• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Syntheses,Crystal Structures and Catalytic Activity of Rhenium Carbonyl Complexes Containing Aryl-Substituted Tetramethylcyclopentadienyl Ligands

    2017-07-05 14:55:49MAZhiHongLIZhanWeiQINMeiLISuZhenHANZhanGangZHENGXueZhongLINJin
    無機化學學報 2017年6期
    關鍵詞:環(huán)戊二烯河北師范大學芳基

    MA Zhi-HongLI Zhan-WeiQIN Mei*,LI Su-ZhenHAN Zhan-GangZHENG Xue-ZhongLIN Jin*,

    (1College of Chemistry&Material Science,Hebei Normal University,Shijiazhuang 050024,China) (2College of Basic Medicine,Hebei Medical University,Shijiazhuang 050017,China) (3Hebei College of Industry and Technology,Shijiazhuang 050091,China)

    Syntheses,Crystal Structures and Catalytic Activity of Rhenium Carbonyl Complexes Containing Aryl-Substituted Tetramethylcyclopentadienyl Ligands

    MA Zhi-Hong1,2LI Zhan-Wei1QIN Mei*,1LI Su-Zhen3HAN Zhan-Gang1ZHENG Xue-Zhong1LIN Jin*,1

    (1College of Chemistry&Material Science,Hebei Normal University,Shijiazhuang 050024,China) (2College of Basic Medicine,Hebei Medical University,Shijiazhuang 050017,China) (3Hebei College of Industry and Technology,Shijiazhuang 050091,China)

    Cyclopentadienes C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh)reacted with Re2(CO)10in refluxing xylene to give new aryl-substituted tetramethylcyclopentadienyl mononuclear metal carbonyl complexes [(η5-C5Me4Ar)Re(CO)3](Ar=Ph(1),4-CH3Ph(2),4-OCH3Ph(3),4-ClPh(4),4-BrPh(5)),respectively.The five new complexes were characterized by elemental analysis,IR,1H NMR and13C NMR spectroscopy.The crystal structures of complexes 1~5 were determined by X-ray crystal diffraction analysis.All five of these complexes have significant catalytic activity in Friedel-Crafts reactions of aromatic compounds with alkylation reagents. CCDC:1463217,1;1506704,2;1484954,3;1484955,4;1506705,5.

    synthesis;mononuclear rhenium carbonyl complex;Friedel-Crafts alkylation reaction;catalysis

    0 Introduction

    Cyclopentadienylligandshavebeenstudied intensively as the most important ligands in organometallicchemistrybecauseoftheircapacityfor binding to hard and soft metal centers in a hemilabile manner,giving the complexes distinctive chemical and physical properties.Substituents on such ligands mayincludephosphines[1-2],amines[3-4],ethers[5-8], sulfids[9-11]and alkenes[12-16],which have been widely studied.These types of complexes have been significantly applied in catalysis and in the construction of molecular materials.Despite these notable contributions,thedevelopmentoffunctionalizedligands bearing other substituents remains a worthwhile task. Ourgrouphasreportedaseriesofsubstituted cyclopentadienyl metal carbonyl complexes,and the electronic and steric effects of the substituents on the final structures and properties of the complexes were discussed[17-19].We have also reported catalytic reactivity of mononuclear substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes in Friedel-Crafts alkylation of aromatic compounds[20].However, few half-sandwich complexes of this type are known for rhenium[21-23].On the other hand,to the best of our knowledge,only a few examples of Friedel-Crafts alkylation reactions catalyzed by rhenium carbonyl complexes have been reported to date[24-25].To develop a deeper understanding of the structures and catalytic activityofsubstitutedcyclopentadienylrhenium carbonyl complexes,herein we report the syntheses, structures and catalytic activity of a series of arylsubstitutedtetramethylcyclopentadienylrhenium carbonyl complexes.

    1 Experimental

    1.1 General considerations

    Schlenkandvacuumlinetechniqueswere employed for all manipulations.All solvents were distilled from appropriate drying agents under nitrogen atmosphere.1H and13C NMR spectra were recorded on a Bruker AvⅢ-500 instrument in CDCl3.IR spectra were recorded as KBr disks on a Thermo Fisher is 50 spectrometer.Agilent 6820 gas chromatograms were used for analysis of samples.Elemental analyses were obtained on a Vario ELⅢanalyzer.The ligand precursors C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh)were synthesized according to the literature[26-27].Treatment of ligand precursors(C5HMe4Ar) with Re2(CO)10afforded the corresponding complexes [(η5-C5Me4Ar)Re(CO)3](Ar=Ph(1),4-CH3Ph(2),4-OCH3Ph(3),4-ClPh(4),4-BrPh(5))(Scheme 1).

    Scheme 1 Syntheses of complexes 1~5

    1.2 Synthesis of complex 1

    A solution of the ligand(C5HMe4Ph)(0.12 g,0.6 mmol)and Re2(CO)10(0.2 g,0.3 mmol)in xylene(15 mL)was refluxed for 48 h.After removal of solvent the residue was loaded onto an alumina column. Elution with petroleum ether developed a colorless band,which was collected and concentrated to afford (η5-C5Me4Ph)Re(CO)3(1)as colorless crystals,yield: 0.19 g(67.4%).m.p.128.3~128.9℃;Anal.Calcd.for C18H17O3Re(%):C,46.24;H,3.66.Found(%):C,45.87; H,3.87;1H NMR(CDCl3,500 MHz):δ 2.11(s,6H, C5Me2),2.24(s,6H,C5Me2),7.29~7.38(m,5H,C6H5);13C NMR(CDCl3,125 MHz):δ 10.85,11.24,97.53, 102.11,105.03,127.75,128.43,132.11,132.64, 197.45;IR(KBr,cm-1):2 006(s),1 931(s),1 900(s).

    1.3 Synthesis of complex 2

    Using a procedure similar to that described above,C5HMe4(4-CH3Ph)was reacted with Re2(CO)10in refluxing xylene for 48 h.After chromatography and elution with petroleum ether,[η5-C5Me4(4-CH3Ph)] Re(CO)3(2)was obtained(0.23 g,76.7%yield)as colorless crystals.m.p.127.0~127.5℃;Anal.Calcd. for C19H19O3Re(%):C,47.39;H,3.98.Found(%):C, 47.58;H,3.81;1H NMR(CDCl3,500 MHz):δ 2.11(s, 6H,C5Me2),2.23(s,6H,C5Me2),2.38(s,3H,CH3),7.18 (s,4H,C6H4);13C NMR(CDCl3,125 MHz):δ 10.85, 11.25,21.14,97.49,102.01,105.01,129.01,129.12, 132.46,137.55,197.55.IR(KBr,cm-1):2 004(s),1 923 (s),1 899(s).

    1.4 Synthesis of complex 3

    Using a procedure similar to that described above,C5HMe4(4-OCH3Ph)was reacted with Re2(CO)10in refluxing xylene for 48 h.After chromatography and elution with petroleum ether,[η5-C5Me4(4-OCH3Ph)] Re(CO)3(3)was obtained(0.19 g,61.9%yield)as colorless crystals.m.p.119.8~120.6℃;Anal.Calcd. for C19H19O4Re(%):C,45.87;H,3.85.Found(%):C, 45.54;H,3.74;1H NMR(CDCl3,500 MHz):δ 2.10(s, 6H,C5Me2),2.23(s,6H,C5Me2),3.84(s,3H,CH3), 6.89(d,J=8.5 Hz,2H,C6H2),7.21(d,J=8.0 Hz,2H, C6H2);13C NMR(CDCl3,125 MHz):δ 10.86,11.25, 55.31,97.43,102.16,104.81,113.77,124.10,133.70, 159.12 197.60.IR(KBr,cm-1):2 005(s),1 918(s), 1 903(s).

    1.5 Synthesis of complex 4

    Using a procedure similar to that described above,C5HMe4(4-ClPh)was reacted with Re2(CO)10in refluxing xylene for 48 h.After chromatography and elution with petroleum ether,[η5-C5Me4(4-ClPh)]Re (CO)3(4)was obtained(0.23 g,73.5%yield)as colorless crystals.m.p.137.8~138.0℃;Anal.Calcd.for C18H16ClO3Re(%):C,43.07;H,3.21.Found(%):C, 43.38;H,3.02;1H NMR(CDCl3,500 MHz):δ 2.10(s, 6H,C5Me2),2.23(s,6H,C5Me2),7.24(d,J=8.0 Hz,2H, C6H2),7.34(d,J=8.5 Hz,2H,C6H2);13C NMR(CDCl3, 125 MHz):δ 10.85,11.24,97.54,102.11,105.04, 127.75,128.43,132.12,132.54,197.46.IR(KBr,cm-1): 2 005(s),1 922(s),1 897(s).

    1.6 Synthesis of complex 5

    Using a procedure similar to that described above,C5HMe4(4-BrPh)was reacted with Re2(CO)10in refluxing xylene for 48 h.After chromatography and elution with petroleum ether,[η5-C5Me4(4-BrPh)]Re (CO)3(5)was obtained(0.21 g,63.6%yield)as colorless crystals.m.p.115.0~116.0℃;Anal.Calcd.for C18H16BrO3Re(%):C,39.56;H,2.95.Found(%):C,39.93; H,3.12;1H NMR(CDCl3,500 MHz):δ 2.10(s,6H, C5Me2),2.23(s,6H,C5Me2),7.17(d,J=8.0Hz,2H,C6H2), 7.50(d,J=8.5 Hz,2H,C6H2).13C NMR(CDCl3,125 MHz):δ 10.83,11.21,97.79,102.01,103.50,121.96, 131.25,131.62,134.18,197.10.IR(KBr,cm-1):2 005 (s),1 920(s),1 900(s).

    1.7 Crystallographic characterization

    Single crystals of complexes 1~5 suitable for X-raydiffractionwereobtainedfromtheslow evaporation of hexane-dichloromethane solutions.All X-ray crystallographic data were collected on a Bruker AXS SMART 1000 CCD diffractometer with graphite monochromated Mo Kα(λ=0.071 073 nm)radiation using the φ-ω scan technique.The structures were solved by direct methods and refined by full-matrix least-squares procedures based on F2using the SHELXL -97 program system[28].Hydrogen atoms were included in calculated positions riding on the parent atoms and refined with fixed thermal parameters.The crystal data and summary ofX-raydatacollectionare presented in Table 1.

    CCDC:1463217,1;1506704,2;1484954,3; 1484955,4;1506705,5.

    1.8 General procedure for catalytic tests

    The catalytic reactions were carried out under anargon atmosphere with magnetic stirring.The required rhenium carbonyl complex(0.04 mmol)was mixed with 1,2-dichloroethane(3.5 mL)in a 25 mL roundbottom flask at room temperature.Aromatic compounds (2 mmol)and tert-butyl halides(4 mmol)were added by syringe.The reaction mixture was stirred at 80℃for 18 h.After cooling to room temperature,the solid catalyst was separated from the reaction mixture by filtration.The filtrate was concentrated by rotary evaporation,and the residue was purified by Al2O3column chromatography,eluting with petroleum ether to give a colorless liquid.The course of the reaction was monitored using an Agilent 6820 gas chromatograph.

    Table 1Crystal data and structure refinement parameters for complexes 1~5

    Continued Table 1

    2 Results and discussion

    2.1 Crystal structures

    The selected bond distances and angles for complexes 1~5 are presented in Table 2 and complex 1 is depicted in Fig.1.The four remaining complexes [(η5-C5Me4Ar)Re(CO)3](Ar=4-CH3Ph(2),4-OCH3Ph (3),4-ClPh(4),4-BrPh(5))are shown in Fig.S1~S4 (Supporting Information).

    Complexes 1~5 are mononuclear substituted tetramethylcyclopentadienyl rhenium carbonyl complexes and have similar structures.Similar to the CpRe(CO)3type(Cp=substituted cyclopentadienyl ligand),all five structuresexhibittypicalthree-leggedpiano-stool structures,in which the rhenium atom is coordinated by a η5-cyclopentadienyl,plus three terminal CO ligands.The Re-CEN(CEN:centroid of the cyclopentadienyl ring)distances are 0.195 1 nm for 1,0.196 2 nm for 2,0.203 8 nm for 3,0.194 2 nm for 4,and 0.195 3 nm for 5,which are correlated with the steric effects of the different cyclopentadienyl substituents. The(O)C-Re-C(O)angle in all of these Re tricarbonyl complexes investigated is very close to 90°,whichmay simply be a consequence of the reduction in nonbondedrepulsionsbetweencarbonylgroups.The dihedral angles between the cyclopentadienyl and phenyl ring planes in these complexes are between 56.03°and 61.86°,to further decrease the intramolecular non-bonding interaction.On the other hand,the average Re-C(O)distances and the Re-C-O angles of thefivecomplexesareconcordantwithrelatedtricarbonyl cyclopentadienyl rhenium(Ⅱ)complexes[29-30].

    Fig.1Molecular structure of complex 1

    Table 2Selected bond lengths(nm)and angles(°)for complexes 1~5

    2.2 Catalytic studies

    Inordertotestthecatalyticcapabilityin Friedel-Crafts alkylation reactions(Scheme 2)catalyzed by these complexes,the effects of the reaction time, yield,economic considerations etc.were considered. The experimental conditions were chosen for catalytic work:1,2-dichloroethane as solvent;the molar ratio of aromatic substrates and alkylation reagents was 1∶2;the amount of catalyst was 2%(molar percentage,substrate asreference);refluxingtemperature;reactiontime:18h.

    Scheme 2[(η5-C5Me4Ar)Re(CO)3]catalyzed Friedel-Crafts alkylation reaction of anisole/phenol with tertbutyl bromide/chloride

    Complexes 1~5 were examined under the experimental conditions,with the results shown in Table 3. Using refluxing 1,2-dichloroethane,mixtures of the corresponding mono-and di-substituted products were obtained.All five complexes proved to be capable of catalyzing Friedel-Crafts alkylation reactions,moreover, the product yields were found to vary with the different catalysts used.In no case there was any detectable alkylation product in the absence of the rhenium complexes.The obvious influence of the different substituents on the catalytic behavior may be due to their modest variations in steric and electronic properties.The higher product yields obtained for thealkylation of anisole and phenol with t-butyl bromide than with t-butyl chloride is expected,since bromide is a better leaving group.

    Table 3Complexes catalyzed reaction of aromatic substrates with different alkylation reagents

    3 Conclusions

    Reactions of aryl-substituted tetramethylcyclopentadienyl ligands C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh)with Re2(CO)10in refluxing xylenefurnishedfivenewmononuclearrhenium carbonylcomplexes.Friedel-Craftsreactionsof aromatic substrates with tert-butyl halides catalyzed by these complexes showed that they have obvious catalytic activity.tert-Butyl halides could be used as alkylation reagents in these reactions.Compared with traditional catalysts,these complexes have some significant practical advantages,namely lower amounts of catalyst,mildreactionconditions,andmore environmentally friendly chemistry.Further studies to elucidate the reaction mechanism and expand the synthetic utility of these catalysts are in progress.

    Supporting information is available at http://www.wjhxxb.cn

    [1]Ishiyama T,Miyoshi K,Nakazawa H.J.Mol.Catal.A:Chem., 2004,221:41-45

    [2]Krutko D P,Borzov M V,Veksler E N,et al.Eur.J.Inorg. Chem.,1999,11:1973-1979

    [3]Jutzi P,Redeker T.Eur.J.Inorg.Chem.,1998,6:663-674

    [4]Shapiro P J,Bunel E,Schaefer W P,et al.Organometallics, 1990,9:867-869

    [5]Hou X F,Cheng Y Q,Wang X,et al.J.Organomet.Chem., 2005,690:1855-1860

    [6]Yeh P H,Pang Z,Johnston R F.J.Organomet.Chem.,1996, 509:123-139

    [7]Dou Y Y,Xie Y F,Tang L F.Appl.Organomet.Chem.,2008, 22:25-29

    [8]Pang Z,Burkey T J.Organometallics,1997,16:120-123

    [9]Huang J,Wu T,Qian Y.Chem.Commun.,2003:2816-2817

    [10]Daugulis O,Brookhart M.Organometallics,2003,22:4699-4704

    [11]Draganjac M,Ruffing C J,Rauchfuss T B.Organometallics, 1985,4:1909-1911

    [12]Schumanna H,Heima A,Schuttea S,et al.Z.Anorg.Allg.Chem.,2006,632:1939-1942

    [13]Erker G,Kehr G,Fr?hlich R.J.Organomet.Chem.,2004, 689:1402-1412

    [14]Luke?ová L,Stepnicka P,Fejfarová K,et al.Organometallics, 2002,21:2639-2653

    [15]Horácek M,Stepnicka P,Gyepes R,et al.Chem.Eur.J., 2000,6:2397-2408

    [16]Castro A,Turner M L,Maitlis P M.J.Organomet.Chem., 2003,674:45-49

    [17]Ma Z H,Zhao M X,Li F,et al.Transition Met.Chem., 2010,35:387-391

    [18]Ma Z H,Wang N,Guo K M,et al.Inorg.Chim.Acta,2013, 399:126-130

    [19]Ma Z H,Guo K M,Wang N,et al.J.Coord.Chem.,2014, 67:64-71

    [20]Ma Z H,Lü L Q,Wang H,et al.Transition Met.Chem., 2016,41:225-233

    [21]Godoy F,Klahn A H,Lahoz F J,et al.Organometallics, 2003,22:4861-4868

    [22]Godoy F,Klahn A H,Oelckers B,et al.Dalton Trans., 2009:3044-3051

    [23]Klahn A H,Oelckers B,Godoy F,et al.J.Chem.Soc. Dalton Trans.,1998:3079-3086

    [24]Nishiyama Y,Kakushou F,Sonoda N.Bull.Chem.Soc.Jpn., 2000,73:2779-2782

    [25]Kuninobu Y,Matsuki T,Takai K.J.Am.Chem.Soc.,2009, 131:9914-9915

    [26]Bensley D M.J.Org.Chem.,1988,53:4417-4419

    [27]Enders M,Ludwig G,Pritzkow H.Organometallics,2001,20: 827-833

    [28]Sheldrick G M.SHELXL-97,Program for Crystal Structure Refinement,University of G?ttingen,Germany,1997.

    [29]Fitzpatrick P J,Le Page Y,Butler I A.Acta Crystallogr. Sect.B,1981,37:1052-1058

    [30]Arancibia R,Godoy F,Buono-Core G E,et al.Polyhedron, 2008,27:2421-2425

    芳基取代四甲基環(huán)戊二烯基錸羰基化合物的合成、晶體結(jié)構(gòu)及催化性能

    馬志宏1,2李戰(zhàn)偉1秦玫*,1李素貞3韓占剛1鄭學忠1林進*,1
    (1河北師范大學化學與材料科學學院,石家莊050024) (2河北醫(yī)科大學基礎醫(yī)學院,石家莊050017) (3河北工業(yè)職業(yè)技術學院,石家莊050091)

    芳基取代的四甲基環(huán)戊二烯C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh)分別與Re2(CO)10在二甲苯中加熱回流,得到了5個單核配合物[(η5-C5Me4Ar)Re(CO)3](Ar=Ph(1),4-CH3Ph(2),4-OCH3Ph(3),4-ClPh(4),4-BrPh(5))。通過元素分析、紅外光譜、核磁共振氫譜對配合物1~5的結(jié)構(gòu)進行了表征,用X射線單晶衍射法測定了配合物的結(jié)構(gòu)。同時,研究了這五種配合物在芳香族化合物Friedel-Crafts烷基化反應中的催化活性。

    合成;單核錸羰基配合物;Friedel-Crafts烷基化反應;催化

    O614.71+3

    A

    1001-4861(2017)06-1074-07

    2017-02-10。收修改稿日期:2017-03-22。

    10.11862/CJIC.2017.117

    國家自然科學基金(No.21372061)、河北省自然科學基金(No.B2013205025,B2014205018)和河北師范大學重點基金(No.L2012Z02)資助項目。

    *通信聯(lián)系人。E-mail:qinmei2005@126.com,linjin64@126.com;會員登記號:S06N0210M1305。

    猜你喜歡
    環(huán)戊二烯河北師范大學芳基
    賀河北師范大學百廿校慶
    河北師范大學美術與設計學院油畫作品選登
    高等學校書法創(chuàng)作教學摭談——以河北師范大學為例
    新型3-氧-3-芳基-2-芳基腙-丙腈衍生物的合成及其抗癌活性
    合成化學(2015年2期)2016-01-17 09:04:21
    一種新型芳基烷基磺酸鹽的制備與性能評價
    化工進展(2015年6期)2015-11-13 00:27:23
    3-芳基苯并呋喃酮類化合物的合成
    中國塑料(2015年10期)2015-10-14 01:13:13
    聚砜包覆雙環(huán)戊二烯微膠囊的制備
    中國塑料(2015年9期)2015-10-14 01:12:21
    甲基環(huán)戊二烯的合成研究
    應用化工(2014年1期)2014-08-16 13:34:08
    基于2-苯基-1H-1,3,7,8-四-氮雜環(huán)戊二烯并[l]菲的Pb(Ⅱ)、Co(Ⅱ)配合物的晶體結(jié)構(gòu)與發(fā)光
    微波輻射一鍋法合成N-(4-芳基噻唑-2-基)-腙類化合物
    亚洲一级一片aⅴ在线观看| 性色av一级| 国产色爽女视频免费观看| 黄色配什么色好看| 国产精品无大码| 国国产精品蜜臀av免费| 国产黄色视频一区二区在线观看| 成人美女网站在线观看视频| 欧美最新免费一区二区三区| 99热网站在线观看| 91久久精品国产一区二区成人| 亚洲欧美清纯卡通| 亚洲av免费高清在线观看| 一本一本综合久久| 五月天丁香电影| 国产 精品1| 日韩 亚洲 欧美在线| 人妻人人澡人人爽人人| 国产免费一区二区三区四区乱码| 久久99热这里只频精品6学生| 视频中文字幕在线观看| 一级毛片久久久久久久久女| 国产高清国产精品国产三级| 亚洲一级一片aⅴ在线观看| 青春草亚洲视频在线观看| 精品一区二区三区视频在线| 午夜免费观看性视频| 欧美最新免费一区二区三区| 国产欧美另类精品又又久久亚洲欧美| 久久久久网色| 男女无遮挡免费网站观看| 中文字幕人妻丝袜制服| 亚洲av福利一区| 国产在视频线精品| 又黄又爽又刺激的免费视频.| 亚洲成人av在线免费| 免费播放大片免费观看视频在线观看| 亚洲高清免费不卡视频| tube8黄色片| 九九在线视频观看精品| 国产亚洲91精品色在线| 欧美精品亚洲一区二区| 国产日韩欧美在线精品| 日韩一本色道免费dvd| 精品久久久久久久久av| 久久久久网色| 日韩一区二区视频免费看| 高清黄色对白视频在线免费看 | 最近的中文字幕免费完整| 亚洲国产毛片av蜜桃av| 日韩欧美 国产精品| 一级片'在线观看视频| 免费观看的影片在线观看| 伊人久久国产一区二区| 插逼视频在线观看| 99久久中文字幕三级久久日本| 热re99久久国产66热| 成年av动漫网址| 国产成人精品福利久久| 国产精品国产三级国产av玫瑰| 精品久久久精品久久久| 精品亚洲成a人片在线观看| 夫妻性生交免费视频一级片| 一级片'在线观看视频| 亚洲欧美中文字幕日韩二区| 日韩成人伦理影院| 最黄视频免费看| 国产高清有码在线观看视频| 新久久久久国产一级毛片| 精品酒店卫生间| 国产男女内射视频| 国产乱来视频区| 亚洲精华国产精华液的使用体验| 婷婷色综合大香蕉| 精品久久久精品久久久| 亚洲三级黄色毛片| 国产精品成人在线| 国产高清有码在线观看视频| 国产高清三级在线| 亚洲国产精品一区二区三区在线| 日韩强制内射视频| 欧美成人精品欧美一级黄| 欧美日本中文国产一区发布| 日韩制服骚丝袜av| 美女cb高潮喷水在线观看| 日本91视频免费播放| 国产探花极品一区二区| 亚洲欧美成人精品一区二区| 女性被躁到高潮视频| a级毛色黄片| 亚洲欧美日韩另类电影网站| 一级毛片 在线播放| 久久久久久久久大av| 国产亚洲午夜精品一区二区久久| 久久午夜综合久久蜜桃| 简卡轻食公司| 夜夜爽夜夜爽视频| 国产熟女欧美一区二区| 中文欧美无线码| 国产成人免费观看mmmm| 美女xxoo啪啪120秒动态图| 一级黄片播放器| 又黄又爽又刺激的免费视频.| 国产伦理片在线播放av一区| 中文字幕人妻丝袜制服| 91午夜精品亚洲一区二区三区| av在线观看视频网站免费| 日本wwww免费看| 最近手机中文字幕大全| 久久久欧美国产精品| 91aial.com中文字幕在线观看| 最近中文字幕高清免费大全6| 女的被弄到高潮叫床怎么办| 国产有黄有色有爽视频| 国产亚洲最大av| 99热这里只有是精品在线观看| 国产一区二区三区综合在线观看 | 国产成人一区二区在线| 少妇人妻久久综合中文| 亚洲四区av| 久久精品熟女亚洲av麻豆精品| 亚洲精品乱码久久久久久按摩| 久久影院123| 欧美成人精品欧美一级黄| 欧美最新免费一区二区三区| 五月伊人婷婷丁香| 成人影院久久| 欧美 亚洲 国产 日韩一| 另类精品久久| 九草在线视频观看| 如日韩欧美国产精品一区二区三区 | 精品一品国产午夜福利视频| 一级毛片黄色毛片免费观看视频| 男女无遮挡免费网站观看| 美女视频免费永久观看网站| 丝袜喷水一区| 内射极品少妇av片p| 欧美区成人在线视频| 亚洲av中文av极速乱| 少妇被粗大猛烈的视频| 午夜免费鲁丝| 久久精品国产亚洲网站| 在线观看免费视频网站a站| 国产有黄有色有爽视频| 欧美bdsm另类| 日韩中文字幕视频在线看片| 久久青草综合色| 日日爽夜夜爽网站| 亚洲av免费高清在线观看| 免费看日本二区| 涩涩av久久男人的天堂| 国产探花极品一区二区| h日本视频在线播放| 亚洲精品久久久久久婷婷小说| 一区在线观看完整版| 国国产精品蜜臀av免费| 2021少妇久久久久久久久久久| 亚洲精品成人av观看孕妇| 观看av在线不卡| 大片电影免费在线观看免费| 亚洲精品日韩在线中文字幕| 国产在线免费精品| 天天操日日干夜夜撸| 午夜av观看不卡| 天美传媒精品一区二区| 亚洲精品456在线播放app| 久久精品国产亚洲av涩爱| 五月伊人婷婷丁香| 免费观看性生交大片5| 亚洲成人手机| 亚洲av在线观看美女高潮| 国产白丝娇喘喷水9色精品| 69精品国产乱码久久久| 国产免费视频播放在线视频| 亚洲精品中文字幕在线视频 | a级一级毛片免费在线观看| 一级毛片黄色毛片免费观看视频| 精品国产一区二区久久| av卡一久久| 成人二区视频| 人妻 亚洲 视频| 夜夜看夜夜爽夜夜摸| 少妇被粗大猛烈的视频| 天堂8中文在线网| 麻豆乱淫一区二区| 欧美激情国产日韩精品一区| 欧美bdsm另类| 好男人视频免费观看在线| 成人漫画全彩无遮挡| 国产视频内射| 国产成人freesex在线| 精华霜和精华液先用哪个| 亚洲,一卡二卡三卡| 国产精品久久久久久久久免| 人妻制服诱惑在线中文字幕| 精品国产乱码久久久久久小说| 在线观看美女被高潮喷水网站| 免费在线观看成人毛片| 国产精品不卡视频一区二区| 肉色欧美久久久久久久蜜桃| 大码成人一级视频| av不卡在线播放| 亚洲精品一区蜜桃| 欧美激情极品国产一区二区三区 | 99久久人妻综合| 国产探花极品一区二区| 日产精品乱码卡一卡2卡三| 狂野欧美激情性xxxx在线观看| 高清欧美精品videossex| 久久久久久久国产电影| 99re6热这里在线精品视频| 久久久久久久久久久久大奶| 国产成人精品婷婷| 五月天丁香电影| 日本欧美视频一区| 国产熟女欧美一区二区| 极品人妻少妇av视频| 亚洲国产最新在线播放| 特大巨黑吊av在线直播| 少妇高潮的动态图| 久久99精品国语久久久| 国产精品一区二区在线不卡| 乱系列少妇在线播放| 久久国产精品男人的天堂亚洲 | 六月丁香七月| 国产69精品久久久久777片| 久久这里有精品视频免费| 久久人妻熟女aⅴ| 一本色道久久久久久精品综合| 一级毛片我不卡| 中文字幕免费在线视频6| 国产探花极品一区二区| 中文欧美无线码| 成人漫画全彩无遮挡| 国产精品一二三区在线看| 久久久欧美国产精品| 免费人妻精品一区二区三区视频| 伦理电影免费视频| 国产日韩欧美视频二区| 亚洲精品一二三| 亚洲精品视频女| av一本久久久久| 涩涩av久久男人的天堂| 成人国产麻豆网| 97精品久久久久久久久久精品| 夫妻性生交免费视频一级片| 高清不卡的av网站| 尾随美女入室| 免费不卡的大黄色大毛片视频在线观看| 国产69精品久久久久777片| 寂寞人妻少妇视频99o| av国产精品久久久久影院| 午夜免费观看性视频| 日本色播在线视频| 国产综合精华液| 久久久久视频综合| 最后的刺客免费高清国语| 一个人免费看片子| 夫妻性生交免费视频一级片| 女人精品久久久久毛片| 嫩草影院入口| 蜜桃久久精品国产亚洲av| 欧美日韩一区二区视频在线观看视频在线| 亚洲一级一片aⅴ在线观看| 色婷婷久久久亚洲欧美| 国产色婷婷99| 91久久精品电影网| 一级毛片电影观看| 一级av片app| 国产在线免费精品| 国产成人91sexporn| 老司机亚洲免费影院| 国产亚洲av片在线观看秒播厂| 成年美女黄网站色视频大全免费 | 国产一区亚洲一区在线观看| 99久久人妻综合| 在线观看免费日韩欧美大片 | 国产欧美日韩精品一区二区| 亚洲av福利一区| 久久精品国产鲁丝片午夜精品| 亚洲熟女精品中文字幕| 丰满饥渴人妻一区二区三| 两个人的视频大全免费| 美女cb高潮喷水在线观看| 五月开心婷婷网| 亚洲国产精品一区三区| 免费人成在线观看视频色| 99热网站在线观看| 十八禁高潮呻吟视频 | 亚洲第一av免费看| 黑人高潮一二区| 久久精品国产a三级三级三级| 91aial.com中文字幕在线观看| 亚洲欧美一区二区三区国产| 永久免费av网站大全| 99九九在线精品视频 | 99久久精品国产国产毛片| 久久这里有精品视频免费| 久久人妻熟女aⅴ| 麻豆成人av视频| 久久热精品热| 国产日韩一区二区三区精品不卡 | 成人特级av手机在线观看| 久热久热在线精品观看| 国产精品一区二区三区四区免费观看| 亚洲av.av天堂| 欧美日韩av久久| 人人妻人人看人人澡| 亚洲美女黄色视频免费看| 日日爽夜夜爽网站| av在线app专区| 国产女主播在线喷水免费视频网站| 男女边吃奶边做爰视频| 国产精品久久久久久精品古装| 人人妻人人澡人人爽人人夜夜| 人人妻人人澡人人看| 能在线免费看毛片的网站| 女的被弄到高潮叫床怎么办| h日本视频在线播放| 国产成人精品婷婷| 蜜臀久久99精品久久宅男| 91久久精品国产一区二区成人| 高清在线视频一区二区三区| 成人毛片60女人毛片免费| 久久午夜综合久久蜜桃| 三上悠亚av全集在线观看 | 噜噜噜噜噜久久久久久91| 在线观看www视频免费| 欧美日本中文国产一区发布| 国产欧美日韩综合在线一区二区 | 免费黄网站久久成人精品| 黑丝袜美女国产一区| 视频区图区小说| 91在线精品国自产拍蜜月| 内地一区二区视频在线| 美女脱内裤让男人舔精品视频| 国产一区亚洲一区在线观看| 国产 精品1| 九草在线视频观看| 黑人高潮一二区| 久久久久国产精品人妻一区二区| 国产伦在线观看视频一区| 少妇人妻 视频| 老司机亚洲免费影院| 尾随美女入室| 日本wwww免费看| 亚洲欧美一区二区三区国产| 精品少妇黑人巨大在线播放| 观看美女的网站| 亚洲性久久影院| 成人漫画全彩无遮挡| kizo精华| 综合色丁香网| 黄色配什么色好看| 嫩草影院入口| 在线天堂最新版资源| videossex国产| 日韩熟女老妇一区二区性免费视频| 日本爱情动作片www.在线观看| 国产精品99久久久久久久久| 久久久久久久精品精品| 亚洲欧美日韩东京热| 精品少妇久久久久久888优播| 亚洲久久久国产精品| 成人漫画全彩无遮挡| 国产精品不卡视频一区二区| 欧美日韩视频高清一区二区三区二| 80岁老熟妇乱子伦牲交| 中国国产av一级| 国产精品人妻久久久久久| 亚洲精品国产色婷婷电影| 免费看不卡的av| 噜噜噜噜噜久久久久久91| 欧美高清成人免费视频www| 亚洲欧洲精品一区二区精品久久久 | 欧美3d第一页| 国产一区二区在线观看日韩| 亚洲不卡免费看| 草草在线视频免费看| 亚洲美女搞黄在线观看| 十分钟在线观看高清视频www | 3wmmmm亚洲av在线观看| 自线自在国产av| 精品国产一区二区久久| 一个人免费看片子| 2018国产大陆天天弄谢| 午夜免费观看性视频| 十分钟在线观看高清视频www | 国产在线视频一区二区| 五月玫瑰六月丁香| 国产91av在线免费观看| 寂寞人妻少妇视频99o| 久久韩国三级中文字幕| 伊人久久国产一区二区| 亚洲精品aⅴ在线观看| 在线观看美女被高潮喷水网站| 亚洲av成人精品一区久久| 免费观看a级毛片全部| 久久久久精品性色| 女性生殖器流出的白浆| 国产精品一区二区在线不卡| av在线老鸭窝| 精华霜和精华液先用哪个| 狂野欧美激情性bbbbbb| 国产av码专区亚洲av| av在线播放精品| 国产又色又爽无遮挡免| 丰满人妻一区二区三区视频av| 国产无遮挡羞羞视频在线观看| 三级国产精品欧美在线观看| 在线观看免费高清a一片| 午夜免费男女啪啪视频观看| 18禁裸乳无遮挡动漫免费视频| 在现免费观看毛片| 精品卡一卡二卡四卡免费| 久久狼人影院| 91aial.com中文字幕在线观看| 午夜老司机福利剧场| 午夜福利,免费看| 777米奇影视久久| 亚洲精品国产av蜜桃| 日韩av不卡免费在线播放| 日韩欧美精品免费久久| 亚洲国产精品一区二区三区在线| 99热6这里只有精品| 街头女战士在线观看网站| 18禁动态无遮挡网站| www.色视频.com| 日本欧美视频一区| 在线观看国产h片| 人妻制服诱惑在线中文字幕| 亚洲综合精品二区| a级毛片在线看网站| 韩国高清视频一区二区三区| 亚洲av成人精品一二三区| 丝袜喷水一区| 精品久久国产蜜桃| 一个人看视频在线观看www免费| av卡一久久| 精品熟女少妇av免费看| 秋霞在线观看毛片| 3wmmmm亚洲av在线观看| 国产精品麻豆人妻色哟哟久久| 九色成人免费人妻av| 久久亚洲国产成人精品v| 久久青草综合色| 成人亚洲欧美一区二区av| 女性被躁到高潮视频| 亚洲精品乱码久久久久久按摩| 热re99久久精品国产66热6| 人人妻人人澡人人看| av在线老鸭窝| 国产高清国产精品国产三级| 女性生殖器流出的白浆| 日韩亚洲欧美综合| 在线观看免费日韩欧美大片 | 久久久久久久亚洲中文字幕| 亚洲精品国产色婷婷电影| 精品人妻熟女毛片av久久网站| 在线观看人妻少妇| 3wmmmm亚洲av在线观看| 亚洲精品中文字幕在线视频 | 日日摸夜夜添夜夜爱| 亚洲在久久综合| 偷拍熟女少妇极品色| 麻豆成人av视频| 欧美日韩视频高清一区二区三区二| 久久这里有精品视频免费| 菩萨蛮人人尽说江南好唐韦庄| 中文字幕免费在线视频6| 3wmmmm亚洲av在线观看| 如何舔出高潮| av播播在线观看一区| 天堂俺去俺来也www色官网| 亚洲欧美精品专区久久| 欧美丝袜亚洲另类| 免费人妻精品一区二区三区视频| 精品人妻熟女av久视频| 天堂中文最新版在线下载| 美女福利国产在线| 国产精品久久久久久久久免| 日韩av在线免费看完整版不卡| 亚洲精品日本国产第一区| 国产成人精品久久久久久| 国产精品嫩草影院av在线观看| 精品熟女少妇av免费看| 亚洲国产最新在线播放| 国产男女超爽视频在线观看| 午夜91福利影院| av天堂中文字幕网| 在线观看免费高清a一片| 欧美日本中文国产一区发布| 久久久久久久精品精品| 亚洲性久久影院| 青青草视频在线视频观看| 亚洲,欧美,日韩| 天美传媒精品一区二区| 亚洲国产精品999| 丰满迷人的少妇在线观看| 国产成人午夜福利电影在线观看| √禁漫天堂资源中文www| 99久久精品一区二区三区| 自拍欧美九色日韩亚洲蝌蚪91 | 精品一区二区免费观看| 黑人巨大精品欧美一区二区蜜桃 | 日韩精品免费视频一区二区三区 | 亚洲av不卡在线观看| 国产精品国产三级专区第一集| 亚洲人与动物交配视频| 伊人亚洲综合成人网| av女优亚洲男人天堂| 肉色欧美久久久久久久蜜桃| 最后的刺客免费高清国语| 亚洲成人av在线免费| 嫩草影院入口| av有码第一页| 啦啦啦中文免费视频观看日本| 成年人免费黄色播放视频 | 国产深夜福利视频在线观看| 国产女主播在线喷水免费视频网站| 男人和女人高潮做爰伦理| 国产免费一级a男人的天堂| 日韩亚洲欧美综合| 永久免费av网站大全| 欧美精品亚洲一区二区| 亚洲av中文av极速乱| 99热这里只有是精品在线观看| 亚洲精品,欧美精品| 丰满饥渴人妻一区二区三| 国产 一区精品| 在线亚洲精品国产二区图片欧美 | 国产一区二区在线观看日韩| 美女视频免费永久观看网站| 69精品国产乱码久久久| 精品99又大又爽又粗少妇毛片| 日韩精品有码人妻一区| 亚洲美女搞黄在线观看| 亚洲av.av天堂| 国产精品麻豆人妻色哟哟久久| 爱豆传媒免费全集在线观看| 国产色婷婷99| 国产精品欧美亚洲77777| 亚洲人成网站在线观看播放| 精品一区在线观看国产| 亚洲精品一二三| 人人澡人人妻人| 国产一区二区三区综合在线观看 | 国产精品.久久久| 久久 成人 亚洲| 国产成人精品福利久久| 热re99久久国产66热| 国产有黄有色有爽视频| 我要看黄色一级片免费的| 成人毛片60女人毛片免费| 亚洲欧美中文字幕日韩二区| a级毛片在线看网站| 99热这里只有是精品在线观看| 如日韩欧美国产精品一区二区三区 | 欧美日韩精品成人综合77777| 三上悠亚av全集在线观看 | 成年av动漫网址| 免费播放大片免费观看视频在线观看| 熟女人妻精品中文字幕| 国产有黄有色有爽视频| 我要看黄色一级片免费的| 夫妻性生交免费视频一级片| 18禁在线播放成人免费| 人人妻人人看人人澡| 天堂8中文在线网| 九草在线视频观看| 成人无遮挡网站| 亚洲电影在线观看av| 国产精品熟女久久久久浪| 久久免费观看电影| 热re99久久精品国产66热6| 99热国产这里只有精品6| 精品人妻一区二区三区麻豆| 亚洲国产欧美在线一区| 少妇的逼水好多| 校园人妻丝袜中文字幕| 久久久国产精品麻豆| 国产成人a∨麻豆精品| 久久久久久久久久久免费av| 日韩免费高清中文字幕av| 成人毛片a级毛片在线播放| 国产精品国产三级国产专区5o| 如日韩欧美国产精品一区二区三区 | 日本wwww免费看| 国产色爽女视频免费观看| 欧美国产精品一级二级三级 | 我要看日韩黄色一级片| 内射极品少妇av片p| av国产久精品久网站免费入址| av.在线天堂| 97精品久久久久久久久久精品| 久久99蜜桃精品久久| 欧美日韩亚洲高清精品| 久久久久久久久大av| 日韩精品免费视频一区二区三区 | 欧美97在线视频| 国产日韩一区二区三区精品不卡 | 伊人久久国产一区二区| 国产日韩一区二区三区精品不卡 | av播播在线观看一区| 亚洲三级黄色毛片| 精品卡一卡二卡四卡免费| 国产精品无大码| 日韩欧美一区视频在线观看 | 国产黄色免费在线视频| 少妇精品久久久久久久| 天堂8中文在线网| 精品人妻偷拍中文字幕| 免费黄频网站在线观看国产| 啦啦啦视频在线资源免费观看| 亚洲精品久久久久久婷婷小说|