shuangyangshuiReaction_07_02_2014_144911

不对称合成的⽂献Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by New Chiral C2-Symmetric Bis(sulfonyl)tetraaza Ligands Complexed with [Ru(g 6-p -cymene)Cl 2]2in WaterXungao Liu ?Tian Zhang ?Yingying Hu ?Liang ShenReceived:3January 2014/Accepted:2April 2014/Published online:18April 2014óSpringer Science+Business Media New York 2014Abstract In this report,a new series of C2-symmetric bis(sulfonyl)tetraaza ligands were synthesized from (1S,2S)-1,2-diarylethylenediamine analogues and tested in the asymmetric transfer hydrogenation (ATH)of aromatic ketones by complexing with [Ru(g 6-p -cymene)Cl 2]2employing sodium formate as hydrogen source in neat water.A moderate to excellent conversion (*99.8%)and overall satisfying enantioselectivity (*92.8%)were obtained with varied electronic and steric effects of the substituents on ligands and substrates.Keywords Bis(sulfonyl)tetraaza áAsymmetric transfer hydrogenation áRuthenium áKetones áHCOONa1IntroductionAsymmetric transfer hydrogenation (ATH)is a typical and effective method to obtain chiral secondary aromatic alcohols,which are essential intermediates in synthesizing physiological active pharmaceuticals under its safe and mild reaction condition.Noyori et al.[1–4]have achieved high enantioselectivity up to 90%with Ru–TsDPEN complexes in the reduction of ketones and imines for the ?rst time since the transition-metal catalyzed ATH was reported in 1970s [5].Since then,lots of efforts have been put into this ?eld using monotosylated 1,2-ethylenediamine [6–12],amino alcohols [13–15],tetraaza [16–21], e.g.especially bis(sulfonyl)tetraaza ligands [18–21]tooptimize the conversion and stereoselectivity of the cata-lytic system.The previous study in our group has provided a useful insight for the design of ef?cient C2-symmetric chiral tetraaza ligands (Fig.1)[22].Inspired by these results,we aimed to explore the electronic and steric effects on the catalytic activity of ligands by developing a new set of bis(sulfonyl)tetraaza ligands derived from (1S,2S)-di-phenylethylenediamine complexed with [Ru(g 6-p -cymene)Cl 2]2and used in the ATH of acetophenone and propiophenone as well as their analogues in water with sodium formate as the hydrogen source [23–25].In this work,we report on the preparation of ?ve C2-symmetric chiralbis(sulfonyl)tetraaza ligands,3a –3e ,which are used in the Ru-catalyzed asymmetric transfer hydrogenation of aromatic ketones,giving the corresponding optically active secondary alcohols in moderate to excellent conversion together with favorable enantioselectivity.2ExperimentalAll ATH reactions were carried out under nitrogen atmo-sphere using oven-dried glassware in oil bath.Acetophe-none and dichloromethane were distilled according to standard methods.(1R,2R)-1,2-bis-(2-hydroxyphenyl)-1,2-diaminoethane and 1,3-benzenedisulfonyl chloride were purchased from Sigma-Aldrich (Steinem,Germany)and TCI(Shanghai,China),respectively.40-nitrobenzal-dehyde,40-tri?uoromethylbenzaldehyde and 20-methyl-oxybenzaldehyde were obtained from J&K chemicals (Shanghai,China).[Ru(g 6-p -cymene)Cl 2]2was from Alfa Aesar (WardHill,Massachusetts,UK).The 1H NMR and 13C NMR spectra were recorded on a 500MHz Bruker spectrometer.Chiral GC analysis was carried out usingX.Liu áT.Zhang áY.Hu áL.Shen (&)College of Material Chemistry and Chemical Engineering,Hangzhou Normal University,Hangzhou 310036,People’s Republic of Chinae-mail:shenchem@/doc/bf3fb130fe4733687e21aa9a.htmlCatal Lett (2014)144:1289–1295DOI 10.1007/s10562-014-1254-0Agilent GC7890A with CP-Chiralsil-Dex-CB Chiral col-umn(Santa Clara,CA,USA).Mass spectra were measured with Agilent(Santa Clara,CA,USA)5979spectrometer. LC–MS was measured with Agilent(Santa Clara,CA,USA) In?nity1290LC and6530Accurate-Mass Q-TOF MS. 2.1Preparation of the C2-Symmetric Bis(sulfonyl)tetraaza Ligands3–3e2.1.1Preparation of(S,S,S,S)-N,N-bis(1,2-diphenylethylenediamino)-1,3-benzenedisulfonylamine(3a)(Scheme1)A solution of(1S,2S)-1,2-diphenylethylenediamine(3mmol,0.637g)in dichloromethane(30mL)was mixed with tri-ethylamine(0.5mL,2.8mmol).The mixture was cooled to 0°C and1,3-benzenedisulfonyl chloride(0.275g,1mmol) dissolved in dichloromethane(10mL)was added dropwise for2h.The mixture was stirred under room temperature for another12h.The solvent was removed under reduced pres-sure.The mixed solid was dissolved in dichloromethane (20mL)and?ltered,and then dichloromethane was removed under reduced pressure.Repeat the procedure of dissolving and?ltering for3times until affording a yellow solution. Finally the solvent was removed under reduced pressure to obtain3a as light yellow powder(0.875g,96%yield).[a]D20: ?88.4°(c0.1,CHCl3).1HNMR(500MHz,DMSO-d6):d (ppm)3.375(6H,br singlet,N H),3.993(2H,d,J=7.5Hz, NH–C H),4.318(2H,d,J=7.5Hz,NH–C H),6.869–6.920 (10H,m,C H of phenyl),7.081–7.090(10H,m,C H of phenyl), 7.192(1H,m,C H of–SO2–phenyl),7.290(2H,dd, J=1.5Hz,8.0Hz,C H of–SO2–phenyl),7.696(1H,singlet, C H of–SO2–phenyl).13C NMR(125MHz,DMSO-d6):d (ppm)60.219(C HNH),64.227(C HNH),124.713,127.310, 127.824,127.984,128.092,128.138,128.289,128.577,129.494,138.412,140.724,140.087,141.092.EI-MS: [M?H]?:633.1290X.Liu et al.2.1.2Preparation of(S,S,S,S)-N,N-bis(1,2-bis(40-methyloxybenzene)ethylenediamino)-1,3-benzenedisulfonyl amine(3b–3e)(Scheme2)(1S,2S)-2was prepared according to the literature proce-dure[26–31].A solution of(1S,2S)-2(3mmol)indichloromethane(30mL)was mixed with excess triethyl-amine(1.5mL).The mixture was cooled to0°C and a solution of1,3-benzenedisulfonyl chloride(0.275g, 1mmol)in dichloromethane(10mL)was added dropwise over2h.After the addition,the mixture was warmed to room temperature and stirred for12h.The resulting reaction mixture was washed with hydrochloric acid(2M, 495mL).The dichloromethane layer was dried over anhydrous MgSO4,?ltered,and the solvent was removed under reduced pressure to obtain3b–3e.3b(0.817g,62%yield)as bright yellow powder.[a]D20: -109°(c0.1,CHCl3).1H NMR(500MHz,DMSO-d6):d(ppm)3.580(s,6H,OC H3),3.648(s,6H,OC H3),3.991 (2H,d,J=8.0Hz,NH–C H),4.283(2H,d,J=8.0Hz, NH–CH),6.441(4H,d,J=8.5Hz,C H of phenyl),6.659 (4H,d,J=9.0Hz,C H of phenyl), 6.761(4H,d, J=8.5Hz,C H ofphenyl),7.014(4H,d,J=9.0Hz, C H of phenyl),7.057(1H,t,J=8.0Hz,C H of–SO2–phenyl),7.300(1H,d,J=1.5Hz,C H of–SO2–phenyl), 7.316(1H,d,J=2.0Hz,C H of–SO2–phenyl),7.655(1H, s,C H of–SO2–phenyl).13C NMR(125MHz,DMSO-d6):d(ppm)55.214(O C H3),55.321(O C H3),59.853(C HNH), 64.256(C HNH),113.405,113.576,124.821,128.908,129.063,129.400,131.002,133.251,142.007,158.251, 158.556.HR-ESI–MS:[M?H]?:747.2480.3c(0.852g,65%yield)as yellow powder.[a]D20:?125°(c0.1,CHCl3).1H NMR(500MHz,CDCl3):d(ppm)3.421 (6H,s,OCH3),3.553(6H,s,OC H3),4.811(2H,s,NH–C H), 5.100(2H,s,NH–C H),6.275(2H,d,J=8.0Hz,C H of phenyl),6.415(2H,d,J=7.5Hz,C H of phenyl), 6.714–6.797(7H,m,C H of phenyl), 6.929(2H,t, J=7.5Hz,8.0Hz,C H of phenyl and–SO2–phenyl),7.118 (2H,td,J=1.0Hz,8.0Hz,C H of phenyl),7.197(2H,dd, J=1.5Hz,8.0Hz,C H of phenyl),7.296(2H,s,C H of –SO2–phenyl),7.434(1H,s,C H of–SO2–phenyl).13C NMR (125MHz,CDCl3):d(ppm)45.784(C HNH), 46.066(C HNH),55.387(O CH3),55.936(O C H3),110.240, 111.316,119.896,120.326,129.118,129.359,129.581, 130.457,140.824,155.838,156.858.HR-ESI-MS: 747.2480.3d(0.826g,59%yield)as brownish red powder.[a]D20: -107°(c0.1,CHCl3).1H NMR(500MHz,CDCl3):Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed1291d (ppm)4.197(4H,s,NH–C H ),6.815(1H,t,J =7.5Hz,C H of –SO 2–phenyl),6.940(1H,d,J =8.0Hz,C H of –SO 2–phenyl),6.978(1H,d,J =7.5Hz,C H of –SO 2–phenyl),7.209(1H,t,J =7.0Hz,8.0Hz,C H of –SO 2–phenyl),7.418(8H,d,J =8.5Hz,C H of phenyl),8.135(8H,d,J =8.5Hz,C H of phenyl).13C NMR (125MHz,DMSO-d 6):d (ppm)45.996(CHNH),82.891,89.176,123.765,123.853,123.896,124.168,128.896,128.925,129.392,129.664.HR-ESI-MS:[M ?H]?:807.1454.3 e (1.056g,70%yield)as pinkish purple solid.[a ]D 20:-95.6°(c 0.1,CHCl 3).1H NMR (500MHz,CDCl 3):d (ppm)4.204(2H,d,J =4.5Hz,NH–C H ),4.490(2H,d,J =5.0Hz,NH–C H ),6.818(1H,t,J=7.5Hz,8.0Hz,C H of –SO 2–phenyl),7.299(4H,d,J =8.0Hz,C H of phenyl),7.357(4H,d,J =8.0Hz,C H of phenyl),7.382(4H,d,J =8.5Hz,C H of phenyl),7.450(4H,d,J =8.5Hz,C H of phenyl),7.546(3H,d,J =8.0Hz,C H of –SO 2–phenyl),7.951(1H,s,C H of –SO 2–phenyl).13C NMR (125MHz,CDCl 3):d (ppm)61.598(C HNH),62.706(C HNH),125.286(CF 3),125.545(CF 3),126.664(CF 3),126.920(CF3),127.275,129.419,129.527,129.919,130.172,140.816,142.535,144.575,146.998.HR-ESI-MS:[M ?H]?:899.1587.2.2General Procedure of ATH in WaterThe complex-precursor [Ru(g 6-p -cymene)Cl 2]2(0.005mmol,3.1mg)and the ligands 3a –3e (0.011mmol)were mixed indegassed water (2mL)and stirred at 40°C for 1h,subse-quently,anhydrous sodium formate (10mmol,0.6801g)and the substrate (1.0mmol)were added.At 60°C the mixture was heated for another 11h.The suspension was extracted with dichloromethane (395mL).The oganic layers were combined,dried over anhydrous MgSO 4,?ltered and con-centrated under reduced pressure,and then passed through a short silicagel column.The enantiomeric excess (ee)was measured by Chiral GC analysis along with the conversion.3Results and DiscussionTo investigate the electronic and steric effects of ligands,we prepared ?ve bis(sulfonyl)tetraaza ligands with dif-ferent substituents as indicated in Schemes 1and 2,using the ATH of acetophenone to be a model reaction.The corresponding results are listed in Table 1.The ligands 3b ,carrying an electron donating group on the phenyl in para-position,displayed lower catalytic conversion (85.3%)and enantioselectivity (82.6%(S)-enantiomer)comparing to 3a (entries 2and 4).The ligands bearing an electron withdrawing group may have a complicated impact on the ligands’activities.As described in Table 1,the reduction under 3e proceeded smoothly giving a conversion of 98.3%better than that of 3a (86.0%)at 40°C (entries 1and 7).The case of entry 2only displayed a slight loss of enantioselectivity about 2.6%comparing to 3a (90.0%)Table 1A comparison of Ru(II)–Ligand 3a –3e catalysts for the asymmetric transfer hydrogenation of acetophenone by sodium formate in waterOOH[Ru(p-cymene)Cl 2]2, ligands 3a-3eS/C 100:1, HCOONa ,H 2OEntry Ligand Conversion (%)a ee (%)a,b Con?guration a 1c 3a 86.092.8S 23a 99.890.0S 3c3b 78.891.7S 43b 85.382.6S 53c 72.478.4S 63d 22.042.3R 7c3e 98.381.5S 83e99.887.4SReaction conditions :Catalyst:1.1910-5mol;HCOONa:1.0910-2mol;substrate:1.0910-3mol;water:2cm 3;temperature60°C;reaction time 11h;nitrogen protectiona Determined by chiral GC (CP-Chiralsil-Dex-CB Chiral column)b Enantiomeric excess cReaction temperature 40°C1292X.Liu et al.Table2A comparison of Ru(II)–Ligand3a–3e catalysts for the asymmetric transfer hydrogenation of aromatic ketones by HCOONa inwater[Ru(p-cymene)Cl],ligands3a-3eS/C100:1,HCOONa,H2O(X=Cl,NO2,OCH3;R=CH3,Cl,CH2Cl,N(CH3)2)Entry Ligand Substrate Conversion(%)(the reduction by-product)ee(%)a,b Con?guration a13a40-chloroacetophenone99.880.4S23b40-chloroacetophenone95.968.5S33c40-chloroacetophenone78.579.6S43d40-chloroacetophenone19.044.2R53e40-chloroacetophenone99.772.3S63a20-chloroacetophenone99.787.8S73b20-chloroacetophenone94.775.6S83c20-chloroacetophenone76.986.3S93d20-chloroacetophenone36.548.5R103e20-chloroacetophenone95.684.5S113a40-nitroacetophenone78.279.4S123b40-nitroacetophenone86.473.2S133e40-nitroacetophenone67.579.2S143a40-methyloxyacetophenone52.491.5S153b40-methyloxyacetophenone48.686.4S163a2-chloroacetophenone56.2(9.8)91.0S173b2-chloroacetophenone51.9(6.7)87.7S183c2-chloroacetophenone52.0(20.5)82.6S193d2-chloroacetophenone65.8(9.8)60.8R203e2-chloroacetophenone57.2(13.9)87.7S213a Propionphenone55.685.2S223b Propionphenone51.879.4S233e Propionphenone96.280.2S243a3-chloropropionphenone33.8(52.6)90.4(85.2)S253a3-N,N-dimethylpionphenone-(99.5)––Reaction conditions:Catalyst:1.1910-5mol;HCOONa:1.0910-2mol;substrate:1.0910-3mol;water:2cm3;temperature60°C; reaction time11h;nitrogen protectiona Determined by chiral GC(CP-Chiralsil-Dex-CB Chiral column)b Enantiomeric excessAsymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed1293(Entry8).It is suggested that the electron donating effect depress the stability of the six-membered metal-ligand-substrate transition state(TS,Fig.2)[19,20,32,33].The double metal complex in TS is con?rmed by the elemental analysis of the isolated Ru(II)complex with3a when mixing1:1ratio of Ru to ligand3a in water at60°C. However the electron withdrawing effect favors the for-mation of hydrogen bonds in TS via increasing the nucle-ophilicity of ligands to Ru(II).The electron effects on activity are in accord with Noyori’s theoretical calculations [32].Moreover,by building a more crowded space around the chiral center in the ligands,both steric hindrance and electron donating effect on the ortho-position(ligand3c, entry5)exerted a more negative in?uence on conversion (72.4%)and enantionselectivity(78.4%,(S)-enantiomer). When(S,S,S,S)-tetraaza ligand and p-cymene were used as ancillaries,two(R)-con?gured Ru(II)centers were obtained,in which two parts of the C2symmetric ligand were bound to metals independently.The transfer hydro-genation via this(R)-con?gured TS with S conformation of carbonyl carbon atom,resulting perhaps from the attractive CH/p interaction between p-cymene ligand of the Ru-complex and the aryl substituent in the substrate,afforded (S)-enantiomer.Surprisingly,when nitro was imported in para-position (3d),the yield of the expected1-phenethylalcohol fallen to 22.0%and a reversion of enantioselectivity was observed. This was out of what we expected as only(S)-enantiomer being the predominant product in the previous reactions. The same reversion was caught in other substrates such asentries4,9and19exhibited in Table2.It is speculated that the delocalized p-bond of nitro causes this distinctness of enantioselectivity and conversion by dragging the hydrogen attached upon the prochiral carbon.Furthermore,the ATH of different aromatic ketones (substrates)was explored under the same conditions as previous.The effect of electron withdrawing had a positive impact on the ATH over the electron donating groups on substrates as shown in entries2,7,12and15in Table2.It may be attributed to the electron withdrawing effect which giving more stable hydrogen bonds consisting in /doc/bf3fb130fe4733687e21aa9a.html -paring the ATH of2-chloroacetophenone and propionphe-none with acetophenone under the same ligands(such as entries20and23in Table2,together with entry8in Table1),we found that a methyl or chlorine atom on a-position of carbonyl group discouraged the performance of ATH.This revealed that the bulkier around the carbonyl,the lower stability of the TS.Notably,in entries16–20,the ATH of2-chloroacetophenone had furnished acetophe-none as a substitution by-product(9.8–20.5%).But we didn’t trace the reduction by-product(1-phenylalcohol), indicating the priority of ATH to the side reaction of chlorine atom replacement.In entry24,the ATH of 3-chloropropionphenone gave much lower yield but more replacement by-product(propionphenone,13.5%)and the reduction by-product(1-phenylpropanol,52.6%).It seems that the nucleophilicity of the R group on substrates enables the ketones to block the ligands to coordinate with the metal center.In order to prove what was hypothesized,we tried the 3-N,N-dimethylpionphenone as a substrate.We failed to get the expected alcohol but all propionphenone with its reduc-tion outcome(1-phenylpropanol),which was in agreement with the results in Wills’and Qu’s experiments[34,35].4ConclusionsHerein we report a new series of C2-symmetric bis(sulfo-nyl)tetraaza ligands.By complexing with Ru(g6-p-cymene)Cl2]2,the ligands exhibited good catalytic activi-ties in the asymmetric transfer hydrogenation of aromatic ketones employing sodium formate as the hydrogen source in neat water at a modest temperature under insert gas protection.A moderate to excellent conversions and overall satisfying enantioselectivities of the chiral secondary alcohols were obtained under ligand3aand3e.The experiment results reveal that the electron donating effect and steric effect corrode the reactivity of the ligands but the electron withdrawing effect enhances the reactivity via consolidating the sixed-membered transition state.How-ever,given the applicability of the catalytic system,the conditions for a wider range of aromatic ketones are still in a further performance optimization.Acknowledgments We express our gratitude to the Public Bene?t Project of Zhejiang Science and Technology Department for?nancial Support through Project No.2012C21098and the National Natural Science Foundation of China(21101048). 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Ｓ ｎ ｑｕ ｕ Ｙｏ ｇ ｉ
ｏ ｔｍｉｅ ｅ ｉｎ ｏ ｌ ｓ ｄ ｃｒｕｉ ｃ ｏ ｉ ｇ ｔｗｅ ｏ ｎ ｒ ｏ ｓ ｒ ａｉｎ． ｐ ｉ ｚ ｄ ｄ ｓｇ ｆｃｏ ｅ ｉｃ ｔ ｏ ｌｎ ｏ ｒｆ ｒｅ ｅ ｇ ｃ ｎ ｅ ｔｏ ｙ ｖ
Ｋｅ ｙｗｏ ｄ ｒ ｓ：ｃ ｏｉ ｇ ｔｗｅ ， ｅｅ ｔ ｎ， ｎ ｒｙ ｃ ｎ ｅ ｖ ｔｏ ｏ ｔｍｉａｉｎ ｏ ｌ ｏ ｒ ｓ ｌｃｉ ｎ ｏ ｅ ｅｇ ｏ ｓ ｒ ａｉｎ， ｐ ｉ ｚ ｔｏ

研 究 论 文 ：７ １ ７ ７ ～７ ６
双 位 点 碱 性 离 子 液 体 对 Ｋｎ ｅ ｅ ａ ｅ 缩 合 ｏｖｎ ｇｌ 反 应 的 协 同 催 化 作 用
刘 伟 ， 刘 哗
（ 东 师 范 大 学 化 学 系上 海 市 绿 色 化 学 与 化 工 过 程 绿 色 化 重 点 实 验 室 ，上 海 ２ ０ ６ 华 ０ ０ ２）
Ｌ Ｕ ｅ ，ＬＩ Ｙ Ｉ Ｗ ｉ Ｕ ｅ
（ ｈ ｎ ｈ ｉＫｅ ｂ ｒ ｔｒ ｆＧｒｅ ｅ ｓｒ ｎ ｈ ｍｉ ｌＰ ｏｅｓｓ Ｓ ａ ｇ ａ ｙＬａ ｏａｏｙ ｏ ｅｎ Ｃｈ ｍｉ ｙａ ｄ Ｃ ｅ ｃ ｒｃｓ ，Ｄｅ ａ ｔ ｎ ｈ ｍｉ ｒ ｔ ａ ｅ ｐ ｒｍｅ ｔｏ Ｃ ｅ ｓ ｙ ｆ ｔ ＥａｔＣｂｎ ｒ ｌＵｎ ｖｒｉ ｓ ｉａ Ｎｏ ｍａ ｉｅｓ ｙ，Ｓ ａ ｇ ａ ０ ０ ２ ，Ｃ ｉａ） ｔ ｈ ｎ ｈ ｉ ０６ ２ ｈｎ
Ｋｎ ｅｅ ａ ｅ反 应 是 由羰 基 化 合 物 （ ｏｖ ｎｇ ｌ 醛或 酮 ） 与 活泼亚 甲基 化 合 物 脱 水 缩 合 形 成 ａ Ｂ双羰 基 化 合 ，一 物， 是合 成碳 碳 双键 的 重要 方 法 ＿ ．该 反 应 自 １ ９ ｌ Ｊ ８４ 年被发 现 以来广 泛用 于人工 合成 香豆 素及 其衍生 物 的过程 （ 香豆 素及 其衍 生物是 合成 药 品 、 化妆 品和香 料 的重 要 中间体 ）２．利 用 Ｋｎ ｅｅ ａｅ 反应 合成 具 ＿ Ｊ ｏｖｎ ｇ ｌ 有 生物 活性 的化合 物 和众多 药物 中间体 近 年来也 引 起 人们 的关 注 ．例如 ， 通过 Ｋｎ ｅ ｅａ ｅ 反应合 成 的 ｏｖ ｎ ｇｌ
维普资讯
第 ２ ９卷 第 ８ 期
Ｖｏ ．２９ Ｎｏ． ８ １

Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - IRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticC. Brominated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticD. Iodinated Hydrocarbons1. Aliphatic and Olefinic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphatic and Olefinicb. Aromatic2. Secondarya. Aliphatic and Olefinicb. Aromatic3. Tertiarya. Aliphatic and Olefinicb. AromaticB. PyridinesC. QuinolinesD. Miscellaneous Nitrogen HeteroaromaticsE. HydrazinesF. Amine SaltsG. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Triazenes (-N=N-NH-)N. Isocyanates (-N=C=O)O. Carbodiimides (-N=C=N-)P. Isothiocyanates (-N=C=S)Q. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticR. Cyanamides (=N-C≡N)S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrites (-O-N=O)W. Nitro Compounds (-NO2)1. Aliphatic2. AromaticX. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. Heterocyclic3. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)K. Sulfamides (R-NH-SO2-NH-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Acetals (R-CH-(-O-R)2)3. Alicyclic Ethers4. Aromatic Ethers5. Furans6. Silicon Ethers (R3-Si-O-R)7. Phosphorus Ethers ((R-O)3-P)8. Peroxides (R-O-O-R)B. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Olefinicc. Aromaticd. Heterocyclic2. Secondarya. Aliphatic and Alicyclicb. Olefinicc. Aromatic3. Tertiarya. Aliphaticb. Olefinicc. Aromatic4. Diols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. α-Diketones and β-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aliphatic Esters of Olefinic Acids4. Aromatic Esters of Aliphatic Acids5. Esters of Aromatic Acids6. Cyclic Esters (Lactones)7. Chloroformates8. Esters of Thio-Acids9. Carbamates10. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - Proton NMRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. AromaticC. Brominated Hydrocarbons1. Aliphatic2. AromaticD. Iodinated Hydrocarbons1. Aliphatic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphaticb. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. AromaticB. PyridinesC. Quaternary Ammonium SaltsD. HydrazinesE. Amine SaltsF. Ylidene Compounds (-CH=N-)G. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Isocyanates (-N=C=O)N. Carbodiimides (-N=C=N-)O. Isothiocyanates (-N=C=S)P. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticQ. Cyanamides (=N-C≡N)R. Isocyanides (-N≡C )S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrates (-O-NO2)W. Nitrites (-O-N=O)X. Nitro Compounds (-NO2)1. Aliphatic2. AromaticY. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)4. Sulfuric Acid Salts (R-O-SO2-O-M)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Alicyclic Ethers3. Aromatic Ethers4. Furans5. Silicon Ethers (R3-Si-O-R)6. Phosphorus Ethers ((R-O)3-P)B. Alcohols (R-OH)1. Primarya. Aliphaticb. Olefinicc. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. Aromatic4. Diols and Polyols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. a-Diketones and b-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aromatic Esters of Aliphatic Acids4. Cyclic Esters (Lactones)5. Chloroformates6. Carbamates7. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - Carbon NMRI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes) and PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. AromaticC. Brominated Hydrocarbons1. Aliphatic2. AromaticD. Iodinated Hydrocarbons1. Aliphatic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphaticb. Aromatic2. Secondarya. Aliphaticb. Aromatic3. Tertiarya. Aliphaticb. AromaticB. PyridinesC. Amine SaltsD. Oximes (-CH=N-OH)E. Quaternary Ammonium SaltsF. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticG. Thiocyanates (-S-C≡N)H. Nitro Compounds (-NO2)1. Aliphatic2. AromaticIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfones (R-SO2-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Alicyclic Ethers3. Aromatic EthersB. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Aromatic2. Secondarya. Aliphatic and Alicyclic3. Tertiarya. Aliphatic4. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. AromaticB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. AromaticG. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aromatic Esters of Aliphatic AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specTable of Contents - MSComing SoonI. HydrocarbonsII. Halogenated HydrocarbonsIII. Nitrogen Containing CompoundsIV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O And P(=O)-O) VI. Sulfur Containing CompoundsVII. Oxygen Containing Compounds (Except -C(=O)-)VIII. Compounds Containing Carbon To Oxygen Double BondsI. HydrocarbonsA. Saturated Hydrocarbons1. Normal Alkanes2. Branched Alkanes3. Cyclic AlkanesB. Unsaturated Hydrocarbons1. Acyclic Alkenes2. Cyclic Alkenes3. AlkynesC. Aromatic Hydrocarbons1. Monocyclic (Benzenes)2. PolycyclicII. Halogenated HydrocarbonsA. Fluorinated Hydrocarbons1. Aliphatic2. AromaticB. Chlorinated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticC. Brominated Hydrocarbons1. Aliphatic2. Olefinic3. AromaticD. Iodinated Hydrocarbons1. Aliphatic and Olefinic2. AromaticIII. Nitrogen Containing CompoundsA. Amines1. Primarya. Aliphatic and Olefinicb. Aromatic2. Secondarya. Aliphatic and Olefinicb. Aromatic3. Tertiarya. Aliphatic and Olefinicb. AromaticB. PyridinesC. QuinolinesD. Miscellaneous Nitrogen HeteroaromaticsE. HydrazinesF. Amine SaltsG. Oximes (-CH=N-OH)H. Hydrazones (-CH=N-NH2)I. Azines (-CH=N-N=CH-)J. Amidines (-N=CH-N)K. Hydroxamic AcidsL. Azo Compounds (-N=N-)M. Triazenes (-N=N-NH-)N. Isocyanates (-N=C=O)O. Carbodiimides (-N=C=N-)P. Isothiocyanates (-N=C=S)Q. Nitriles (-C≡N)1. Aliphatic2. Olefinic3. AromaticR. Cyanamides (=N-C≡N)S. Thiocyanates (-S-C≡N)T. Nitroso Compounds (-N=O)U. N-Nitroso Compounds (=N-N=O)V. Nitrites (-O-N=O)W. Nitro Compounds (-NO2)1. Aliphatic2. AromaticX. N-Nitro-Compounds (=N-NO2)IV. Silicon Containing Compounds (Except Si-O)V. Phosphorus Containing Compounds (Except P-O and P(=O)-O) VI. Sulfur Containing CompoundsA. Sulfides (R-S-R)1. Aliphatic2. Heterocyclic3. AromaticB. Disulfides (R-S-S-R)C. Thiols1. Aliphatic2. AromaticD. Sulfoxides (R-S(=O)-R)E. Sulfones (R-SO2-R)F. Sulfonyl Halides (R-SO2-X)G. Sulfonic Acids (R-SO2-OH)1. Sulfonic Acid Salts (R-SO2-O-M)2. Sulfonic Acid Esters (R-SO2-O-R)3. Sulfuric Acid Esters (R-O-S(=O)-O-R)H. Thioamides (R-C(=S)-NH2)I. Thioureas (R-NH-C(=S)-NH2)J. Sulfonamides (R-SO2-NH2)K. Sulfamides (R-NH-SO2-NH-R)VII. Oxygen Containing Compounds (Except -C(=O)-)A. Ethers1. Aliphatic Ethers (R-O-R)2. Acetals (R-CH-(-O-R)2)3. Alicyclic Ethers4. Aromatic Ethers5. Furans6. Silicon Ethers (R3-Si-O-R)7. Phosphorus Ethers ((R-O)3-P)8. Peroxides (R-O-O-R)B. Alcohols (R-OH)1. Primarya. Aliphatic and Alicyclicb. Olefinicc. Aromaticd. Heterocyclic2. Secondarya. Aliphatic and Alicyclicb. Olefinicc. Aromatic3. Tertiarya. Aliphaticb. Olefinicc. Aromatic4. Diols5. Carbohydrates6. PhenolsVIII. Compounds Containing Carbon To Oxygen Double BondsA. Ketones (R-C(=O)-R)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. α-Diketones and β-DiketonesB. Aldehydes (R-C(=O)-H)C. Acid Halides (R-C(=O)-X)D. Anhydrides (R-C(=O)-O-C(=O)-R)E. Amides1. Primary (R-C(=O)-NH2)2. Secondary (R-C(=O)-NH-R)3. Tertiary (R-C(=O)-N-R2)F. Imides (R-C(=O)-NH-C(=O)-R)G. Hydrazides (R-C(=O)-NH-NH2)H. Ureas (R-NH-C(=O)-NH2)I. Hydantoins, Uracils, BarbituratesJ. Carboxylic Acids (R-C(=O)-OH)1. Aliphatic and Alicyclic2. Olefinic3. Aromatic4. Amino Acids5. Salts of Carboxylic AcidsK. Esters1. Aliphatic Esters of Aliphatic Acids2. Olefinic Esters of Aliphatic Acids3. Aliphatic Esters of Olefinic Acids4. Aromatic Esters of Aliphatic Acids5. Esters of Aromatic Acids6. Cyclic Esters (Lactones)7. Chloroformates8. Esters of Thio-Acids9. Carbamates10. Esters of Phosphorus AcidsPublished by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specSaturated HydrocarbonsNormal Alkanes1. C-H stretching vibration:CH3 asymmetric stretching, 2972-2952 cm-1CH3 symmetric stretching, 2882-2862 cm-1CH2 asymmetric stretching, 2936-2916 cm-1CH2 symmetric stretching, 2863-2843 cm-12. C-H bending vibration:CH3 asymmetric bending, 1470-1430 cm-1CH2 asymmetric bending, 1485-1445 cm-1(overlaps band due to CH3 asymmetricbending)3. C-H bending vibration:CH3 symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)4. C-H wagging vibration:CH2 out-of-plane deformations wagging, 1307-1303 cm-1 (weak) 5. CH2 rocking vibration:(CH2)2 in-plane deformations rocking, 750-740 cm-1(CH2)3 in-plane deformations rocking, 740-730 cm-1(CH2)4 in-plane deformations rocking, 730-725 cm-1(CH2) ≥ 6 in-plane deformations rocking, 722 cm-1Splitting of the absorption band occurs in most cases (730 and 720 cm-1) when the long carbon-chain alkane is in the crystalline state (orthorombic or monoclinic form).Coming Soon!Click on a vibrational mode link in the table to the leftor the spectrum above to visualize the vibrational mode here.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Saturated HydrocarbonsBranched Alkanes1. C-H stretching vibration:CH3 asymmetric stretching, 2972-2952 cm-1CH3 symmetric stretching, 2882-2862 cm-1CH2 asymmetric stretching, 2936-2916 cm-1CH2 symmetric stretching, 2863-2843 cm-12. C-H bending vibration:CH3 asymmetric bending, 1470-1430 cm-1CH2 asymmetric bending, 1485-1445 cm-1(overlaps band due to CH3 symmetric bending)3. C-H bending vibration:-C-C(CH3)-C-C- symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)-C-C(CH3)-C(CH3)-C-C- symmetric bending, 1380-1365 cm-1(when CH3 is attached to a C atom)(CH3)2CH- symmetric bending, 1385-1380 cm-1and 1365 cm-1(two bands of about equal intensity)-C-C(CH3)2-C- symmetric bending,1385-1380 cm-1and 1365 cm-1 (two bands of about equal intensity).(CH3)3C- symmetric bending, 1395-1385 cm-1and 1365 cm-1(two bands of unequal intensity with the 1365 cm-1 band as the much stronger component of the doublet).4. Skeletal vibration:-C-C(CH3)-C-C-,1159-1151cm-1-C-C(CH3)-C(CH3)-C-C-,1130-1116 cm-1(CH3)CH-,1175-1165 cm-1 and 1170-1140 cm-1-C-C(CH3)2-C-,1192-1185 cm-1(CH3)3C-, 1255-1245 cm-1 and 1250-1200 cm-15. C-H rocking vibration:(CH2)2 in-plane deformations rocking, 750-740 cm-1(CH2)3 in-plane deformations rocking, 740-730 cm-1(CH2)4 in-plane deformations rocking, 730-725 cm-1(CH2) ≥ 6 in-plane deformations rocking, 722 cm-1Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Saturated Hydrocarbons Cyclic AlkanesCyclopropanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 3100-3072 cm -1 ring CH 2 symmetric stretching, 3030-2995 cm -12. Ring deformation vibration:ring deformation, 1050-1000 cm -13. C-H deformation vibration: CH 2 wagging, 860-790 cm -1Cyclobutanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 3000-2974 cm -1 ring CH 2 symmetric stretching, 2925-2875 cm -12. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1444 cm -13. Ring deformation vibration:ring deformation, 1000-960 cm -1 888-838 cm -14. C-H deformation vibration:ring CH 2 rocking, 950-900 cm -1Cyclopentanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, 2960-2952 cm -1 ring CH 2 symmetric stretching, 2866-2853 cm -1 2. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1455 cm -1 3. Ring deformation vibration:ring deformation, 1000-960 cm -1 4. C-H deformation vibration:ring CH 2rocking, 930-890 cm -1Cyclohexanes1. C-H stretching vibration:ring CH 2 asymmetric stretching, ca 2927 cm -1ring CH 2 symmetric stretching, ca 2854 cm -1 2. C-H deformation vibration:ring CH 2 asymmetric bending, ca 1462 cm -1 3. C-H deformation vibration:ring CH 2 wagging, ca 1260 cm -1 4. Ring deformation vibration:ring deformation, 1055-1000 cm -1 1000- 952 cm -1 5. C-H deformation vibration:ring CH 2 rocking, 890-860 cm -16. The spectra of cyclic alkanes of five or more ring carbons show ring CH 2 stretching frequencies which overlap those of CH 3 and CH 2 groups of their alkyl substituents. These frequencies also overlap thoseof the CH 3 and CH 2 stretching frequencies of acylic alkanes. When samples of unknown composition are examined for the presence of such ring structures, the absorption bands of their spectra at the C-H stretching region should havethe best possible resolution.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Numerous references cite the spectral region of 2800-2600 cm-1 for obtainingconfirmatory evidence of the presence of saturated simple ring structures. Absorptionat this region consists of a weak band or bands whose pattern and band locations arehelpful in confirming or indicating the presence of these rings. Although such absorptionfeatures have a limited diagnostic value, it is most reliable when the absorption occursin the spectra of simple saturated aliphatic hydrocarbons.Cycloalkanes (8, 9, and 10 C atoms)1 C-H stretching vibration:ring CH2 asymmetric stretching, ca 2930 cm-1ring CH2 symmetric stretching, ca 2850 cm-12. C-H deformation vibration:ring CH2 asymmetric bending, 2 or 3 absorption bands,1487-1443 cm-1Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specUnsaturated HydrocarbonsAcyclic AlkenesMonosubstituted Alkenes (vinyl)1. C=C stretching vibration:C=C stretching, 1648-1638 cm-12. C-H deformation vibration:trans CH wagging, 995-985 cm-1CH2 wagging, 910-905 cm-13. C-H stretching vibration:CH2 asymmetric stretching, 3092-3077 cm-1CH2 symmetric stretching and CH stretching, 3025-3012 cm-1 4. C-H deformation vibration:CH2 asymmetric bending, 1420-1412 cm-15. C-H deformation vibration overtone:overtone of CH2 wagging, 1840-1805 cm-1Asymmetric Disubstituted Alkenes (vinylidine)1. C=C stretching vibration:C=C stretching, 1661-1639 cm-12. C-H deformation vibration:CH2 wagging, 895-885 cm-13. C-H stretching vibration:CH2 stretching asymmetric, 3100-3077 cm-14. C-H deformation vibration overtone:overtone of CH2 wagging, 1792- 1775 cm-1Symmetric Disubstituted Alkenes (cis)1. C=C stretching vibration:C=C stretching, 1662- 1631 cm-12. C-H deformation vibration:cis CH wagging, 730- 650 cm-13. C-H stretching vibration:CH stretching, 3050-3000 cm-1Symmetric Disubstituted Alkenes (trans)1. C=C stretching vibration:C=C stretching, ca 1673 cm-1, very weak or absent2. C-H deformation vibration:trans CH wagging, 980-965 cm-13. C-H stretching vibration:CH stretching, 3050-3000 cm-1Trisubstituted Alkenes1. C=C stretching vibration:C=C stretching, 1692-1667 cm-12. C—H deformation vibration:C-H wagging, 840-790 cm-13. C-H stretching vibration:C-H stretching, 3050-2990 cm-1Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Tetrasubstituted Alkenes1. C=C stretching vibration:C=C stretching, 1680-1665 cm-1, very weak or absentNOTES: The C=C stretching vibration of molecules which maintain acenter of symmetry absorbs very weakly, if at all, in the infrared region and,usually, is difficult to detect. This is true of the trans isomers and thetetrasubstitutedC=C linkages.When two or more olefinic groups occur in the hydrocarbon molecule, the infraredabsorption spectrum shows the additive and combined absorption of theunsaturatedgroups. However, if the unsaturated groups are subject to conjugation, the C=Cstretchingfrequency, usually, is lowered and a splitting of the C=C stretching frequencyband occurs.Conjugation also intensifies the C=C stretching frequency of trans unsaturatedgroups.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Go to: home • ir • proton nmr • carbon nmr• mass specUnsaturated Hydrocarbons Cyclic AlkenesEndocyclic C=CEndocyclic C=C corresponds to cis symmetrically disubstituted C=C of acyclic alkenes.1. C=C stretching, vibration:C=C stretching, near 1650 cm -1(except cyclobutene, 1560 cm -1 and cyclopentene, 1611 cm -1)2. C-H deformation vibration: CH wagging, 730- 650 cm -13. C-H stretching vibration:CH stretching, 3075- 3010 cm -1(usually two bands, asymmetric stretching and symmetric stretching for 4, 6, 7, and 8 membered rings)1- substituted endocyclic C=C1- substituted endocyclic C=C corresponds to trisubstituted acyclic alkenes.1. C=C stretching vibration:C=C stretching, near 1650 cm -1 (frequency raised)2. C-H deformation vibration: CH wagging, 840-790 cm -13. C-H stretching vibration:CH stretching, near 3000 cm -11.2- disubstituted endocyclic C=C1. C=C stretching vibration:C=C stretching, 1690-1670 cm -1 (4, 5, and 6 membered rings)Exocyclic C=CH 2Exocyclic C=CH 2 corresponds to the asymmetrically disubstituted C=C of acyclic alkenes (vinylidine).1. C=C stretching,1678-1650 cm -1 (4, 5, and 6 membered rings)2. C-H deformation vibration:=CH 2 wagging, 895-885 cm -13. C-H stretching vibration:=CH 2 stretching, near 3050 cm -1NOTES: The C=C stretching frequency of both the endocyclic HC=CH and the exocyclic C=CH 2 is sensitive to ring strain. As the ring size decreases from 6 to 4 members, the C=C stretching frequency of the endocyclic HC=CH is lowered. However, for the C=C stretching frequency of exocyclic C=CH 2, a gradual increase in the C=C stretching frequency occurs as the ring gets smaller. Substitution of methyl groups for the hydrogens of the endocyclic HC=CH and the exocyclic C=CH 2 cause an increase in the C=C stretching frequency.When two or more C=C groups occur in the hydrocarbon molecule, the infrared absorption spectrum shows the additive and combined absorption effects of the unsaturated groups. If such groups are subject to conjugation, the C=C stretching frequency is lowered and asplitting of the C=C stretching frequency band occurs.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division. © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.Unsaturated Hydrocarbons AlkynesMonosubstituted Alkynes (RC ≡CH)1. C ≡C stretching vibration:C ≡C stretching, 2140-2100 cm -12. C-H stretching vibration:≡CH bending, ca 3300 cm -13. C-H deformation vibration: ≡CH bending, 642-615 cm -14. C-H deformation vibration overtone:overtone of ≡CH deformation, 1260-1245 cm -1Disubstituted Alkynes (RC ≡CR')1. C ≡C stretching vibration:C ≡C stretching, 2260-2190 cm -1 (unconjugated)NOTES: Although the intensity of the absorption band caused bythe C ≡C stretching vibration is variable, it is strongest when the alkyne group is monosubstituted. When this group is disubstituted in open chain compounds, the intensity of the C ≡C stretching vibration band diminishesas its position in the molecule tends to establish a pseudo center of symmetry. In some instances this band is too weak to be detected and, thus, its absence in the spectrum does not, necessarily, establish proof of the absence of this linkage.Occasionally, the spectra of disubstituted alkynes show two or more bands at the C ≡C stretching region.Conjugation with olefinic double bonds or aromatic rings tend to slightly increase the intensity of the C ≡C stretching vibration band and shift it toa lower frequency.Coming Soon!Click on a vibrational mode link in the table to the left or the spectrum above to visualize the vibrational modehere.Published by Bio-Rad Laboratories, Inc., Informatics Division . © 1978-2004 Bio-Rad Laboratories, Inc. All Rights Reserved.。