有机化学10_Reactions of Alcohols,Amines, Ethers, Epoxides

有机化学反应、实验操作、试剂、仪器及术语一、化学反应1.elimination reaction 消去反应2.nitration reaction 硝化反应3.silver mirror reaction 银镜反应4.hydrolysis of salts 盐类的水解5.salting-out 盐析6.saponification 皂化反应7.esterification 酯化反应9.substitution 取代反应二、实验操作1.fractionation 分馏2.endothermic reaction 吸热反应3.exothermic reaction 放热反应4.precipitation 沉淀5.to precipitate 沉淀6.to distill 蒸馏7.distillation 蒸馏8.to calcine 煅烧9.to oxidize 氧化10.alkalinization 碱化11.to oxygenate, to oxidize 脱氧, 氧化12.to neutralize 中和13.to hydrogenate 氢化14.to hydrate 水合,水化15.to dehydrate 脱水16. fermentation 发酵17.solution 溶解bustion 燃烧19.fusion, melting 熔解20.hydrolysis 水解21. dissolution 分解22.synthesis 合成23.reversible 可逆的三、试剂1.ethyl acetate 乙酸乙酯2.solution of bromine in carbon tetrachloride 溴的四氯化碳溶液3.sodium bromide 溴化钠4.bromine water 溴水5.oxidizing agent（oxidant）氧化剂6.aluminium oxide 氧化铝7.iron (III) oxide 氧化铁8.Ethanol 乙醇9.ethana1 乙醛10.reducing agents（reductant）还原剂11.silver nitrate 硝酸银12.ethanoic acid 乙酸13.sodium carbonate 碳酸钠14.detergent 洗涤剂15.potassium iodide paper 淀粉碘化钾试纸16.hydrochloric acid 盐酸17.sulphuric acid 硫酸18.nitric acid 硝酸19.aqua fortis 王水20.fatty acid 脂肪酸anic acid 有机酸22.hydrate 水合物23.hydroxide 氢氧化物,羟化物24.hydracid 氢酸25.hydrocarbon 碳氢化合物26.anhydride 酐27.alkaloid 生物碱28.Aldehyde 醛29.oxide 氧化物30.phosphate 磷酸盐31.acetate 醋酸盐32.potassium carbonate 碳酸钾33.soda 苏打34.sodium carbonate 碳酸钠35.caustic potash 苛性钾36.caustic soda 苛性钠37.hydrosulphuric acid 氢硫酸38.hydrogen sulfide 氢化硫39.iodide 碘化钾40.hydrogen peroxide 过氧化氢41.bicarbonate ammonium 碳酸氢铵42.sodium bicarbonate 碳酸氢钠43.carbohydrate 糖类44.hydrocarbon weak 烃45.derivative of hydrocarbon 烃的衍生物46.acetic 乙酸四、仪器1.flask 烧瓶3.graduated flask 量筒4.test tube 试管5.burette 滴定管6.pipette 吸液管7.adapter 接液管8.air condenser 空气冷凝管9.Beaker 烧杯10.boiling flask 烧瓶11.boiling flask-3-neck 三口烧瓶12.burette clamp 滴定管夹13.burette stand 滴定架台14.Busher funnel 布氏漏斗15.Claisen distilling head 减压蒸馏头16.condenser-Allihn type 球型冷凝管17.condenser-west tube 直型冷凝管18.crucible tongs 坩埚钳19.crucible with cover 带盖的坩埚20.distilling head 蒸馏头21.distilling tube 蒸馏管22.Erlenmeyer flask 锥型瓶23.evaporating dish (porcelain) 瓷蒸发皿24.filter flask(suction flask) 抽滤瓶25.florence flask 平底烧瓶26.fractionating column 分馏柱27.Geiser burette (stopcock) 酸氏滴定管28.graduated cylinder 量筒29.Hirsch funnel 赫氏漏斗30.long-stem funnel 长颈漏斗31.medicine dropper 滴管32.Mohr burette for use with pinchcock 碱氏滴定管33.Mohr measuring pipette 量液管34.mortar 研钵35.pestle 研杵36.pinch clamp 弹簧节流夹37.plastic squeeze bottle 塑料洗瓶38.reducing bush 大变小转换接头39.rubber pipette bulb 吸耳球40.screw clamp 螺旋夹41.separatory funnel 分液漏斗42.stemless funnel 无颈漏斗43.test tube holder 试管夹44.test tube 试管45.Thiele melting point tube 提勒熔点管46.transfer pipette 移液管47.tripod 三角架48.volumetric flask 容量瓶49.watch glass 表皿50.wide-mouth bottle 广口瓶五、术语1.anion 阴离子2.cation 阳离子3.isomer 同分异构体4.allotrope carbon 同素异形体5.Isotope 同位素6.homo1og 同系物7.valence, valency 价8.monovalent 单价9.bivalent 二价10.halogen 成盐元素11.derivative 衍生物。

常用化学单词1. 元素周期表：The periodic table of the elements2. 化学键与分子结构：Chemical bonds and molecular structure3. 化学反应与反应类型：Chemical reactions and reaction types4. 酸碱反应与pH值：Acid-base reactions and pH value5. 氧化还原反应：Oxidation-reduction reactions6. 化学计量与摩尔质量：Chemical stoichiometry and molar mass7. 有机化学与烃类：Organic chemistry and hydrocarbons8. 醇、酚、醚：Alcohols, phenols, ethers9. 醛、酮、酯：Aldehydes, ketones, esters10. 羧酸、酰胺、酯类：Carboxylic acids, amides, esters11. 硝基化合物、胺类：Nitro compounds, amines12. 磺酸、硫酸酯、磷酸酯：Sulfonates, sulfates, phosphates13. 卤素、含氧酸、含氧酸盐：Halogens, oxygen acids, oxygen acid salts14. 金属有机化合物：Organometallic compounds15. 配位化合物、络合物：Coordination compounds, complexes16. 碳水化合物、氨基酸、蛋白质：Carbohydrates, amino acids, proteins17. 核苷酸、核酸、酶：Nucleotides, nucleic acids, enzymes18. 无机酸、碱、盐：Inorganic acids, alkalis, salts19. 高分子化合物：Polymer compounds20. 纳米材料：Nano materials这些是常用的一些化学单词，涵盖了化学学科的多个领域。

Amines脂肪胺 aliphatic amineAmines芳香胺 aromatic aminePrepared by Yang RLIntroduction to amine*Nomenclature乙胺 ethylamine对硝基苯胺 p-nitroaniline(2S,3S)-3-甲基-2-戊胺 (2S,3S)-3-methyl-2-pentanaminePrepared by Yang RL Prepared by Yang RLAminesNomenclature氨 ammonia伯胺 primary amine仲胺 secondary amineR N R R 叔胺 tetriary aminePrepared by Yang RL二甲胺 dimethylamine甲乙胺 ethylmethylamine季铵 quaternary aminePrepared by Yang RL1Nomenclature甲(基)乙(基)环丙胺 cyclopropylethylmethylamineNomenclature2-甲氨基苯酚 2-methylaminophenol N-甲基苯胺 N-methylaniline2-氨基乙醇 2-aminoethanol4-二甲氨基苯甲醛 4-dimethyl aminobenzaldehydePrepared by Yang RLPrepared by Yang RLNomenclatureN-乙基乙二胺 N-ethyl-1,2ethanediamineNomenclature氢氧化三甲乙铵 ethyltrimethylammonium hydroxideN,N-二甲基-3-己胺 N,N-dimethyl-3hexanaminePrepared by Yang RL Prepared by Yang RL氯化四甲铵 tetramethylammonium chlorideNomenclatureAmino氨基 amino N,4-二甲基-N-乙基苯胺 N-ethyl-N,4-dimethylbenzenamine 次氨基 nitrilloPrepared by Yang RL Prepared by Yang RL甲氨基 methylamino亚氨基 imono乙胺 ethylamine氯化四甲铵 tetramethylammonium chloride2#Preparationof amines#Chiralityof AminesPrepared by Yang RLPrepared by Yang RL#Preparationof amines#Chiralityof AminesPrepared by Yang RLPrepared by Yang RLStructure of amines#PhysicalpropertiesPrepared by Yang RLPrepared by Yang RL3Basicity of AminesBasicity of AminespKb = 4.74Prepared by Yang RLPrepared by Yang RLBasicity of Amines#Purifyingan AminePrepared by Yang RLPrepared by Yang RLBasicity of AminesAmines (CH3)2NH CH3NH2 (CH3)3N NH3 C6H5NH2 C6H5NHCH3 C6H5N(CH3)2Prepared by Yang RLAlkylation of AminesbasicpKb 3.22 3.37 4.20 4.76 9.40 9.6 9.62脂肪仲胺 脂肪伯胺 脂肪叔胺 氨 芳香胺Prepared by Yang RL4Acylating reaction* (酰化反应)Formation of Sulfonamides (磺酰胺)N, N-二甲基乙酰胺 Sulfonamides (磺酰胺) 乙酰苯胺Prepared by Yang RL Prepared by Yang RLApplication of acylating reactionSulfonamides对氨基苯磺酰胺 (磺胺) Sulfanilamide1/3磺胺嘧啶 Sulfadiazine2/3Prepared by Yang RL Prepared by Yang RLApplication of acylating reaction#Hinsbergreactionno reactionPrepared by Yang RL Prepared by Yang RL5Nitrosation of aminesDiazo compounds (重氮盐)Prepared by Yang RLPrepared by Yang RLNitrosation of amines#Reactionof diazo compoundsPrepared by Yang RLPrepared by Yang RLNitrosation of aminesCoupling reaction (偶联反应)0~5ºC 重氮盐 Diazo compoundsPrepared by Yang RL Prepared by Yang RL对二甲氨基偶氮苯 p-dimethylamino-azobenzene6#Azocompounds (偶氮化合物)N,N-二甲 基苯胺Nitrosation of amines三乙胺 N,N-二甲 基苯胺 三乙胺顺-偶氮苯 mp. 71.4ºC反-偶氮苯 mp. 68ºCPrepared by Yang RLPrepared by Yang RL＋ HCl, NaNO2＋ NaOHNitrosation of aminesNitrosation of aminesyellow (l)yellow (s)Prepared by Yang RL Prepared by Yang RLNitrosation of aminesElectrophilic substitutionPrepared by Yang RLPrepared by Yang RL7The End8。

Job/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22FULL PAPERDOI:10.1002/ejoc.201402221Exploring the Reactivity of Chiral Glycidic Amides for Their Applications inSynthesis of Bioactive CompoundsFrancisco Sarabia,*[a]Carlos Vivar-García,[a]Cristina García-Ruiz,[a]Antonio Sánchez-Ruiz,[a][‡]María Soledad Pino-González,[a]Miguel García-Castro,[a][‡‡]andSamy Chammaa [a][‡‡]Dedicated to Professor Rosa María Claramunt on the occasion of her 65th birthdayKeywords:Synthetic methods /Nucleophilic substitution /Diastereoselectivity /Sulfonium salts /Glycidic amidesA new class of chiral sulfonium salts,derived from L -and D -methionine,has been designed and successfully employed in our laboratories for the diastereoselective synthesis of glycidic amides.The epoxy amides obtained were converted cleanly into 1,2-difunctionalized products through oxirane ring-opening reactions with different types of nucleophiles.The resulting ring-opened products represent valuable andIntroductionWe recently described the design,synthesis and reactivity of a new class of chiral sulfonium ylides derived from α-amino acids,structurally characterized by the presence of a bicyclic system.[1,2]After an extensive study of these chiral reagents,particularly those derived from l -and d -meth-ionine,namely sulfonium salts 1and 2,we demonstrated their efficiency in the asymmetric synthesis of glycidic amides 3and 4,which were obtained in good-to-excellent yields with exclusive trans selectivity and excellent dia-stereoselectivity by using a broad range of aldehydes,in-cluding aliphatic,aromatic,α,β-unsaturated and heterocy-clic derivatives (Scheme 1).[2]In continuation of these stud-ies,the next step in this research was to explore the syn-thetic possibilities that the resulting epoxy amides may pro-vide in the field of asymmetric synthesis.[3]To this end we planned a study of the reactivity of these epoxy amides towards nucleophilic reagents of various types,including ni-[a]Department of Organic Chemistry,Faculty of Sciences,University of Malaga,Campus de Teatinos s/n,29071Málaga,Spain E-mail:frsarabia@uma.eshttp://webdeptos.uma.es/organica/[‡]Current address:School of Chemistry,Manchester Interdisciplinary Biocentre,University of Manchester,Manchester,M17DN,UK[‡‡]Current address:Max-Planck Institute fur MolekularePhysiologie,Otto-Hahn-Strasse 11,44227Dortmund,GermanySupporting information for this article is available on the WWW under /10.1002/ejoc.201402221..Chem.0000,0–0©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim1useful building blocks for the synthesis of different bioactive products.Thus,the expedient synthesis of clavaminol H as well as the synthesis of key precursors for other bioactive compounds,for example,polyketide-derived natural prod-ucts,have been achieved,demonstrating the synthetic effi-ciency and utility of this chemistry.trogen,sulfur and alkyl-type nucleophiles that could poten-tially provide access to a wide array of 1,2-functionalized systems through regio-and stereocontrolledring-openingScheme 1.Stereoselective synthesis of epoxy amides from a new class of chiral sulfonium salts and their potential reactivity.Job/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22F .Sarabia et al.FULL PAPERreactions.The synthesis of 1,2-functionalized systems is of great importance in organic synthesis,particularly in the field of natural products.[4,5]For example,1,2-amino alcohols [6]or polypropionate-derived chains [7]represent some of the many examples of 1,2-functionalized systems that would be accessible by this methodology.In fact,we have already employed these chiral reagents in the asym-metric synthesis of bengamides and their analogues,[8]glo-bomycin and related cyclodepsipeptides,[9]and the natural compounds sphingosine and sphinganine.[2]In this article we wish to report the utility of the epoxy amides prepared from this new class of sulfur ylides in the stereoselective synthesis of 1,2-functionalized derivatives and their applica-tion in the synthesis of some bioactive compounds of bio-medical interest.Results and DiscussionRing-Opening Reactions with Nitrogen Nucleophiles and their Synthetic ApplicationsFor this initial study we selected simple epoxy amides,prepared according to the methodology described in the preceding article,[2]as substrates.For the reactions with ni-trogen nucleophiles,amines were tested and found to smoothly open the oxirane ring of the epoxy amides in a completely regioselective manner by heating at reflux in methanol to give 2-amino-3-hydroxy amides.[10]In general,both primary and secondary amines,including ammonia and aniline,were shown to be efficient nucleophiles,provid-ing the corresponding ring-opened products 5–22in yields of 54–93%(Scheme 2and Table 1).The complete regio-and stereoselectivity displayed by these epoxy amides in their reactions with amines and other nucleophiles,such as carbon nucleophiles,have been theoretically rationalized [11]and extensively demonstrated by us in our previous contri-butions in this field.[3,12]Experimentally,NMR analysis of the crude ring-opened products revealed complete regio-selectivity in favour of the formation of the C-2ring-opened products instead of the corresponding 3-amino-2-hydroxy regioisomers.Thus,for the aliphatic compounds 16–22,ob-servation of a 1H NMR signal as a doublet in the range 3.36–4.11ppm and a downfield signal with different multi-plicities are in accordance with oxirane ring-opened prod-ucts with an amino group installed at the 2-position.In contrast,for the C-3ring-opened products,we should ob-serve a downfield shift for the protons at the 2-position (4.39–4.50ppm),which should be more deshielded by the effect of the hydroxy group,and an upfield shift for the protons at the 3-position (2.91–3.61ppm).In addition,our total syntheses of the natural products sphinganine and sphingosine from epoxy amides 3j and 3k [2]via 2-amino-3-hydroxy amides 21and 22(entries 17and 18,Table 1)un-ambiguously demonstrated the regioselectivity at C-2of the oxirane ring-opening reaction.Less clear was the establish-ment of the regioselectivity at the 2-position for the aro-matic compounds 5–15because either proton at the 2-or 3-position could appear as a doublet in the same region for©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim.Chem.0000,0–02both the C-2and C-3ring-opened products.In particular,we observed doublets in the range 3.61–4.83ppm for all these compounds,which did not allow an unambiguous as-signment of the regioisomer formed.However,the observa-tion in the 13C NMR spectra of signals in the range 71.6–75.9ppm,assigned to C-3,is in accordance with the C-2ring-opened products because the corresponding regioiso-mers would show signals at around 85ppm for C-2due to the presence of a hydroxy group at this position.Further-more,the reduction of the 2-azido-3-hydroxy derivative 23a ,the structure of which was unambiguously assigned,as will be described later (see Scheme 3),furnished a product with identical physical and spectroscopic properties to that ob-tained for the ring-opening of epoxy amide 3a with ammo-nia (compound 5),thus providing confirmation of the re-gioselectivity of the reaction.On the other hand,the corre-sponding syn ring-opened products were not detected,which indicates that possible anchimeric assistance by the methyl sulfide group during the oxirane ring-opening pro-cess does notoccur.Scheme 2.Reactions of epoxy amides with amines and azide.Rea-gents and conditions:a)see Table 1for conditions and yields;b)see Table 2for conditions and yields.Another nitrogen nucleophile worthy of consideration is the azide anion.In contrast to amines,with the azide as nucleophile,we found remarkable differences depending on the nature of the starting epoxy amide and the azide em-ployed.For this study we started with the reactions of ep-oxy amides 3a and 3l with NaN 3in DMF at 70°C or in MeOH at reflux,obtaining a 1:4and 1:2mixture of re-gioisomers 23a /23b and 24a /24b in combined yields of 86and 68%,respectively.The preference of the azide anion to react at the 3-position in reactions with epoxy amides has already been reported by Sharpless and co-workers,[13]which was remarkably boosted by the use of Mg(N 3)2,[14]and which we observed for 3a and 3l (see Table 2).Our interest in the C-2ring-opened products prompted us to study this reaction in more detail by screening a variety of different reaction conditions,as summarized in Table 2.Intriguingly,when acetic acid was used in stoichiometric amounts in DMF ,a significant reversal of regiochemistry in favour of the C-2ring-opened product was observed,particularly for aliphatic epoxy amide 3l ,together with an improvement in the combined yield compared with pre-Job/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22Table 1.Reactions of epoxy amides 3with amines.Entry Epoxy amide (R)X Amino hydroxy amide [a](Yield [%])13a (R =C 6H 5)NH 25(69)23a (R =C 6H 5)NHMe 6(72)33a (R =C 6H 5)NHBn 7(75)43a (R =C 6H 5)NHAllyl 8(93)53a (R =C 6H 5)NHPh 9(54)63a (R =C 6H 5)NMe 210(68)73b (R =4-MeC 6H 4)NHMe 11(71)83c (R =4-MeOC 6H 4)NH 212(65)93c (R =4-MeOC 6H 4)NHMe 13(83)103d [R =3,4-(BnO)2C 6H 3]NHMe 14(74)113e (R =4-ClC 6H 4)NHMe 15(74)123f (R =CH 3CH 2)NHMe 16(62)133g [R =(CH 3)2CH]NH 217(73)143g [R =(CH 3)2CH]NHMe 18(84)153h (R =Cy)NHMe 19(73)163i (R =C 6H 5CH 2)NHMe 20(65)173j [R =CH 3(CH 2)14]NH 221(72)183k [R =(E )-CH 3(CH 2)12CH=CH]NH 222(75)[a]Reagents and conditions:5.0equiv.of amine or NH 3,MeOH,reflux,6–8h.viously tested reaction conditions.A similar regioselectivity was obtained when the reaction was performed in MeOH in the presence of ammonium chloride and H 2O,although a lower yield was obtained.In an attempt to improve the regioselectivity,other acids,such as TFA,TfOH and Lewis acids,were investigated.From these studies,TfOH (condi-tions G,Table 2)showed a slight increase of the C-2ring-opened product compared with AcOH,with the other acids not proving beneficial.Although it is not clear what the role of the acid is in the regioselectivity of this reaction,we surmised that the protonation of the relatively basic amide carbonyl group could activate the 2-position for nucleo-philic attack.Fortunately,for epoxy amides containing larger alkyl groups (epoxy amides 3m and 3n ),the regiose-lectivity increased to 5:1in favour of the C-2ring-opened products (25a and 26a )under acidic conditions,reaching a ratio of 6:1when TfOH was used in the reaction of 3m .More hindered epoxy amides,such as 3g ,delivered the cor-responding 2-azido-3-hydroxy derivative 27a in a good yield (76%)with no detection of the 3-azido-2-hydroxy re-gioisomer 27b (Scheme 2and Table 2).Our interest in the azido ring-opened products lies in the remarkable advantages that this functional group presents compared with the corresponding amino ring-opened prod-ucts,such as the ease of handling over their amino counter-parts and,in addition,the possibility of being readily trans-formed into the corresponding aziridines,which are inter-esting and useful building blocks.[4]Thus,when azido alcohols 23a ,25a and 27a were treated with Ph 3P,[15]azirid-ines 28,29and 30were efficiently obtained in yields of 62,92and 89%,respectively.Interestingly,when a mixture of azido alcohols,such as 23a /23b ,was used,only one azirid-ine (28)was obtained.In an attempt to obtain the corre-sponding amino alcohols from the azido alcohols,these re-actions with Ph 3P were performed in the presence of water,however,the aziridines were again the only observed .Chem.0000,0–0©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim 3Table 2.Reactions of epoxy amides 3with azide.Epoxy amide Reaction conditions [a]Azido alcohol (combined (R)yield [%];C-2/C-3ring-opened products ratio)3a (C 6H 5)A:MeOH,70°C23a /23b (86;1:4)B:MeOH,MgSO 4,70°C 23a /23b (82;0:100)C:DMF ,70°C23a /23b (73;1:4)D:DMF ,AcOH,70°C 23a /23b (75;1:2.5)3l (CH 3)A:MeOH,70°C24a /24b (68;1:2)B:MeOH,MgSO 4,70°C 24a /24b (85;1:4)C:DMF ,70°C24a /24b (61;1:2)D:DMF ,AcOH,70°C 24a /24b (78;3:1)E:MeOH,NH 4Cl,70°C 24a /24b (74;2.6:1)F:DMF ,TF A,70°C 24a /24b (81;3:1)F Ј:DMF ,TF A,25°C no reactionG:DMF ,TfOH,70°C 24a /24b (73;4:1)H:DMF ,Zn(OTf)2,70°C 24a /24b (52;1:2)3m [CH 3(CH 2)8]A:MeOH,70°C25a /25b (72;1.2:1)B:MeOH,MgSO 4,70°C 25a /25b (86;1:2.6)C:DMF ,70°C25a /25b (56;1:2)D:DMF ,AcOH,70°C 25a /25b (75;5:1)G:DMF ,TfOH,70°C 25a /25b (92;6:1)3n [CH 3(CH 2)9]A:MeOH,70°C26a /26b (85;1.2:1)D:DMF ,AcOH,70°C 26a /26b (94;5:1)3g [(CH 3)2CH]D:DMF ,AcOH,70°C27a /27b (76;100:0)[a]All reactions were carried out by using 10.0equiv.of NaN 3.ucts.We have ascribed these results to the formation of hin-dered phosphazide or iminophosphorane intermediates during the Staudinger reaction,which were unable to react with water and thus intramolecular attack of the hydroxy group on either the phosphazide or iminophosphorane in-termediate was favoured,followed by an intramolecular Mitsunobu-type reaction of the resulting oxyphosphonium derivative to form the corresponding aziridines.[16]To over-come this hurdle,we executed this reaction with Me 3P in the presence of water to afford the corresponding amino alcohols 5and 17from azido alcohols 23a and 27a with no aziridines being detected (Scheme 3).On the other hand,when TMSN 3was used as the source of azide anion in the presence of a Lewis acid [Yb(OTf)3,Zn(OTf)2or ZrCl 4],[17]only aromatic epoxy amides reacted to give the corresponding 3-azido-2-trimethylsilyloxy deriv-atives 31–36.In these cases,the opposite regioselectivity ob-served with respect to the ring-opening reactions with amines is explained by the acidic conditions required for the introduction of azide that leads to the activation of the benzylic position,which is attacked by the azide nucleo-phile.In contrast,aliphatic epoxy amides were unreactive towards TMSN 3,giving only the starting material.Even for the aromatic epoxy amides,we found a considerable differ-ence in reactivity depending on the nature of the substituent present on the aromatic ring,with a p -methoxy substituent being the most reactive and not requiring the presence of a Lewis acid to obtain the desired ring-opened product 31.Identical results were observed for the reactions of 3,4-di-O -benzyl and p -acetamide derivatives 3d and 3o ,with the ring-opened products 32and 33being obtained in yields of 76and 88%,respectively.For the unsubstituted phenyl derivative 3a ,the p -methyl derivative 3b and the 2-naphthyl derivative 3p ,extended reaction times were required forJob/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22F .Sarabia et al.FULLPAPERScheme 3.Reactivity of azido alcohols:synthesis of aziridines and amino alcohols.Reagents and conditions:a)1.5equiv.Ph 3P,THF ,25°C,6h,62%for 28,92%for 29,89%for 30;b)1.5equiv.Me 3P,THF/H 2O,25°C,6h,74%for 5,86%for 17.completion and the corresponding ring-opened products 34–36were obtained in poor yields of 12,15and 23%,respectively.For other epoxy amides,such as the p -chloro and p -nitro derivatives,ring-opened products were not de-tected even after long reaction times.During the elabora-tion of these reactions and subsequent purification and iso-lation of the corresponding 3-azido ring-opened products,we observed in some cases the deprotection of the sensitive trimethylsilyl group (products 33,34and 37;Table 3).The extension of this reaction to heterocyclic epoxy amides was considered of interest because the corresponding ring-opened products frequently occur within the molecular frameworks of many bioactive compounds.In addition,when we investigated the efficacy of this ring-opening reac-tion with heterocyclic epoxy amides,we came upon a number of interesting observations.Thus,when 3-furyl (3q ),2-thienyl (3r )and 2-benzofuryl (3s )epoxy amides were sub-mitted to the reaction with TMSN 3in the presence of cata-lytic Yb(OTf)3,the C-3ring-opened products 37,38and 39were cleanly formed.In contrast to electron-donating heterocyclic systems,π-deficient heterocyclic systems con-taining epoxy amides (3t or 3u )were completely unreactive under these conditions.The use of other catalysts [Zn-(OTf)2,TiCl 4,BF 3],solvents (DMF ,THF)or reaction tem-peratures (40,70°C)were similarly unsuccessful (Table 3).©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim.Chem.0000,0–04Table 3.Reactions of aromatic and heterocyclic epoxy amides 3with trimethylsilylazide.[a]Reagents and conditions: 2.5equiv.TMSN 3,0.2equiv.Yb-(OTf)3,CH 2Cl 2,25°C,6–8h.Interestingly,during the optimization of this reaction,we found that,for example,for epoxy amides 3r and 3s ,when these reactions were performed with Zn(OTf)2as catalyst,mixtures of diastereomeric C-3ring-opened products 38/38Јand 39/39Јwere formed in an approximate ratio of 1:1(Scheme 4).The epimerization at the 3-position could be ascribed to the formation of the carbocation intermediate I ,which can be stabilized by the electron-donating hetero-cyclic system through canonical form II ,which can lead to the loss of the C-3stereochemical centre and subsequent epimerization at this position by nucleophilic attack by the azide anion (Scheme 5,hypothesis I).However,the fact that this isomerization was not observed when the reaction was carried out with Yb(OTf)3led us to consider a more plaus-ible hypothesis.Thus,a second rationale to justify this isomerization was based on the possible formation of a (TfO)ZnN 3or Zn(N 3)2species [18]that can coordinate to the epoxy amide to form intermediate A and activate it for ring-opening.From this intermediate A ,two different pathways are possible:an intramolecular attack of the azide anion on the epoxide at the 3-position with retention of the configu-ration (pathway a),[19]which should deliver the products 38Јand 39Јafter silylation of intermediate B ,or an intermo-lecular attack by the azide anion that would produce theJob/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22way b).The observation of 1:1mixtures of products 38/38Јor 39/39Јshould be the result of competition between the two possible pathways.In the case of Yb(OTf)3as catalyst,itis likely that species of the type (TfO)2YbN 3,(TfO)-Yb(N 3)2or Yb(N 3)3are not formed [20]due to the strong acidic character of Yb 3+in contrast to the soft anion azide.Therefore,in this case,intramolecular attack does not occur to produce exclusively the anti ring-opened product at the 3-position (Scheme 5).Scheme 4.Reactions of heterocyclic epoxy amides with trimethyl-silyl azide catalyzed by Zn(OTf)2.Reagents and conditions:a)2.5equiv.TMSN 3,0.2equiv.Zn(OTf)2,25°C,6h,73%for 38/38Ј(1:1),82%for 39/39Ј(1:1).The synthetic value of the previously described amino ring-opened products was demonstrated in our earlier stud-ies through the efficient and expedient syntheses of sphin-ganine (40)and sphingosine (41;see Scheme 6).[2]In ad-dition,many of the ring-opened products described above are considered to be valuable building blocks for the synthe-sis of other bioactive compounds.For example,amino hy-droxy amide 19represents the structural core of the potent anti-HIV agent Aplaviroc [21]and the thiophene derivative 38represents the 3-amino-2-hydroxy system of the thio-phene analogue [22]of the very well-known anti-HIV agent Nelfinavir.[23]To prove the utility and generality of this methodology in the synthesis of natural products,we ex-tended our studies to other related sphingoid-type bases [24]such as clavaminol H (42)and the more structurally com-plex and biologically relevant phytosphingosine (43).Clavaminol H (42)belongs to the clavaminol family of natural products,recently isolated from the Mediterranean ascidian Clavelina phlegraea .[25]These natural products dis-play cytotoxic activities against different cancer cell lines,namely A549(lung carcinoma),T47D (breast carcinoma)and AGS (gastric carcinoma),by activation of apoptosis,with clavaminol A being the most active member.Although clavaminol H is not as active as the other clavaminols,inter-estingly,deacetyl clavaminolH (46)retains significant ac-tivity against AGS carcinomas.[25b]It is worth noting that the clavaminols possess the opposite configuration to that of the well-known sphingolipids,which require the use of the sulfonium salt 2for the stereoselective synthesis of the.Chem.0000,0–0©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim 5Scheme 5.Rationale of the epimerization of the reactions of hetero-cyclic epoxy amides with trimethylsilyl azide catalyzed by Zn-(OTf)2.oxirane ring with the correct configuration.Thus,when decanal (44)was exposed to sulfonium salt 2under basic conditions,epoxy amide 4m was obtained in 82%yield as a single diastereoisomer.Following the synthetic scheme implemented for sphinganine and sphingosine,epoxy amide 4m was subjected to ammonia in methanol at reflux to pro-vide 2-amino-3-hydroxy amide 45in a good yield of 74%,which was treated with NH 3·BH 3/LDA to give the amino diol 46,which corresponds to the deacetyl derivative of cla-vaminol H,in a reasonable yield of 61%.Finally,acetyl-ation of 46followed by selective ester cleavage furnished clavaminol H (42)in almost quantitative yield,the physical and spectroscopic data of which are in complete agreement with those reported for the natural product (Scheme 6).[25–27]This synthesis represents the shortest route reported thus far for clavaminol H (eight steps),con-sidering the longest linear sequence includes the prepara-tion of the chiral sulfonium salt 2from commercially avail-able d -methionine,which was obtained in an overall yieldJob/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22F .Sarabia et al.FULL PAPERof 25%and with the additional advantage of generating the two required chiral centres in a single step compared with the synthesis reported previously in the literature [26–28]in which the two chiral centres were generated in different pro-cesses.Scheme 6.Synthesis of clavaminol H (42)and other sphingoid-type bases from epoxy amides.Reagents and conditions:a)1.0equiv.44,1.0equiv.2,1.0equiv.3.0m aqueous NaOH solution,t BuOH,25°C,overnight,82%;b)5.0equiv.30%aqueous NH 3solution,MeOH,70°C,8h,74%;c)7.0equiv.LDA,7.0equiv.NH 3·BH 3,THF ,0Ǟ25°C,0.5h;then 1.0equiv.45,25°C,overnight,61%;d)5.0equiv.Ac 2O,pyr,0Ǟ25°C,overnight;then 3.0equiv.NaOMe,MeOH 0°C,0.5h,98%.LDA =lithium diisoprop-ylamide.On the other hand,phytosphingosine (43)[29]is a bio-active metabolite extensively found in the membranes of fungi,plants,bacteria and mammals,and is involved in the cellular growth and heat stress response of yeast.[30]In ad-dition,phytosphingosine is the lipidic component of the synthetic α-galactosyl ceramide KRN7000,[31]an immuno-stimulant of invariant natural killer cells with significant biomedical implications.[32]For all these reasons,phyto-sphingosine represents a valuable synthetic target for or-ganic chemists.[33]The synthesis of this important natural product commenced from epoxy amide 3v ,prepared ac-cording to our described asymmetric epoxidation method-ology in a high yield of 89%from pentadecanal.[2]The transformation of 3v into epoxy alcohol 47[34]was followed by conversion to the olefin 48[35]according to the method-ology developed by Ibuka and co-workers [36]and not re-quiring purification by chromatographic methods to give 48in an overall yield of 67%from 47.Dihydroxylation of the olefin [37]and subsequent oxidative cleavage of the resulting diol with NaIO 4[38]afforded the required aldehyde 49in 89%yield.This aldehyde was then subjected to a second sulfonium ylide reaction by treatment with 1in the presence of base using a two-phase protocol to avoid possible ©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim.Chem.0000,0–06merization side-reactions.[39]Epoxy amide 50was obtained in 73%yield and with excellent stereoselectivity.With this epoxy amide in hand,we proceeded with the ring-opening reaction with ammonia following a similar strategy to that described above for sphingosine,sphingonine and clavami-nol H.However,in contrast to the good results obtained for the above cases and,in general,for the epoxy amides described in Table 1,on this occasion the reaction was un-successful with recovery of the starting material together with the formation of degradation products with no detec-tion of the desired amino derivative 51.In light of this dis-couraging result,and with the experience gathered during studies on the ring-opening reactions of this kind of epoxy amides with sodium azide,we decided to attempt the instal-lation of the amino group in the sterically hinderedepoxyScheme 7.Synthesis of phytosphingosine (43)from epoxy amide 3v .Reagents and conditions:a)3.0equiv.LiEt 3BH,THF ,0°C,0.5h,89%;b)1.2equiv.TsCl, 1.5equiv.Et 3N,0.02equiv.4-DMAP,CH 2Cl 2,0°C,2h;c)4.0equiv.KI,acetone/DMF (4:1),reflux, 1.5h;then 1.0equiv.Ph 3P,0.1equiv.I 2,0°C,1h;d)2.0equiv.TBSCl,2.5equiv.imidazole,DMF ,25°C,6h,67%over three steps from 47;e)1.0.05equiv.OsO 4,2.0equiv.NMO,t BuOH/H 2O,25°C,18–24h,89%;2.6.0equiv.NaIO 4,MeOH/H 2O (2:1),0°C,2h,quantitative;f)1.2equiv.1,1.2equiv.3.0m aqueous NaOH solution,CH 2Cl 2/H 2O (1:1),25°C,overnight,85%;g)5.0equiv.30%aqueous NH 3solution,MeOH,70°C,8h,decomposition;h)10.0equiv.NaN 3, 1.0equiv.AcOH,DMF ,70°C,12h,92%;i)7.0equiv.LDA,7.0equiv.NH 3·BH 3,THF ,0Ǟ25°C,0.5h;then 1.0equiv.52,25°C,overnight,degradation;j)10.0equiv.LiAlH 4,THF ,65°C,8h,57%.4-DMAP =4-(di-methylamino)pyridine,TBS =tert -butyldimethylsilyl,NMO =4-methylmorpholine N -oxide.Job/Unit:O42221/KAP1Date:06-05-1419:20:13Pages:22visioning good regioselectivity at the 2-position,as was ob-tained previously.Thus,when 50was exposed to an excess of sodium azide in the presence of 1.0equiv.of AcOH in DMF at 70°C for 12h,we obtained the 2-azido-3-hydroxy amide derivative 52in an excellent 92%yield and with com-plete regioselectivity.Identical regioselectivity was found when the reaction was carried out in DMF in the absence of AcOH,albeit in a lower 75%yield and requiring a longer reaction time (2–3d)for completion.Having pre-pared the key product 52,we then attempted its direct re-duction by reaction with H 3NBH 3in the presence of LDA,[40]as for compounds 21,22and 45.However,the result was a complex mixture of degradation products,with the desired amino diol 53not being detected.Fortunately,when 52was reduced with an excess of LiAlH 4in THF at 65°C,[41]phytosphingosine 43was obtained directly in a reasonable yield of 57%as a result of the reduction of the amide and azide functional groups and the cleavage of the silyl ether of compound 53(Scheme 7).Ring-Opening Reactions with ThiolsWith regard to sulfur-type nucleophiles such as thiols,we found that they were less efficient,as expected.[17]Thus,the reaction proved to be feasible only for aromatic epoxy amides in the presence of a Lewis acid.[42]Furthermore,only the p -methoxy derivative 3c displayed sufficient and reproducible reactivity towards thiophenol to give the cor-responding sulfide 54in 77%yield following subsequent acetal cleavage by using Yb(OTf)3as catalyst in CH 2Cl 2at 0°C (Scheme 8).For other aromatic epoxy amides (epoxy amides 3a and 3b ),a complex mixture of degradation prod-ucts was obtained under the same conditions as used for 3c .The use of other Lewisacid catalysts [Zn(OTf)2,ZrCl 4,Sc(OTf)3,TiCl 4,Ti(O i Pr)4,SnCl 4],various temperatures (25,40°C,reflux)and solvents (THF ,DMF ,MeCN)were fruitless in all cases,resulting in complex mixtures of degra-dation products or recovery of the starting material.The reduced efficiency displayed by these epoxy amides towardsScheme 8.Reactions of epoxy amides with thiols.Reagents and conditions:a)2.5equiv.PhSH,0.3equiv.Yb(OTf)3,CH 2Cl 2,0°C,2d,77%for 54;b)3.0equiv.Super-H,THF ,0°C (see ref.[2]);c)see ref.[43].Chem.0000,0–0©0000Wiley-VCH Verlag GmbH &Co.KGaA,Weinheim 7epoxy alcohols pounds of the type 55)as starting materials for the instal-lation of sulfide moieties,as has already been carried out by others to obtain products of the type 56,which have proven to be efficient chiral ligands for stereoselective reac-tions mediated by palladium.[43]Ring-Opening Reactions with Me 2CuLiCarbon nucleophiles in the form of organocuprate rea-gents were also considered to be of interest and synthetic importance.In this case,treatment of aromatic or aliphatic epoxy amides with the Gilman reagent [44]smoothly pro-vided the corresponding ring-opened products with com-plete regioselectivity at the 2-position.It is important to note this complete regioselectivity displayed by the epoxy amides intheir reactions with lithium dimethylcuprate,which contrasts the mixed regioselectivity usually observed in the reactions of simple epoxy alcohols.[45]The crude ring-opened products were transformed into the corresponding silyl derivatives 57–66,which were purified and isolated in good overall yields (52–94%yields;Table 4).Table 4.Reactions of epoxy amides 3with Me 2CuLi.Entry Epoxy amide (R)2-Methyl amide [a](yield [%])13a (R =C 6H 5)57(69)23g [R =(CH 3)2CH]58(72)33h (R =Cy)59(75)43i (R =C 6H 5CH 2)60(58)53w [R =CH 3(CH 2)3]61(54)63x [R =CH 3(CH 2)5]62(78)73y [R =CH 3(CH 2)7]63(94)83z [R =CH 3(CH 2)10]64(72)93a Ј[R =CH 3(CH 2)12]65(52)103j [R =CH 3(CH 2)14]66(56)[a]Reagents and conditions:a)2.5equiv.Me 2CuLi,THF ,0°C,6–8h;b)1.5equiv.TBSOTf, 2.0equiv.2,6-lutidine,CH 2Cl 2,0°C,0.5h.The excellent regioselectivity combined with the good yields obtained in these ring-opening reactions of epoxy amides with Me 2CuLi makes this methodology useful and suitable for the synthesis of polypropionate-derived natural products.In fact,we have successfully employed non-chiral sulfonium salts in the synthesis of typical polypropionate frameworks based on the asymmetric induction offered by chiral aldehydes.[46]In this case,however,the access to these structural motifs was limited to the stereochemical induc-。

化学品英文IntroductionChemicals are substances that are used in various industries, including manufacturing, agriculture, healthcare, and construction. Chemicals have benefits for human beings, but improper use or handling can be hazardous. This paper presents an overview of various chemicals, their properties, uses, and potential hazards.1. AcidsAcids are chemical compounds that have a pH of less than 7. They are used for many purposes, including cleaning, etching, and processing of various industries. Examples of common acids include hydrochloric acid, sulfuric acid, and nitric acid. Acids can cause severe burns and skin irritations if they come into contact with the skin. Inhalation of acid fumes may result in respiratory problems.2. AlcoholsAlcohols are organic compounds that contain a hydroxyl group (-OH). They are commonly used in the production of beverages, solvents, and perfumes. Examples of alcohols include ethyl alcohol, isopropyl alcohol, and methanol. Alcohols are flammable and can cause irritations to the eyes and skin.3. AldehydesAldehydes are organic compounds that have a carbonyl group (-CHO). They are used as intermediates in the production of various chemicals and plastics. Examples of aldehydes include formaldehyde, acetaldehyde, andpropionaldehyde. Aldehydes are toxic and have carcinogenic properties. Prolonged exposure to aldehydes may cause respiratory problems and skin irritations.4. AminesAmines are organic compounds that contain a nitrogen atom. They are used in many industries, including pharmaceuticals, fertilizers, and pesticides. Examples of amines include ethylamine, diethylamine, and triethylamine. Amines can irritate the eyes and respiratory system. Some amines are toxic and can cause serious health problems with prolonged or repeated exposure.5. HalogensHalogens are a group of elements that include fluorine, chlorine, bromine, and iodine. They are used in various industries, including water treatment, chemical manufacturing, and agriculture. Halogens are highly reactive and can cause skin irritations, eye damage, and respiratory problems.6. HydrocarbonsHydrocarbons are organic compounds that contain only hydrogen and carbon atoms. They are used in many industries, including petroleum processing, fuel production, and plastics manufacturing. Examples of hydrocarbons include methane, propane, and benzene. Hydrocarbons can be flammable and can cause respiratory problems if inhaled in large quantities.7. Organic acidsOrganic acids are carboxylic acids that contain carbon atoms. They are used in many industries, including food production, pharmaceuticals, and plastics manufacturing. Examples of organic acids include citric acid, aceticacid, and lactic acid. Organic acids can irritate the skin and eyes and can be harmful if ingested or inhaled in large quantities.8. Oxidizing agentsOxidizing agents are chemical compounds that release oxygen when they react with other substances. They are used as disinfectants, bleaching agents, and in the production of various chemicals. Examples of oxidizing agents include hydrogen peroxide, potassium permanganate, and sodium hypochlorite. Oxidizing agents can be toxic and can cause skin irritations and respiratory problems.9. SolventsSolvents are substances that can dissolve other substances. They are used in many industries, including manufacturing, painting, and cleaning. Examples of solvents include water, alcohol, and acetone. Solvents can be flammable and can cause irritations to the skin and respiratory system.10. GasesGases are substances that are in a gaseous state at room temperature and pressure. They are used in various industries, including medical, food processing, and welding. Examples of gases include oxygen, nitrogen, and carbon dioxide. Gases can be dangerous and can cause asphyxiation and explosions if not handled properly.ConclusionChemicals are an essential part of modern life and play a vital role in many industries. However, exposure to some chemicals can be dangerous and can cause serious health problems. It is important to understand theproperties of chemicals and their potential hazards. Proper handling, storage, and disposal of chemicals are essential for the safety of workers and the environment.。

1.有机化合物的官能团和重要的基团官能团functional group双键double bond三键triple bond烃基hydroxy group琉基mercapto硫轻基sulfhydryl group羰基carbonyl group氨基amino group亚氨基imino group硝基nitro group亚硝基nitroso group氰基cyano group羧基carboxyl group磺基sulpho group烷基alkyl group苯基phenyl group卡基benzyl group芳基aryl group烯基allyl group烷氧基alkoxyl group酰基acyl group活性亚甲基active methylene group2.有机化合物的类型烃hydrocarbon石蜡paraffin脂肪烃aliphatic hydrocarbon烷烃alkane烯烃alkene炔烃alkyne共扼二烯烃conjugated diene脂环烃alicyclic hydrocarbon螺环化合物spiro compound桥环化合物bridged ring compound芳烃aromatic hydrocarbon非苯芳烃nonbenzenoid aromatic hydrocarbon 稠环芳烃condensed aromatics卤代烃halohydrocarbon醇alcohol酚phenol醚ether环氧化合物epoxide冠醚crown ether硫醇thiol硫酚thiophenol硫醚sulfide二硫化物disulfide亚磺酸sulfinic acid磺酸sulfonic acid 亚砜sulfoxide砜sulfone醛aldehyde酮ketone半缩醛hemiacetaI半缩酮hemiketal缩醛acetal缩酮ketal西佛碱shiff's base肟oxime腙hydrozone缩氨脲semicarbazoneα,β-不饱和酮α,β--unsaturated ketone 醌quinone羧酸carboxylic acid酰卤acid halide酸酐acid anhydride酯ester酰胺amide內酯lactone内酰胺lactam月青nitrile取代酸substituted acid羟基酸hydroxy acid醇酸alcoholic acid酚酸phenolic acid酮酸keto acidB-酮酸酯B-ketone ester乙酰乙酸乙醋ethyl acetoacetate亚硝基化合物nitroso compound硝基化合物njtro compound亚胺imine胺amine伯胺primary amine仲胺secondary amine叔胺tertiary amine季铵盐quaternary ammonium salt季铵碱quaternary ammonium hydroxide 重氮盐diazonium salt偶氮化合物azo compound胍guanidine氨基酸amino acid磷phosphine磷酸酯phosphate亚磷酸酯phosphite膦酸酯phosphonate膦酸phosphonic acid3.杂环化合物吡咯pyrrol呋喃furane噻吩thiophone吲哚indole卟吩porphine咪唑imidazole噻唑thioazole吡啶pyridine喹啉quinoline异喹啉isoquinoline吡喃鎓盐pyrylium salts 黄酮flavone嘧啶pirimidine嘌呤purine4.有机天然产物肽peptide多肽polypeptide核酸nucleic acid核苷nucleoside核苷酸nucleotide生物碱alkaloid碳水化合物carbohydrate单糖monosaccharide醛糖aldoses酮糖ketosesD-核糖ribose D-2-脱氧核糖deoxyribose 葡萄糖glucose果糖fructose糖脎osazone糖苷glucoside低聚糖oligosaccharide 麦芽糖maltose蔗糖sucrose纤维二糖cellobiose环糊精cyclodextrin多糖polysaccharide淀粉starch纤维素cellulose类脂lipid萜类化合物terpenoid甾族化合物steroid脂肪fat油oil脂肪酸fatty acid甘油三羧酸酯triglyceride磷脂phospholipid磷脂酸phosphalidic acid蜡wax5.有机化合物的结构理论价键理论valence-bond theory分子轨道理论molecular orbital theory 共振论resonance theory凯库勒式Kekule formula路易斯式Lewis formulaσ键σ bondπ键π bond键能bond energy键角bond angle键长bond Iength成键轨道bonding orbital反键轨道antibonding orbital最高已占轨道HOMO highest occupied molecular orbital 最低末占轨道LUMO lowest unoccupied molecular orbital 诱导效应inductive effect共轭效应conjugated effectπ,π-共轭π,π- conjugationp,π-共轭p,π- conjugation超共轭作用hyperconjugation离域能delocalization energy共振能resonance energy给电子基团electron donating group吸电子基团electron withdrawing group芳性aromaticity休克尔规律Huckel's rule两性离子Zwitterion6.有机化学中的同分异构异构体isomer构造constitution构型configuration构象conformation构造异构constitutional isomerism立体异构stereo isomerism构型异构configurational isomerism顺反异构cis-trans isomerism次序规则sequence ruIe同侧Zugammen Z异侧Entgegen E顺式cis反式trans对映异构enantiomerism = 光学异构旋光异构optical isomerism旋光性optical activity旋光度optical rotation比旋光度specific rotation对称面plane of symmetry对称中心center of symmetry对称轴axis of symmetry手性chirality手性分子chiral molecules对映异构体，对映体enantiomer 非对映体diastereomer外消旋体raceme左旋体leveisomer右旋体dextroisomer内消旋体mesomer费歇尔投影式Fischer projection相对构型relative configuration绝对构型absolute configurationR -构型R -configurationS -构型S -configuration赤式erythro苏式threo外消旋化racemization拆分resolution光学纯度Optical Purity对映体过量百分数enantiomeric excess立体专一性反应stereospecific reaction 立体选择性反应stereoselective reaction不对称合成asymmetric synthesis构象异构conformational isomerism构象分析conformational analysis锯架式perspective formula 纽曼投影式Newman projection formula椅式chair form船式boat form直立键a键axial bond 平伏键e键equatorial bond互变异构tautomerism酮式keto-form烯醇式enol-form差向异构化epimerization变旋现象mutamerism哈武斯式Haworth form7.有机反应的名称取代反应substitution reaction加成反应addition reaction马尔科夫尼可夫规律Markovnikov rule 共轭加成conjugate addition消去反应elemination reaction查依采夫规律Saytzeff rule霍夫曼规律Hofmann rule硼氢化反应hydroboration催化加氢catalytic hydrogenation 聚合反应polymerization单体monomer聚合物polymer硝化反应nitration卤化反应halogenation磺化反应sulfonation烷基化反应alkylation酰基化反应acylation酯化反应esterification酯交换反应transesterification脱羧反应decarboxylation 氯甲基化反应chloromethylation傅列德尔-克拉夫茨反应Friedel-Crafts reaction格利雅反应Grignard reaction 格利雅试剂(格氏试剂) Grignard reagent赖默-梯曼反应Reimer-Tiemann reaction 卤仿反应haloform reaction水解反应hydrolysis reaction醇解反应alcoholysis reaction氨解反应ammonolysisi reaction皂化saponification插烯作用vinylogy缩合condensation克莱森缩合Claisen condensation安息香缩合benzoin condensation羟醛缩合aldol condensation列弗尔马茨基反应Reformatsky reaction迈克尔反应Michael reaction诺文格尔反应Knoevenagel reaction加布里反应Gabriel reaction乙酰乙酸乙酯合成法acetoacetic ester synthesis 丙二酸酯合成法malonic ester synthesis 威廉逊合成法William Son synthesis海森堡试验Hinsberg test重氮化反应diazotization reaction偶联反应coupling reaction脱氨基反应deamination reaction维悌希反应Wittig reaction氧化反应oxidation reaction还原反应reduction reaction周环反应pericyclic reaction环加成反应cycloaddition reaction电环化反应electrocyclic reaction坎尼扎罗反应Cannizzaro reaction齐齐巴宾反应Chichibabin reaction狄尔斯-阿德尔反应Diels-alder reaction斐林试剂Fehling reagent托伦试剂Tollens reagent沃克还原Wolff-Kishner reduction罗森蒙德还原Rosenmund reduction克莱门森还原Clemmenson reduction考普重排Cope rearrangement霍夫曼重排Hofmann rearrangement嚬哪醇重排pinacol rearrangement弗里茨重排Fries rearrangement克莱森重排Claisen rearrangement二烯体diene亲二烯体dienophile分子轨道对称守恒原理conversation of orbital symmetry8.有机反应机理均裂homolytic异裂heterolytic活性中间体active intermediate碳正离子carbocation碳负离子carbanion烯醇负离子enolate anion自由基，游离基free radical卡宾，碳烯carbene氮烯nitrene速度决定步骤rate-determining step哈蒙特假定Hammond postulate能线图energy profile过渡状态transition state邻基参与neighboring group participation动力学控制kinetic control热力学控制thermodynamic control离去基团leaving group底物substrate亲电试剂electrofphile亲核试剂nucleophile亲电加成反应electrophilic addition亲电取代反应electrophilic substitution定位规律orientation rule亲核取代反应nucleophilic substitutionSN2 反应机理SN2 reaction mechanismSN1 反应机理SN1 reaction mechanism瓦尔登转化Walden inversion亲核加成反应nucleophilic addition亲核加成-消去反应nucleophilic addition-elimination reaction 消去反应机理elimination reaction mechanismE1 反应机理E1 reaction mechanismE2 反应机理E2 reaction mechanism反式消去anti elimination重排反应机理rearrangement reaction mechanism 自由基反应free radical reaction链引发chain initation链增长chain propagation链终止chain termination9.有机化合物的光谱红外光谱IR Infrared spectra傅立叶变换Fourier Transform指纹区finger print region吸收频率absorption frequency紫外光谱UV Ultraviolet spectra电子跃迁elctronic transition吸光度absorbance摩尔消光系数molar extinction coefficient发色团chromophore助色团auxochrome核磁共振NMR Nuclear Magnetic Resonance1HNMR 谱1HNMR spectra13CNMR 谱13CNMR spectra屏蔽效应shielding effect化学位移chemical shift自旋偶合spin-spin coupling自旋裂分spin-spin splitting偶合常数coupling constant质子去偶proton spin decoupling 质子偏共振去偶proton off-resonance decoupling质谱Mass Spectra(MS)电子流轰击election impact (EI)快原子轰击fast atom bombarment (FAB)分子离子峰molecular ion peak同位素峰isotopic peak基峰base peak质荷比(m/z) mass-to-charge ratio10.分子间作用力氢键hydrogen bond色散力dispersion force 范德华力Van Der Waals force 偶极-偶极作用力dipole-dipole interraction force11.物理性质熔点melting point沸点boiling point密度density溶解度solubility偶极矩dipole moment12.有机化合物的酸碱性酸性acidity碱性basicity<HTML>本站材料仅为本院教师与学生教学所用，请勿它用！</HTML>有机化合物编辑[yǒu jīhuàhéwù]有机化合物主要由氢元素、碳元素组成，含碳的化合物，但是不包括一氧化碳、二氧化碳和以碳酸根结尾的物质。

Learning Supplementsin Organic Chemistry有机化学双语教学辅助材料（专业术语及英文解释）Glossary of Organic ChemistryAcetate(醋酸盐). (CH3COO-, C2H3O2-). acetate ion.1. an ion formed by removing the acidic hydrogen of acetic acid, HC2H3O2. 2. a compound derived byreplacing the acidic hydrogen in acetic acid. 3. A fiber made of cellulose acetate.Acetic acid(乙酸). (CH3COOH, C2H4O2). ethanoic acid; vinegar acid; methanecarboxylic acid.A simple organic acid that gives vinegar its characteristic odor and flavor. Glacial acetic acid is pureacetic acid.Acetone (丙酮).[CH3COCH3 or (CH3)2CO]. trivial name for propanone, formed by the oxidation of2-propanolwith KMnO4.Achiral(非手性的). A molecule that's superimposable on its mir ror image. Achiral molecules do not rotateplane-polarized light.Achiral molecule(非手性分子). a molecule that does not contain a stereogenic carbon; an achiral moleculehas a plane ofsymmetry and is superimposable on its mirror image.Acid anhydride（酸酐）[(RCO)2O]. Compare with acid .Nonmetallic oxides or organic compounds that react with water to form acids . For example, SO2, CO2,P2O5, and SO3 are the acid anhydrides of sulfurous, carbonic, phosphoric, and sulfuric acids, respectively. Acetic anhydride (CH3CO)2O) reacts with water to form acetic acid.Acid dissociation constant（酸电离常数）.(Ka) acid ionization constant. Compare with base hydrolysis constant.The equilibrium constant for the dissociation of an acid into a hydrogen ion and an anion. For example, the acid dissociation constant for acetic acid is the equilibrium constant for HC2H3O2(aq)H+(aq) + C2H3O2-(aq), which is Ka = [H+][C2H3O2-]/[HC2H3O2].Acid halide(酰卤)（RCOX）. acid chloride; acyl halide; acyl chloride.Compounds containing a carbonyl group bound to a halogen atom.Acid(酸). (Lat. acidus, sour) Compare with base.A proton donor or an electron pair acceptor. 1. a compound which releases hydrogen ions (H+) in solution (Arrhenius). 2. a compound containing detachable hydrogen ions (Bronsted-Lowry). 3. a compound that can accept a pair of electrons from a base (Lewis)..Acid-base indicator(酸碱指示剂).A weak acid that has acid and base forms with sharply different colors. Changes in pH around the acid's pKa are "indicated" by color changes.Acid/base reaction（酸/碱反应）. a reaction in which an acidic H atom is transferred from one molecule toanother.Addition compound(加成化合物). complex compound. Compare with hydrate.An addition compound contains two or more simpler compounds that can be packed in a definite ratiointo a crystal. A dot is used to separate the compounds in the formula. For example, ZnSO4·7 H2Oan addition compound of zinc sulfate and water. This represents a compound, and not a mixture, because there is a definite 1:7 ratio of zinc sulfate to water in the compound. Hydrates are a commontype of addition compound.Addition reaction(加成反应). A reaction in which two molecules are combined to yield asingle product. Typical of the reactions of alkenes and alkynes.-al(醛，后缀). A suffix added to the systematic names of organic compounds that contain an aldehyde group-(C=O)-H. For example, the systematic name of acetaldehyde, CH3CHO, is ethanal.Alcohol(醇). (ROH) Compare with phenol and hydroxide.A molecule containing a hydroxyl (OH) group. Also a functional group. An alcohol is an organic compound with a carbon bound to a hydroxyl group. Examples are methanol, CH3OH; ethanol, CH3CH2OH; propanol, CH3CH2CH2OH. Compounds with -OH attached to an aromatic ring are calledphenols rather than alcohols.Aldehyde(醛). (RCHO)A molecule containing a terminal carbonyl (CHO) group. Also a functional group. An aldehyde is anorganic compound with a carbon bound to a -(C=O)-H group. Examples are formaldehyde (HCHO),acetaldehyde, CH3CHO, and benzaldehyde, C6H6CHO.Aliphatic(脂肪族的). Compare with aromatic .An organic compound that does not contain ring structures.Alkaline earth(碱土金属). An oxide of an alkaline earth metal, which produces an alkaline solution inreaction with water.Alkali metal(碱金属). (a metal in Group IA on the periodic table): active metals which may be used to reactwith analcohol to produce the corresponding metal alkoxide and hydrogen gas.Alkaline(碱的，碱性的). Having a pH greater than 7.Alkane(烷烃). (RH，CnH2n+2) paraffin. Compare with hydrocarbon and alkene. A molecule containing onlyC-H and C-C single bonds. A series of organic compounds with general formula CnH2n+2. Alkane names endwith -ane. Examples are propane (with n=3) and octane (with n=8).Alkene(烯烃). (CnH2n) A molecule containing one or more carbon-carbon double bonds. Also a functionalgroup. A compound that consists of only carbon and hydrogen, that contains at least one carbon-carbondouble bond. Alkene names end with -ene. Examples are ethylene (CH2=CH2); 1-propene (CH2=CH2CH3),and 2-octane (CH3CH=CH(CH2)4CH3).Alkoxide(醇盐, 烷氧根负离子). (RO- M+) alkoxide ion.An ionic compound formed by removal of hydrogen ions from the hydroxyl group in an alcohol usingreactive metals, e.g. sodium. For example, potassium metal reacts with methanol (CH3OH) to produce potassium methoxide (KOCH3).Alkoxy group（烷氧基）(RO-).a substituent containing an alkyl group linked to an oxygen.Alkyl benzene（烷基苯）(C6H5-R). a benzene ring that has one alkyl group attached; the alkyl group(exceptquaternary alkyl groups) is susceptible to oxidation with hot KMnO4 to yield benzoic acid (C6H5CO2H).Alkyl(烷基). (-CnH2n+1) alkyl group. A molecular fragment derived from an alkane by dropping a hydrogenatom from the formula. Examples are methyl (-CH3) and ethyl (-CH2CH3).Alkyne(炔烃). (CnH2n-2) A molecule containing one or more carbon-carbon triple bonds. Also a functionalgroup. A compound that consists of only carbon and hydrogen, that contains at least one carbon-carbontriple bond. Alkyne names end with -yne. Examples are acetylene (CHidentCH); 1-propyne (CHidentCCH3), and2-octyne (CH3CidentC(CH2)4CH3).Allenes(丙二烯). Propa-1,2-diene (CH2=C=CH2) and derivatives. In allenes the two πbonds are orthogonal(see below), as are the two terminal hydrogens at one end, with respect to those at the other.Allo-(同分异构的). prefix that designates the more stable of a pair of geometric isomers. allo- is sometimesused less precisely to designate isomers or close relatives of a compound.Allyl(烯丙基). allylic; allyl group; allyl radical.A molecular fragment derived by removing a methyl hydrogen from propene (-CH2-CH=CH2). Forexample, "allyl chloride" is 3-chloropropene, Cl-CH2-CH=CH2.Allylic carbon(烯丙基正离子). (CH2=CH-CH2+)An sp3 carbon adjacent to a double bond.Amide(酰胺)(RCONH2). A molecule containing a carbonyl group attached to a nitrogen (-CONR2). Also afunctional group. An amide is an organic compound that contains a carbonyl group bound to nitrogen: .The simplest amides are formamide (HCONH2) and acetamide (CH3CONH2).Amine(胺)(RNH2). Compare with ammine.A molecule containing an isolated nitrogen = (NR3). Also a functional group. An amine is an organiccompound that contains a nitrogen atom bound only to carbon and possibly hydrogen atoms. Examples are methylamine, CH3NH2; dimethylamine, CH3NHCH3; and trimethylamine, (CH3)3N.Amino acid(氨基酸). Amino acids are molecules that contain at least one amine group (-NH2) and at leastone carboxylic acid group (-COOH). When these groups are both attached to the same carbon, the acid is an alpha-amino acid. alpha-amino acids are the basic building blocks of proteins.Amino group（氨基）. the -NH2 group.Ammine(氨络物). Compare with amine.A metal ion complex containing ammonia as a ligand. The ammonia nitrogen is bound directly to ametal ion in ammines; amines differ in that the ammonia nitrogen is directly bound to a carbon atom.Ammonia(氨，氨水). (NH3) Compare with ammonium.Pure NH3 is a colorless gas with a sharp, characteristic odor. It is easily liquified by pressure, and isvery soluble in water. Ammonia acts as a weak base. Aqueous solutions of ammonia are (incorrectly)referred to as "ammonium hydroxide".Ammonium ion(铵根离子). (NH4+) ammonium.NH4+ is a cation formed by neutralization of ammonia, which acts as a weak base.Amphiprotic solvent(两性溶剂). Compare with aprotic solvent.Solvents that exhibit both acidic and basic properties; amphiprotic solvents undergo autoprotolysis.Examples are water, ammonia, and ethanol.Amphoteric(两性的). ampholyte.A substance that can act as either an acid or a base in a reaction. For example, aluminum hydroxidecan neutralize mineral acids ( Al(OH)3 + 3 HCl = AlCl3 + 3 H2O ) or strong bases ( Al(OH)3 + 3 NaOH =Na3AlO3 + 3 H2O).Aniline（苯胺；苯胺的）. (C6H5NH2).a primary (1) amine in which the NH 2 group is bonded directly to abenzene ring..ngstrom (.)(埃，1/10 纳米).Unit of length named after the Swedish physicist, now being superseded by nanometer (nm). 1 . = 10–10 m so that a bond length of 1.54 . is given by 0.154 nm.Anhydrous(无水的). anhydrous compound; anhydride. Compare with hydrate.A compound with all water removed, especially water of hydration. For example, strongly heating copper(II) sulfate pentahydrate (CuSO4·5H2O) produces anhydrous copper(II) sulfate (CuSO4).Anion(阴离子). Compare with cation.A negatively charged atom or molecule. An anion is a negatively charged ion. Nonmetals typically form anions.Anomers(异头物). Anomers are cyclic diastereoisomers that differ only at the hemiacetal carbon. Theanomeric carbon in a sugar is the only carbon that is bonded to two oxygen atoms.Anti(希腊字头，反；抗；对；阻) (see also Anti addition; Anti periplanar). Substituents are anti if they are onopposite sides of a defined reference plane in a molecule. Anti is used to assign stereochemistry toproducts of, for example, asymmetric aldol reactions. The main chain is drawn in the plane of the paper and substituents on opposite sides of the plane are termed anti.Anti addition(反式加成). A reaction in which the two groups of a reagent X-Y add on opposite faces of acarbon-carbon bond. Anti addition of X–Y occurs when X and Y are added to opposite faces of a double bond.Anti clinal(反错构象). When the C–C–C–C dihedral angle is between 90° and 150°, i.e. 120 .30°, theconformation is said to be anti clinal.Anti conformation(反式构象). A type of staggered conformation in which the two big groups are opposite ofeach other in a Newman projection.Anti periplanar (sometimes called Anti)(反式共平面). Term given to a molecular fragment, e.g.X–C(1)–C(2)–Y, or C(1)–C(2)–Y (in this second case, a lone pair of electrons in a p-orbital replacesthe X–C bond), in which the dihedral angle is 180°, or more generally 180 .30°.Anti-aromatic(反芳香性的). A highly unstable planar ring system with 4n pi electrons.Antibonding orbital(反键轨道). antibonding; antibonding molecular orbital.A molecular orbital that can be described as the result of destructive interference of atomic orbitals on bonded atoms. Antibonding orbitals have energies higher than the energies its constituent atomicorbitals would have if the atoms were separate.Anti-periplanar (a.k.a. anticoplanar)(反平面). The conformation in which a hydrogen and a leaving groupare in the same plane and on opposite sides of a carbon-carbon single bond. The conformation required for E2 elimination.Aprotic solvent(非质子溶剂；疏质子溶剂). Compare with amphiprotic solvent.Solvents that do not contain O-H or N-H bonds. A solvent that does not act as an acid or as a base; aprotic solvents don't undergo autoprotolysis. Examples are pentane, pet ether, and toluene.Aqua regia(王水).A mixture of nitric and hydrochloric acids, usually 1:3 or 1:4 parts HNO3 to HCl, used to dissolvegold.Arene(芳香烃). (ArH)A hydrocarbon that contains at least one aromatic ring.Aromatic(芳香族的). A planar ring system that contains uninterrupted p orbitals around the ring and a total of4n+2 pi electrons. Aromatic compounds are unusually stable compounds.Aromatic compound(芳族化合物).A compound containing an aromatic ring. Aromatic compounds have strong, characteristic odors. Aromatic ring(芳环). (Ar)An exceptionally stable planar ring of atoms with resonance structures that consist of alternating double and single bonds, e. g. benzene:Aryl(芳基). (Ar-) aryl group.An aromatic group as a substituent. A molecular fragment or group attached to a molecule by an atom that is on an aromatic ring.Aspirin（阿司匹林；乙酰水杨酸）.trivial name for the compound acetylsalicylic acid; formed by treating salicylicacid with aceticanhydride.Asymmetric carbon atom（不对称碳原子；手性碳原子）. a carbon atom with four different substituents; astereogenic carbon.Atactic(不规则的). This adjective describes a polymer whose stereogenic centres along the polymer chainare randomly oriented.Atropisomers(位阻异构体). Stereoisomers that arise from restricted rotation around a single bond in whichthe barrier to rotation is sufficiently high for the stereoisomers to be isolated. Certain ortho disubstituted biphenyls are atropisomers, and the stereoisomers referred to in this case are enantiomers.Average bond enthalpy(平均键焓). Compare with bond enthalpy.Average enthalpy change per mole when the same type of bond is broken in the gas phase for manysimilar substancesAxial bonds(直立键). A bond perpendicular to the equator of the ring (up or down), typically in a chaircyclohexane. In the chair conformation of cyclohexanes, axial bonds are described as being: (a) parallel to the C3 axis, or (b) perpendicular to a general plane that contains the majority of carbon atoms.Axial chirality(轴手性；轴不对称). Chirality that has its origins in the non-planar disposition of groups withrespect to an axis,and exemplified by 1,3-dichloroallene, certain alkylidenecyclohexanes and4-substituted cyclohexanone oximes.Axial(轴的).1. An atom, bond, or lone pair that is perpendicular to equatorial atoms, bonds, and lone pairs in a trigonal bipyramidal molecular geometry.Azo(偶氮). azo compound; azo group; azo dye.The azo group has the general structure Ar-N=N-Ar', where Ar and Ar' indicate substituted aromaticrings. Compounds containing the azo compounds are often intensely colored and are economically important as dyes. Methyl orange is an example of an azo dye.Base hydrolysis constant(碱水解常数). (Kb) base ionization constant; basic hydrolysis constant. Comparewith acid dissociation constant.The equilibrium constant for the hydrolysis reaction associated with a base. For example, Kb for ammonia is the equilibrium constant for NH3(aq) + H2O(ell) doublearrowNH4+(aq) + OH-(aq), or Kb =[NH4+][OH-]/[NH3].Base(碱). alkali; alkaline; basic. Compare with acid.A proton acceptor or an electron pair donor.1. a compound that reacts with an acid to form a salt.2. a compound that produces hydroxide ions inaqueous solution (Arrhenius). 3. a molecule or ion that captures hydrogen ions.(Bronsted-Lowry).4. amolecule or ion that donates an electron pair to form a chemical bond.(Lewis).Benzaldehyde（苯甲醛；安息香醛）.(C6H5CHO).simplest aromatic aldehyde, formed by the controlledoxidation of benzyl alcohol; vigorous oxidation yields benzoic acid.Benzene（苯）. an aromatic cyclic hydrocarbon of formula C6H6.Benzoic acid（苯甲酸）(C6H5CO2H): simplest aromatic carboxylic acid, formed by the vigorous oxidation ofalkyl benzene, benzyl alcohol, and benzaldehyde.Benzyl group(苄基；苯甲基) (C6H5CH2-). A benzene ring plus a methylene (CH2) unit (C6H5-CH2-).Benzylic position( ). The position of a carbon attached to a benzene ring.Benzyne(苯炔; 脱氢苯). A highly reactive intermediate. A benzene ring with a triple bond.Bicyclic(二环的). A molecule with two rings that share at least two carbons.Binary compound(二元化合物). Compare with compound.A compound that contains two different elements. NaCl is a binary compound; NaClO is not.Bond energy(键能). bond enthalpy(键焓).Compare with bond enthalpy.Energy change per mole when a bond is broken in the gas phase for a particular substance.Bond length(键长).The average distance between the nuclei of two bonded atoms in a stable molecule.Bond order(键级).1. In Lewis structures, the number of electron pairs shared by two atoms.2. In molecular orbital theory,the net number of electron pairs in bonding orbitals (calculated as half the difference between the number of electrons in bonding orbitals and the number of electrons in antibonding orbitals.Bridgehead carbon(桥头碳原子). In an unsubstituted hydrocarbon that consists of two or more fused orbridged rings, with two or more carbons in common, the bridgehead carbons are tertiary carbons common to two or more rings. Bridgehead carbons can be substituted by, for example, Cl,OH, etc. Inbicyclo[2.2.1]heptane the bridgehead carbons are C(1) and C(4); in bicyclo[4.4.0]decane they are C(1) and C(6).Br.sted acid(布朗斯特酸). Compare with acid.A material that gives up hydrogen ions in a chemical reaction.Br.sted base(布朗斯特碱). Compare with base.A material that accepts hydrogen ions in a chemical reaction.Brosylate (4-bromobenzenesulfonate, 4-BrC6H4SO3)(对甲基苯磺酸盐). Slightly mbetter leaving groupgroup than tosylate in substitution and elimination reactions. Usually abbreviated to OBs.Buffer(缓冲液). pH buffer; buffer solution.A solution that can maintain its pH value with little change when acids or bases are added to it. Buffer solutions are usually prepared as mixtures of a weak acid with its own salt or mixtures of saltsof weak acids. For example, a 50:50 mixture of 1 M acetic acid and 1 M sodium acetate buffers pHaround 4.7.Cahn–Ingold–Prelog (CIP) R/S convention(R/S构型命名法). The most widely used method for assignmentof configuration to stereogenic centres (and chiral axes). Substituents at stereogenic centres are given ranking numbers 1, 2, 3 and 4, associated with decreasing atomic number; configuration is then assigned as in Chapter 2.Canonical forms (also called resonance structures)(共振结构式). These are different mLewis structures thatare alternative ways of representing the actual structure of a molecule that contains delocalized bonds. One draws several possible structures that all have the same number of unpaired electrons, and in which the relative positions of the nuclei are the same. Each canonical structure contributes inproportion to its stability, so that the structure is a weighted average of all canonical structures. These delocalized canonical structures have no individual existence. As an example, aromatic compounds and amides are weighted averages of two or more canonical forms (or Lewis structures);in the case of an amide, these are, for example, R12N–C(=O)R2 and R12N+=C(O–)R2.Carbanion(负碳离子). A negatively charged carbon atom.Carbene(碳烯). A reactive intermediate, characterized by a neutral, electron-deficient carbon center with twosubstituents (R2C:).Carbocation(碳正离子). A positively charged carbon.Carbonyl(羰基). carbonyl group.A carbon double bonded to oxygen (C=O). A divalent group consisting of a carbon atom with a double-bond to oxygen. For example, acetone (CH3-(C=O)-CH3) is a carbonyl group linking twomethyl groups. Also refers to a compound of a metal with carbon monoxide, such as iron carbonyl,Fe(CO)5.Carboxylic acid(羧酸)(RCOOH). carboxyl; carboxyl group.A molecule containing a carboxyl (COOH) group.Also a functional group. A carboxylic acid is an organic molecule with a -(C=O)-OH group. The group is also written as -COOH and is called a carboxyl group. The hydrogen on the -COOH group ionizes in water; carboxylic acids are weak acids.The simplest carboxylic acids are formic acid (H-COOH) and acetic acid (CH3-COOH).Carotene(胡萝卜素).Carotene is an unsaturated hydrocarbon pigment found in many plants. Carotene is the basic buildingblock of vitamin A.Catalyst（催化剂）a substance which changes the rate of a chemical reaction but is unchanged at the end ofthe reaction; an example would be the Pt used in the hydrogenation of alkenes.Cation(阳离子). Compare with anion.A positively charged molecule or atom. A cation is a positively charged ion. Metals typically form cations.Chair conformation(椅式构象). Typically, the most stable cyclohexane conformation. Looks like a chair. Thelowest energy conformation of cyclohexane. All the vicinal C–H bonds are staggered; this conformation has very little angle strain or torsion strain.Chelate(螯合的).A stable complex of a metal with one or more polydentate ligands. For example, calcium complexeswith EDTA to form a chelate.Chemical bond(化学键). bond; bonding; chemical bonding.A chemical bond is a strong attraction between two or more atoms. Bonds hold atoms in moleculesand crystals together. There are many types of chemical bonds, but all involve electrons which areeither shared or transferred between the bonded atoms.Chemical shift(化学位移). The location of an NMR peak relative to the standard tetramethylsilane (TMS),given in units of parts per million (ppm).Chiral center(手性中心). asymmetric center.A carbon or other atom with four nonidentical substituents. An atom in a molecule that causes chirality,usually an atom that is bound to four different groups. A molecule can have chirality without having achiral center, and a molecule may also have more than one chiral centers.Chiral molecule(手性分子). A molecule that's not superimposable on its mirror image. Chiral molecules rotateplane-polarized light.Chiral(手性的). chirality(手性).Having nonsuperimposable mirror images. For example, a shoe or a glove is chiral.A chiral (or handed) molecule is one that is not superimposable on its mirror image. The adjective isideally restricted to single molecules. An object such as a helix can also be described as chiral.The property of non-identity of an object with its mirror image. An object, e.g. a molecule in a givenconfiguration or conformation, is said to be chiral when it is not identical with its mirror image.Cis(顺式). Groups or atoms are cis when they lie on the same side of an identifiable reference plane in amolecule.Two identical substituents on the same side of a double bond or ring.Concerted(一致的；协同的). In a concerted reaction the bonding changes occur in a single step andsimultaneously.Condensation reaction(缩合反应). A reaction in which a small molecule (usually HO or HX) is produced inthe combination of two other molecules.2Configuration(构型). The three-dimensional arrangement (or sequence) in space of atoms, or functionalgroups, that characterizes a stereoisomer. In order to change a configuration, bond breaking and bond re-forming in a different sequence must occur. Enantiomers have opposite configurations.Configurations are denoted by R/S; D/L; E/Z. Configuration should be contrasted withconformation, in which changes are brought about only by bond rotation.Conformation (boat)( 船式构象). A conformation of cyclohexane that, by virtue of two eclipsed C–C bondsand a 1,4 non-bonded H...H interaction, is of higher energy than the chair conformation. So called because it resembles a boat when viewed sideways on.Conformation (chair)( 椅式构象). The lowest energy conformation of cyclohexane, in which all C–C bondsare staggered, and which has very little angle or torsional strain. This conformation resembles a chair when viewed sideways on.Conformation (eclipsed)(重叠式构象). When, for example, in ethane the dihedral angle .between a pair ofhydrogens on adjacent carbons is 0°; this is the least stable conformation. In butane, both C–C–C–Cdihedral angles of 0.(synperiplanar) and 120.(anticlinal) are eclipsed; the C–H bonds are eclipsedhere also. Some rigid molecules, e.g. bicyclo[2.2.1]heptane, have the C–H bonds at C(2), C(3), C(5)and C(6) locked in an eclipsed conformation.Conformation (skewed)(扭曲式构象). As above, but with the value of between 0° and 60°; there are aninfinite number of skewed conformations.Conformation (staggered)(交叉式构象). As above but with ..= 60°; in the case of ethane, the most stableconformation. Butane has a gauche staggered conformation in which the C–C–C–C dihedral angle is60°and an antiperiplanar staggered conformation in which the corresponding dihedral angle is 180°.Conformation(构象). The instantaneous spatial arrangements of atoms. Conformations can change byrotation around single bonds. The instantaneous spatial arrangements of atoms. Conformations can change by rotation around single bonds.Conformers(构象异构体). conformation(构象).Molecular arrangements that differ only by rotations around single bonds. For example, the "boat" and"chair" forms of cyclohexane are conformers.Conjugate acid(共轭酸). The acid that results from protonation of a base.Conjugate base(共轭碱). The base that results from the deprotonation of an acid.Conjugated double bonds(共轭双键). Double bonds separated by one carbon-carbon single bond. Alternating double bonds.Conjugation(共轭).A general feature of molecules which haveadjacent p-orbitals as in molecules withalternating multiple bonds. Electrons are said to be delocalized through extended π bonding.Conrotatory(顺旋). This adjective indicates that both p-orbitals at the terminal carbons (and the substituentsat these carbons) of a conjugated acyclic hydrocarbon rotate in the same sense, both clockwise or both anti-clockwise, during ring closure. Also applied to the reverse step, namely ring opening.Constitutional isomers(构造异构体). Molecules with the same molecular formula but with atoms attached indifferent ways.Coordination number(配位数).The number of bonds formed by the central atom in a metal-ligand complex.Coupling constant( 耦合常数). The distance between two neighboring lines in an NMR peak (given in unitsof Hz).Coupling protons(耦合质子). Protons that interact with each other and split the NMR peak into a certainnumber of lines following the n+1 rule.Covalent bond(共价键). covalent; covalently bound. Compare with covalent compound and ionic bond.Bond in which the two electrons are shared between the two atoms.A covalent bond is a very strong attraction between two or more atoms that are sharing their electrons.In structural formulas, covalent bonds are represented by a line drawn between the symbols of the bonded atoms.A compound made of molecules- not ions. The atoms in the compound are bound together by sharedelectrons. Also called a molecular compound.Cyclic compound（环状化合物）a molecule which has the two ends of the carbon chain connected togetherto form a ring.Crystal field splitting energy(晶体场分裂能). (Delta)Ligands*complexed to a metal ion will raise the energy of some of its d orbitals and lower the energyof others. The difference in energy is called the crystal field splitting energy.Crystal field theory( 晶体场理论). crystal field.The color, spectra, and magnetic properties of metal-ligand complexes can be explained by modelingthe effect of ligands on metal's d orbital energies.Cupric. (Cu2+) cupric ion(二价铜的).Deprecated. 1. the copper(II) ion, Cu2+. 2. A compound that contains copper in the +2 oxidation state.Cuprous. (Cu+) cuprous ion(亚铜的).Deprecated. 1. the copper(I) ion, Cu+. 2. A compound that contains copper in the +1 oxidationstate.Cycloaddition reaction( 环化加成反应). In the context of pericyclic reactions, this term refers to twomolecules, the same or different, with one or more .bonds, that combine to form a cyclic compound withcreation of two new .bonds in a concerted, bimolecular reaction. Of course, cycloaddition reactions mayproceed stepwise, but these are not pericyclic reactions.D-. D-isomer(D-异构体). Compare with L- .Prefix used to designate a dextrorotatory enantiomer .D-. D-isomer(D-异构体). Compare with L-.Prefix used to designate a dextrorotatory enantiomer.Dehydration（脱水）an elimination reaction in which an alcohol reacts with concentrated acid to yield analkene plus water.Dehydrogenases(脱氢酶). Enzymes that operate in conjunction with a cofactor,usually NADH. Despite thename, dehydrogenases catalyse both dehydrogenation (oxidation) and reduction reactions, under appropriate conditions.dehydrohalogenation(脱去卤化氢). Loss of a hydrohalic acid (like HBr, HCl, and so on) to form adouble bond.Delta value (a.k.a. d value)(δ：化学位移值). The chemical shift. The location of an NMR peak relative to thestandard tetramethylsilane (TMS), given in units of parts per million (ppm).Dextrorotatory (d)( 右旋的). Having the property of rotating plane-polarized light clockwise.Description given to a chiral compound that rotates the plane of polarized light (usually of wavelength589.6 nm, the sodium D line) in a clockwise sense as the observer looks into the propagating beam.Diastereoisomers(非对映异构体). Stereoisomers that are not mirror images of each other. Stereoisomers。