CN109096324B - 一种二烷基酰基氯化锗合成方法与应用 - Google Patents
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- 229910052732 germanium Inorganic materials 0.000 claims description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- MXIUWSYTQJLIKE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)=O MXIUWSYTQJLIKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 4
- 238000005086 pumping Methods 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- QQMUZJHHPDIYCM-UHFFFAOYSA-N C1(=CC=CC=C1)[Ge]([Ge](C)(C)C)(C)C Chemical compound C1(=CC=CC=C1)[Ge]([Ge](C)(C)C)(C)C QQMUZJHHPDIYCM-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YDLBHMSVYMFOMI-SDFJSLCBSA-N germacrene Chemical compound CC(C)[C@H]1CC\C(C)=C\CC\C(C)=C\C1 YDLBHMSVYMFOMI-SDFJSLCBSA-N 0.000 description 1
- 229930001612 germacrene Natural products 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- C07F7/30—Germanium compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及有机化学技术领域,为解决目前合成二烷基酰基氯化锗的方法不多的问题,本发明提出了一种二烷基酰基氯化锗合成方法,在惰性气体保护下,在有机溶剂中,二烷基锗烯与酰氯反应,反应结束后浓缩有机相,得到二烷基酰基氯化锗。反应条件温和、产率高、产物纯度高的优点,而且工艺简单。同时本发明还提出了二烷基酰基氯化锗作为自由基引发剂在烯烃聚合中的应用。
Description
技术领域
本发明涉及有机化学技术领域,具体涉及一种二烷基酰基氯化锗合成方法与应用。
背景技术
酰基锗化学物,由于其具有生理惰性,在可见光诱导的烯烃聚合反应中可以作为自由基引发剂,在齿科材料的制备,3D打印和硬质涂覆中有着不可替代的作用。我们研究发现二烷基酰基氯化锗在可见光区域有较强的紫外吸收,而且吸收范围较宽,显示这类化合物可以作为可见光诱导的自由基引发剂,在烯烃聚合领域有着潜在的应用前景。
第一例酰基锗化合物是利用(,(-二溴烷基锗的水解反应制得,随后,Corey等人对该方法进行了改进。但是,这些方法需使用较毒的氯化汞等试剂,不适用与工业生产4。现在常见的合成酰基锗化合物的方法主要有:1)三芳基锗化金属(Ph3GeM, M= Li, K, Cu等)与酰氯、酰胺、酯或硫代酯反应生成三芳基酰基锗及其衍生物;2)在过渡金属钯催化下,五甲基苯基二锗烷与酰氯反应生成二甲基苯基酰基锗;3)通过锗代烯醇醚的水解制备三烷基酰基锗化合物;4)最近,Haas等人利用四-三甲基硅基锗烷,在叔丁醇钾和过量的氟化钾作用下,与芳基酰氯反应制备出四酰基锗烷。从以上合成路线可以看出,方法1)、2)和3)可方便构建三烷基酰基锗化合物,方法4)可以合成三烷基酰基锗和四酰基锗化合物。但是,用这些合成方法无法构建二烷基酰基氯化锗。
发明内容
为解决目前合成二烷基酰基氯化锗的方法不多的问题,本发明提出了一种二烷基酰基氯化锗合成方法,反应条件温和、产率高、产物纯度高的优点,而且工艺简单。
同时本发明还提出了二烷基酰基氯化锗作为自由基引发剂在烯烃聚合中的应用。
本发明是通过以下技术方案实现的:一种二烷基酰基氯化锗合成方法为:在惰性气体保护下,在有机溶剂中,二烷基锗烯与酰氯反应,反应结束后浓缩有机相,得到二烷基酰基氯化锗。
所述的二烷基酰基氯化锗具有如(I)所示的结构式:
式中,R 选自C6H5、4-CH3C6H4、4-CF3C6H4、4-CH3OC6H4、4-FC6H4、3,5-(CF3)2 C6H3、4-ClC6H4、 t Bu、CH3、CH2CH3、 CH2CH2CH3中的一种。
反应结构式如下所示:
式中,R 选自C6H5、4-CH3C6H4、4-CF3C6H4、4-CH3OC6H4、4-FC6H4、3,5-(CF3)2 C6H3、4-ClC6H4、 t Bu、CH3、CH2CH3、 CH2CH2CH3中的一种。
二烷基锗烯与酰氯的摩尔比为1:1.1-2。锗烯是一种不稳定的活泼中间体,在有机锗化学中,他为合成新键和杂环化合物提供了方便简捷的途径。
所述酰氯的结构式如(II)所示:
式中,R 选自C6H5、4-CH3C6H4、4-CF3C6H4、4-CH3OC6H4、4-FC6H4、3,5-(CF3)2 C6H3、4-ClC6H4、 t Bu、CH3、CH2CH3、 CH2CH2CH3中的一种。作为优选,酰氯选自苯甲酰氯、取代苯甲酰氯、叔丁基酰氯中的一种。
所述的有机溶剂选自非质子性溶剂,作为优选,有机溶剂选自苯、甲苯、二甲苯、正己烷、正戊烷、环己烷、四氢呋喃、乙二醇二甲醚中的一种。
所述的合成方法在室温下反应10-15分钟,室温为15~30℃,作为优选,最后浓缩有机相后,用正己烷在-20℃条件下重结晶。
所述的二烷基酰基氯化锗合成方法得到的二烷基酰基氯化锗在可见光诱导的烯烃聚合反应中作为自由基引发剂的应用。
与现有技术相比,本发明的有益效果是:具有反应条件温和、产率高、产物纯度高的优点,而且工艺简单。
具体实施方式
下面通过实施例对本发明作进一步详细说明,实施例中所用原料均采用市购产品或采用常规方法制备。
所举实施例只用于解释本发明,并非用于限制本发明的范围。
实施例1
将10 mL Schlenk反应管进行无水无氧处理,在氮气保护下,取二烷基锗烯(100mg, 0.24 mmol)于反应管中,并用除水除氧的四氢呋喃溶解得到深橘黄色的溶液。然后,用1 mL注射器量取过量的苯甲酰氯(39mg, 0.28 mmol)。在室温条件下,缓缓打入到反应管中。反应混合液的颜色由橘黄色立刻变为浅黄色,再搅拌反应10分钟,浓缩溶剂,然后用正己烷在-20℃条件下重结晶,得到黄色的固体二烷基苯甲酰基氯化锗,收率为85%。
二烷基苯甲酰基氯化锗:mp:153-155 oC; 1H NMR (400 MHz, CDCl3) δ8.09-8.07(m, 2H), 7.60 (s, 1H), 7.54-7.52(m, 2H), 2.22-2.11(m, 4H), 0.30 (s, 18H),0.17(s, 18H); 13C NMR(101 MHz, CDCl3) δ 221.66, 137.38, 133.85, 130.12, 128.55,33.63, 18.57, 3.86, 3.10。
实施例2
将10 mL Schlenk反应管进行无水无氧处理,在氮气保护下,取二烷基锗烯(100mg, 0.24 mmol)于反应管中,并用除水除氧的环己烷溶解得到深橘黄色的溶液。然后,用1mL注射器量取过量的甲基苯甲酰氯(41mg, 0.27mmol)。在室温条件下,缓缓打入到反应管中。反应混合液的颜色由橘黄色立刻变为浅黄色,再搅拌反应15分钟,浓缩溶剂,然后用正己烷在-20℃条件下重结晶,得到黄色的固体二烷基对甲基苯甲酰基氯化锗,收率为83%。
对甲基苯甲酰基氯化锗:mp:151-153 oC; 1H NMR (400 MHz, CDCl3) δ7.98-7.96(m, 2H), 7.33-7.31 (m, 2H), 2,44 (s, 3H), 2.21-2.12 (m,4H), 0.30 (s,18H),0.17 (s,18H);13C NMR(101 MHz, CDCl3) δ 220.81, 144.95, 135.02, 130.33, 129.25,33.64, 21.81, 18.51, 3.88, 3.10。
实施例3
将10 mL Schlenk反应管进行无水无氧处理,然后放入到高纯氮气的手套箱中,取锗烯(100 mg,0.24 mmol)于反应管中,并用除水除氧的正己烷溶解得到深橘黄色的溶液。用1 mL注射器量取过量的三氟甲基苯甲酰氯(74.6mg,0.36 mmol)。在室温条件,缓缓打入到反应管中。反应混合液的颜色由橘黄色立刻变为浅黄色,再搅拌反应13分钟,浓缩溶剂,然后用正己烷在-20℃条件下重结晶,得到黄色固体二烷基对三氟甲基苯甲酰基氯化锗,收率为90%。
二烷基对三氟甲基苯甲酰基氯化锗:mp: 156-157 oC; 1H NMR (400 MHz, CDCl3)δ8.20-8.18 (m, 2H), 7.80-7.78 (m, 2H), 2.23-2.13(m, 4H), 0.30 (s, 18H),0.17(s,18H); 13C NMR(101 MHz, CDCl3) δ 221.67, 135.04, 134.72, 130.19, 125.66,125.62, 124.83, 122.11, 33.64, 18.86, 3.89, 3.07。
实施例4
将10 mLSchlenk反应管进行无水无氧处理,在氮气保护下,取二烷基锗烯(100mg,0.24 mmol)于反应管中,并用除水除氧的二甲苯溶解得到深橘黄色的溶液。然后,用1mL注射器量取过量的叔丁基酰氯(58mg,0.48 mmol)。在室温条件下,缓缓打入到反应管中。反应混合液的颜色由橘黄色立刻变为浅黄色,再搅拌反应12分钟,浓缩溶剂,然后用正己烷在-20℃条件下重结晶,得到黄色的固体二烷基叔丁酰基氯化锗,收率为86%。
二烷基叔丁酰基氯化锗: mp:139-140oC; 1H NMR (400 MHz, CDCl3) δ 2.08(m,4H), 1.38(s, 9H) 0.22(s, 18H),0.20 (s,18H); 13C NMR(101 MHz, CDCl3) δ237.88,50.09, 33.38, 27.18, 19.54, 4.06, 3.29。
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