical group C1C[SiH2]SC1 SMDVDXOWTRMZKF-UHFFFAOYSA-N 0.000 claims description 3
- OQSYLKFTEGTGRY-UHFFFAOYSA-N 1-butylazasilole Chemical class C(CCC)N1[SiH]=CC=C1 OQSYLKFTEGTGRY-UHFFFAOYSA-N 0.000 claims description 2
- GXNIVBNTIVOURQ-UHFFFAOYSA-N 1H-azasilole Chemical compound N1[SiH]=CC=C1 GXNIVBNTIVOURQ-UHFFFAOYSA-N 0.000 claims 1
- KHCHZPGCGMXNAB-UHFFFAOYSA-N 3-(azasilol-1-yl)-N,N-dimethylpropan-1-amine Chemical group CN(CCCN1[SiH]=CC=C1)C KHCHZPGCGMXNAB-UHFFFAOYSA-N 0.000 claims 1
- NQOWMUPBSKYHOX-UHFFFAOYSA-N C[Si](N1[Si](=CC=C1)C)(C)C Chemical class C[Si](N1[Si](=CC=C1)C)(C)C NQOWMUPBSKYHOX-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 125000000962 organic group Chemical group 0.000 abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012280 lithium aluminium hydride Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- FIRQYUPQXNPTKO-UHFFFAOYSA-N ctk0i2755 Chemical compound N[SiH2]N FIRQYUPQXNPTKO-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SBWCARQXLPGQNH-UHFFFAOYSA-N 1-methylsilolane Chemical compound C[SiH]1CCCC1 SBWCARQXLPGQNH-UHFFFAOYSA-N 0.000 description 1
- LVTKZSMLKHTKTB-UHFFFAOYSA-N 2,2-dimethoxythiasilolane Chemical compound CO[Si]1(OC)CCCS1 LVTKZSMLKHTKTB-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001018515 Monanthocitrus Species 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- VYIRVGYSUZPNLF-UHFFFAOYSA-N n-(tert-butylamino)silyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N[SiH2]NC(C)(C)C VYIRVGYSUZPNLF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
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- C01B21/00—Nitrogen; Compounds thereof
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- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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Abstract
氢化硅杂吡咯和氢化硅杂氮杂吡咯是其中的硅键合到环系统上的碳和氮原子以及硅原子上有一个或二个氢原子的一类新的杂环化合物。所述化合物如式(I)所示；其中，R是取代或未取代的有机基团以及R’是烷基基团。这些化合物通过开环反应和各种有机和无机的羟基基团反应，以及可以用于生产氮化硅或碳氮化硅膜。
Description
相关申请的交叉引用
本申请要求2015年6月16日提交的美国临时申请号62/180,351的优先权，其全部内容通过引用并入本文。
发明背景
当前,对用于包括半导体和微机电系统(MEMS)的纳米特征设备的分子层沉积有极大兴趣。快速且优选定量沉积单分子层并且只有少量副产物是理想的。对于各种电介质、钝化和停蚀的应用，碳氮化硅膜特别令人感兴趣。
用于生产氮化硅或碳氮化硅膜的已知体系的实施例包括，在U.S.专利号4,200,666中描述的使用三甲硅烷基胺((SiH3)3N)和惰性气体以及任选的氨；如A.Hochberg等所描述，在800℃下，在LPCVD系统中的二乙基硅烷和氨的体系((Mat.Res.Soc.Symp,24,509(1991))；以及由B.Arkles描述的化学气相沉积(CVD)方法中的环状硅氮烷和氨的体系(J.Electrochemical Soc.，卷133,No.1，第233-234页(1986))。
最近，在美国专利号6,586,056中以及由M.Tanaka等(J.ElectrochemicalSociety,147,2284(2000))分别描述含卤化物的前体，例如四碘硅烷和六氯乙硅烷。不幸的是，有着与前体腐蚀性相关的操作困难、以及膜污染和副产物。
另一个方法是使用双(叔丁基氨基)硅烷，其在低至550℃的温度下生产合理质量的SiN膜(J.Gumpher等，J.Electrochem.Soc.，151，G353(2004))或者如美国专利申请公开号2011/0256734中描述的等离子体辅助脉冲沉积法。在这2个例子中，有着膜的碳污染以及与基底稳定性不兼容的热和等离子状态的高能量需求的困难。在EP 2644609 A2中找到其他可选方法的综述，其提出了氟化前体。尽管这样的氟化前体理论上允许较低的沉积温度，但所引入的氟常常影响硅基结构的电性能。
已知的环状氮杂硅烷在硅原子上含有烷基(如，甲基)或烷氧基(如，乙氧基)取代基(见B.Arkles等,环状氮杂硅烷：用于纳米技术的挥发性偶联剂(“Cyclic Azasilanes:Volatile Coupling Agents for Nanotechnology”)在Silanes and Other CouplingAgents，卷3，K.Mittal(编)VSP(Brill),第179-191页(2004))。在感兴趣的主要应用中，这些化合物因或者含有过量的碳或者由于环上硅原子的取代向膜中引入氧而不被接受。因此，对在低温下沉积氮化硅的新型氮化硅和碳氮化硅前体的需求仍不能满足。
发明内容
本发明一实施例中的氢化硅杂吡咯(hydridosilapyrroles)或氢化硅杂氮杂吡咯(hydridosilaazapyrrole)如式(I)所示：
其中，R是碳或硅原子键合到吡咯环氮的取代或未取代的有机基团以及R’是烷基基团。
制备如式(I)的氢化硅杂吡咯或氢化硅杂氮杂吡咯的方法：
其中，R是碳或硅原子键合到吡咯环氮的取代或未取代的有机基团以及R’是烷基基团，所述方法包括还原硅上具有烷氧基(alkoxide)的环状氮杂硅烷。
一种如式(II)的硫代硅杂环戊烷(thiasilacyclopentane)：
其中R"和R"'独立地为氢或烷基。
发明详述
本发明涉及称为氢化硅杂吡咯(或环状氮杂硅烷基氢化物(cyclicazasilylhydrides))和氢化氮杂吡咯的一类新环状氮杂硅烷。不同于在硅原子上含有烷基或烷氧基取代基的已知环状氮杂硅烷，本发明的物质是一类可以从硅原子上的取代基中还原或消除碳和氧成分的氢化硅烷(hydridosilanes)。
本发明的氢化硅杂吡咯和氢化氮杂吡咯有如式(I)所示的一般结构：
这些化合物的主要特征包括五原子环结构，其中环上硅原子与碳原子和氮原子键合以及至少一个氢原子键合到该硅原子上。如式(I)所示，所述氮可以键合到环上的碳或第二个氮上，形成环状二氮杂硅烷(也称为氢化硅杂氮杂吡咯或二氮杂硅杂环戊烷(diazasilacyclopentane))。
在式(I)中，R可以是任何取代的或未取代的有机基团，其中碳或硅键合到环氮上。示例性的基团包括，但不限于，烷基、芳基、酯、手性有机基团和三甲基硅烷基。优选为具有至多六个碳原子的小的烃基(包括苯基)和氮取代的烃，例如二甲基氨基乙基。R’可以是任何烷基，优选地具有至多约二十个碳原子，更优选地少于约六个碳原子，最优选地为甲基、乙基、丙基、或丁基。
本发明化合物的简单具体实施例包括N-甲基-2-硅杂(sila)吡咯和N-丁基-2-硅杂(sila)吡咯：
其他实施例包括那些在氮上具有更复杂官能取代基，包括手性苯乙胺、三甲基硅烷基基团和叔胺基团。
在一个实施例中，所述环状结构在3位上还含有另外的氮原子，形成环状二氮杂硅烷。二个示例性的环状二氮杂硅烷包括：
本发明还涉及一种制备上述氢化硅杂吡咯的方法。所述方法涉及还原在硅原子上具有烷氧基取代的相应的环状氮杂硅烷，如下述示例性方案所示：
因此，对本发明方法可以生产的氢化硅杂吡咯的唯一限制是合成含烷氧基的前体的能力。
本发明的物质通过开环反应与无机和有机羟基基团(包括硅质、铝、和钛基材上的羟基基团)，如下所示，以及和有机羟基基团(包括醇)定量反应。
这些物质也可以在均相溶液中与分离的硅醇(如，三乙基硅烷醇)反应，也能够与包括胺和硫醇在内的其它质子类物质反应。
取决于期望的最终产物，甲硅烷基氢化物官能度(functionality)可以保持完整或可以脱氢以形成碳氮化硅，可以用作区域特异性(regiospecific)还原剂，或可以经过氢化硅烷化。因此，本发明的物质对许多应用具有吸引力，包括形成氮化硅和碳氮化硅膜。
本发明还涉及如式(II)所示的一类新的硫代硅杂环戊烷化合物：
在式(II)中，R"和R"'独立地为氢或含有一到约二十个碳原子的烷基基团，最优选地为氢或甲基。该类的优选化合物是如下所示的1-硫杂(thia)-2-硅杂(sila)环戊烷；其他优选的或示例性的该类化合物也如下所示。在这些结构中，R"和R"'优选地为氢或甲基：
硫代硅杂环戊烷经历与羟基的反应表面产生含有硫醇基团的膜。在该反应中形成的所述硫醇基团可以与烯烃或其它巯基化合物反应以进一步改性表面。
本发明的硫代硅杂环戊烷化合通过类似于上述生产氢化硅杂吡咯的方法描述：通过还原在硅上具有烷氧基的硫代硅杂环戊烷化合物。例如，如下所示，由2,2-烷氧基-1-硫杂-2-硅杂环戊烷作为起始原料制备1-硫杂-2-硅杂环戊烷：
本发明将结合下述非限制性实施例描述。
实施例1：N-丁基-2-硅杂吡咯(正丁基氮杂硅杂环戊烷)的合成
在氩气氛下，向配备冷却浴、机械搅拌器、釜温度计、加料漏斗和干冰蒸馏头的2升4颈烧瓶中加入400ml 2-甲基四氢呋喃，随后分批加入25.3g(0.67mol)的氢化铝锂。该混合物冷却到-10℃，并保持-5至0℃，在2小时通过加料漏斗加入203.4g(1.0mol)的N-正丁基-氮杂-二甲氧基硅杂(sila)环戊烷。加入完成后，将釜混合物保持在0℃约2小时。向所述釜中加入345g矿物油。在釜温80℃，0.5mmHg下，搅拌所述釜混合物。减压再蒸馏粗产物，得到68.1g(产率48％)的标题化合物，b.p.：60-2/25mmHg，密度@20℃：0.783，FTIR：vS-H:2120.0(vs)。
实施例2：N-(3-二甲氨基丙基)-2-甲基-2-硅杂吡咯(N-二甲基氨基丙基-氮杂-1-
甲基-硅杂环戊烷)的合成
在氩气氛下，向配备冷却浴、机械搅拌器、釜温度计、加料漏斗和干冰蒸馏头的2升4颈烧瓶中加入300ml 2-甲基四氢呋喃，随后分批加入9.5g(0.25mol)的氢化铝锂。该混合物冷却到-10℃，并保持-5至0℃，在2小时通过加料漏斗加入162.3g(0.75mol)的N-正二甲氨基丙基-氮杂-甲基甲氧基硅杂环戊烷。加入完成后，将釜混合物保持在0℃约2小时。向所述釜中加入260g矿物油。在釜温80o，0.5mmHg下，搅拌所述釜混合物。减压再蒸馏粗产物，得到标题化合物，b.p.：52-4/0.5mmHg，密度@20℃：0.857，FTIR：vS-H:2111(vs)。
实施例3：N-三甲基甲硅烷基-2-硅杂吡咯(N-三甲基硅烷基-氮杂-1-甲基-硅杂环
戊烷)的合成
在氩气氛下，向配备冷却浴、机械搅拌器、釜温度计、加料漏斗和干冰蒸馏头的2升4颈烧瓶中加入400ml 2-甲基四氢呋喃，随后分批加入25.3g(0.67mol)的氢化铝锂。该混合物冷却到-10℃，并保持-5至0℃，在2小时通过加料漏斗加入203.4g(1.0mol)的N-三甲基硅烷基-氮杂-二甲氧基硅杂环戊烷。加入完成后，将釜混合物保持在0℃约2小时。向所述釜中加入345g矿物油。在釜温80o，0.5mmHg下，搅拌所述釜混合物。减压再蒸馏粗产物，得到标题化合物，b.p.：48-50/10mmHg，密度@20℃：0.846,，FTIR：vS-H:2120(vs)。
实施例4：1-硫杂-2-硅杂环戊烷的合成
在氩气氛下，向配备冷却浴、机械搅拌器、釜温度计、加料漏斗和干冰蒸馏头的2升4颈烧瓶中加入490ml二甘醇二甲醚，随后分批加入27.8g(0.0.73mol)的氢化铝锂。该混合物冷却到-10℃，并保持-5到0℃，在2小时通过加料漏斗加入200.4g(1.22mol)的2,2-二甲氧基-1-硫杂-2-硅杂环戊烷。加入完成后，将釜混合物保持在0℃约2小时。在釜温80℃下，0.5mmHg下，搅拌所述釜混合物。减压再蒸馏粗产物，得到含～50％二甘醇二甲醚的标题化合物：b.p.：55/1.2mmHg，密度@20℃：0.827，FTIR：vS-H:2140(vs)。
本领域技术人员将会理解，可以对上述实施例进行改变而不背离其广泛的发明构思。因此，应该理解，本发明不限于所公开的特定实施例，而是旨在涵盖由所附权利要求限定的本发明的精神和范围内的修改。
Claims (5)
1.如式(I)的氢化硅杂吡咯或氢化硅杂氮杂吡咯：
其中，所述氢化硅杂吡咯是N-丁基-2-硅杂吡咯；或者，所述氢化硅杂吡咯是N-(3-二甲基氨基丙基)-2-硅杂吡咯；或者，所述氢化硅杂吡咯是(N-三甲基硅烷基-2-甲基-硅杂吡咯)。
2.N-叔丁氧基羧基-2-硅杂-5-氮杂-吡咯。
3.一种如式(II)的硫代硅杂环戊烷：
其中R"和R"'独立地为氢或具有1至20个碳的烷基基团。
4.如权利要求3所述的硫代硅杂环戊烷，其中所述的硫代硅杂环戊烷为1-硫杂-2-硅杂环戊烷。
5.制备如式(II)的硫代硅杂环戊烷的方法：
其中R"和R"'独立为氢或具有1至20个碳的烷基基团，所述方法包括还原在硅上具有至少一个烷氧基的硫代硅杂环戊烷。
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