Chlorobenzene_Introduction

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33546氯苯

氯苯1.标识中文名氯苯；一氯代苯英文名 chlorobenzene；monochlorobenzene分子式 C6H5CI相对分子质量 112.56CAS号 108—90—7危险性类别第3.3类高闪点易燃液体化学类别卤代芳烃2.主要组成与性状主要成分纯品外观与性状无色透明液体，具有不愉快的苦杏仁味。

主要用途作为有机合成的重要原料。

3.健康危害侵入途径吸入、食入、经皮吸收。

健康危害对中枢神经系统有抑制和麻醉作用；对皮肤和粘膜有刺激性。

急性中毒：接触高浓度可引起麻醉症状，甚至昏迷。

脱离现场，积极救治后，可较快恢复，但数日内仍有头痛、头晕、无力、食欲减退等症状。

液体对皮肤有轻度刺激性，但反复接触，则起红斑或有轻度浅表性坏死。

慢性中毒：常有眼痛、流泪、结膜充血；早期有头痛、失眠、记忆力减退等神经衰弱症状，重者引起中毒性肝炎，个别可发生肾脏损害。

5.急救措施皮肤接触脱去被污染的衣着，用肥皂水和清水彻底冲洗皮肤。

眼睛接触提起眼睑，用流动清水或生理盐水冲洗，就医。

吸入迅速脱离现场至空气新鲜处。

保持呼吸道通畅。

如呼吸困难，给输氧。

如呼吸停止，立即进行人工呼吸。

就医。

食入饮足量温水，催吐，就医。

5.燃爆特性与消防燃烧性易燃闪点(℃) 28爆炸下限(％) 1.3 引燃温度(℃) 590爆炸上限(％) 9.6最小点火能(mJ) 无资料最大爆炸压力(MPa) 0.560危险特性易燃，遇明火、高热或与氧化剂接触，有引起燃烧爆炸的危险。

与过氯酸银、二甲亚砜反应剧烈。

灭火方法喷水冷却容器，可能的话将容器从火场移至空旷处。

灭火剂：雾状水、泡沫、干粉、二氧化碳、砂土。

6.泄漏应急处理迅速撤离泄漏污染区人员至安全区，并进行隔离，严格限制出入。

切断火源。

建议应急处理人员戴自给正压式呼吸器，穿消防防护服。

尽可能切断泄漏源，防止进入下水道、排洪沟等限制性空间。

小量泄漏：用砂土或其它不燃材料吸附或吸收。

也可以用不燃性分散剂制成的乳液刷洗，洗液稀释后放人废水系统。

酰化-09

氨化剂：氨以及非位阻胺
构型保持
利用甲醇乙醇的挥发性促进反应的进行
• 碱催化
• 常用的碱：醇钠、氨基钠、氢化钠、丁基鋰等 • 活性酯使反应易进行：对硝基苯酯、异丙烯酯、氰基甲酯
• Lewis酸催化反应：AlCl3、S代光气：碳酸二甲酯、双光气、三光气
O RNH2 + CH3O C OCH3 O O RNH C OCH3 + RNH C NHR 热分解 RN
酰基：RCOO HO O H O R O O R S O O HO S O
酰基
O HO P OH O HO P O P
磺酰基 or 硫酰基磷酰基
ArOH
ArOCOR'
ROH
O- Acylation， ROCOR' 酯化反应 S- Acylation
RSH
R3CH
RSCOR'
R3C
COR' C- Acylation，
杂多酸有很强的活性（与硫酸相近，左右，温度可高可低），产品的色泽要好些。缺点是杂多酸溶于醇等，（水，有机），难回收。因此对附载型研究较多。
活性炭 Al2O3 SiO 2 分子筛阳离子交换树脂膨润土等
载体
3）强酸性离子交换树脂（-SO3H）条件温和，选择性好，后处理简单，可循环使用，但活性弱。一般以固定床反应（塔式）
碱 3
11. 2. 4 用酰胺的N-酰化
(1 ) 用尿素的N-酰化简单易得，代替光气
O NH2 + H2N O NH C NH2 + C NH2 + HCl O NH C NH + NH4Cl
(2) 用甲酰胺的N-酰化
O NH2 + H2N C H O NH C H + NH3

清华大学有机合成课件

----Preparation of Alkene---1. Dehydrohalogenation of alkyl halide C C H X
Ease of dehydrohalogenayion of alkyl halides 3o>2o>1o alcohol
+ KOH
C C
+ KX + H2O
Examples: Cl + CH3CHCH2CH3 + CH3CH2CH2CH2Cl AlCl3 CH3 C CH2CH3
chief product
CH2CH2CH2CH3
2. Conversion of side chain O R
Zn(Hg)n, HCl or N2H4, base
CH2R Clemmensen or
----Preparation of Alkylbenzene---1. Friedel-Crafts alkylation + R X
Lewis acid
R + HX
R may rearrange
Lewis acid: AlCl3, BF3, HF, etc. Ar X cannot be used in place of R X
C C OH OH
syn-Hydroxylation
C C
RCO2OH
C O
C
H2O,H+
C OH
OH C
ห้องสมุดไป่ตู้
anti-Hydroxylation
6. Aldol condensation 7. Reduction of carbonyl compounds 8. Reduction of acid and esters

2-4-二硝基氯苯合成

绿色硝化技术合成 2,4-二硝基氯苯
胡衍甜，吕早生，孙昱，唐月娇，严莉（武汉科技大学化学工程与技术学院，湖北武汉 430081）
摘要本文主要介绍采用绿色硝化体系 N2O5/HNO3,以对氯硝基苯为原料,制备 2,4-二硝基氯苯。首先通过单因素实验，确定了各因素的最佳条件，然后通过正交实验找到了优化的工艺条件为：当对氯硝基苯为 5g 时， N2O5 浓度为 0.3g/ml(N2O53g，HNO310ml)，反应温度为 50℃，反应时间为 70min，此时， 2，4-二硝基氯苯的产率能达到 96.73%，纯度为 100%。关键词对氯硝基苯；N2O5/HNO3；2，4-二硝基氯苯
10
8
6
4
2
0
0
10
20
30
40
50
60
70
温度/℃
图 3.2 反应温度对产量的影响 Fig.3.2 Effect of reaction temperature on the yiled 从图中我们可以看出，在 50℃内，产物的量随着温度的升高而升高，超过
50℃后，产物的量随着温度的升高而减少。说明当温度超过 50℃时，N2O5开始分解，体系的硝化能力减弱。因此，最佳的反应温度为 50℃。 3.3 N O 浓度对 2，4-二硝基氯苯产量的影响
Table 1 Factors and levels
反应时间/min 70
反应温度/℃ 45
N O 浓度（g/ml）
25
0.25
80
50
0.3
90
55
0.35
表 1 的正交实验方案的实验结果如表 2
表 2 正交实验结果

氮杂环卡宾

N‑Heterocyclic Carbene-Palladium(II)-1-Methylimidazole Complex-Catalyzed Direct C−H Bond Arylation of(Benz)imidazoles with Aryl ChloridesZheng-Song Gu,†Wen-Xin Chen,†and Li-Xiong Shao*,†,‡†College of Chemistry and Materials Engineering,Wenzhou University,Chashan University Town,Wenzhou,Zhejiang Province 325035,People’s Republic of China‡College of Chemistry and Life Sciences,Zhejiang Normal University,Jinhua,Zhejiang Province321004,People’s Republic of China *Supporting InformationINTRODUCTIONC2-arylated(benz)imidazoles are frequently found in various pharmaceuticals,biologically active compounds and materials.1 Recently,the transition metal-catalyzed direct C−H bond arylation of(benz)imidazoles has been noticed as a potentially more eﬃcient and convenient alternative for the straightfor-ward synthesis of such compounds.2However,during the past years,the scope of the arylating reagents is limited to the more active aryl iodides and bromides.3To the best of our knowledge,only very few examples on the palladium-catalyzed direct C2-arylation of(benz)imidazoles using aryl chlorides in the presence of phosphine ligands were reported to date, despite their lower cost and more easy availability.4Therefore, despite that some progress has been made in the direct C2-arylation of(benz)imidazoles,the research for eﬃcient methods using the more applicable,while less active,aryl chlorides as the arylating reagents is still in great demand.5 Previously,we have reported that a well-deﬁned N-heterocyclic carbene-Pd(II)-1-methylimidazole[NHC-Pd(II)-Im]complex 1can easily activate aryl chlorides in traditional C−C couplings such asα-arylation of carbonyl compounds,6Suzuki−Miyaura coupling,7Mizoroki−Heck reaction,8Hiyama reaction9and C−N coupling.10Furthermore,in a very recent communication,we found that NHC-Pd(II)-Im complex1can also eﬃciently catalyze the direct C−H bond arylation of(benzo)oxazoles using aryl chlorides as the arylating reagents.11These results thus prompted us to further investigate its application in activating aryl chlorides toward the direct C2-arylation of (benz)imidazoles.Herein,we report these results in detail.■RESULTS AND DISCUSSIONInitially,1-methylbenzimidazole2a(0.49mmol)was chosen as the model substrate for the reaction with chlorobenzene3a(2.0equiv)in the presence of NHC-Pd(II)-Im complex1(2.0mol%)under various conditions.For example,in theﬁrst round, toluene/H2O(2.0mL/0.5equiv)was chosen as the solvents to evaluate the eﬀect of bases.The best result was achieved usingKO t Bu as the base to give the desired product4a in89%yield (Table1,entry6),while in the presence of other bases such asK2CO3,KOH,K3PO4·3H2O,LiO t Bu and NaO t Bu,almost no product could be detected(Table1,entries1−5).The replacement of solvents from toluene/H2O to THF/H2O anddioxane/H2O resulted in product4a only being isolated in48 and40%yields,respectively(Table1,entries7and8).In addition,in the presence of other solvents such as DMSO/ H2O,DMF/H2O,CH3CN/H2O and DME/H2O,no desired product could be detected(Table1,entries9−12). Furthermore,after careful investigations,it was found that the amount of H2O dramatically aﬀected the reaction.That is,the introduction of0.5equiv of H2O was found to be necessary for such transformation.For instance,only18%yield of product4a was obtained when dry toluene was used as the solvent(Table 1,entry13).When1.0equiv of H2O was added,a signiﬁcantly higher yield(84%)was achieved(Table1,entry14).However, when the amount of H2O was increased to3.0equiv,the yield of4a drastically decreased to5%(Table1,entry15).These results thus encouraged us to further investigate the eﬀect of H2O.It is known that KO t Bu will be partially hydrolyzed to KOHand HO t Bu under the above reaction conditions.Therefore, three more control experiments were carried out:(1)the combination of KO t Bu(1.5equiv),KOH(0.5equiv)and HO t Bu(0.5equiv)was introduced instead of KO t Bu(2.0Received:May9,2014Published:May28,2014©2014American Chemical /10.1021/jo5010058|.Chem.2014,79,5806−5811equiv)and H 2O (0.5equiv),and product 4a was obtained in a comparable yield (84%)(Table 1,entry 6and Scheme 1,eq 1);(2)the combination of KO t Bu (1.5equiv)and HO t Bu (0.5equiv)was introduced,and product 4a was also formed in a comparable yield (82%)(Table 1,entry 6and Scheme 1,eq 2);(3)the combination of KO t Bu (1.0equiv)and HO t Bu (1.0equiv)was introduced,and a similar yield of product 4a was observed (84%)(Table 1,entry 14and Scheme 1,eq 3).On the basis of these results,although the real function of H 2O was unclear at this stage,it could be inferred that when a combination of toluene and H 2O was used as the solvent,HO t Bu derived from the hydrolysis of KO t Bu might play an important role in such transformation.12We next explored the scope of the C2-arylation of 1-methylbenzimidazole 2a with a variety of aryl chlorides 3under the identical optimal experimental conditions.Under the suitable conditions,the procedure proved to be general on all substrates tested (Table 2).It seems that the substituents on the aryl chlorides 3a ﬀected the reactions to some extent.For example,for the reaction involving sterically hindered 2-methylphenyl chloride 3d ,good yields are obtained by simplyincreasing the catalyst loading,although only moderate yield can be obtained under the optimal reaction conditions (Table 2,entries 3and 4).For electron-rich aryl chlorides such as 4-methoxyphenyl chloride 3e and 4-dimethylaminophenyl chloride 3g ,slightly higher catalyst loading or elevated temperature is necessary for the achievement of higher yields (Table 2,entries 5and 6;entries 8and 9).In addition,heteroaryl chlorides such as 2-chloropyridine 3k and 2-chlorothiophene 3l could be used,giving rise to the desired products 4k and 4l in acceptable yields,respectively (Table 2,entries 13and 14).The reaction was further investigated using a variety of benzimidazoles 2and aryl chlorides 3as the substrates under the optimal conditions.As can be seen from Table 3,all 1-methylbenzimidazoles 2,regardless of electron-rich substituents such as 5,6-Me 2(2b ),5-Me (2c ),5-MeO (2e )or electron-poor substituents such as 5-F (2d )attaching on the phenyl groups,could react with aryl chlorides 3smoothly to give the desired C2-arylated products 4in good to high yields (Table 3,entries 1−17).In addition,it seems that for the reactions involving electron-poor 5-F-benzimidazole 2d ,better yields can be achieved under identical conditions (Table 3,entries 11−15).1-Benzylbenzimidazole 2f was also suitable for this reaction to give the corresponding products 4ad −4ag in good yields (Table 3,entries 18−21).Encouraged by the above results using benzimidazoles as the substrates,the optimal conditions were then expanded to theTable 1.Optimization for Complex 1Catalyzed Direct C −H Bond Arylation of 1-Methylbenzimidazole 2a with Chlorobenzene 3aentry a solvent base yield (%)1toluene/H 2O K 2CO 3ND2toluene/H 2O KOH ND3toluene/H 2O K 3PO 43H 2O ND4toluene/H 2O LiO t Bu ND5toluene/H 2O NaO t Bu <56toluene/H 2O KO t Bu 897THF/H 2O KO t Bu 488dioxane/H 2O KO t Bu 409DMSO/H 2O KO t Bu ND10DMF/H 2O KO t Bu ND11CH 3CN/H 2O KO t Bu ND12DME/H 2O KO t Bu ND13toluene KO t Bu 1814b toluene/H 2O KO t Bu 8415c toluene/H 2O KO t Bu 5a If not otherwise speci ﬁed,all reactions were carried out using 2a (0.49mmol),3a (2.0equiv),base (2.0equiv),1(2.0mol %)in organic solvents (2.0mL)and H 2O (0.5equiv)at 120°C for 6h.b H 2O (1.0equiv)was added.c H 2O (3.0equiv)was added.Scheme 1.Three Control Experiments Table 2.NHC-Pd(II)-Im 1Catalyzed Direct C −H Bond Arylation of 1-Methylbenzimidazole 2a with Aryl Chlorides 3aIf not otherwise speci ﬁed,all reactions were carried out using 2a (0.49mmol),3(2.0equiv),1(X mol %),KO t Bu (2.0equiv)in toluene/H2O (2.0mL/0.5equiv)at 120°C for 6h.b The temperature was 130°C./10.1021/jo5010058|J.Org.Chem.2014,79,5806−58115807reactions between 1-methylimidazole and aryl chlorides.It was found that the ratio between two substrates dramatically a ﬀected the reaction.For example,when the reaction between 1-methylimidazole (0.49mmol)and chlorobenzene (2.0equiv)was carried out under the optimal conditions shown in Table 1,entry 6,the desired C2-arylated product was obtained only in 29%yield,along with the 2,5-diarylated byproduct in 8%yield.To our pleasure,subtly changing the ratio of the substrates will result in exclusive C2-arylated selectivity.For instance,when excess 1-methylimidazole (2.0equiv)was used as the substrate,the desired C2-arylated products could be achieved in good to high yields as the sole product under the optimal conditions.The results are shown in Table 4.It seems that substituents on the aryl chlorides have some e ﬀect on the reaction.For example,aryl chlorides having electron-rich groups such as 4-Me (3b )and 3-Me (3c )gave better yields than that having electron-neutral (3a )and electron-poor 4-F group (3i )(Table 4,entries 2and 3vs entries 1and 5).In addition,2-methylphenyl chloride 3d gave inferior result (74%),maybe partially due to its steric hindrance (Table 4,entry 4).■CONCLUSIONS In conclusion,NHC-Pd(II)-Im complex,as the nonphosphine complex,was ﬁrst used as the catalyst in the direct C −H bond arylation of (benz)imidazoles using the less expensive,less active,and easily available aryl chlorides as the arylating reagents.Under the optimal conditions,various (benz)-imidazoles can react with kinds of activated,unactivated,and deactivated aryl chlorides smoothly to give the desired C2-arylated products in good to high yields.13For instance,both substrates bearing electron-rich,-neutral,and -poor substituents are tolerated in such transformation.The NHC-Pd(II)complex catalyzed direct C −H bond arylation between (benz)imidazoles and aryl chlorides reported in this paper will become a good,economical,and e ﬃcient supplement to the traditional methods for the formation of 2-aryl (benz)imidazoles.■EXPERIMENTAL SECTIONGeneral Remarks.Melting points are uncorrected.NMR spectra wererecordedat 300/500(for 1H NMR)or 75/125MHz (for 13CNMR),respectively.1H NMR and 13C NMR spectra recorded inCDCl 3solutionswere referenced to TMS (0.00ppm)and the residual solvent peak (77.0ppm),respectively.J -values are in anic solvents used were dried by standard methods.The mass analyzer type for thehigh resolution mass spectra (HRMS,ESI)is quadrupole.Other commercially obtained reagents were used without further puri ﬁcation.Flash column chromatography was performed on silica gel.General Procedure for the NHC-Pd(II)-Im Complex 1Catalyzed Reactions Between (Benz)imidazoles and Aryl Chlorides.Under N 2atmosphere,KO t Bu (0.98mmol),NHC-Pd(II)-Im complex 1(0.0098mmol),toluene (2.0mL),H 2O (0.245mmol),benzimidazoles 2(0.49mmol)and aryl chlorides 3(0.98mmol)weresuccessivelyadded into a Schlenk reaction tube.Themixture wasstirred vigorously at 120°C for 6h.Then the solvent wasremoved under reduced pressure,and the residue was puri ﬁed by ﬂashchromatography (eluent:petroleum ether/ethyl acetate =10:1forbenzimidazole derivatives and 3:1for imidazole derivatives)to give thepure products pound 4a :3j white solid (90.7mg,89%);1H NMR (CDCl 3,300MHz,TMS)δ7.85−7.76(m,3H),7.57−7.52(m,3H),7.41−7.29(m,3H);13C{H}NMR (CDCl 3,75MHz)δ153.7,142.9,136.5,130.1,129.7,129.4,128.6,122.7,122.4,119.8,109.6,pound 4b :3j white solid (92.6mg,85%);1H NMR (CDCl 3,300MHz,TMS)δ7.85−7.80(m,1H),7.64(d,J =8.1Hz,2H),7.36−7.25(m,5H),3.80(s,3H),2.42(s,3H);13C{H}NMR (CDCl 3,75MHz)δ153.8,142.8,139.7,136.4,129.24,129.17,127.1,122.5,122.2,119.5,109.5,31.5,21.3.Compound 4c :3j white solid (94.0mg,86%);1H NMR (CDCl 3,500MHz,TMS)δ7.83−7.81(m,1H),7.60(s,1H),7.49(d,J =7.5Hz,1H),7.37(t,J =7.5Hz,1H),7.34−7.28(m,4H),3.79(s,3H),2.42(s,3H);13C{H}NMR (CDCl 3,75MHz)δ153.8,142.7,138.5,136.4,130.4,130.1,129.9,128.3,126.2,122.6,122.3,119.6,109.5,31.5,21.3.Compound 4d :14white solid(80.4mg,74%);1H NMR (CDCl 3,500MHz,TMS)δ7.84−7.82(m,1H),7.44−7.30(m,7H),3.63(s,3H),2.27(s,3H);13C{H}NMR (CDCl 3,75MHz)δ153.7,142.9,Table 3.NHC-Pd(II)-Im 1Catalyzed Direct C −H Bond Arylation of Benzimidazoles 2with Aryl Chlorides 3entry a 2(R 2/R 3)3(R 1)yield (%)12b (5,6-Me 2/Me)3a (H)4m ,8722b 3b (4-Me)4n ,843b 2b 3e (4-OMe)4o ,8242b 3i (4-F)4p ,865b 2b 3j (4-vinyl)4q ,8462c (5-Me/Me)3a 4r ,8672c 3b 4s ,858b 2c 3e 4t ,8492c 3i 4u ,8810b 2c 3j 4v ,86112d (5-F/Me)3a 4w ,97122d 3b 4x ,96132d 3e 4y ,86142d 3i 4z ,96152d 3j 4aa ,88162e (5-OMe/Me)3a 4ab ,86172e 3b 4ac ,84182f (H/benzyl)3a 4ad ,84192f 3b 4ae ,8520b 2f 3e 4af ,82212f 3j 4ag ,84a If not otherwise speci ﬁed,all reactions were carried out using 2a (0.49mmol),3(2.0equiv),1(2.0mol %),KO tBu (2.0equiv)in toluene/H 2O (2.0mL/0.5equiv)at 120°C for 6h.b NHC-Pd(II)-Im 1(3.0mol %)was added.Table 4.NHC-Pd(II)-Im 1Catalyzed Direct C −H Bond Arylation of 1-Methylimidazole 5with Aryl Chlorides 3entry a 3(R 1)[X]t (°C)yield (%)13a (H)21204ah ,8623b (4-Me)31404ai ,9933c (3-Me)31304aj ,9743d (2-Me)41404ak ,7453i (4-F)41404al ,8463j (4-vinyl)31304am ,87a All reactions were carried out using 5(2.0equiv),3(0.75mmol),KO tBu (2.0equiv),1(X mol %)in toluene/H 2O (2.0mL/0.5equiv)for 12h./10.1021/jo5010058|J.Org.Chem.2014,79,5806−58115808137.9,135.5,130.4,130.2,129.9,129.8,125.7,122.5,122.2,119.8, 109.4,30.5,19.6.Compound4e:3j white solid(96.2mg,82%);1H NMR(CDCl3, 300MHz,TMS)δ7.82−7.78(m,1H),7.72(d,J=7.5Hz,2H), 7.40−7.29(m,3H),7.05(d,J=7.5Hz,2H),3.89(s,3H),3.86(s, 3H);13C{H}NMR(CDCl3,75MHz)δ160.6,153.6,142.8,136.5, 130.7,122.38,122.37,122.2,119.4,114.0,109.4,55.3,31.6. Compound4f:15white solid(96.8mg,83%);1H NMR(CDCl3, 500MHz,TMS)δ7.84−7.82(m,1H),7.46−7.40(m,2H),7.34−7.30 (m,4H),7.07−7.05(m,1H),3.89(s,3H),3.88(s,3H);13C{H} NMR(CDCl3,75MHz)δ159.7,153.6,142.8,136.5,131.3,129.6, 122.8,122.4,121.6,119.8,115.9,114.6,109.6,55.4,31.7. Compound4g:16white solid(83.8mg,68%);1H NMR(CDCl3, 500MHz,TMS)δ7.80(dd,J=6.0,2.5Hz,1H),7.69(d,J=9.0Hz, 2H),7.35(dd,J=6.0,2.5Hz,1H),7.36−7.27(m,2H),6.81(d,J= 9.0Hz,2H),3.87(s,3H),3.05(s,6H);13C{H}NMR(CDCl3,75 MHz)δ154.6,151.0,143.0,136.6,130.3,121.94,121.91,119.1,117.2, 111.6,109.2,40.1,31.7.Compound4h:yellow liquid(107.2mg,87%);1H NMR(CDCl3, 300MHz,TMS)δ7.86−7.80(m,1H),7.39−7.28(m,4H),7.12−7.11 (m,1H),7.01−6.97(m,1H),6.87−6.83(m,1H),3.84(s,3H),3.01 (s,6H);13C{H}NMR(CDCl3,75MHz)δ154.7,150.6,142.8,136.5, 130.7,129.0,122.5,122.2,119.6,117.2,113.6,113.4,109.5,40.5,31.6; MS(ESI)252[M+H]+;HRMS(ESI)calcd for C16H18N3[M+H]+ 252.1495,found252.1506;IR(neat)ν2363,1607,1483,1436,1348, 1284,1242,1126,1062,990,956,845,776,737,695cm−1. Compound4i:17white solid(90.8mg,82%);1H NMR(CDCl3, 500MHz,TMS)δ7.82−7.80(m,1H),7.74(dd,J=8.5,5.0Hz,2H), 7.38−7.29(m,3H),7.21(t,J=8.5Hz,2H),3.82(s,3H);13C{H} NMR(CDCl3,125MHz)δ163.6(d,J C−F=249.0Hz),152.7,142.8, 136.5,131.3(d,J C−F=8.5Hz),130.2,126.3(d,J C−F=3.1Hz),123.8, 122.8,122.5,119.8,115.8(d,J C−F=21.6Hz),109.6,31.6. Compound4j:white solid(98.6mg,86%);mp116−117°C;1H NMR(CDCl3,300MHz,TMS)δ7.84−7.81(m,1H),7.71(d,J=8.1 Hz,2H),7.52(d,J=8.1Hz,2H),7.35−7.27(m,3H),6.75(dd,J= 17.7,10.8Hz,1H),5.84(d,J=17.7Hz,1H),5.34(d,J=10.8Hz, 1H),3.80(s,3H);13C{H}NMR(CDCl3,75MHz)δ153.1,142.3, 138.8,136.3,135.9,129.5,128.9,126.3,122.8,122.5,119.4,115.4, 109.6,31.6;MS(ESI)235[M+H]+;HRMS(ESI)calcd for C16H15N2[M+H]+235.1230,found235.1228;IR(neat)ν1630, 1464,1402,1377,1322,1250,993,909,851,821,760,745,738,702 cm−1.Compound4k:18white solid(57.5mg,56%);1H NMR(CDCl3, 300MHz,TMS)δ8.69−8.67(m,1H),8.38(d,J=8.1Hz,1H), 7.85−7.80(m,2H),7.44−7.28(m,4H),4.25(s,3H);13C{H}NMR (CDCl3,75MHz)δ150.5,150.2,148.5,142.3,137.2,136.8,124.7, 123.7,123.3,122.6,119.9,109.9,32.6.Compound4l:16white solid(61.0mg,58%);1H NMR(CDCl3, 300MHz,TMS)δ7.81−7.77(m,1H),7.57−7.55(m1H),7.51−7.49 (m,1H),7.35−7.26(m,3H),7.19−7.16(m,1H),3.94(s,3H);13C{H}NMR(CDCl3,75MHz)δ147.7,142.6,136.4,132.3,128.5,127.9,127.8,122.9,122.6,119.6,109.3,31.6.Compound4m:white solid(100.6mg,87%);mp171−172°C;1H NMR(CDCl3,300MHz,TMS)δ7.76−7.73(m,2H),7.57(s,1H), 7.54−7.47(m,3H),7.15(s,1H),3.81(s,3H),2.42(s,3H),2.40(s, 3H);13C{H}NMR(CDCl3,75MHz)δ152.9,141.5,135.2,131.9, 131.2,130.5,129.4,129.3,128.6,119.8,109.8,31.6,20.6,20.3;MS (ESI)237[M+H]+;HRMS(ESI)calcd for C16H17N2[M+H]+ 237.1386,found237.1402;IR(neat)ν1601,1534,1438,1381,1318, 1176,1020,1000,924,846,818,771,690cm−1.Compound4n:white solid(103.0mg,84%);mp122−123°C;1H NMR(CDCl3,300MHz,TMS)δ7.63(d,J=7.8Hz,2H),7.57(s, 1H),7.29(d,J=7.8Hz,2H),7.12(s,1H),3.77(s,3H),2.41(s,3H), 2.40(s,3H),2.38(s,3H);13C{H}NMR(CDCl3,75MHz)δ152.7, 140.6,139.7,134.8,131.9,131.3,129.25,129.18,126.9,119.3,109.8, 31.6,21.3,20.5,20.2;MS(ESI)251[M+H]+;HRMS(ESI)calcd for C17H19N2[M+H]+251.1543,found251.1552;IR(neat)ν1604, 1478,1461,1377,1323,1180,1140,1107,1014,871,850,819,729, 681cm−1.Compound4o:white solid(107.0mg,82%);mp147−148°C;1H NMR(CDCl3,300MHz,TMS)δ7.72(d,J=8.7Hz,2H),7.56(s, 1H),7.13(s,1H),7.01(d,J=8.7Hz,2H),3.86(s,3H),3.82(s,3H), 2.41(s,3H),2.38(s,3H);13C{H}NMR(CDCl3,75MHz)δ160.6, 153.0,141.5,135.2,131.6,131.0,130.7,122.9,119.6,114.0,109.7, 55.4,31.6,20.6,20.3;HRMS(ESI)calcd for C17H19N2O[M+H]+ 267.1492,found267.1495;IR(neat)ν1610,1481,1436,1382,1320, 1289,1242,1171,1022,875,831,792,750,717cm−1. Compound4p:white solid(107.0mg,86%);mp172−173°C;1H NMR(CDCl3,300MHz,TMS)δ7.74−7.68(m,2H),7.55(s,1H), 7.20−7.12(m,3H),3.77(s,3H),2.41(s,3H),2.38(s,3H);13C{H} NMR(CDCl3,75MHz)δ163.5(d,J C−F=248.8Hz),151.6,140.6, 134.8,132.2,131.6,131.3(d,J C−F=8.4Hz),130.2,126.0,123.5, 119.4,115.7(d,J C−F=21.7Hz),109.9,31.6,28.8,20.5,20.2;MS (ESI)255[M+H]+;HRMS(ESI)calcd for C16H15N2F[M+H]+ 255.1292,found255.1294;IR(neat)ν1607,1525,1436,1377,1318, 1219,1157,1003,837,809,730,706,674cm−1.Compound4q:white solid(107.9mg,84%);mp142−143°C;1H NMR(CDCl3,300MHz,TMS)δ7.74(d,J=8.4Hz,2H),7.58(s, 1H),7.53(d,J=8.4Hz,2H),7.15(s,1H),6.75(dd,J=17.4,11.1Hz, 1H),5.85(d,J=17.4Hz,1H),5.36(d,J=11.1Hz,1H),3.84(s,3H), 2.41(s,3H),2.38(s,3H);13C{H}NMR(CDCl3,75MHz)δ152.2, 140.7,138.7,136.0,134.9,132.1,131.5,129.4,129.0,126.3,119.4, 115.2,109.8,31.7,20.5,20.2;MS(ESI)263[M+H]+;HRMS(ESI) calcd for C18H19N2[M+H]+263.1543,found263.1545;IR(neat)ν1627,1461,1382,1323,1143,1059,1008,990,903,841,761,716, 686cm−1.Compound4r:white solid(93.6mg,86%);mp122−123°C;1H NMR(CDCl3,500MHz,TMS)δ7.73−7.71(m,2H),7.61(s,1H), 7.50−7.46(m,3H),7.22(d,J=8.0Hz,1H),7.12(d,J=8.0Hz,1H), 3.77(s,3H),2.49(s,3H);13C{H}NMR(CDCl3,125MHz)δ153.3, 142.6,134.4,132.0,129.8,129.5,129.2,128.5,124.2,119.2,109.1, 31.5,21.4;MS(ESI)223[M+H]+;HRMS(ESI)calcd for C15H15N2 [M+H]+223.1230,found223.1232;IR(neat)ν1494,1461,1372, 1322,1013,927,862,793,768,743,701,675cm−1.Compound4s:white solid(98.4mg,85%);mp118−119°C;1H NMR(CDCl3,300MHz,TMS)δ7.75(d,J=8.1Hz,2H),7.60(s, 1H),7.31(d,J=8.1Hz,2H),7.24(d,J=8.1Hz,1H),7.13(d,J=8.1 Hz,1H),3.81(s,3H),2.49(s,3H),2.42(s,3H);13C{H}NMR (CDCl3,75MHz)δ153.3,142.1,140.0,134.3,132.3,129.33,129.26, 126.6,124.3,119.0,109.1,31.7,21.5,21.4;MS(ESI)237[M+H]+; HRMS(ESI)calcd for C16H17N2[M+H]+237.1386,found 237.1401;IR(neat)ν1613,1475,1444,1377,1318,1020,878, 848,821,789,747,727cm−1.Compound4t:white solid(103.7mg,84%);mp105−106°C;1H NMR(CDCl3,300MHz,TMS)δ7.66(d,J=8.7Hz,2H),7.58(s, 1H),7.18(d,J=8.4Hz,1H),7.08(d,J=8.1Hz,1H),6.98(d,J=9.0 Hz,2H),3.82(s,3H),3.74(s,3H),2.48(s,3H);13C{H}NMR (CDCl3,75MHz)δ160.6,153.2,142.5,134.4,131.9130.6123.8, 122.1,118.9,113.9,108.9,55.2,31.5,21.4;MS(ESI)253[M+H]+; HRMS(ESI)calcd for C16H17N2O[M+H]+253.1335,found 253.1344;IR(neat)ν1607,1481,1464,1448,1385,1328,1179, 1245,1109,833,781,763,738,682cm−1.Compound4u:white solid(103.4mg,88%);mp129−130°C;1H NMR(CDCl3,300MHz,TMS)δ7.77−7.68(m,2H),7.58(s,1H), 7.27−7.11(m,4H),3.81(s,3H),2.49(s,3H);13C{H}NMR(CDCl3, 75MHz)δ163.6(d,J C−F=249.1Hz),152.3,142.2,134.3,132.5, 131.4(d,J C−F=8.5Hz),125.8,124.5,123.5,119.1,115.8(d,J C−F= 21.7Hz),109.2,31.6,28.8,21.5;MS(ESI)241[M+H]+;HRMS (ESI)calcd for C15H14N2F[M+H]+241.1136,found241.1132;IR (neat)ν1607,1537,1467,1381,1315,1235,1152,838,804,791,756, 733,682cm−1.Compound4v:white solid(104.5mg,86%);mp121−122°C;1H NMR(CDCl3,300MHz,TMS)δ7.68(d,J=8.1Hz,2H),7.60(s, 1H),7.49(d,J=8.1Hz,2H),7.19(d,J=8.4Hz,1H),7.10(d,J=8.4 Hz,1H),6.73(dd,J=17.7,10.8Hz,1H),5.82(d,J=17.7Hz,1H), 5.32(d,J=10.8Hz,1H),3.75(s,3H),2.48(s,3H);13C{H}NMR (CDCl3,75MHz)δ152.9,142.6,138.6,135.9,134.5,132.0,129.4, 129.0,126.2,124.2,119.1,115.2,109.0,31.6,21.4;MS(ESI)249[M +H]+;HRMS(ESI)calcd for C17H17N2[M+H]+249.1386,found/10.1021/jo5010058|.Chem.2014,79,5806−5811 5809249.1390;IR(neat)ν1621,1455,1382,1323,1250,1146,1059, 1017,985,899,843,791,739,686cm−1.Compound4w:white solid(107.5mg,97%);mp102−103°C;1H NMR(CDCl3,300MHz,TMS)δ7.73−7.70(m,2H),7.50−7.45(m, 4H),7.25−7.22(m,1H),7.02(td,J=9.0,2.4Hz,1H),3.80(s,3H);13C{H}NMR(CDCl3,75MHz)δ159.4(d,J C−F=236.0Hz),154.8,142.7(d,J C−F=12.6Hz),132.9,129.9,129.3(d,J C−F=19.1Hz), 128.6,111.1,110.7,109.9(d,J C−F=10.2Hz),105.1(d,J C−F=24.1 Hz),31.7;MS(ESI)227[M+H]+;HRMS(ESI)calcd for C14H12N2F[M+H]+227.0979,found227.0976;IR(neat)ν1621, 1593,1489,1472,1424,1374,1326,1143,1020,956,900,852,791, 776,751,702cm−1.Compound4x:a white solid(113.0mg,96%);mp117−118°C;1H NMR(CDCl3,300MHz,TMS)δ7.63(d,J=8.1Hz,2H),7.47(dd,J =9.3,2.4Hz,1H),7.33−7.25(m,3H),7.04(td,J=9.3,2.4Hz,1H), 3.83(s,3H),2.43(s,3H);13C{H}NMR(CDCl3,75MHz)δ159.5 (d,J C−F=236.3Hz),154.9,142.4,142.3,140.4,132.8,129.3(d,J C−F= 14.7Hz),126.3,111.2,110.8,110.0(d,J C−F=10.2Hz),105.0(d,J C−F =24.2Hz),31.8,21.4;MS(ESI)241[M+H]+;HRMS(ESI)calcd for C15H14N2F[M+H]+241.1136,found241.1147;IR(neat)ν1618, 1593,1483,1430,1382,1326,1242,1124,1014,955,855,828,803, 775,734,716cm−1.Compound4y:white solid(107.9mg,86%);mp105−106°C;1H NMR(CDCl3,300MHz,TMS)δ7.67(d,J=8.7Hz,2H),7.44(dd,J =9.0,2.4Hz,1H),7.23(dd,J=9.0,4.5Hz,1H),7.04−6.98(m,3H), 3.85(s,3H),3.80(s,3H);13C{H}NMR(CDCl3,75MHz)δ160.9, 159.4(d,J C−F=235.7Hz),154.8,142.6(d,J C−F=12.8Hz),132.8, 130.7,121.6,114.1,110.8,110.5,109.8(d,J C−F=10.2Hz),104.9(d, J C−F=24.1Hz),55.3,31.8;MS(ESI)257[M+H]+;HRMS(ESI) calcd for C15H14N2FO[M+H]+257.1085,found257.1098;IR(neat)ν1610,1481,1436,1334,1292,1242,1183,1115,1020,955,844, 826,796,778,741,716cm−1.Compound4z:a white solid(114.8mg,96%);mp124−125°C;1H NMR(CDCl3,300MHz,TMS)δ7.73(dd,J=8.4,5.4Hz,2H),7.45 (dd,J=9.3,2.4Hz,1H),7.29−7.18(m,3H),7.04(td,J=9.3,2.4Hz, 1H),3.82(s,3H);13C{H}NMR(CDCl3,75MHz)δ163.7(d,J C−F= 249.6Hz),159.5(d,J C−F=236.3Hz),153.9,142.6(d,J C−F=12.8 Hz),132.8,131.3(d,J C−F=8.5Hz),130.2,125.6(d,J C−F=3.2Hz), 115.9(d,J C−F=21.8Hz),111.3,111.0,110.0(d,J C−F=10.1Hz), 105.1(d,J C−F=24.1Hz),31.7;MS(ESI)245[M+H]+;HRMS (ESI)calcd for C14H11N2F2[M+H]+245.0885,found245.0895;IR (neat)ν1587,1483,1430,1388,1326,1233,1155,1121,1090,961, 850,803,733cm−1.Compound4aa:white solid(108.8mg,88%);mp144−145°C;1H NMR(CDCl3,300MHz,TMS)δ7.74(d,J=7.8Hz,2H),7.54(d,J =7.8Hz,2H),7.47(d,J=9.0Hz,1H),7.31(dd,J=9.0,4.5Hz,1H), 7.08(t,J=9.0Hz,1H),6.77(dd,J=17.4,10.8Hz,1H),5.87(d,J= 17.7Hz,1H),5.38(d,J=10.8Hz,1H),3.88(s,3H);13C{H}NMR (CDCl3,75MHz)δ159.4(d,J C−F=236.2Hz),154.5,142.7(d,J C−F =12.8Hz),139.0,135.8,132.9,129.4,128.6,126.4,115.5,111.0(d, J C−F=26.0Hz),109.9(d,J C−F=10.3Hz),105.1(d,J C−F=24.1Hz), 31.8;MS(ESI)252[M+H]+;HRMS(ESI)calcd for C16H14N2F[M +H]+253.1136,found253.1150;IR(neat)ν1624,1481,1438,1405, 1326,1273,1143,1000,959,909,895,851,803,738,712cm−1. Compound4ab:19white solid(100.4mg,86%);1H NMR(CDCl3, 300MHz,TMS)δ7.75−7.72(m,2H),7.53−7.47(m,3H),7.31(d,J =2.1Hz,1H),7.23(d,J=8.7Hz,1H),6.95(dd,J=9.0,5.4Hz,1H), 3.86(s,3H),3.80(s,3H);13C{H}NMR(CDCl3,75MHz)δ156.4, 153.5,142.9,130.9,129.7,129.6,129.2,128.6,112.9,110.0,101.5, 55.7,31.6.Compound4ac:white solid(103.7mg,84%);mp100−101°C;1H NMR(CDCl3,300MHz,TMS)δ7.63(d,J=8.1Hz,2H),7.32−7.30 (m,3H),7.23(d,J=8.7Hz,1H),6.95(dd,J=8.7,2.4Hz,1H),3.87 (s,3H),3.80(s,3H),2.43(s,3H);13C{H}NMR(CDCl3,75MHz)δ156.3,153.9,143.4,139.7,131.2,129.3,129.1,127.2,112.6,109.8, 101.7,55.8,31.7,21.3;MS(ESI)253[M+H]+;HRMS(ESI)calcd for C16H17N2O[M+H]+253.1335,found253.1351;IR(neat)ν1618,1590,1486,1433,1377,1332,1273,1194,1160,1028,948,826, 798,729,713cm−1.Compound4ad:20white solid(117.1mg,84%);1H NMR(CDCl3, 300MHz,TMS)δ7.88(d,J=8.1Hz,1H),7.68−7.66(m,2H), 7.44−7.38(m,3H),7.31−7.23(m,4H),7.20−7.15(m,2H),7.06(d,J =6.6Hz,2H),5.40(s,2H);13C{H}NMR(CDCl3,75MHz)δ154.0, 143.0,136.2,136.0,129.9,129.8,129.1,128.9,128.6,127.6,125.8, 122.9,122.5,119.8,110.4,48.2.Compound4ae:20white solid(124.2mg,85%);1H NMR(CDCl3, 300MHz,TMS)δ7.88(d,J=7.8Hz,1H),7.58(d,J=7.8Hz,2H), 7.29−7.15(m,8H),7.07(d,J=6.9Hz,2H),5.41(s,2H),2.38(s, 3H);13C{H}NMR(CDCl3,75MHz)δ154.0,142.5,140.1,136.2, 135.8,129.4,129.0,128.9,127.6,126.6,125.8,122.9,122.6,119.6, 110.4,48.3,21.3.Compound4af:20white solid(126.2mg,82%);1H NMR(CDCl3, 300MHz,TMS)δ7.86(d,J=8.1Hz,1H),7.63(d,J=8.7Hz,2H), 7.34−7.25(m,4H),7.23−7.15(m,2H),7.10−7.07(m,2H),6.97−6.92(m,2H),5.42(s,2H),3.81(s,3H);13C{H}NMR(CDCl3,75 MHz)δ160.9,153.8,142.4,136.2,135.8,130.6,129.0,127.7,125.8, 122.8,122.7,121.7,119.4,114.1,110.3,55.2,48.3.Compound4ag:white solid(127.6mg,84%);mp134−135°C;1H NMR(CDCl3,300MHz,TMS)δ7.90(d,J=7.8Hz,1H),7.67(d,J =7.2Hz,2H),7.47(d,J=7.2Hz,2H),7.30−7.08(m,8H),6.73(dd, J=17.4,10.5Hz,1H),5.82(d,J=17.4Hz,1H),5.45(s,2H),5.33(d, J=10.5Hz,1H);13C{H}NMR(CDCl3,75MHz)δ153.5,142.5, 138.9,136.0,135.81,135.78,129.2,128.9,128.7,127.6,126.4,125.7, 123.0,122.7,119.6,115.4,110.4,48.2;MS(ESI)311[M+H]+; HRMS(ESI)calcd for C22H19N2[M+H]+311.1543,found 311.1551;IR(neat)ν1604,1452,1388,1354,1326,1242,1157, 1076,980,917,854,778,761,724,716,695cm−1.Compound4ah:21colorless liquid(101.9mg,86%);1H NMR(500 MHz,CDCl3,TMS)δ7.62(d,J=8.0Hz,2H),7.45−7.38(m,3H), 7.11(s,1H),6.95(s,1H),3.72(s,3H);13C{H}NMR(125MHz, CDCl3)δ147.7,130.5,128.5,128.45,128.36,128.3,122.2,34.3. Compound4ai:22colorless liquid(127.8mg,99%);1H NMR(500 MHz,CDCl3,TMS)δ7.52(d,J=8.0Hz,2H),7.26(d,J=8.0Hz, 2H),7.10(d,J=0.9Hz,1H),6.95(d,J=0.9Hz,1H),3.73(s,3H), 2.40(s,3H);13C{H}NMR(125MHz,CDCl3)δ147.9,138.4,129.1, 128.4,128.2,127.7,122.0,34.6,21.2.Compound4aj:23colorless liquid(125.1mg,97%);1H NMR(500 MHz,CDCl3,TMS)δ7.47(s,1H),7.38(d,J=7.5Hz,1H),7.32(t,J =7.5Hz,1H),7.20(d,J=7.5Hz,1H),7.10(d,J=1.5Hz,1H),6.93 (d,J=1.5Hz,1H),3.71(s,3H),2.39(s,3H);13C{H}NMR(125 MHz,CDCl3)δ147.8,138.1,130.3,129.3,129.2,128.11,128.10, 125.3,122.1,34.3,21.2.Compound4ak:colorless liquid(95.5mg,74%);1H NMR(500 MHz,CDCl3,TMS)δ7.34−7.24(m,4H),7.13(s,1H),6.97(s,1H), 3.47(s,3H),2.22(s,3H);13C{H}NMR(125MHz,CDCl3)δ147.6, 138.2,130.3,130.22,130.18,129.1,128.0,125.4,120.4,33.2,19.5;MS (ESI)173[M+H]+;HRMS(ESI)calcd for C11H13N2[M+H]+ 173.1073,found173.1088;IR(neat)ν1623,1557,1471,1401,1338, 1282,1143,1116,1013,987,914,906,844,791,750,717,685cm−1. Compound4al:24colorless liquid(110.8mg,84%);1H NMR(500 MHz,CDCl3,TMS)δ7.60(dd,J=8.5,5.5Hz,2H),7.14(t,J=8.5 Hz,2H),7.10(d,J=1.0Hz,1H),6.96(d,J=1.0Hz,1H),3.72(s, 3H);13C{H}NMR(125MHz,CDCl3)δ162.9(d,J C−F=247.1Hz), 146.9,130.5(d,J C−F=8.3Hz),128.3,126.8(d,J C−F=3.3Hz),122.3, 115.5(d,J C−F=21.6Hz),34.3.Compound4am:colorless liquid(120.0mg,87%);1H NMR(500 MHz,CDCl3,TMS)δ7.60(d,J=8.5Hz,2H),7.48(d,J=8.5Hz, 2H),7.11(d,J=1.0Hz,1H),6.94(d,J=1.0Hz,1H),6.74(dd,J= 18.0,10.5Hz,1H),5.81(dd,J=18.0,0.5Hz,1H),5.30(dd,J=10.5, 0.5Hz,1H),3.72(s,3H);13C{H}NMR(125MHz,CDCl3)δ147.4, 137.5,136.1,129.8,128.5,128.3,126.1,122.4,114.6,34.4;MS(ESI) 185[M+H]+;HRMS(ESI)calcd for C12H13N2[M+H]+185.1073, found185.1083;IR(neat)ν1600,1504,1467,1454,1338,1275, 1129,1017,949,914,846,804,778,727,692cm−1./10.1021/jo5010058|.Chem.2014,79,5806−5811 5810ASSOCIATED CONTENT*Supporting InformationCopy of1H and13C NMR spectra of compounds4.This material is available free of charge via the Internet at http://.■AUTHOR INFORMATIONCorresponding Author*Fax:86-577-86689300.E-mail:shaolix@.NotesThe authors declare no competingﬁnancial interest.■ACKNOWLEDGMENTSFinancial support from Open Research Fund of Top Key Discipline of Chemistry in Zhejiang Provincial Colleges and Key Laboratory of the Ministry of Education for Advanced Catalysis Materials(Zhejiang Normal University)(No.ZJHX201305)is greatly appreciated.■REFERENCES(1)For some selected examples,please see:(a)Zhou,B.-H.;Li,B.-J.; Yi,W.;Bu,Z.-Z.;Ma,L.Bioorg.Med.Chem.Lett.2013,23,3759−3763.(b)Do,T.T.;Bae,J.H.;Yoo,S.I.;Lim,K.T.;Woo,H.Y.;Kim, J.H.Mol.Cryst.Liq.Cryst.2013,581,31−37.(c)Rahim,A.S.A.; Salhimi,S.M.;Arumugam,N.;Pi,L.C.;Yee,N.S.;Muttiah,N.N.; Keat,W.B.;Hamid,S.A.;Osman,H.;Mat,I.b.J.Enzyme Inhib.Med. 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颗粒状活性炭吸附和再生英文版

Granular Activated Carbon Absorption and RegenerationDESCRIPTIONGranular activated carbon (GAC) absorption has been used successfully for the advanced (tertiary) treatment of municipal and industrial wastewater. GAC is used to adsorb the relatively small quantities of soluble organics (See Table 1) and inorganic compounds such as nitrogen, sulfides, and heavy metals remaining in the wastewater following biological or physical-chemical treatment. Adsorption occurs when molecules adhere to the internal walls of pores in carbon particles produced by thermal activation.TABLE 1 ORGANIC COMPOUNDS AMENABLE TO ABSORPTION BY GACClassExampleAromatic solvents Benzene, toluene, xylene Polynuclear aromatics Naphthalene, biphenyl Chlorinated aromatics Chlorobenzene, PCBs, endrin, toxaphene, DDTPhenolicsPhenol, cresol, resorcinol, nitrophenols,chlorophenols, alkyl phenols GAC systems are generally composed of carbon contactors, virgin and spent carbon storage, carbon transport systems, and carbon regeneration systems (See Figure 1). The carbon contactor consists of a lined steel column or a steel or concrete rectangular tank in which the carbon is placed to form a “filter” bed. A fixed bed downflow column contactor (See Figure 2) is often used to contact wastewater with GAC. Wastewater is applied at the top of the column, flows downward through the carbon bed, and is withdrawn at the bottom of the column. The carbon is held in place with an underdrain system at the bottom of the contactor. Provisions for backwash and surface wash of the carbon bed are required to prevent buildup of excessive headloss due to accumulation of solids and to prevent the bed surface from clogging.Aromatic amines & high molecular weight aliphatic aminesAniline, toluene diamineSurfactantsAlkyl benzene sulfonatesSoluble organic dyes Methylene blue, textiles,dyesFuelsGasoline, kerosene, oil Chlorinated solventsCarbon tetrachloride, percholoroethylene Aliphatic & aromatic acids Tar acids, benzoic acidsPesticides/herbicides2,4-D, atrazine, simazine, aldicarb, alachlor, carbofuranSource: WEF MOP 8, 1998.FIGURE 1 GAC ADSORPTIONSCHEMATICExpanded bed and moving bed carbon contactors have been developed to overcome problems associated with headloss buildup experienced with fixed bed downflow contactors. In an expanded bed system, wastewater is introduced at the bottom of the contactor and flows upward, expanding the carbon bed, much as the bed expandsSource: U.S. EPA, 1984.during backwash of a fixed bed downflow contactor. In the moving bed system, spent carbon is replaced continuously so that the headloss does not build up. Carbon contactors may be operated under either pressure or gravity flow. The choice between pressure and gravity flow generally depends on the available pressure (head) within the wastewater treatment plant and cost.waiting truck. Regenerated or virgin carbon is then hydraulically transported from a second truck or from a separate compartment in the first truck to the contactor, then to a commercial reactivation facility. Generally, systems which contain at least one million pounds of carbon find on-site regeneration to be cost effective.Carbon regeneration is accomplished primarily by thermal means. Organic matter within the pores of the carbon is oxidized and thus removed from the carbon surface. The two most widely used regeneration methods are rotary kiln and multiple hearth furnaces. Approximately 5 to 10 percent of the carbon is destroyed in the regeneration process or lost during transport and must be replaced with virgin carbon. The capacity of the regenerated carbon is slightly less than that of virgin carbon. Repeated regeneration degrades the carbon particles until an equilibrium is eventually reached providing predictable long term system performance. See Figure 3 for a schematic of the carbon regeneration process.Source: Tchobanoglous and Burton, 1991.FIGURE 2 TYPICAL DOWNFLOWCARBON CONTACTORAll carbon contactors must be equipped with carbon removal and loading mechanisms to allow spent carbon to be removed and virgin or regenerated carbon to be added. Spent, regenerated, and virgin carbon is typically transported hydraulically by pumping as a slurry. Carbon slurries may be transported with water or compressed air, centrifugal or diaphragm pumps, or eductors.When the carbon contactor effluent quality reaches minimum water quality standards, the spent carbon is removed from the contactor for regeneration. Small systems usually find regeneration of their spent carbon at an off-site commercial reactivation facility to be the most convenient and economical method. In this case, the spent carbon is hydraulically transported from the contactor to aSource: WEF MOP 8, 1998FIGURE 3 REGENERATION SCHEMATICAPPLICABILITYTypically, GAC adsorption is utilized in wastewater treatment as a tertiary process following conventional secondary treatment or as one of several unit processes composing physical-chemicaltreatment. In wastewater treatment plants utilizing biological secondary treatment, GAC adsorption is generally located after filtration and prior to disinfection. When utilized in a physical-chemical treatment process, GAC adsorption is generally located following chemical clarification and filtration and prior to disinfection. In addition, GAC adsorption systems have a relatively small footprint making them suitable for facilities with limited land availability.The successful application of carbon adsorption for municipal wastewater treatment depends on the quality and quantity of the wastewater delivered to the adsorption system. For a carbon contactor to perform effectively, the feed water to the unit should be of uniform quality (suspended solids concentrations less than 20 mg/l) and without surges in flow. Wastewater constituents that may adversely affect carbon adsorption include suspended solids, BOD5, and organics such as methylene blue active substances or phenol and dissolved oxygen. Environmental factors that must be considered include pH and temperature because they may impact solubility, which affects the adsorption properties of the wastewater components onto carbon (WEF MOP 8, 1998).ADVANTAGES AND DISADVANTAGESB e f o r e d e c i d i n g w h e t h e r c a r b o n adsorption/regeneration meets the needs of a municipality, it is important to understand the advantages and disadvantages of both the adsorption and regeneration process.Advantages (Adsorption)C For wastewater flows which contain asignificant quantity of industrial flow, GACadsorption is a proven, reliable technologyto remove dissolved organics.C Space requirements are low.• GAC adsorption can be easily incorporated into an existing wastewater treatmentfacility. Advantages (Regeneration)C Systems are reliable from a processstandpoint.C Reduces solid waste handling problemscaused by the disposal of spent carbon.C Saves up to 50 percent of the carbon cost. Disadvantages (Adsorption)C Under certain conditions, granular carbonbeds may generate hydrogen sulfide frombacterial growth, creating odors andcorrosion problems.C Spent carbon, if not regenerated, maypresent a land disposal problem.C Wet GAC is highly corrosive and abrasive.C Requires pretreated wastewater with lowsuspended solids concentration. Variationsin pH, temperature, and flow rate may alsoadversely affect GAC adsorption. Disadvantages (Regeneration)C Air emissions from the furnace containvolatiles stripped from the carbon. Carbonmonoxide is formed as a result ofincomplete combustion. Therefore,afterburners and scrubbers are usuallyneeded to treat exhaust gases.C The induced draft fan of a multiple hearthfurnace may produce a noise problem.C The process is most effective when operatedon a 24-hour basis, requiring around-the-clock operator attention.C The process is subject to more mechanicalfailures than other wastewater treatmentprocesses.DESIGN CRITERIAPrior to the design of GAC systems, a pilot plant study should be performed to determine if the technology will meet discharge permit requirements and to quantify optimum flow rate, bed depth, and operating capacity on a particular wastewater. This information is required to determine the dimensions and number of carbon contactors required for continuous treatment.The sizing of carbon contactors is based on contact time, hydraulic loading rate, carbon bed depth, and number of contactors. The carbon contact time typically ranges from 15 to 35 minutes depending on the application, wastewater constituents and desired effluent quality. Hydraulic loading rates of 4 to 10 gpm/sq.ft are typically used for upflow carbon columns. For downflow carbon columns, hydraulic loading rates of 3 to 5 gpm/sq.ft are used. Carbon bed depth varies typically within a range of 10 to 40 feet depending on carbon contact time (Tchobanoglous, 1991).The number of contactors should be sufficient to ensure enough carbon contact time to maintain effluent quality while one column is off line during removal of spent carbon or maintenance. The normal practice is either to use two columns in series and rotate them as they become exhausted or to use multiple columns in parallel so that when one column becomes exhausted, the effluent quality will not be significantly affected (WEF MOP 8, 1998). Regeneration facilities are typically sized based on carbon dosage or use rate. The dosage rate depends on the strength of the wastewater applied to the carbon and the required effluent quality. Typical dosage rates for filtered, secondary effluent range from 400 to 600 lbs/mil.gall., while typical dosage rates for coagulated, settled and filtered raw wastewater (physical-chemical) range from 600 to 1800 lbs/mil.gall.PERFORMANCENiagara Falls Wastewater Treatment Plant Niagara Falls, New York The Niagara Falls Wastewater Treatment Plant (NFWTP) has been operating as a physical- chemical activated carbon secondary treatment facility since 1985. With a design average daily flow capacity of 48 mgd, it is the largest municipal physical-chemical activated carbon wastewater treatment plant in operation in the United States. The treatment process consists of chemically assisted primary sedimentation, granular activated carbon adsorption, oxidation, and disinfection. The influent pH can be adjusted to compensate for industrial discharge. The current average daily flow is 35 mgd. Industrial flow to the plant is approximately 17 percent of the total flow.The activated carbon system at NFWTP includes 28 carbon beds which are 17.3 feet wide by 42 feet long. Each carbon bed is approximately 8.5 feet in depth and contains 180,000 pounds of carbon. Primary effluent percolates downward by gravity through the GAC bed. Each carbon bed provides chemical adsorption of pollutants from the wastewater, physical filtration of solids, and biological degradation from the incidental anaerobic activity that occurs within.The carbon beds at NFWTP operate in parallel. During dry weather, there are typically 17 carbon beds in operation with a primary effluent application rate of approximately 2.2 gpm/sq.ft. During wet weather, additional beds are placed in operation. All beds are operated at an application rate of approximately 3gpm/sq.ft (Roll, 1996). Backwash of the carbon beds is based on headloss. Regeneration of the spent carbon is performed on- site in a multiple hearth furnace. Each filter bed is separately removed from service and emptied of carbon. The carbon is fed to the furnace at a rate of about 2,000 lbs/hr. The regenerated carbon is kept in storage until an empty bed becomes available. Normal operating losses, which average 5.5 percent, require the addition of virgin carbon to maintain inventory levels. At present, the four month regeneration process to regenerate all of the carbon is performed once per year.Three storage tanks are used during on-site regeneration. The spent carbon storage tank has a capacity of 2.5 carbon beds; the regenerated carbonstorage tank can hold 1.5 beds of carbon and the virgin carbon storage tank has a capacity of 1 carbon bed. Carbon is moved about the plant in a slurry through an eductor system.With GAC adsorption, the NFWTP has achieved very low effluent organic compound concentrations. On a daily basis, the facility receives approximately 800 pounds of influent priority pollutants which are reduced by the treatment process to 12 pounds in the effluent to the Niagara River. The effluent discharge permit issued to NFWTP by the New York State Department of Environmental Conservation includes effluent limitations for volatile compounds, acid compounds, base/neutral compounds, pesticides, metals, and cyanide. Millard H. Robbins Reclamation Facility, Upper Occoquan Sewerage Authority, Centreville, VirginiaThe Millard H. Robbins Reclamation Facility (MHRRF) provides biological, tertiary treatment to an average daily wastewater flow of 24 mgd. Industrial flow to the plant is approximately 10 percent of the total flow. The treatment process consists of primary sedimentation, conventional activated sludge with nitrification, lime addition for phosphorous removal, clarification, two-stage recarbonization, flow equalization, multimedia filtration, GAC adsorption, post filtration and disinfection. The MHRRF discharges its effluent to Bull Run which flows into the Occoquan Reservoir. This reservoir serves as raw water storage for the potable water supply to portions of northern Virginia.The activated carbon system at MHRRF includes 32 upflow carbon columns which are 10 feet in diameter and 40 feet tall. Each column has a capacity of 1mgd and contains approximately 75,000 pounds of carbon. Flow is pumped through the columns by a pump station which also serves the multimedia filters and post filtration system. Post filtration is provided following the GAC columns to remove carbon fines from the effluent to maintain the Virginia Pollutant Discharge Elimination System (VPDES) permit requirement for turbidity of 0.5 NTU. The carbon columns at MHRRF are operated in parallel. During average daily flow periods, approximately 24 columns are in operation with the remaining eight columns brought on line during daily peak flow periods. During wet weather, flows in excess of 32 mgd are stored in a 90 million gallon pond.Regeneration of the spent carbon is performed on- site in a multiple hearth furnace. The regeneration process takes approximately 8 to 10 weeks to regenerate approximately one-third of the carbon in all 32 columns and is performed twice each year. Consequently, it takes approximately 18 months (three regeneration cycles) to regenerate the total quantity of carbon in the columns. Spent carbon is removed from the bottom of each column and transported to the regeneration furnace through an eductor system. The regenerated carbon is then added at the top of each column. The cost for on- site regeneration at MHRRF is approximately $0.35 per pound. Normal operating losses, which average 5 to 7 percent of the total quantity of GAC in use, require the addition of virgin carbon to maintain inventory levels. Most of the carbon attrition occurs during regeneration with approximately 10 to 12 percent of the total carbon regenerated lost during the regeneration process. Carbon is moved about the plant in a slurry through an eductor system.GAC adsorption is utilized at MHRRF to remove non-biodegradable, soluble organics. COD is used as the surrogate indicator of non-biodegradable organics removal by the GAC columns. Currently, the Virginia Pollutant Discharge Elimination System (VPDES) discharge permit limit for COD is 10 mg/l. Following GAC regeneration, effluent COD concentrations range from 6 to 7 mg/l, which corresponds to approximately 50 percent removal of COD. As the GAC in the columns becomes exhausted, the percentage removal of COD declines to approximately 25 percent. When the effluent COD concentration has increased to 9 mg/l, GAC regeneration is initiated.OPERATION AND MAINTENANCEThe proper operation and maintenance of GAC adsorption and regeneration systems ensures theefficient removal of soluble organics from secondary effluent. A routine O&M schedule following manufacturer’s recommendations should be developed and implemented for any GAC adsorption and regeneration system. Regular O&M includes the following:C Backwash of carbon contactor based onheadloss or flow.C Flush carbon transport piping to preventclogging.C Backwash frequently after loading carbon tominimize clogging of backwash nozzles bycarbon fines.C Store an adequate supply of spent carbon toallow continuous operation of theregeneration furnace.C Test and calibrate instrumentation andcontrols on a routine basis.COSTSThe construction and operation and maintenance costs of carbon adsorption and regeneration depend on the characteristics of the wastewater to be treated, the capacity of the plant, and the plant site. Therefore, the designer is responsible for selecting a system that will meet the National Pollutant Discharge Elimination System NPDES permit requirements at the lowest cost possible. Once the optimum flow rate, bed depth, and operating capacity of GAC for a particular wastewater are determined, comparative costs for different carbon contactor configurations and the cost of on-site regeneration versus off-site regeneration can be estimated. Following a thorough engineering and economic analysis of alternatives, the final equipment configuration can be selected. Construction costs include the carbon contactors, carbon transport system, carbon storage tanks, carbon regeneration system (if applicable), influent wastewater pumps (if applicable) and contactor backwash system. Operation and maintenance costs include the purchase of virgin carbon, on-site regeneration or purchase of regenerated carbon, electrical power to operate pumps and controls, flushing of carbon slurry piping, and replacement of parts. Currently, the cost of virgin carbon ranges from $0.70 to $1.20 per pound and the cost to purchase regenerated carbon ranges from $0.50 to $0.78 per pound.Operational costs depend on the characteristics of the influent wastewater and the adsorption capacity of the GAC. For example, influent wastewater which contains suspended solids concentrations greater than 20 mg/l will require more frequent backwashing of the contactor to prevent clogging of the carbon bed.REFERENCESOther Related Fact SheetsOther EPA Fact Sheets can be found at the following web address:/owmitnet/mtbfact.htm1. “Activate d Carbon Absorption &Adsorption.” [/sce%26g/business_solutions/technology/ewtwaca.htm].2. Culp, Russel L., Wesner, George Mack, andCulp, Gordon L., 1978. Handbook ofAdvanced Wastewater Treatment, 2nd Ed.Van Nostrand Reinhold Co., NY.3. Naylor, William F. and Rester, Dennis O.,1995. Determining Activated CarbonPerformance. Pollution Engineering, July1.4. Perrich Jerry R., 1981. Activated CarbonAdsorption for Wastewater Treatment,CRC Press, FL.5. Roll, Richard and Crocker, Douglas,“Evolutio n Of A Large Activated CarbonSecondary Treatment System”, WEFTEC,1996, WEF Annual Conference, Dallas.6. Tchobanoglous, George and Burton,Franklin L., 1991. Wastewater EngineeringTreatment Disposal, Reuse, Metcalf andEddy Inc., 3rd Ed.7. U.S. EPA, 1984. Granular ActivatedCarbon Systems Problems and Remedies,U.S. EPA 800/490/9198, U.S. EPA,Washington, D.C.8. Water Environment Federation, Design ofMunicipal Wastewater Treatment Plants,MOP Ni. 8, 1998.ADDITIONAL INFORMATIONCalgon Carbon CorporationDan BrooksP.O. Box 7171Pittsburgh, PA 15230-0717Department of Wastewater FacilitiesWastewater Treatment PlantRichard R. Roll, P.E., D.E.E1200 Buffalo Avenue, P.O. Box 69Niagara Falls, NY 14302-0069William NaylorSenior Applications EngineerNorit America, Inc.Marshall, TX 75671The mention of trade names or commercialproducts does not constitute endorsement orrecommendation for use by the U.S. EnvironmentalProtection Agency.For more information contact:Municipal Technology BranchU.S. EPAMail Code 42041200 Pennsylvania Avenue, NWWashington, D.C., 20460。

苝酰亚胺

Liquid Crystalline Perylene Diimide Outperforming Nonliquid Crystalline Counterpart:Higher Power Conversion Eﬃciencies(PCEs) in Bulk Heterojunction(BHJ)Cells and Higher Electron Mobility in Space Charge Limited Current(SCLC)DevicesYoudi Zhang,†Helin Wang,†Yi Xiao,*,†Ligang Wang,‡Dequan Shi,‡and Chuanhui Cheng*,‡†State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian116024,People’s Republic of China‡School of Physical and Optoelectronic Engineering,Dalian University of Technology,Dalian116024,People’s Republic of China *Supporting Informationoptimized eﬃciency of0.94%.By contrast,the devices based on PDI-1,aﬃciency of0.22%.Atomic force microscopy(AFM)images conﬁrmordered morphology.In space charge limited current(SCLC)deviceselectron mobility of2.85×10−4cm2/(V s)(at0.3MV/cm)which issame conditions for thermal annealing at120°C.semiconductor,perylene diimides,liquid crystalline,space charge limited current1.INTRODUCTIONIn recent years,liquid crystalline(LC)semiconductors have received considerable attention in theﬁelds of organicelectronics.1−4Not only because they are readily dissolvable,butalso because they self-assemble into highly ordered morphology5 to eﬀectively eliminate the structural and electronic defects.6,7LCmaterials are highly desirable for solution-processable devices.8It isnot surprising that some space charge limited current(SCLC) devices and organicﬁeld-eﬀect transistors(OFET)devices basedon LC semiconductors have shown very high charge mobility.9−13 However,in theﬁeld of bulk heterojunction(BHJ)organic solar cells,the applicability of LC materials have not been well-recognized.14Actually,amorphous fullerenes derivatives,e.g.,PCBM,ﬁrmly occupy the dominant status as electron acceptors in BHJ cells,although have poor absorption in solar spectrum. Generally speaking,there is still a wide gap between non-fullerene organic acceptors and fullerenes in terms of BHJ eﬃciency.Among all the reported nonfullerene acceptors,one representative class is perylene diimides(PDIs),which have very strong absorption in the visible region and exhibit high electron mobility.However,because of their large,rigid,and planar conjugation cores,the seriousπ−πstacking and poor solubility of the PDIs and their analogues are problematic for BHJ cells;they tend to aggregate excessively to form islets,which not only damages the morphology of the BHJ active ﬁlms but also generates carrier traps.A variety of strategies have been put forward to reduce the extent ofπ−πstacking,improve solubility,and control the aggregation state.15These working concepts include the introduction of swallow tail-type long, branchy,andﬂexible alkyl side chains onto the two imide sites,16−18copolymerization of PDI and other conjugated monomer on the perylene bay sites,19direct connection of two PDI segments on the imide site to form nonplanar and nonconjugate dimers,20and combination of PDI and donor on the imide site to form co-oligomers,21etc.Herein,we propose the utilization of liquid crystalline PDI derivatives,e.g.,LC-1,as a new means parallel to the above-mentioned ones helping to improve the applicability of PDIs in BHJ cells.In this work,LC-1,which is a structurely simple PDI derivative acting as the model of our strategy,has been adopted as the acceptor in the fabrication of BHJ cells’active layers with P3HT as the donor.Devices based on LC-1exhibit remarkably higher conversion eﬃciency than the nonliquid crystalline counterpart PDI-1.15To better understand the reason whyReceived:August9,2013Accepted:October15,2013Published:October15,2013LC-1is in favor of BHJ solar cells,its LC properities have been thoroughly characterized by di ﬀerential scanning calorimetry (DSC),polarization optical microscopy (POM),and X-ray di ﬀraction (XRD);In addition,in spin-coated SCLC devices,LC-1’s intrinsic electron mobility is much higher than that of PDI-1.2.RESULTS AND DISCUSSION2.1.Fundamental Characteristics of LC-1Material.LC-1molecule was designed and synthesized according to a previous procedure,22as shown in Scheme 1.Solubility of LC-1was 40mg/mL in the common organic solution, e.g.,dichloromethane,chloroform,chlorobenzene,and dichloro-benzene,and it was very important for applied in BHJ solar cells.IN addition,the absorption spectra of LC-1do not have to change for modi ﬁcation of PDI N-terminal chains at 527nm in the solution and at 495nm in the ﬁlm (see Figure 1).Thethermogravimetric analysis (TGA)curve showed the enhanced thermal stability for LC-1with a decomposition onset temperature (T d )of ∼333.7°C (see Figure 2).2.2.Photovoltaic Device Performance.In the compar-ison investigation on BHJ devices using liquid crystalline LC-1and n PDI-1,respectively,as acceptor materials,cells based on LC-1exhibited remarkably superior performances.For the device with P3HT:LC-1as an photovoltaic active layer,the optimum power conversion e ﬃciency (PCE)was 0.94%,which is ∼4times that of a device based on the P3HT:PDI-1(maximum PCE of 0.22%).These data supported our hypothesis that liquid crystalline acceptor materials are more advantageous in BHJ solar cells.Interestingly,there exists the regularity in the high dependence of devices ’s performances on the annealing temperature,which is related to the broad temperature range of LC-1’s liquid crystalline phase.Keeping the P3HT:LC-1weight ratio ﬁxed at 1:2in the active layer,and setting a series annealing temperature (50,80,100,120,150,and 165°C),we tested the J −V curves of a group of BHJ devices (100mW cm −2AM 1.5G),as recorded in Figure 3,and we summarized the corresponding data in Table 1.Particularly,the correlation between annealing temperature and PCE and the correlation between annealing temperature and short-circuit current (J SC )had been clearly demonstrated in Figure 4.With the increase in annealing temperature from 50°C to 120°C,the continuous and obvious enhancements in device parameters including J SC ,open-circuit voltage (V OC ),and ﬁll factor (FF)were found.The increased J SC may result from a reorientation and enhanced ordering of the LC-1during annealing,which would facilitate charge transport.However,at >120°C,further increases in the annealing temperature induced a decrease in device performance.Thus,using thermal annealing at 120°C resulted in the best data:PCE =0.94%,V OC =0.41V,J SC =5.42mA cm −2,and FF =0.42.In the control experiment,the BHJ device unannealed at 25°C only showed a much lower PCE of 0.23%,which is only a quarter of the optimum e ﬃciency.When we changed the P3HT:LC-1blended ratio into 1:1,the similar regularity on the e ﬀects of annealing temperature toScheme 1.Synthetic Routes of the Investigated LC-1MoleculeFigure 1.Normalized absorption spectra of (■)LC-1chloroform solution (1×10−5),(○)LC-1ﬁlm,and (●)P3HT:LC-1blended ﬁlm.Figure 2.TGA thermograms of liquid crystalline molecule LC-1measured under nitrogen ﬂow (50mL min −1)at a heating rate of 10°C min −1.Figure 3.Current −voltage (J −V )curves of photovoltaic devices using P3HT:LC-1as active layers at temperatures of 25and 120°C and weight ratios of 1:1and 1:2,respectively.The curves correspond to the curve of P3HT:LC-1using (□)a weight ratio of 1:1at 25°C,(■)a weight ratio of 1:1at 120°C,(○)a weight ratio of 1:2at 25°C,and (●)a weight ratio of 1:2at 120°C.device data had also been observed;Again,the best performance (PCE =0.74%,V OC =0.38V,J SC =5.03mA cm −2,and FF of 0.39)was obtained under the condition of thermal annealing at 120°C.However,in the BHJ devices using the nonliquid crystalline PDI-1as the acceptor,thermal annealing did not seem to be as bene ﬁcial as it did to LC-1.After annealing at 120°C,a device of P3HT:PDI-1(1:1)showed a J SC value of 1.6mA cm −2,V OC =0.34V,FF =0.40,and an e ﬃciency of 0.22%.These data were much lower than those obtained from the P3HT:LC-1device annealing at 120°C,but were similar to those of the unannealed P3HT:LC-1device.The above facts indicated that the improvement induced by thermal annealing was more related to LC-1’s liquid crystalline feature than to the perylene diimide conjugation core.To better understand the e ﬀects of the P3HT:LC-1weight ratio to photovoltaic performances,the comparisons of di ﬀerent parameters (e.g.,external quantum e ﬃciencies (EQE)and internal quantum e ﬃciencies (IQE))were carried out.As shown in Figure 5A,the highest EQE (∼17%)was obtained for the blends of 1:2at 490nm,while for P3HT:LC-1(1:1)devices,the highest EQE value is just ∼13%at 485nm,the tested result implied that the increased proportion of LC-1molecule produced more photocurrent in the blended ﬁlms and also veri ﬁed the improved J SC observed in LC-1devices,which showed higher EQE values (peak EQE =17%)over the entire range of the active layer absorption from 350nm to 700nm,a signi ﬁcant portion of that photocurrent is due to absorption by the acceptor phase,followed by hole transfer to the donor.As shown in Figure 5B,the IQE tests also suggested that much more charge carriers were generated for P3HT:LC-1(1:2)(∼22%)under sunlight,compared with that of the doping ratio of 1:1(∼16%).2.3.Atomic Force Microscopy Images.Atomic force microscopy (AFM)images revealed that the active layer morphology of P3HT:LC-1were greatly in ﬂuenced by their weight ratios and the thermal annealing.As shown in Figure 6,a P3HT:LC-1ratio of 1:2produced much smoother morphology than ratio of 1:1;Also,the morphology after thermal annealing at 120°C was much smoother than that unannealed at 25°C.The root-mean-square (RMS)surface roughness values could be the indicators for the quality of ﬁlms:the smaller the RMS surface roughness,the better the ﬁlm morphology.On one hand,the smallest RMS surface roughness of 4.67nm for a doping ratio of 1:2under the thermal annealing at 120°C had been determined;this value was smaller than 5.50nm,which corresponds to the ﬁlm without annealing.On the other hand,for the unannealed ﬁlm with a doping ratio of 1:1,the RMS surface roughness value was 7.61nm,but after annealing at 120°C,the value decreased toTable 1.Performance of the Devices with Di ﬀerent Weight Ratios and Thermal Annealing Conditions of P3HT:LC-1from o -Dichlorobenzene Solution Used for Spin Coatingtemperature [°C]PCE [%]J SC [mA cm −2]V OC [V]FF P3HT:LC-1Weight Ratio =1:1250.16 1.770.350.26500.43 3.580.360.33800.55 4.250.360.361000.65 4.330.400.381200.74 5.030.380.391500.67 4.310.410.381650.50 3.200.390.40P3HT:LC-1Weight Ratio =1:2250.23 1.880.360.34500.64 4.160.380.40800.71 4.670.370.411000.86 4.890.400.441200.94 5.420.410.421500.77 4.650.440.38P3HT:PDI-1Weight Ratio =1:1a1650.61 4.220.390.371200.22 1.600.340.40aThe mixing solution of P3HT:PDI-1was used as an organicphotovoltaic activelayer.Figure 4.Relationship chart of PCE and J SC versus temperature to P3HT:LC-1at di ﬀerent temperatures and weightratios.Figure 5.(A)External quantum e ﬃciencies (EQE)and (B)internal quantum e ﬃciencies (IQE)of P3HT:LC-1at di ﬀerent weight ratios.6.40nm.The decrease in the roughness of the blend ﬁlms after annealing was due to the fact that the LC-1molecules were self-organized into ordered structures at 120°C within the liquid crystalline phase.The phenomenon that the increase in the proportion of LC-1in the blended ﬁlm can improve morphology should also be ascribed to liquid crystalline characteristics.Because of the nonliquid crystalline feature of PDI-1,the morphology of the P3HT:PDI-1ﬁlms would not be improved by the thermal annealing;the RMS surface roughness was high,up to 9.29nm,even after annealing at 120°C.Since the smooth morphology leaded to an e ﬃcient charge separation,higher J SC and PCE for BHJ PV devices based on the thermally annealed blend ﬁlms of P3HT:LC-1than those of P3HT:PDI-1can be partially explained.2.4.Charge Mobility.Charge mobility within an active layer ﬁlm is another critical factor for BHJ cells.Since we had already found that,in P3HT:LC-1BHJ devices,thermal annealing greatly improved the PCE,for the sake of deeper interpretation of such e ﬀect,it would be useful to evaluate LC-1’s electron mobility at di ﬀerent annealing temperature.Hence,we adopted the space charge limited current (SCLC)method,12,23−26which is suitable for determining organic semiconductors ’intrinsic carrier mobility under steady-state current.Consistent with the former P3HT:LC-1bulk hetero-junction solar cells device structure,the SCLC devices ’structure was designed to be ITO/ZnO (∼30nm)/LC-1(∼250nm)/LiF (1.5nm)/Al (100nm).J −V curves of the SCLC devices with spin-coated LC-1as the active layer annealed at di ﬀerent temperatures were recorded (Figure 7),and the correspondingparameters have been collected in Table 2.The SCLC in this case of mobility,depending on the ﬁeld,can be approximated by the following formula:27,28εεμγ=J E LE 98exp (0.89)020where E is the electric ﬁeld across the sample;εand ε0are the relative dielectric constant and the permittivity of the free space,respectively;and L is the thickness of the organic layer,with μ0the zero-ﬁeld mobility and γdescribing the ﬁeld activation of the mobility.With the increase in annealing temperature,the electron mobility of LC-1ﬁrst increased sharply,e.g.,from 4.90×10−6cm 2/(V s)at 25°C to 1.72×10−5cm 2/(V s)(at 0.3MV/cm)at 50°C;such a tendency of increase ceased at 120°C,where the electron mobility achieved the highest value,2.85×10−4cm 2/(V s),which is 50times higher than that of the unannealed device (25°C);Then,further temperature elevation would result in an apparent decrease in electron mobility,e.g.,to 2.93×10−5cm 2/(V s)at 150°C.Amazingly,such a correlation between the electron mobility of LC-1and annealing temperature exhibited the same regularity as that of the PCE of P3HT:LC-1BHJ solar cells.Hence,the best PCE of BHJ solar cells at 120°C can be reasoned by the highest electron mobility of LC-1at this temperature.29,30The SCLC device using the nonliquid crystalline PDI-1had also been tested.However,even if PDI-1ﬁlm had undergone the thermal annealing at 120°C,the SCLC electron mobility was determined to be 5.83×10−5cm 2/(V s),which is only one quarter of that of LC-1.This fact could be used to explain why BHJ cells using LC-1as an acceptor outperformed those using PDI-1.In BHJ organic solar cells,the balanced charge carrier mobilities reveal that LC-1increases the FF and PCE,because of charge separation.31,32To investigate the carrier mobilities (electron and hole)in the blend ﬁlms,the J −V characteristics of the hole-only (ITO/PEDOT:PSS/LC-1or PDI-1:P3HT/Au structure)and electron-only (Al/LC-1or PDI-1:P3HT/LiF/Al structure)devices were measured for the as-cast and annealed blended ﬁlms (see Tables 3and 4).The hole and electron mobilities were extracted using the SCLC model 33,34(Figure 8).For the annealed blended ﬁlm at 120°C,the values of the hole and electron mobilities are ∼1.07×10−6and ∼1.28×10−5cm 2/(V s),respectively.However,the hole and electron mobilities fortheFigure 6.AFM height images (5μm ×5μm)of blended thin ﬁlms of P3HT:LC-1before thermal annealing (A)at 25°C,P3HT:LC-1=1:1;(B)at 120°C,P3HT:LC-1=1:1;(C)at 25°C,P3HT:LC-1=1:2)and after thermal annealing ((D)at 120°C,P3HT:LC-1=1:2;and (E)at 120°C,P3HT:PDI-1=1:1).Figure 7.Current density versus voltage (J −V )characteristics of anelectron-only device based on (●)LC-1at 25°C,(○)LC-1at 120°C,(■)LC-1at 165°C,and (□)PDI-1at 120°C at an electric ﬁeld strength of 0.3MV/cm.Table 2.Performance of the Single Electron Devices LC-1with Di ﬀerent Thermal Annealing Conditions fromChloroform Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μ[cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-125 4.90×10−61.16×10−70.006850 1.72×10−57.81×10−60.0014802.91×10−5 1.05×10−50.00181003.92×10−5 1.02×10−60.0066120 2.85×10−4 1.92×10−50.0049150 2.93×10−5 3.95×10−70.0078165 1.74×10−55.37×10−60.0021PDI-1a1205.83×10−5 4.35×10−70.0089aThe single electron device based on PDI-1from chloroform solution used for spin coating at an electric ﬁeld of 0.3MV/cm.as-cast blend are ∼1.07×10‑7and 8.20×10−8cm 2/(V s),respectively.As the annealing temperature increases up to 120°C,the hole mobility and electron mobility increase,which can be attributed to the improvement of ﬁlm morphology and,thereby,is the reason for the higher PCE.However,the hole mobility and electron mobility of the PDI-1:P3HT ﬁlm are 5.52×10−5and 4.58×10−7cm 2/(V s)at 120°C,respectively.Obviously,the strong aggregation tendency of nonliquid crystalline PDI-1can result in more charge recombination and unbalanced charge transport in the blend ﬁlms,which explains the lower performance of PDI-1:P3HT BHJ devices.Since the investigations of all of the above devices had indicated that the annealing temperature played a decisive role in improving the PCE,mobility,and morphology,thoroughly investigating the thermal properties of LC-1should be carried out to provide deeper insight into the correlation between the liquid crystalline phase and the suitable annealing temperature.2.5.Di ﬀerential Scanning Calorimetry (DSC),Polar-ization Optical Microscopy (POM),and X-ray Di ﬀraction (XRD).As shown in Figure 9,the DSC heating curve of LC-1showed two reversible transitions:at 54°C and 172°C.The corresponding transitions upon cooling were observed at 158°C and 41°C.Such information indicated a broad liquid crystalline phase (∼112°C),which was conductive to optimizing the annealed temperature for organic photovoltaic devices.The P3HT:LC-1BHJ devices that underwent annealing at 120°C generated a highest PCE,possibly because this annealing temperature was in the upper section of the liquid crystalline phase.POM (see Figure 10)experiments upon cooling from the isotropic melt gave evidence for a highly ordered mesophase which is a typical characteristics for the liquid crystalline materials.22,35−37Figure 10A at 120°C showed that the entire glass substrate covered a very compact and uniform ﬁlm composed of small snow ﬂake-like textures,in contrast to Figure 10B at 165°C with the larger and inhomogenous islets.The results implied that thermal annealing at di ﬀerent temperature would in ﬂuence the particle size and uniformity in the mesophases to di ﬀerent extents and,thus,a ﬀect the electron mobility 38and PCE.So,there was no wonder that annealing atTable 3.Electron Mobilities of LC-1:P3HT with Di ﬀerent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μe [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 258.20×10−87.76×10‑90.004350 2.33×10−6 1.24×10−70.005380 3.33×10−6 1.36×10−70.00581009.42×10−6 4.43×10−70.0056120 1.28×10−5 1.44×10−60.0040150 3.34×10−6 3.10×10−80.0085165 1.96×10−72.33×10−80.0081PDI-1:P3HT a 1204.58×10−73.89×10−90.0087aThe electron mobility based on PDI-1:P3HT blended ﬁlm from o -dichlorobenzene solution used for spin coating at an electric ﬁeld of 0.3MV/cm.Table 4.Hole Mobilities of LC-1:P3HT with Di ﬀerent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μh [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 25 1.07×10−79.32×10−90.004450 2.70×10−7 4.02×10−80.003580 3.97×10−7 4.94×10−80.00391009.12×10−7 4.85×10−70.0011120 1.07×10−6 2.21×10−70.0029150 5.83×10−7 2.49×10−80.0057165 3.20×10−75.08×10−80.0033PDI-1:P3HT a 1205.52×10−52.18×10−70.0101aThe hole-only mobility based on PDI-1:P3HT blended ﬁlm from o -dichlorobenzene solution used for spin coating at an electric ﬁeld of 0.3MV/cm.Figure 8.Current density versus voltage (J −V )characteristics of (A)electron-only devices and (B)hole-only devices based on (◇)LC-1:P3HT at 25°C,(■)LC-1:P3HT at 120°C,(□)LC-1:P3HT at 165°C,and (◆)PDI-1at an electric ﬁeld strength of 0.3MV/cm.Figure 9.Di ﬀerential scanning calorimetry (DSC)traces of LC-1at a ramp rate of 10°C/min.120°C resulted in highest electron mobility of LC-1and the best performance in BHJ solar cells.Also,XRD experiments were in accordance with a columnar smectic ordering of the mesogens.The di ﬀractogram of LC-1from 25°C to 165°C are shown in Figure 11.The di ﬀractionpeaks of the 25°C sqample showed a relatively weak and wide single peak at 2θ=2.55°(corresponding to 34.61Å).However,upon further heating LC-1into a liquid crystalline phase,a strong and narrow di ﬀraction peak at 2θ=2.14°(41.23Å)and 2θ=25.85°(3.44Å)appeared and became more and more sharp as the temperature increased.The re ﬂection at 25.85°in the wide-angle regime depicts a moderate intracolumnar long-range order with a π−πstacking distance of d ππ=3.44Å.LC-1crystalline at 165°C was the best and was much better than that at 25°C.Meanwhile,we found that,at higher temperature,the overall di ﬀraction peaks move slightly toward the direction of the small-angle di ﬀraction.While new di ﬀraction peaks at 2θ=9.2°,15.1°,and 17.8°emerged at higher temperature,the original peak with 2θ=21.1°in the 25°C di ﬀractogram disappeared in the wide-angle regime.These changes re ﬂected that,in the liquid crystalline phase,LC-1has a highly ordered columnar smectic phase,which is similar to the results of Jin,who had studied a series of LC PDI derivatives containing amino-acids eater and found they have the parallel stacking forms in LC phase.XRD di ﬀraction patterns of the blended LC-1:P3HT (2:1)ﬁlms reveal that thermal annealing is critical for the ﬁlms ’crystallinity,as shown in Figure 12.The best annealing temperature is 120°C,which results in sharper and stronger peaks at 2θ= 2.43°and 4.66°than other temperatures.Although these two 2θpeaks are the distinct packing characteristics of all the perylenediimides,they do not appear in the XRD patterns of the ﬁlms annealed at lowertemperatures (25,80,and 100°C).Thus,the side chains of LC-1endue this PDI derivative a reasonable self-tunability in packing behavior.While P3HT shows only very weak and broad di ﬀraction peaks,indicating quite disordered donor phases,the highly ordered arrangement in the blend ﬁlm annealed at 120°C can only be attributed to liquid crystalline phase of LC-1.The above XRD results of the blended ﬁlms are identical to that of the pure LC-1,which again con ﬁrms that thermal annealing at a higher temperature within liquid crystalline phase will produce optimum PCE in BHJ organic solar cells.3.CONCLUSIONIn summary,we have developed and characterized a liquid crystalline perylene diimide acceptor LC-1.It exhibited a liquid crystalline phase with a broad temperature range from 41°C to 158°C,which is essential for optimizing the thermal annealing to improve the morphology of organic ﬁlms,charge mobility,and device e ﬃciency.The LC properties of LC-1have been thoroughly investigated by DSC,POM,and XRD.During device investigation,it is found that 120°C is the best temperature for thermal annealing,which results in the highest electron mobility in SCLC devices and highest PCE in BHJ solar cells.This temperature is in the upper part of the LC phase,at which LC-1forms highly ordered ﬁlms with compact and uniform crystalline particles.The BHJ devices,using P3HT:LC-1(1:2)as organic photovoltaic active layer under-going thermal annealing at 120°C,shows an optimized e ﬃciency of 0.94%.In contrast,the devices based on PDI-1,which is a nonliquid crystalline PDI counterpart,only obtain a much lower e ﬃciency of 0.22%.Atomic force microscopy (AFM)images con ﬁrm that the active layers composed of P3HT:LC-1have smooth and ordered morphology.In SCLC devices fabricated via the spin-coating technique,LC-1shows the intrinsic electron mobility of 2.85×10−4cm 2/(V s),which is almost 5times that of the PDI-1value (5.83×10−5cm 2/(V s))under the same conditions for thermal annealing at 120°C.Because of the broad temperature range of the liquid crystalline phase of LC-1,thermal annealing at higher temperatures will result in mild aggregation and thus,improve the order and morphology of the LC-1:P3HT blended ﬁlms,which is favorable for the balanced electron and hole transport and thereby higher PCE.However,when using nonliquid crystalline PDI-1as an acceptor,its strong aggregation results in poor exciton dissociation and charge transport of the blend ﬁlms.Figure 10.Polarizing optical microscopy (POM)images of LC-1(under crossed polarizers)at (A)120°C and (B)165°C.Figure 11.X-ray di ﬀraction (XRD)patterns of LC-1at 25,80,100,120,150,and 165°C.Figure 12.XRD patterns of LC-1:P3HT (2:1)blended ﬁlms from o -dichlorobenzene solution used for spin coating on ITO/PEDOT:PSS substrate.In addition,the blend ﬁlms are measured at room temperature (RT)without annealing and after annealing at 80,100,120,150,and 165°C.Thus,LC-1is more competent than PDI-1.This concept of utilizing liquid crystalline perylene diimide is worth extending to other types of non-fullerene organic semiconductors in order to discover more e ﬃcient alternatives to PCBM and further improve the performances of BHJ solar cells.4.EXPERIMENTAL SECTIONSynthesis of LC-1.N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-peryle-netetracarboxyldiimide and LC-1was synthesized according to procedures reported by Jin ’s group.22N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-perylenetetracarboxyldiimide (6.95g,12.99mmol)was dissolved in an aqueous solution of 5%NaHCO 3(100mL).ALIQUAT 336(9.6g,ca.20mmol)was dissolved in a 2:1(v/v)ethanol/water mixture (120mL).The two solutions were mixed and stirred at room temperature for 30min.The mixture was then extracted three times with petroleum ether (500mL),and the combined petroleum ether solution was evaporated to dryness.The residue was further dried at 75°C for 2h in a vacuum oven and then dissolved in dimethylformamide (DMF)(100mL).1-Bromooctade-cane (9.54g,28.6mmol)was added and the mixture was stirred at room temperature for 12h.The mixture was then poured into methanol (400mL).The product was collected as an orange powder via suction ﬁltration and washed thoroughly with methanol.After drying,the product LC-1at 75°C in a vacuum oven to constant weight,it was puri ﬁed by column chromatography on silica gel using 4:1(v/v)CH 2Cl 2/n -hexane as the eluent.Yield:10.50g (78%).1H NMR (400MHz,CDCl 3,δ)8.58(d,2H),8.43(t,2H),5.79(m,1H),4.29−4.10(m,2H),1.82−1.54(m,5H),1.19(d,30H),0.87(t,3H);13C NMR (100MHz,CDCl 3,δ)170.44,162.73,134.69,131.76,129.47,126.38,123.22,65.89,49.77,32.10,29.86,29.71,29.54,29.38,28.66,26.10,22.87,14.98,14.30;HRMS (MALDI-TOF,m/z):[M +Na]+calcd for C 66H 90N 2O 8Na,1061.6595;found,1061.6569.1H and 13C NMR spectra of the ﬁnal product,LC-1,are provided in the Supporting Information.Materials Characterization.1H and 13C NMR spectra were recorded using a 400MHz Bruker in CDCl 3at 293K using TMS as a reference.Accurate mass correction was measured with MALDI ToF mass spectrometer (MALDI micro MX).Thermogravimetric analysis (TGA)were carried out using a Mettler −Toledo TGA/SDTA 851e at a heating rate of 10°C min −1under nitrogen ﬂow of 20mL min −1.Di ﬀerential scanning calorimetry (DSC)analyses were performed on a DSC Q100(TA Instruments).DSC curves were recorded at a scanning rate of 10°C min −1under nitrogen ﬂow.Phase transitions were also examined using a POM Nikon Diaphot 300with a Mettler FP 90temperature-controlled hot stage.X-ray di ﬀraction (XRD)measurements were performed on a Bruker D8Avance equipped with a Huber quartz monochromator 611with Cu K α1=1.54051Å.Film thicknesses were determined on an Alphastep 500surface pro ﬁlometer.UV-vis absorption spectra in chloroform (CHCl 3)solution were recorded in a UV-vis spectrophotometer (Model HP8453)at room temperature using a glass cuvette with a path length of 1cm.Device Preparation and Characterization.BHJ organic device preparation proceeds as follows.A 15Ωcm −2resistor of indium-doped tin oxide (ITO)substrate was purchased from Xiangcheng Science and Technology Co.,Ltd.,and then the substrates underwent a cleaned course in an ultrasonic bath with acetone,ethanol,and ultrapure water and dried for 1h under a blast dry oven.Subsequently,the glasses were cleaned in oxygen plasma treatment for 10min,and a PEDOT:PSS (Clevios P VP AI 4083,H.C.Starck)solution was then spin-coated at 2000rpm for 60s onto the cleaned ITO surface,resulting in a thickness of ∼40nm,as determined with a Dektak surface pro ﬁlometer.The PEDOT:PSS layer was annealed for 30min at 120°C in air.A solution of active layer P3HT (Rieke No.4002-E)and LC-1were simultaneously dissolved in dichlorobenzene in a weight ratio of 1:1at a concentration of 15mg mL −1and stirred for 1h at a temperature of 90°C in an oil bath.Before deposition of the active layer,the mixed solution of P3HT:LC-1was ﬁltered through a polytetra ﬂuoroethylene(PTFE)syringe ﬁlter (0.45μm pore size).The active layer was then spin-coated on top of the PEDOT:PSS ﬁlm at 600rpm (dichlorobenzene)for 18s resulting in a ﬁlm thickness of ∼96nm.Aluminum counter electrodes were evaporated through a shadow mask on top of the active layer with a thickness of ∼100nm.The ﬁlms were annealed at 120°C for 30min in the vacuum state.The active area of the pixels,as de ﬁned by the overlap of anode and cathode area,was 12mm 2.The photovoltaic performance was determined under simulated sunlight,using a commercial solar simulator (Zolix ss150solar simulator,China).Device Characterization.The external quantum e ﬃciency (EQE)characterization of all devices was performed in air.The light output from a xenon lamp was monochromated by a Digichrom Model 240monochromator,and the short-circuit device photocurrent was monitored by a Keithley electrometer as the monochromator was scanned.A calibrated silicon photodiode (818-UV Newport)was used as a reference in order to determine the intensity of the light incident on the device,allowing the EQE spectrum to be deduced.■ASSOCIATED CONTENT*Supporting Information 1H and 13C NMR spectra of LC-1.Thermal gravimetric analysis (TGA)of LC-1.UV-vis absorption spectra of LC-1in chloroform (CHCl 3)solution and the ﬁlm.This material is available free of charge via the Internet at .■AUTHOR INFORMATIONCorresponding Authors*E-mail:xiaoyi@.*E-mail:chengchuanhui@.Author ContributionsThe manuscript was written through contributions of all authors.All authors have given approval to the ﬁnal version of the manuscript.NotesThe authors declare no competing ﬁnancial interest.■ACKNOWLEDGMENTSThis work was supported by National Natural Science Foundation of China (No.21174022),National Basic Research Program of China (No.2013CB733702)and Specialized Research Fund for the Doctoral Program of Higher Education (No.20110041110009).■REFERENCES(1)Li,Q.,Ed.Self-Organized Organic Semiconductors:From Materials to Device Applications ;John Wiley &Sons:Hoboken,NJ,2011.(2)Li,Q.,Ed.Liquid Crystals Beyond Displays:Chemistry,Physics,and Applications ;John Wiley &Sons:Hoboken,NJ,2012.(3)Li,L.;Kang,S.W.;Harden,J.;Sun,Q.;Zhou,X.;Dai,L.;Jakli,A.;Kumar,S.;Li,Q.Liq.Cryst.2008,35,233−239.(4)Zhou,X.;Kang,S.-W.;Kumar,S.;Li,Q.Liq.Cryst.2009,3,269−274.(5)Zhou,X.;Kang,S.-W.;Kumar,S.;Kulkarni,R.R.;Cheng,S.Z.D.;Li,Q.Chem.Mater.2008,20,3551−3553.(6)Fitzner,R.;Elschner,C.;Weil,M.;Uhrich,C.;Koerner,C.;Riede,M.;Leo,K.;Pfeiffer,M.;Reinold, E.;Mena-Osteritz, E.;Baeuerle,P.Adv.Mater.2012,24,675−680.(7)Schrader,M.;Fitzner,R.;Hein,M.;Elschner,C.;Baumeier,B.;Leo,K.;Riede,M.;Baeuerle,P.;Andrienko,D.J.Am.Chem.Soc.2012,134,6052−6056.(8)Sun,Q.;Dai,L.;Zhou,X.;Li,L.;Li,Q.Appl.Phys.Lett.2007,91,253505/1−253505/3.(9)Struijk,C.W.;Sieval,A.B.;Dakhorst,J.E.J.;van Dijk,M.;Kimkes,P.;Koehorst,R.B.M.;Donker,H.;Schaafsma,T.J.;Picken,。

溴到硼酸酯

Journal of
Materials Chemistry C
Published on 20 November 2014. Downloaded on 08/12/2016 07:54:22.
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Cite this: J. Mater. Chem. C, 2015, 3, 861
However, these oligouorene functionalized oligomers may suﬀer from the unwanted long wavelength emission under long-term device operation, similar to polyuorene-based macromolecules.34–36
Received 26th September 2014 Accepted 17th November 2014 DOI: 10.1039/c4tc02173h /MaterialsC
Starburst 4,40,400-tris(carbazol-9-yl)triphenylamine-based deep-blue ﬂuorescent emitters with tunable oligophenyl length for solution-processed undoped organic lightemitting diodes†
Introduction
Since 1987, organic light-emitting diodes (OLEDs) have attracted tremendous attention due to their potential applications in at-panel displays and solid-state lightings.1–10 To achieve fullcolor displays, three primary RGB luminescent materials with excellent stability, eﬃciency and color purity are required. With respect to green and red counterparts, it seems to be a big challenge to develop blue emitters, especially deep-blue ones that have a Commission Internationale de l'Eclairage (CIE) y coordinate value of <0.10, because the intrinsic wide bandgap would inevitably result in ineﬃcient charge injection to an emitting layer (EML).11 Therefore, great eﬀorts should be paid to the design of deep-blue emitters to push forward the commercialization of full-color OLEDs.

马齿苋提取液

1. 2. 3. 4. 5. 6. 7.
Acute oral toxicity study in rats 对老鼠的口服毒性测试 Primary cutaneous irritation test in rats 对老鼠皮肤的一次性刺激性测试 Continuous cutaneous irritation test in rabbits 对兔子皮肤的连续性刺激性测试 Eye irritation test in rabbits 对兔子眼睛的刺激性测试 Guinea pig maximization test 对豚鼠的最大耐受性测试 Reverse mutation test using bacteria 对细菌的细胞突变测试 Chromosome aberration test in cultured cells. 对培养的细胞的染色体畸变测试
Portulaca Extract
Anti-irritation抗刺激性(1)
测试方法 (人体斑贴测试) / 由日本头发科学协会实验室测试实验材料 1. 志愿者 2. 使用剂量 * 5% 的马齿苋提取液 (Bioland Ltd., / Lot No.:NMP-L-122663) 45个志愿者年龄在25~55岁之间 0.01g
Natural product 天然产品
马齿苋提取液 Portulaca Extract
CONTENTS 目录
Ⅰ. Desc 1. Portulaca Extract 马齿苋提取液 1) Introduction 简介 2) Main effect 主要作用 3) Application 应用
Ⅱ. Evaluation 1. Cell Cytotoxity 测试马齿苋提取液对细胞的毒性 2. Allergy Estimation 过敏性评估 3. Anti-Inflammatory 测试马齿苋提取液抗炎症、抗红肿的功效 4. Anti-Irritation 测试马齿苋提取液抗刺激的功效 5. Safety Test 安全性评估

注射用盐酸吡硫醇制备流程

注射用盐酸吡硫醇制备流程英文回答：Preparation of Pyrithione Hydrochloride for Injection.Introduction:Pyrithione hydrochloride is a broad-spectrum antifungal and antibacterial agent that is used to treat a variety of infections. It is a synthetic compound that is prepared by the reaction of pyrithione sodium with hydrochloric acid. The resulting product is a white or off-white powder that is soluble in water.Materials:Pyrithione sodium.Hydrochloric acid.Water.Activated carbon.Equipment:Reaction vessel.Stirrer.Thermometer.Vacuum filter.Drying oven.Procedure:1. Dissolve pyrithione sodium in water in the reaction vessel.2. Add hydrochloric acid to the solution and stir untilthe reaction is complete.3. Filter the solution through activated carbon to remove impurities.4. Vacuum filter the solution to remove the solvent.5. Dry the product in a drying oven.Quality Control:The product should meet the following specifications:Appearance: White or off-white powder.Assay: 98.0% to 102.0%。

克罗茨纳赫笔记研究读本

克罗茨纳赫笔记研究读本Title: Research Reader on the Croizonneach NotesTitle: 克罗茨纳赫笔记研究读本Section 1: Introduction to the Croizonneach NotesThe Croizonneach Notes are a collection of annotations and observations compiled by the renowned German philosopher, Immanuel Kant.These notes were named after the French Huguenot refugee, Henry Croizonneach, who was known to have interacted extensively with Kant.第一部分：克罗茨纳赫笔记简介克罗茨纳赫笔记是由著名德国哲学家康德所编写的注释和观察集。

这些笔记以其法国胡格诺难民、亨利·克罗茨纳赫的名字命名，他据称与康德有广泛的互动。

Section 2: Content Analysis of the NotesA thorough examination of the Croizonneach Notes reveals a treasure trove of insights into Kant"s philosophical ideas and his views on various subjects such as ethics, aesthetics, and politics.These notes provide valuable context for understanding his famous works like the "Critique of Pure Reason" and the "Metaphysics of Morals".第二部分：笔记内容分析对克罗茨纳赫笔记的彻底审查揭示了对康德哲学思想和他对伦理学、美学和政治等主题看法的宝贵见解。

芳香烃的定义（Definitionofaromatichydrocarbons）

芳香烃的定义（Definition of aromatic hydrocarbons）Definition of aromatic hydrocarbonsbrief introductionAromatic compounds historically refer to a class of aromatic smelling substances obtained from plant gums but are now known as aromatic aromatic hydrocarbonsMost of the substances are odorless. Therefore, the word "fragrance" has lost its original meaning, only because it is used to this day. [1] aromatic compounds are collectively known as carbon ring compounds and derivatives whose rules are consistent with the rules of shock. They have a conjugated system closed circular molecules; II electronic meet 4n+2, and highly delocalized bond; Changping homogenization. Therefore, the compound has a highly unsaturated condition, but the nature is relatively stable, such as easy and difficult to replace, and the addition of oxygen. This section focuses on the structure, nomenclature, chemical properties, localization effects and applications of aromatic hydrocarbons in organic synthesis. [2]?nameTwo cases: first, the nomenclature of single ring aromatic hydrocarbons, usually using the benzene ring as the parent, and alkyl as the substituent. Two is a complex structure of aromatic hydrocarbons, usually in the alkyl group as the parent material, benzene as a substituent. For example: 1, 2- xylene; 2- methyl -3- phenyl pentane; two benzene methane and so on. For thenomenclature of polyfunctional compounds, attention should be paid to the priority order of functional groups. The priority in the front is the parent. Generally as follows: positive ions, COOH, SO3H, COOR, COCl, CONH2, CN, CHO, CO, OH, SH, NH2, alkyne, ene, ether, X, NO2 and so on. [2]?structureThe structural characteristics of benzene molecules: 1 and 6 C are SP2 hybrid 2, all atoms coplanar 3, and there is a closed ring conjugated system in the molecule,The bond length is 4 and the stability is high. [2]?Edit the source of this episode of aromatic hydrocarbonsAromatic hydrocarbons are mainly derived from coal, tar and petroleum. Aromatic hydrocarbons are insoluble in water and soluble in organic solvents. Aromatic hydrocarbons are generally lighter than water; boiling points vary with aromatic hydrocarbonsIncrease in molecular weight. Aromatic hydrocarbons are easy to substitute and can react under certain conditions. Such as benzene and chlorine in the presence of iron catalyst to produce chlorobenzene and hydrogen chloride, in the light, there is an additional reaction to produce six benzene chloride (C6H6Cl6). Aromatic hydrocarbons are mainly used in pharmaceuticals, dyes, and other industries.Edit this paragraph nature introductionElectrophilic substitution reactionThere are mainly five aspects: halogen: with the halogen and iron powder or the corresponding three iron halide present, the benzene ring on which H can be replaced by the trans polycyclic aromatic hydrocarbons can occurShould. The reaction activity of halogen is: F>Cl>Br>I, the activity of benzene derivative is: alkyl benzene > benzene > benzene ring, there is a derivative of electron withdrawing group. When halogenated benzene occurs, if the catalyst is used, the reaction of H substitution on benzene ring can occur; if, in light, the reaction of H substituted on the side chain can occur. Application: authentication. (carbon tetrachloride solution bromine or bromine) such as benzene, hexane, styrene: identification. (answer: step1: Step2: Fe bromine, bromine; powder). Nitration: in the presence of concentrated sulfuric acid and concentrated nitric acid (mixed acid), nitrobenzene can be introduced into the benzene ring at the water bath temperature of 55 degrees Celsius to 60 degrees Celsius to produce nitrobenzene. The rate of nitration of different compounds is the same as above. Sulfonation: the reaction with concentrated sulfuric acid,The sulfonic acid group can be introduced into the benzene ring. The reaction is a reversible reaction. In acidic aqueous solution, acid radical detachment, so that it can be used for group protection. The sulfonation products of alkyl benzene change with temperature: the product of counterpoint is obtained at high temperature, and aromatic hydrocarbons aremainly obtained at low temperature - chemical reactionsOrtho product. F-C alkylation: when conditions such as anhydrous AlX3 and other Lewis acids exist, benzene and derivatives can react with RX, olefins and alcohols to introduce alkyl groups into benzene rings. This is a reversible reaction, often resulting in multicomponent substitution, and in the process of reaction, the rearrangement of C cations occurs, often without the desired product. The reaction cannot be carried out when the benzene ring is attached to an electron withdrawing group. For example, benzene, toluene, ethylbenzene and cumene are synthesized from benzene. F-C acylation: the condition is the same as above. Benzene and derivatives can react with RCOX, anhydride and so on, and introduce RCO- groups into benzene ring. This reaction does not rearrange, but does not occur when the benzene ring is attached to an electron withdrawing group. Such as: benzene, synthesis of cumene, acetophenone. Summary: the electrophilic substitution reaction activity connected to electron withdrawing substituted benzenes reaction is faster than that of benzene, and connected to the electronic medium more, the greater the activity; on the contrary, connected with electron withdrawing groups substituted benzenes reaction speed less than benzene, electron withdrawing and more connected, more active. [2]?Addition reactionAnd H2: in the presence of catalysts such as Pt, Pd and Ni, hydrogen can be reacted with hydrogen to produce cyclohexane. And Cl2: under light conditions, free radical addition reactions can occur, resulting in 666. [3]?oxidation reactionBenzene itself is difficult to oxidize. But there is a hydrogen atom and benzene hydrocarbon homologues of adjacent carbons, both R- carbon chain length can be oxidized in Potassium Permanganate under acidic conditions, usually generate benzoic acid. Benzene derivatives without alpha -H are difficult to oxidize. The reaction is used to synthesize carboxylic acids, or to discriminate between them. Phenomenon: Potassium Permanganate solution faded purple red.Positioning effectThe two kind of orientating neighbor and para locating base is also called the first kind of locating base, which includes all the electron donating base and the halogen. They introduce newly introduced groups into their ortho and para positions. The electron group activates the benzene ring, while X2 causes the benzene ring to become passivated. The intermediate position group, also known as the second type of base group, contains all the electron withdrawing groups except the halogen. They move new introduced groups into their spaces. They all make the benzene ring passivation. Two localization rules of substituted benzene: the original two substituents have the same positioning function and enter the common positioning position. Such as toluene, toluene and so on. The localization of the two substituents is inconsistent. There are two cases: two, the substituent belongs to the same kind, but the location effect is stronger; if the two substituent belongs to different classes, then the first kind of location base determines. [3]?Edit the classification of aromatic hydrocarbons in this paragraphAccording to the different structure can be divided into three categories: single ring aromatic hydrocarbons, such as benzene, polycyclic aromatic hydrocarbons, such as naphthalene, anthracene, phenanthrene, etc.; polycyclic aromatic hydrocarbons, such as biphenyl, triphenylmethane. Mainly from petroleum and coal tar. Aromatic hydrocarbons are the most basic ingredients in the organic chemical industry. Modern drugs, explosives, dyes,The vast majority are composed of aromatic hydrocarbons. Fuels, plastics, rubber and saccharin are also made from aromatic hydrocarbons.Edit the paragraph descriptionbrief introductionAccording to the different structure can be divided into three categories: monocyclic aromatic hydrocarbons namely benzene homologues; the polycyclic aromatic hydrocarbons, such as naphthalene, anthracene, phenanthrene, etc.; polycyclic aromatic hydrocarbons, such as biphenyl, triphenylmethane. Mainly from petroleum and coal tar. Aromatic hydrocarbons are the most basic ingredients in the organic chemical industry. The vast majority of modern drugs, explosives, dyes are made from aromatic hydrocarbons. Fuels, plastics, rubber and saccharin are also made from aromatic hydrocarbons.Polycyclic aromatic hydrocarbonsPolycyclic aromatic hydrocarbons (PolycyclicAromaticHydrocarbons, PAH), a chemical compound containing two or more than two benzene rings, is the first known chemical carcinogen. In early 1775 the British surgeon Pott proposed a child sweeping the chimney, multiple scrotal cancer in adulthood, the reason is that the coal dust particles through the clothes rub into the skin of the scrotum is actually caused by the soot caused by polycyclic aromatic hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs) were also the first chemical carcinogens to be successful in animal experiments. In 1915, Japanese scholars Yamagiwa and Ichikawa were caused by polycyclic aromatic hydrocarbons in coal tar. Prior to 50s, polycyclic aromatic hydrocarbons were considered to be the most important carcinogenic factor, and one of the various carcinogens after 50s. But on the whole, it still plays an important role in carcinogens, because it is still the largest class of carcinogens and is widely distributed. Air, soil, water and plants all have their presence,Even 3 4- pyrene was isolated from limestone under fifty meters deep into the stratum. In nature, it exists mainly in coal, petroleum, tar and bitumen, and can also be produced by incomplete combustion of hydrocarbon containing compounds. The exhaust fumes from automobiles, aircraft and various motor vehicles and smoke in cigarettes contain a variety of carcinogenic polycyclic aromatic hydrocarbons. Open burning (fire, burning) can produce a variety of carcinogenic polycyclic aromatic hydrocarbons. Smoke, baking and baking canbe contaminated by polycyclic aromatic hydrocarbons. The carcinogenic polycyclic aromatic category has been found to have more than 400 kinds of carcinogenic polycyclic aromatic hydrocarbons and their carcinogenic derivatives. According to its chemical structure, it can be divided into two categories: benzene ring and heterocycle.Benzene ring polycyclic aromatic hydrocarbonsBenzene is a single ring aromatic hydrocarbon, which is the parent of polycyclic aromatic hydrocarbons. In the past, benzene has no carcinogenic effect. In recent years, through animal experiments and clinical observation, benzene has been found to inhibit hematopoietic system, and long-term exposure to high concentrations of benzene can cause leukemia. In 1965, 60 cases of acute and chronic leukemia caused by benzene were reported.Tricyclic aromatic hydrocarbonsPolycyclic aromatic hydrocarbons do not cause cancer, more than tricyclic polycyclic aromatic hydrocarbons are carcinogenic. Tricyclic aromatic hydrocarbons two isomers of anthracene and phenanthrene noncancerogenic. But some of their methyl derivatives are carcinogenic. For example, 9, 10-, two methyl anthracene, 1,2,9,10-, four methyl phenanthrene and so on are carcinogenic. Phenanthrene has a strong carcinogenicity in many of its derivatives, especially 15H-, a and two methyl and three methyl derivatives, which have strong carcinogenicity.[4]?Aromatic hydrocarbonsFour aryl hydrocarbons have six isomers, and experiments have shown that only 3, 4-, phenanthrene, phenanthrene have moderate carcinogenicity, and 1, 2-, anthracene, anthracene and bend have very weak carcinogenicity. Their methyl derivatives are 2-, methyl, -3, 4-, and phenanthrene are potent carcinogens. 1, 2- benzanthracene, and many other kinds of alkyl methyl substituted derivatives have a certain carcinogenic, such as 9 10-, two 2- methyl -1, benzanthracene is currently known carcinogenic polycyclic aromatic hydrocarbons in the fastest and most active skin carcinogen. Flexor can be a carcinogenic agent with low carcinogenic activity, but its derivatives, 3- methyl and 5- methyl, have a strong carcinogenic effect. [4]?Five ring aromatic hydrocarbonThere are fifteen isomers of the five ring aromatic hydrocarbons, five of which are carcinogenic. 3, 4- is particularly strong carcinogen benzopyrene, 1, 2, 5, two 6- benzanthracene is a strong carcinogen, 1, 2, 3, two 4- of triphenylene as strong carcinogens, 1, 2, 7, two 8- benzanthracene and 1, 2, 5, and two 6- benzene the Philippines for weak carcinogen. [4]?Six ring aromatic hydrocarbonThe six aromatic hydrocarbons are more heterogeneous than the five aromatic hydrocarbons, but only more than 10 species have been tested for carcinogenicity. In 3, 4, 8, 9- two is a strong carcinogen, 1, 2, 3, two 4- 3, a strong carcinogen benzopyrene,4, 9, two 10- 2, 3 and 1 of benzo pyrene, 7-, methyl derivatives 4- two benzopyrene have obvious carcinogenic effects, the remaining six non carcinogenic polycyclic aromatic hydrocarbons effect of weak or carcinogenic. Aromatic hydrocarbons with more than seven rings have been studied less.Other polycyclic aromatic hydrocarbonsCarcinogenic and other polycyclic aromatic hydrocarbons are also numerous, as follows are examples. Fluorene: fluorene itself is not carcinogenic,But some of its derivatives are carcinogenic. For example, 1, 2, 5, 6- two, benzo fluorene, 1, 2, 7, 8- two, benzo fluorene and 1, 2, 3, 4-, two, fluorene, fluorene have been proved to have certain carcinogenicity, such as can cause skin cancer in mice. 2, 3-, fluorene, anthracene and 7, 8- fluorene anthracene Anthracene has a strong carcinogenic effect, the carcinogenic effect on mice skin second only to 3, 4- benzopyrene. Anthracene: it has a strong carcinogenicity, and many of its methyl and other alkyl derivatives also have strong carcinogenicity. For example, 3- is an extremely powerful carcinogen that causes cancer in the skin, cervix, lung and other cancers. In the intestine, the action of bacteria can lead to the conversion of cholic acid to methyl cholesterol, a chemical carcinogen that may have carcinogenic effects on humans. [4]?Heterocyclic polycyclic aromatic hydrocarbonsPolycyclic aromatic hydrocarbons; polycyclic carbon atoms in the ring are replaced by atoms of nitrogen, oxygen, sulfur, etc.;heterocyclic compounds are polycyclic aromatic hydrocarbons. Among heterocyclic aromatic hydrocarbons, some compounds have certain carcinogenicity. Examples are given ofnitrogen-containing, benzene fused heterocycles. Benzo acridine: the 10 carbon atom in the anthracene molecule ring is replaced by a nitrogen atom. Benzo (a) acridine and benzo (c) acridine have no carcinogenicity, but some of their methyl derivatives have carcinogenicity. For example, 8, 10, 12-, three methyl benzene (a), acridine and 9, 10, 12-, three methyl benzene (a) acridine are strong carcinogens, 7, 9-, two methyl benzene (c), acridine and 7, 10-, two methyl benzene (c) acridine is a very strong carcinogen. The carcinogenic power of the latter two is stronger than that of 3-. Two benzo acridine: two of the two studied in benzene, three isomers, i.e., benzo (a,(H) acridine, and two benzo (C, H) acridine, three have carcinogenicity. Some alkyl derivatives of two benzo (a, H) acridine and two benzo (a, J) acridine have carcinogenicity, such as two benzo (a, H) acridine 8-, ethyl and 14- n-butyl derivatives are carcinogenic. Carbazole: a compound of 9 carbon atoms substituted by nitrogen atoms in the fluorene molecule ring. Some single benzene and benzene derivatives have been confirmed many of its carcinogenicity. For example, 7-H- two, benzo (a, g) carbazole and 7-H- two benzo (C, g) carbazole have carcinogenic effects on mice. The latter N- methyl and N- ethyl derivatives have weak carcinogenic activity. In recent years, some two aza carbazole compounds have been found, and they also have obvious carcinogens. Among them, 11- aza two - benzo (C, I) carbazole and 1- aza - two benzo (a, I) carbazole are moderately strong carcinogens. The carcinogenicity ofnitrogen-containing heterocyclic heterocycles was first studied in the 50s of this century. The carcinogenic effects of these compounds are not as deep and widespread as those studied for polycyclic aromatic hydrocarbons, and most lack sufficient evidence of human carcinogenicity. These compounds are widely distributed in nature, many of them are alkaloids and other biological substances in plants, many of them are synthetic drugs. Therefore, attention should be paid to the use of these compounds. Aromatic hydrocarbons with more than seven rings have been studied less. Other polycyclic aromatic hydrocarbons are carcinogenic and other polycyclic aromatic hydrocarbons are numerous. Fluorene fluorene is not carcinogenic in itself, but some of its derivatives have carcinogenicity. For example, 1, 2, 5, 6-, two, fluorene, 1, 2, 7, 8-, two, fluorene and 1, 2, 3,4- two, fluorene, fluorene and so on have been proved to have certain carcinogenicity, if can cause skin cancer in mice. 2, 3-, fluorene, anthracene and 7, 8- fluorene anthracene Anthracene has a strong carcinogenic effect, the carcinogenic effect on mice skin second only to 3, 4- benzopyrene. It has strong carcinogenicity, and many of its methyl and other alkyl derivatives also have strong carcinogenicity. For example, 3- is an extremely powerful carcinogen that causes cancer in the skin, cervix, lung and other cancers. In the intestine, the action of bacteria can lead to the conversion of cholic acid to methyl cholesterol, a chemical carcinogen that may have carcinogenic effects on humans. Heterocyclic polycyclic aromatic hydrocarbons; polycyclic aromatic hydrocarbons; polycyclic carbon atoms are replaced by atoms of nitrogen, oxygen, sulfur, etc.; heterocyclic compounds are polycyclicaromatic hydrocarbons. Among heterocyclic aromatic hydrocarbons, some compounds have certain carcinogenicity. Examples are given of nitrogen-containing, benzene fused heterocycles. Two, three acridine benzene two acridine, more research has three isomers, namely two benzene (a, H) acridine, and two benzene (C, H) acridine, both have carcinogenicity. Some alkyl derivatives of two benzo (a, H) acridine and two benzo (a, J) acridine have carcinogenicity, such as two benzo (a, H) acridine 8-, ethyl and 14- n-butyl derivatives are carcinogenic. Carbazole is a compound of 9 - dimensional carbon atoms substituted by nitrogen atoms in fluorene molecular rings. Some single benzene and benzene derivatives have been confirmed many of its carcinogenicity. For example, 7-H- two, benzo (a, g) carbazole and 7-H- two benzo (C, g) carbazole have carcinogenic effects on mice. The latter N- methyl and N- ethyl derivatives have weak carcinogenic activity.In recent years, some two aza carbazole compounds have been found, and they also have obvious carcinogens. Among them, 11- aza two - benzo (C, I) carbazole and 1- aza - two benzo (a, I) carbazole are moderately strong carcinogens. The carcinogenicity of nitrogen-containing heterocyclic heterocycles was first studied in the 50s of this century. The carcinogenic effects of these compounds are not as deep and widespread as those studied for polycyclic aromatic hydrocarbons, and most lack sufficient evidence of human carcinogenicity. These compounds are widely distributed in nature, many of them are alkaloids and other biological substances in plants, many of them are synthetic drugs. Therefore, attention should be paid to the use of these compounds. Aromatic compounds not all aromatic compounds arearomatic flavor, because the beginning of the chemical industry in the study and exposure to such substances from some dyes, some flowers and fragrance that these substances, so called aromatic.Edit this segment of polycyclic aromatic hydrocarbonsbrief introductionPolycyclic aromatic hydrocarbons (Polycyclic, Aromatic, Hydrocarbons, PAH), molecules containing two or more than two benzene compounds of the structure, is the first known chemical carcinogens. In early 1775 the British surgeon Pott proposed a child sweeping the chimney, multiple scrotal cancer in adulthood, the reason is that the coal dust particles through the clothes rub into the skin of the scrotum is actually caused by the soot caused by polycyclic aromatic hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs) were also the first chemical carcinogens to be successful in animal experiments. In 1915, Japanese scholars Yamagiwa and Ichikawa were caused by polycyclic aromatic hydrocarbons in coal tar.Prior to 50s, polycyclic aromatic hydrocarbons were considered to be the most important carcinogenic factor, and one of the various carcinogens after 50s. But on the whole, it still plays an important role in carcinogens, because it is still the largest class of carcinogens and is widely distributed. Air, soil, water and plants all existed, and 3, 4- pyrene was isolated from limestone, even fifty meters below the depth of the stratum. In nature, it exists mainly in coal, petroleum, tar and bitumen, and can also be produced by incompletecombustion of hydrocarbon containing compounds. The exhaust fumes from automobiles, aircraft and various motor vehicles and smoke in cigarettes contain a variety of carcinogenic polycyclic aromatic hydrocarbons. Open burning (fire, burning) can produce a variety of carcinogenic polycyclic aromatic hydrocarbons. Smoke, baking and baking can be contaminated by polycyclic aromatic hydrocarbons.Carcinogenic polycyclic aromatic speciesMore than 400 kinds of derivatives of carcinogenic polycyclic aromatic hydrocarbons and carcinogenicity have been found. According to its chemical structure, it can be divided into two categories: benzene ring and heterocycle.Benzene ring polycyclic aromatic hydrocarbonsBenzene is a single ring aromatic hydrocarbon, which is the parent of polycyclic aromatic hydrocarbons. In the past, benzene has no carcinogenic effect. In recent years, through animal experiments and clinical observation, benzene has been found to inhibit hematopoietic system, and long-term exposure to high concentrations of benzene can cause leukemia. In 1965, 60 cases of acute and chronic leukemia caused by benzene were reported.。

4-氯硫代苯酚结构式

4-氯硫代苯酚结构式英文回答：4-Chlorothiophenol is an organic compound with the molecular formula C6H5ClOS. It is also known as 4-chlorobenzenethiol. The structure of 4-chlorothiophenol consists of a phenyl ring attached to a sulfur atom, which is further attached to a chlorine atom.This compound is commonly used as a building block in organic synthesis. It can be used to introduce a chlorine atom into various organic molecules, allowing for the synthesis of a wide range of compounds. For example, 4-chlorothiophenol can be used to prepare 4-chlorobenzenesulfonyl chloride, which is an important intermediate in the synthesis of pharmaceuticals and agrochemicals.In addition to its synthetic applications, 4-chlorothiophenol also has some interesting properties. Itis a colorless to pale yellow solid with a strong, unpleasant odor. It is soluble in organic solvents like ethanol and acetone, but only slightly soluble in water. This compound is also known to exhibit some antimicrobial activity, making it useful in certain applications.To illustrate the versatility of 4-chlorothiophenol,let's consider an example. Suppose I want to synthesize a compound that contains a chlorine atom. I can start with 4-chlorothiophenol and use it as a starting material. By reacting it with another compound, such as an alcohol or an amine, I can introduce the chlorine atom into the desired position. This allows me to create a wide range of compounds with different properties and applications.中文回答：4-氯硫代苯酚是一种有机化合物，化学式为C6H5ClOS。

傅克烷基反应的英文范例

傅克烷基反应的英文范例The Friedel-Crafts alkylation reaction is a widely used organic reaction that involves the introduction of an alkyl group onto an aromatic ring. It is named after the chemists Charles Friedel and James Crafts who first discovered this reaction in 1877. This reaction is an important tool in organic synthesis and has numerous applications in the pharmaceutical, agrochemical, and materials industries.Here is an example of the Friedel-Crafts alkylation reaction:Reactants:Benzene (aromatic compound)。

Chloromethane (methylating agent)。

Aluminum chloride (Lewis acid catalyst)。

Procedure:1. In a dry and inert atmosphere, mix benzene and chloromethane in a reaction flask.2. Add a small amount of aluminum chloride as a catalyst.3. Stir the reaction mixture at a suitable temperature, typically around room temperature or slightly higher.4. Allow the reaction to proceed for a specific period, usually a few hours.5. Quench the reaction by adding a suitable quenching agent, such as water or an alcohol, to destroy any excess reagents or side products.6. Extract the desired product from the reaction mixture using an appropriate solvent.7. Purify the product using techniques such asdistillation, chromatography, or recrystallization.Example reaction:Benzene + Chloromethane (methylating agent) --> Toluene (methylbenzene) + Hydrochloric acid.In this example, the benzene molecule reacts with chloromethane in the presence of aluminum chloride as a catalyst. The result is the substitution of a hydrogen atom on the benzene ring with a methyl group, forming toluene. Hydrochloric acid is produced as a byproduct of the reaction.It is important to note that the Friedel-Crafts alkylation reaction has limitations, such as thepossibility of multiple alkylations, rearrangements, and side reactions. These limitations can be overcome by using appropriate reaction conditions, controlling the stoichiometry of the reactants, and selecting suitable catalysts.Overall, the Friedel-Crafts alkylation reaction is a valuable tool in organic synthesis, allowing the introduction of alkyl groups onto aromatic rings to create a wide range of functionalized aromatic compounds.。

氯代三硝基苯及其衍生物的合成与研究

氯代三硝基苯及其衍生物的合成与研究摘要卤代多硝基苯通常为合成含能材料的中间体，与硝基吡唑缩合可生成能量高，感度低的含能化合物，因此将氯代三硝基苯和硝基吡唑化合物相结合，在吡唑环上引入苦基，不仅增加其能量，还能降低感度。

本文通过氯代三硝基苯和3,4-二硝基吡唑（DNP）的C-N缩合反应以及氯代三硝基苯之间的C-C偶联反应，制备得到了两种能量高、耐热性能好的含能化合物：3-(3,4-二硝基吡唑-1-基)-2,4,6-三硝基苯酚和3-(3,4-二硝基吡唑-1-基)-2,4,6-三硝基苯，并对其结构进行了表征。

首先通过间二氯苯的硝化制备了1, 3-二氯-2, 4, 6-三硝基苯（DCTNB），对DCTNB 合成条件进行了优化。

当发烟硫酸为100 mL、硝酸钾为35.5 g、反应温度为160℃、反应时间为4 h时，DCTNB的产率可达75.4%。

通过薄层色谱和熔点测试对DCTNB纯度进行初步鉴定，采用红外光谱、核磁共振光谱等对其结构进行了表征。

其次以DCTNB和DNP为原料，在缚酸剂作用下发生C-N缩合生成3-(3,4-二硝基吡唑-1-基)-2,4,6-三硝基苯酚，对其进行了分离提纯。

运用薄层色谱、红外光谱、核磁氢谱、碳谱和高分辨质谱进行了表征。

研究了缚酸剂、反应温度、反应时间和溶剂对缩合反应的影响，得出较佳条件：缚酸剂为三乙胺，反应温度为60℃，反应时间为2 h，溶剂为二甲基亚砜，产率为62.4%。

并对DCTNB和DNP缩合反应的可能机理进行了分析；以2,4,6-三硝基氯苯（PiCl）和DNP为原料，在缚酸剂作用下发生C-N缩合生成3-(3,4-二硝基吡唑-1-基)-2,4,6-三硝基苯，对其进行分离提纯，采用红外光谱、核磁共振光谱等对产物的结构进行了表征。

其性能和应用前景有待进一步研究。

再分别以DCTNB和PiCl/DCTNB为原料，铜粉为催化剂，高温下发生C-C缩合生成耐热炸药2,2′,2″,4,4′,4″,6,6′,6″-九硝基三联苯（NONA）；将铜粉用碘化亚铜替换，二甲基亚砜代替硝基苯为溶剂，进行Ullmann偶联反应，分离提纯产物，对产物进行表征，分析未成功获得NONA的原因。

chlorophenols 氯酚

tion (LLE) with organic solvents [4,5], solid phase extraction (SPE) with different sorbents such as synthetic resins [6], and C,, [7] or graphitized carbon cartridges [8,9]. In every case, large volumes of sample have to be processed and then the final extracts must be concentrated. This solvent evaporation step has been shown to result in major losses of several chlorophenols [lo]. Chlorophenols are usually determined by use of chromatographic techniques such as HPLC [1 l] or GC [12]. However, because of their high polarity, they give broad, tailed peaks if separated directly (without prior derivatization) by GC. The effect worsens as the chromatographic column used ages 1131. It is therefore advisable to convert chlorophenols into less polar forms in order to improve peak shape, resolution and sensitivity [ 141. Acetylation is the most frequently used reaction for this purpose [ 15,161. Alternative derivatizing agents,

丁晴胶材质英文说明书

丁晴胶材质英文说明书First, the introductionA synthetic rubber made from the copolymerization of butadiene and acrylonitrile. It is an oil resistance (especially nitrile rubber alkane oil), aging resistance of good synthetic rubber. There are five kinds of acrylonitrile content (%) in nitrile rubber: 42~46,36~41,31~35,25~30, and 18~24. The more acrylonitrile content, the better the oil resistance, but the cold resistance is decreased accordingly. It can be used in 120℃ air or 150℃ oil. In addition, it also h as good water resistance, air tightness and excellent bonding performance. It is widely used in making a variety of oil-resistant rubber products, a variety of oil-resistant gaskets, gaskets, casing, soft packaging, soft hose, printing and dyeing rubber roller, cable rubber materials, etc., in the automobile, aviation, petroleum, photocopying and other industries have become an essential elastic materials.Second, basic performanceNitrile rubber, also known as butadiene monoacry lonitrile rubber, is referred to as NBR, and has an average molecular weight of about 700,000. Gray-white to pale yellow massive orpowdery solid with a relative density of 0.95 to 1.0. The nitrile vitrification temperature Tg= one 52℃, brititile Tb= one 47℃, and nitrile Tg= one 22℃. The solubility parameters were defined as = 8.9 to 9.9, and they were dissolved in ethyl acetate, butyl acetate, chlorobenzene, methyl ethyl ketone, etc. Nitrile rubber has excellent oil resistance, its oil resistance is second only to polysulfur rubber and fluorine rubber, and has the wear resistance and air tightness. The disadvantage of nitrile rubber is not resistant to ozone and aromatic groups, halogenated hydrocarbons, ketones and ester solvents, and should not be used as insulating materials. Heat resistance is better than but adiene rubber, neoprene, can work at 120℃. Air tightness is second only to buty l rubber. The performance of nitrile rubber is affected by the content of acrylonitrile. With the increase of tensile strength, acrylonitrile content, heat resistance, oil resistance, air tightness, and hardness will increase, but the elasticity and cold resistance will decrease. Ozone resistance and electric insulation performance of nitrile rubber are not good. Good water resistance.。

氯苯中氯的杂化类型

氯苯中氯的杂化类型氯苯是一种含有氯原子的芳香族化合物。

氯原子可以以不同的杂化类型存在于氯苯中，包括sp杂化、sp2杂化和sp3杂化。

这些不同的杂化类型决定了氯苯分子的结构和化学性质。

在本文中，我们将深入探讨氯苯中氯的杂化类型以及对分子性质的影响，并讨论其在化学反应中的应用。

1. sp杂化的氯苯在sp杂化的氯苯中，氯原子的两个轨道分别与两个相邻的碳原子上的杂化轨道重叠。

这样的排列使得氯原子与相邻的碳原子之间存在着较强的σ键作用。

sp杂化的氯苯分子呈线性形状，碳原子和氯原子之间的键角约为180度。

这种结构使得分子更加稳定，同时也降低了反应性。

2. sp2杂化的氯苯在sp2杂化的氯苯中，氯原子的一个轨道与一个相邻的碳原子上的sp2杂化轨道重叠，形成较强的σ键。

另一个轨道则与芳香环上的π电子轨道重叠，形成一个π键。

sp2杂化的氯苯分子呈平面结构，碳原子和氯原子之间的键角约为120度。

这种结构使得分子具有较高的反应性，尤其是在芳香族化合物的反应中。

3. sp3杂化的氯苯在sp3杂化的氯苯中，氯原子的轨道与相邻的碳原子上的sp3杂化轨道重叠，形成较强的σ键。

sp3杂化的氯苯分子呈三维结构，碳原子和氯原子之间的键角约为109.5度。

这种结构使得分子更富有空间性，对于某些化学反应具有特殊的环境要求。

以上是关于氯苯中氯的杂化类型的基本介绍。

通过对氯苯分子中氯原子杂化类型的了解，我们可以预测其在化学反应中的行为，从而为有机合成和材料科学的研究提供指导。

氯苯作为一种重要的化学中间体，具有广泛的应用。

氯苯可以通过与亲电试剂的取代反应来引入其他官能团，从而合成各种有机化合物。

氯苯还可以用作溶剂、燃料添加剂或作为染料和荧光剂的原料。

总结回顾：通过本文的探讨，我们深入了解了氯苯中氯的杂化类型以及对分子性质的影响。

sp杂化的氯苯具有稳定性较高，反应性较低的特点；sp2杂化的氯苯具有较高的反应性，尤其在芳香族化合物反应中表现突出；sp3杂化的氯苯则在某些化学反应中具有特殊的环境要求。

《对氯苯甲醛》word版

医药、染料中间体，用于制造芬那露、氨苯氨酪酸等。
生产方法
（1）由对氯甲苯氯化水解而得：将对氯甲苯和三氯化磷加入反应锅，在光照下升温至155℃，通入氯气。控制温度在160-170℃，通氯至计算量，得氯化液。搅拌下将其加入浓硫酸中，常温搅拌5h。静置分层，取下层液放入冰水中结晶，冷至5℃以下过滤。滤饼用冰水洗涤得粗品，减压蒸馏，收集108-111℃（3.33kPa）馏分即得成品。（2）对氯甲苯二氧化锰氧化法：先将对氯甲苯加入反应锅，再加入70%硫酸，在70℃以下慢慢加入二氧化锰。加毕，反应0.5h，再用水蒸气蒸馏。另外，对氯甲苯用空气氧化也可以得到对氯苯甲醛。
偶氮二异丁腈催化氯化法
将对氯甲苯加入反应器中，加热至160℃，加入偶氮二异丁腈为催化剂，通入氯气进行反应，以GC法控制反应终点，控制不要生成4-α，α，α-四氯甲苯，然后真空蒸馏，收集116～126℃/3kPa馏分，收率为87％，前馏分对氯甲苯和对氯氯苄回收套用。
将上述得到的4-氯亚苄基二氯放入反应器中，加入SnCl2和适当的水在回流下反应4h，经后处理得白色结晶为产品，纯度96％，收率94％。
中文名称:
4-氯苯甲醛
中文同义词:
对氯苯甲醛;氨气;4-氯苯甲醛;环丙沙星杂质B对照品;氫氧化銨;對氯苯甲醛;4-氯苯甲醛,98%;氧化
英文名称:
4-Chlorobenzaldehyde
英文同义词:
p-chlorobenzenecarboxaldehyde;P-CHLOROBENZALDEHYDE;PCAD;4-Chlorobenzoic aldehyde;4-CHLOROBENZALDEHYDE;AMMONIA WATER;AMMONIA SOLUTION, STRONG;AMMONIA NO 1

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INTRODUCTION
Chlorobenzene was one of the earliest heavy organic chemicals that is, those chemicals which were produced industrially in large amounts. The former United Alkali Company first produced chlorobenzene industrially at Widnes, England, in 1909. Chlorobenzene first acquired importance during the World War I, when it was required in high tonnage for making phenol in picric acid manufacture.
Chlorobenzene is a colorless, mobile liquid with an almond like odor. At ordinary temperature and pressure chlorobenzene is unaffected by the presence of air, moisture, or light, and upon prolonged boiling, shows no tendency to split off chlorine. The chlorine atom in chlorobenzene is unreactive at ordinary temperatures and pressures. At moderate temperatures, chlorobenzene is unaffected by steam, alkalis, hydrochloric acid, and dilute sulphuric acid. Even boiling for several hours with alcoholic KOH has no effect on chlorobenzene. It is soluble in all proportions in ether, chloroform, benzene, alcohol and carbon disulphide. It is insoluble in water. Hydrolysis, with the formation of Phenol takes place at 450°C to 500°C in the presence of a catalyst or with alcoholic alkalis or with water under pressure at high temperatures. Aniline may be prepared by reaction with concentrated ammonium hydroxide under pressure in the presence of copper catalyst. Of technical importance is the preparation of DDT by condensation of chlorobenzene with chloral in the presence of fuming Sulphuric Acid. Chlorination of chlorobenzene in the presence of a variety of catalysts produces prominently o and p-Dichlorobenzenes isomers. Chlorobenzene forms both binary and ternary azeotropic mixtures with water and a number of organic liquids.
Chlorobenzenes are less toxic than benzene. Liquid chlorobenzenes produce mild to moderate irritation upon skin contact. Contact with eye tissue at normal temperature cause s pain, mild to moderate irritation, and possibly some
transient corneal injury. Prompt washing with large quantities of water is extremely helpful. Continued contact may cause roughness or a mild burn. Absorption through the skin is slow and with short-term exposure over a limited period of time, no significant amounts will enter the body. Since the monochlorobenzene vapor forms explosive mixtures with air, open flames and smoking should not be allowed where chlorobenzene is stored or used.。