CN109608487A - 六甲基二硅氨基钠的制备方法 - Google Patents
六甲基二硅氨基钠的制备方法 Download PDFInfo
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- CN109608487A CN109608487A CN201811521987.6A CN201811521987A CN109608487A CN 109608487 A CN109608487 A CN 109608487A CN 201811521987 A CN201811521987 A CN 201811521987A CN 109608487 A CN109608487 A CN 109608487A
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 32
- 239000011734 sodium Substances 0.000 title claims abstract description 32
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- -1 silicon amine alkane Chemical class 0.000 claims description 4
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000002585 base Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000005595 deprotonation Effects 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
Classifications
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- 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
本发明涉及化工合成技术领域,尤其涉及六甲基二硅氨基钠的制备方法,该制备方法是以六甲基二硅胺烷、金属钠为原料,先将其加入溶剂中,再滴加助剂进行反应;在六甲基二硅氨基钠的制备过程中,烯烃类、炔烃类、芳烃类等不饱和烃及它们的衍生物中的一种或几种混合物及其他非烃类助剂实务加入,使产品制备反应速率快,制备温度低;通过助剂的滴加,反应过程更容易控制,操作简便;产品收率高,产物质量好;而现有技术在反应过程中,极易产生氢气,导致生产过程危险性增加,本发明在制备过程中避免了氢气产生,且本发明所述的六甲基二硅氨基钠的制备方法具有反应容易控制、操作简便、产品收率高、产物质量好等优点。
Description
技术领域
本发明涉及化工合成技术领域,尤其涉及六甲基二硅氨基钠的制备方法。
背景技术
六甲基二硅氨基钠(NaHMDS)属于非亲核性强碱,通常作为碱被用于去质子化碳氢化合物;可用于形成烯醇的反应,烯醇酯立体专一克莱森重排反应,将醛转化为硅亚胺的反应,生成缩水甘油酸酯的反应,β内酰胺的反应,芳基烷基醚的选择性断裂反应。六甲基二硅氨基钠可以对大部分的醇和含α氢的羰基化合物(包括羧酸、酯、醛、和酮)起去质子化作用,在四氢呋喃溶液中,六甲基二硅氨基钠主要以二聚体的形式存在,而在其去质子化其他物质时会先行分解成单体再参加反应。
鉴于其有以上广泛用途,所以市场上有大量的六甲基二硅氨基钠出售,也有众多生产厂家生产。但市售六甲基二硅氨基钠的质量无保障,不如现做现用好。鉴于此,本发明人检索了国内的维普、CNKI、万方及中国专利等数据库,均没有查到其有效、操作性好的六甲基二硅氨基钠的制备方法。
发明内容
本发明的目的是为了解决现有技术中存在的缺点,而提出了一种新的六甲基二硅氨基钠的制备方法。
为了实现上述目的,本发明是通过以下技术方案实现的:
本发明通过提供一种六甲基二硅氨基钠(NaHMDS)的制备方法,包括如下步骤:
(1)、向反应瓶中加入六甲基二硅胺烷、金属钠及溶剂,搅拌,升温至少5个小时;
(2)、控温滴加助剂进行反应;反应式如下:
优选的,所述的六甲基二硅胺烷与金属钠的重量比为1∶1至20∶1;所述的六甲基二硅胺烷与助剂的重量比为1∶1至20∶1。
优选的,所述的滴加助剂及控温反应的温度为35℃——100℃。
优选的,所述的溶剂为:选自醚类或烷烃类溶剂中的一种。
优选的,所述的溶剂为:选自醚类或烷烃类溶剂中的几种混合溶剂。
优选的,所述的助剂为:选自不饱和烃及它们的衍生物中的一种或几种混合物的助剂。
优选的,所述的助剂为烯烃类、炔烃类、芳烃类的助剂。
优选的,所述的助剂为选自非烃类助剂。
有益效果:与现有的技术相比,本发明的有益效果是:
1、烯烃类、炔烃类、芳烃类等不饱和烃及它们的衍生物中的一种或几种混合物及其他非烃类助剂加入,使产品制备反应速率快,温度低;
2、通过助剂的滴加,使反应过程更容易控制,操作简便;
3、本发明产品收率高,成品质量好;
4、在现有生产技术中,以氢化钠为原料的生产工艺,极易产生氢气,导致生产过程危险性增加,本发明的制备过程中避免了氢气产生。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
将六甲基二硅胺烷100g,金属钠50g加入500ml的乙醚溶剂中,在回流装置中加热至35℃,滴加作为助剂的正戊烯40g,随着正戊烯的不断加入,反应放出大量热量使体系持续升温,此时应控制滴加速度,使温度控制在35~40℃直至滴加完毕,继续搅拌控温反应5小时后即得到六甲基二硅氨基钠的乙醚溶液。
实施例2
将六甲基二硅胺烷100g,金属钠50g加入500ml的2-甲基四氢呋喃溶剂中,在回流装置中加热至35℃,滴加作为助剂的苯乙烯40g,随着苯乙烯的不断加入,反应放出大量热量使体系持续升温,此时应控制滴加速度,使温度控制在35~40℃直至滴加完毕,继续搅拌控温反应5小时后即得到六甲基二硅氨基钠的2-甲基四氢呋喃溶液。
实施例3
将六甲基二硅胺烷100g,金属钠50g加入500ml的四氢呋喃溶剂中,在回流装置中加热至35℃,滴加作为助剂的六甲基磷酰胺40g,随着六甲基磷酰胺的不断加入,反应放出大量热量使体系持续升温,此时应控制滴加速度,使温度控制在35~40℃直至滴加完毕,继续搅拌控温反应5小时后即得到六甲基二硅氨基钠的四氢呋喃溶液。
实施例4
将六甲基二硅胺烷100g,金属钠50g加入500m1的甲基叔丁基醚溶剂中,在回流装置中加热至35℃,滴加作为助剂的己炔40g,随着己炔的不断加入,反应放出大量热量使体系持续升温,此时应控制滴加速度,使温度控制在35~40℃直至滴加完毕,继续搅拌控温反应5小时后即得到六甲基二硅氨基钠的甲基叔丁基醚溶液。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种六甲基二硅氨基钠(NaHMDS)的制备方法,其特征在于:包括如下步骤:
(1)、向反应瓶中加入六甲基二硅胺烷、金属钠及溶剂,搅拌,升温至少5个小时;
(2)、控温滴加助剂进行反应;
反应式如下:
。
2.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的六甲基二硅胺烷与金属钠的重量比为1∶1至20∶1;所述的六甲基二硅胺烷与助剂的重量比为1∶1至20∶1。
3.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的滴加助剂及控温反应的温度为35℃——100℃。
4.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的溶剂为:选自醚类或烷烃类溶剂中的一种。
5.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的溶剂为:选自醚类或烷烃类溶剂中的几种混合溶剂。
6.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的助剂为:选自不饱和烃及它们的衍生物中的一种或几种混合物的助剂。
7.根据权利要求6所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的助剂为烯烃类、炔烃类、芳烃类的助剂。
8.根据权利要求1所述的六甲基二硅氨基钠的制备方法,其特征在于:所述的助剂为非烃类助剂。
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CN112707929A (zh) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | 一种制备双三甲基二硅基氨基锂的工艺 |
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US4595779A (en) * | 1984-12-24 | 1986-06-17 | Lithium Corporation Of America, Inc. | Stable lithium diisopropylamide and method of preparation |
CN104387415A (zh) * | 2014-11-25 | 2015-03-04 | 浙江硕而博化工有限公司 | 一种制备六甲基二硅烷胺基锂溶液的方法及其反应装置 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US4595779A (en) * | 1984-12-24 | 1986-06-17 | Lithium Corporation Of America, Inc. | Stable lithium diisopropylamide and method of preparation |
CN104387415A (zh) * | 2014-11-25 | 2015-03-04 | 浙江硕而博化工有限公司 | 一种制备六甲基二硅烷胺基锂溶液的方法及其反应装置 |
Non-Patent Citations (1)
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Cited By (1)
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CN112707929A (zh) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | 一种制备双三甲基二硅基氨基锂的工艺 |
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