CN111100159B - 一种含三(三甲基硅基)硅烷基亚甲基取代的杂环化合物的合成方法 - Google Patents
一种含三(三甲基硅基)硅烷基亚甲基取代的杂环化合物的合成方法 Download PDFInfo
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 title abstract description 5
- -1 silylmethylene Chemical group 0.000 title description 4
- 238000006467 substitution reaction Methods 0.000 title description 3
- 238000001308 synthesis method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000007363 ring formation reaction Methods 0.000 claims abstract 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 13
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 3
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical group COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- SQMFULTZZQBFBM-UHFFFAOYSA-N bis(trimethylsilyl)silyl-trimethylsilane Chemical compound C[Si](C)(C)[SiH]([Si](C)(C)C)[Si](C)(C)C SQMFULTZZQBFBM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
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- 238000005259 measurement Methods 0.000 description 5
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- 239000011941 photocatalyst Substances 0.000 description 4
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- 229960003138 rose bengal sodium Drugs 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
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- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 2
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- UALZRFRMEYMLCQ-UHFFFAOYSA-N 3-methyl-1-prop-2-ynoxybut-2-ene Chemical compound CC(C)=CCOCC#C UALZRFRMEYMLCQ-UHFFFAOYSA-N 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- FNQWESREZCCUCW-UHFFFAOYSA-N dimethyl 2-(3-methylbut-2-enyl)-2-prop-2-ynylpropanedioate Chemical compound COC(=O)C(C(=O)OC)(CC#C)CC=C(C)C FNQWESREZCCUCW-UHFFFAOYSA-N 0.000 description 1
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- 239000002547 new drug Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical compound C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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Abstract
本发明提供了一种含三(三甲基硅基)硅烷基亚甲基取代的杂环化合物的合成方法,以含有不同取代基的1,n‑烯炔(n=6,7)和三(三甲硅烷基)硅烷为原料,有机染料为催化剂,在可见光照射条件下进行1,n‑烯炔的氢硅化环化反应,得到所述的杂环化合物,并通过1H NMR、13C NMR、IR、HRMS和X‑Ray单晶衍射对所目标产品的结构进行了表征和分析。该方法具有底物合成简单、反应条件温和、转化率高、后处理方便等优点。
Description
技术领域
本发明属于有机合成领域,特别涉及一类含硅烷基杂环化合物的简便合成方法。
背景技术
含硅化合物在生物体内具有独特的生理效应。用硅原子取代已知药物分子中特定的碳原子可以进一步改善原有药物的药动学性能,优化其药效。同时,硅替代药在新药研发领域也有巨大的应用前景。氮杂、氧杂五元环及六元环均是抗真菌药物的核心结构单元,其广泛作用于有机合成、医农及制药工业。
在已有的报道中,我们发现大多是通过过渡金属催化Si-H、C-H键官能化构建C-Si键。例如,文献(J.L.Speier,J.A.Webster,G.H.Barnes,J.Am.Chem.Soc.1957,79,974;b)B.D.Karstedt(General Electric Company),US3775452A,1973.)开发的铂催化剂,可以有效地实现Si-H键的直接活化,然后进行氢化硅烷化反应。近几年有文献(Du X.,Huang Z.;Advances in base-metal-catalyzed alkene hydrosilylation;ACS Catalysis,2017,7(2):1227-1243)报导了发现以铁,镍和钴等金属配合物可以作为有效的氢化硅烷化催化剂。但是,这些研究大都局限于C(sp2)或C(sp3)的直接氢硅加成,关于含硅烷基环状化合物的合成研究很少。文献(Zhou R.,Goh Y.Y.,Liu H.,et al;Visible-Light-MediatedMetal-Free Hydrosilylation of Alkenes through Selective Hydrogen AtomTransfer for Si-H Activation;Angewandte Chemie International Edition,2017,56(52):16621-16625)报导了可见光条件下硅原子自由基的产生是借助于有机碱或硅硫醇等氢原子转移催化剂,因此,该反应条件相对复杂,极大的限制了工业上的应用。
发明内容
本发明的目的是提供一种合成三(三甲基硅基)硅烷基亚甲基取代的杂环化合物的简便方法。
实现本发明目的的技术方案是:将不同取代基的1,n-烯炔(n=6、7)、三(三甲基硅基)硅烷((TMS)3SiH)、有机染料催化剂加入到溶剂中,室温下光照反应,TLC监测反应进程,待反应完全后经柱层析分离提纯得到产品,
其中,R1为甲基、H、苯基;R2为甲基、H;R3为对甲苯磺酰胺基(TsN)、氧原子(O)、丙二酸二甲酯基(C(CO2Me)2);m=1、2。
进一步的,有机染料催化剂选自曙红(Eosin Y)、茜素红S(Alizarin Red S)、酸性红94(Acid Red 94)和荧光素(Fluorescein)中任意一种,优选Eosin Y。
进一步的,反应体系的溶剂为乙酸乙酯(EtOAc)、1,2-二氯乙烷(DCE)、乙腈(MeCN)、四氢呋喃(THF)、N,N-二甲基甲酰胺(DMF)和甲苯(Toluene)任意一种,优选乙腈(MeCN)。
进一步的,不同取代基的1,n-烯炔、三(三甲基硅基)硅烷、有机染料催化剂的摩尔比例为1.0:1.0~4.0:0.05~0.20,优选1:4.0:0.05。
进一步的,光照反应采用可见光,其光源为11W日光灯、23W日光灯、40W日光灯中任意一种,优选23W日光灯。
进一步的,反应温度为20~60℃,优选20℃。
与现有技术相比,本发明的优点和效果在于:(1)本发明底物合成方法简单;(2)本发明涉及到光催化反应,光催化剂为廉价易得、安全无害的有机染料;(3)本发明涉及到的光催化反应,光源为家用普通白炽灯,不需要特殊光源,反应设施简易;(4)本发明反应条件温和,操作简单安全;(5)本发明转化率高,原子经济性高,符合绿色化学理念。
具体实施方式
实施例1
称取4-甲基-N-(3-甲基-2-丁烯基)-N-炔丙基苯磺酰胺83.1mg(0.3mmol)、EosinY10.2mg(0.015mmol)放入反应瓶中,加入2mL乙腈溶液,再量取三(三甲基硅基)硅烷((TMS)3SiH)368μL(1.2mmol),在氮气保护下置于23W日光灯的照射下搅拌反应,TLC检测反应进度,约24h后,待反应完全,经柱层析分离提纯(石油醚:乙酸乙酯=15:1),得到白色固体,记为产物1,产率为91%。
产物1的结构表征如下:
白色固体,熔点为68-70℃;1H NMR(400MHz,CDCl3):δ7.65(d,J=8.0Hz,2H),7.27(d,J=7.7Hz,2H),5.36(s,1H),3.61(q,J=13.9Hz,2H),3.25–3.12(m,2H),2.38(s,3H),1.75(dd,J=13.3,6.8Hz,1H),1.21(dd,J=7.9,6.3Hz,1H),0.85(d,J=6.7Hz,3H),0.74(d,J=6.6Hz,3H),0.11(s,27H);13C NMR(CDCl3,150MHz):δ155.1,135.5,132.7,129.0,127.8,114.6,53.9,52.4,49.7,30.4,20.7,18.0,1.1.IR(neat):ν=2955,1350,1247,1166,1095,1042,835cm-1;HRMS(ESI)理论计算值[C24H47NNaO2SSi4]+[M+Na]+:548.2297,实际测量值:548.2305.
反应条件同实施例1,使用不同种类的有机染料催化剂,产物产率如下表1所示。
表1不同种类的有机染料催化剂时产物的产率
光催化剂 | Eosin Y | Alizarin Red S | Fluorescein | Acid Red 94 |
产率(%) | 74 | 45 | 22 | 20 |
由上表可知,当其他反应条件不变,光催化剂为Eosin Y时,产物的产率最高。
反应条件同实施例1,使用不同当量的催化剂,产物产率如下表2所示。
表2不同当量的有机染料催化剂时产物的产率
Eosin Y(equiv) | 0.05 | 0.10 | 0.20 |
产率(%) | 74 | 70 | 76 |
由上表可知,当其他反应条件不变,光催化剂Eosin Y的用量为0.05-0.20当量时,产物的产率变化不明显,均在74%左右。考虑到经济问题,优选0.05当量。
反应条件同实施例1,使用不同种类的溶剂,产物产率如下表3所示:
表3不同种类的溶剂时产物的产率
溶剂 | EtOAc | DCE | MeCN | Toluene | THF | DMF |
产率(%) | 67 | <5 | 74 | <5 | 70 | <5 |
由上表可知,当其他反应条件不变,溶剂为MeCN时,产物的产率最高。
反应条件同实施例1,当其他反应条件不变,改变(TMS)3SiH的用量,产物产率如下表4所示:
表4不同当量的(TMS)3SiH用量时产物的产率
(TMS)<sub>3</sub>SiH(equiv) | 1.0 | 2.0 | 3.0 | 4.0 |
产率(%) | 45 | 74 | 84 | 91 |
由上表可知,当其他反应条件不变,(TMS)3SiH的用量为4倍当量时,产物的产率最高。
反应条件同实施例1,使用不同光源时,产物产率如下表5所示。
表5不同光源时产物的产率
白炽灯 | 11W | 23W | 40W |
产率(%) | 56 | 74 | 70 |
由上表可知,当其他反应条件不变,使用23W家用白炽灯作为光源,所得产物的产率最高。
反应条件同实施例1,调节不同反应温度时,产物产率如下表6所示。
表6不同反应温度时产物的产率
反应温度(℃) | 室温(约20) | 40 | 60 |
产率(%) | 74 | 70 | 71 |
由上表可知,当其他反应条件不变,不同反应温度对产率影响不大。考虑到经济问题,优选室温条件。
实施例2
采用实施例1相同的方法和反应条件,当4-甲基-N-(3-苯基烯丙基)-N-炔丙基苯磺酰胺为原料时,得到如下不同的五元氮杂环目标产物2。
产物2结构表征如下:
白色固体;熔点78-81℃;1H NMR(400MHz,CDCl3):δ7.65(d,J=8.1Hz,2H),7.32–7.22(m,4H),7.18(d,J=7.3Hz,1H),7.09(d,J=7.2Hz,2H),5.29(s,1H),3.80–3.59(m,2H),3.20(dd,J=9.1,6.9Hz,1H),3.03(dd,J=9.2,5.1Hz,1H),2.94–2.85(m,1H),2.79(dd,J=13.6,6.4Hz,1H),2.56(dd,J=13.6,8.8Hz,1H),2.41(s,3H),0.11(s,27H);13C NMR(CDCl3,150MHz):δ155.3,143.6,139.3,132.5,129.6,128.9,128.5,127.9,126.3,114.4,53.5,52.9,47.8,39.5,21.5,1.1;IR(neat):ν=2952,2895,1351,1247,1165,1040,837cm-1;HRMS(ESI)理论计算值[C28H47NNaO2SSi4]+[M+Na]+:596.2297,实际测量值:596.2285..
实施例3
采用实施例1相同的方法和反应条件,当2-甲基-4-炔丙氧基-2-丁烯为原料时,得到如下不同的五元氧杂环目标产物3。
产物3结构表征如下:
无色油状液体;1H NMR(400MHz,CDCl3):δ5.43(s,1H),4.18(s,2H),3.82(m,2H),2.52(s,1H),1.84(tt,J=13.4,6.7Hz,1H),0.93(d,J=6.9Hz,3H),0.85(d,J=6.8Hz,3H),0.17(s,27H);13C NMR(150MHz,CDCl3):δ159.9,110.3,73.1,70.5,53.2,30.6,21.0,18.2,1.2;IR(neat):ν=2956,2894,1246,1073,835cm-1;HRMS(ESI)理论计算值[C17H40NaOSi4]+[M+Na]+:395.2048,实际测量值:395.2045.
实施例4
采用实施例1相同的方法和反应条件,当2-(3-甲基-2-丁烯基)-2-炔丙基丙二酸二甲酯为原料时,得到如下不同五元全碳环目标产物4。
产物4结构表征如下:
无色油状液体;1H NMR(400MHz,CDCl3):δ5.30(s,1H),3.70(d,J=15.0Hz,6H),2.88(dd,J=64.0,16.7Hz,2H),2.59(s,1H),2.41(dd,J=12.0,8.4Hz,1H),1.94(dd,J=11.7,6.7Hz,1H),1.83–1.74(m,1H),0.92(d,J=6.9Hz,3H),0.75(d,J=6.7Hz,3H),0.16(s,27H);13C NMR(CDCl3,150MHz):δ172.3,172.1,159.7,111.6,58.7,52.7,52.6,51.3,43.5,34.2,30.0,21.2,16.2,1.2;IR(neat):ν=2955,2894,1739,1245,834cm-1;HRMS(ESI)理论计算值[C22H46NaO4Si4]+[M+Na]+:509.2365,实际测量值:509.2367.
实施例5
采用实施例1相同的方法和反应条件,当N-(4-甲基-3-戊烯基)-N-炔丙基对甲苯磺酰胺为原料时,得到如下不同六元环目标产物5。
产物5结构表征如下:
无色油状液体;1H NMR(600MHz,CDCl3):δ7.64(s,2H),7.33(s,2H),5.40(s,1H),3.78(d,J=12.0Hz,1H),3.26(d,J=5.1Hz,1H),3.11(d,J=12.0Hz,1H),2.73(s,1H),2.44(s,3H),1.77(s,2H),1.52(s,1H),1.26(s,1H),0.81(s,3H),0.72(s,3H),0.21(s,27H);13CNMR(CDCl3,150MHz):δ150.4,143.4,132.3,129.6,128.1,119.7,52.1,49.9,42.6,26.9,25.9,21.5,21.4,19.8,1.1;IR(neat):ν=2950,1671,1601,1350,1248,1165,836cm-1;HRMS(ESI)理论计算值[C25H49NNaO2SSi4]+[M+Na]+:562.2453,实际测量值:562.2445。
由以上数据,可知本发明提供了一种含三(三甲基硅基)硅烷基亚甲基取代的杂环化合物的有效合成方法。
Claims (5)
2.如权利要求1所述的方法,其特征是,R1为甲基、H、苯基;R2为甲基、H;R3为对甲苯磺酰胺基、氧原子、丙二酸二甲酯基。
3.如权利要求1所述的方法,其特征是,1,n-烯炔衍生物: (TMS)3SiH : 催化剂的摩尔比例为1.0 : 1.0~4.0 : 0.05~0.20。
4.如权利要求1所述的方法,其特征是,反应温度为20~60oC。
5.如权利要求1所述的方法,其特征是,可见光的光源为11 W日光灯、23 W日光灯、40W日光灯中任意一种。
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