有机化学Chap12(2012-1)

1、1Chapter 12 Nitrogenous Compounds and AlkaloidsSection 1 Amine. Classification and NomenclatureNH3ammoniaR-NH-RR-NH2primary aminesecondary amineN RRR1tertiary amine2quaternary ammonium saltquaternary ammonium hydratetertiary amineQuaternary ammonium hydrates are strong base. The basicity of quaterna

2、ry ammonium hydrates are similar to sodium hydroxide.-OHN RR1R2RAgOHN RRR1R2XN RR1R2R+X-+季铵盐季铵碱-OHN RR1R2RAgOHN RRR1R2XN RR1R2R+X-+3胺：有机非离子型胺：有机非离子型 (amine )铵：离子型铵：离子型 (ammonium ion )氨：氨水、氨气或有机基团氨：氨水、氨气或有机基团 ( ammonia，amino )4aliphatic amines:aromatic amines:CH3CH2NHCH3NHCH35The systematic nomenclat

3、ure names amines analogously to alcohol. Another method names amines as substituted alkanes. . The names of aromatic amines are base on the parent compound, called benzenamine（苯胺）（苯胺） by the official world and aniline (or aminobenzene) by everyone elseAmines bearing different R are named by ordering

4、 the groups alphabetically6CH3NH2methylamine(CH3CH2)2NHdiethylamine(CH3CH2)3NtriethylamineN CH2CH3PhCH2CH3Benzylethylmethylamine 甲乙苄胺甲乙苄胺NCH3CH3N,N-dimethylaniline7CH3CH CH2CH2NH2CH3NCH3CH3C12H25PhCH2+-Br1-amino-3-methylbutanebenzyldodecyldimethyl ammonium bromide or bromo-geramine, 溴化二甲基十二烷基苄基铵溴化二甲

5、基十二烷基苄基铵新洁尔灭，苯扎溴铵，新洁尔灭，苯扎溴铵，disinfector（消毒剂）（消毒剂）8II. Structure of Amines9 ammoniamethylamineanilinetrimethylamine10. Preparation of Aromatic AmineAr NO2HAr NH2NO2CHCH2H2,cat.CH2CH3NH2NO2CH CH2NH2CH CH2Fe/HClFe/HCl can reduce nitro group but can not reduce carbon-carbon double bond.Ni, Pd, Pt11. Che

6、mical Properties:1. Basicity and Salt FormingOH-+ H-OHRNRHRNRH2+A strongly basic amine is a good competitor for H+ and its ammonium ion is a relatively weak acid (more stable); a weakly basic amine is less effective competitor for H+, and its ammonium ion is a relatively strong acid.ammonium ion12Se

7、quence of the basicity of aminesArNH2NH3R3NRNH2R2NH+OH-R4N Ar2NH Ar3N ArNH2NH3R3NRNH2R2NH+OH-R4N Ar2NH Ar3N 13HClH2NOC OCH2CH2N(C2H5)2OC OCH2CH2N(C2H5)2H2N+HCl-Procaine （普鲁卡因）（普鲁卡因）HClH2NOC OCH2CH2N(C2H5)2procaine hydrochloride, local anesthesia14H2NClClCHCH2NHC(CH3)3OHHClH2NClClCHCH2NHC(CH3)3OHHCl盐

8、酸双氯醇胺、盐酸克仑特罗盐酸双氯醇胺、盐酸克仑特罗 Clenbuterol hydrochloride, Spiropent 瘦肉精瘦肉精152. AcylationR-NH2RCOClR-NHOC RR-NH2(RCO)2OR-NHOC Ramide 16R2NH(RCO)2OR2NOC RR2NHRCOClR2NOC RR3NRCOCl or (RCO)2O17Acetanilide had been used as antifebric, but its toxicity is too high. NHC2H5OOC CH3Phenacetin非那西丁非那西丁NHOC CH3Acetan

9、ilideParacetamol扑热息痛扑热息痛OC CH3NHHO183. SulfonylationSO2Clbenzene sulfonyl chlorideSO2ClCH3p-toluenesulfonyl chloride19crystal-I effectweak acidSO2N-RNa+-SO2Cl + RNH2SO2NHRbenzene sulfonamideSO2Cl + R2NHSO2NR2SO2Cl + R3N20The above reaction is named Hinsberg Reaction（兴兴斯堡反应斯堡反应 ）. Using this reaction

10、 can distinguish primary, secondary and tertiary amines. The products of primary amines react with benzene sulfonyl chloride is weak acid, so can dissolve in sodium hydroxide solution. The products of secondary amines are crystal, and can not dissolve in sodium hydroxide solution. For tertiary amine

11、s, this reaction can not take place.214. React with nitrous acid (HNO2)(1) Primary aminesR-NH2HNO2complex products + N2HNO2NH2OH + N222(2) Secondary aminesR2NHHNO2R2N-NONHCH3N-CH3NOHNO2nitrosoamines (yellow oil)亚硝胺亚硝胺23(3) Tertiary aminesR3NHNO2R3N HNO2Aliphatic tertiary amines do not react with nit

12、rous acid to give an isolable product.24NCH3CH3HNO2NCH3CH3ONemerald green solidActually, we use sodium nitrite/hydrochloric acid NaNO2/HCl instead of nitrous acid (HNO2).N(CH3)2NaNO2 / HClN(CH3)2ONHCl(H3C)2NNOH Clyellow solid25Because primary amines react with nitrous acid will give nitrogen gas; se

13、condary amines will produce yellow oil and the products of aromatic tertiary amines are yellow solid. So it is easy to distinguish primary, secondary and tertiary amine by reacting with nitrous acid.26Something More:Nitrosoamines are important because many are known to be potent carcinogens. This fi

14、nding has led to a controversy over the use of sodium nitrite (NaNO2) as a preservative in foods because it might be a nitrosating agent under physiological conditions, or under the conditions in which food is prepared. The classic example is the frying of bacon, which generates nitrosoamines. Howev

15、er, the evidence is not definitive on this point. Many foods (spinach), even our own bodies, produce nitrites.27N-Nitrosodimethylamine 28NH2Br2/H2ONH2BrBrBrwhite precipitation5. Special Reaction of Aniline29V. Important AminesHOCH2CH2N(CH3)3OH+-OCH2CH2N(CH3)3OH+OCCH3-Choline（胆碱胆碱）Acetylcholine（乙酰胆碱）

16、（乙酰胆碱）30HOHOCH2CH2NH2Dopamine (DA，多巴胺), the decrease of DA will cause parkinsonism.31瑞典阿尔维德卡尔松(Arvid Carlsson ) 美国保罗格林加德 (Paul Greengard ) 奥地利埃里克坎德尔 (Eric Kandel ) The Nobel Prize in Physiology or Medicine 2000 32NHHOCH2CH2NH25-Hydroxytryptamine (5-羟色胺羟色胺) , Serotonine (血清胺血清胺 )33NHH3COCH2CH2NH COCH

17、3Melatonin (MLT) 褪黑素褪黑素(又称松果体素或脑白金又称松果体素或脑白金) 34F3COCHCH2CH2NHCH3Fluoxetine (氟西汀氟西汀 )Prozac (百忧解百忧解) Are you prozac today?35NHOOOFParoxetine，Seroxat（帕罗西汀，赛乐特）（帕罗西汀，赛乐特） 36(S)和(R)-西布曲明37HOHOCHCH2NHCH3OHepinephrineHOHOCHCH2NH2OHnorepinephrineHOHOCHCH2NCH(CH3)2OHisoprenaline, synthetic medicine 38CH CH

18、 NHCH3CH3OHephedrineCH CH NH2OH CH3Phenylpropanolamine , PPAN，N-二甲基二甲基-(4-氯苯基氯苯基)-2-吡啶丙胺顺丁烯二酸盐吡啶丙胺顺丁烯二酸盐,马来马来酸氯苯那敏酸氯苯那敏 ,扑尔敏扑尔敏 39CH2CHNHCH3CH3deoxyephedrine, “ice,” a popular pep pill.CH CH NH2OH CH3phenylpropanolamine , PPA40CH2CHNHCH3CH3？CH CH NHCH3CH3OH41CH2CHNHCH3CH3Can we use Clemmensen Reacti

19、on to reduce the carbonyl group? Why?85% H2NNH2H2O/NaOHC CH-NHCH3CH3OH+ CrO3/CH CH NHCH3CH3OHRoute 1:42Clemmensen ReactionCOHR-R-( )R-Zn-Hg/HClCH2H R-( )Zn-Hg/HCl: zinc amalgam43Route 2:CH CH NHCH3CH3OH PCl3CH CH NHCH3CH3Cl H2,NiCH2CH NHCH3CH344OOCH2CHNHCH3CH3Ecstasy, 3,4-methylenedioxymethamphetami

20、ne (MDMA) 爱它死爱它死, 3,4-亚甲二氧基甲基安非他命亚甲二氧基甲基安非他命, 快乐丸快乐丸, E仔仔, 摇头丸摇头丸4546Picture of Some MDMA (Ecstasy) pills 47MDMA在2001年被美国食品药物管理局（Food and Drug Administration；FDA）批准用于创伤后应激障碍（post-traumatic stress disorder)患者的试验。48Section 2 Diazo and Azo Compounds. Diazotization Reactionbenzene diazonium chlorideNH2N

21、aNO2/HClN NCl-+( )Cl-N2+05 重氮正离子主要的共振结构：重氮正离子主要的共振结构：49CH2 N N:+. ._50. Reaction of Diazo Salt1. SubstitutionN2Cl-H /H2O+OH + N2+N2Cl-Cl + N2CuCl+N2Cl-Br + N2CuBr+51N2Cl-I + N2KI+N2Cl-CN + N2CuCN/KCN+H3PO2: hypophosphorous acid (次磷酸次磷酸)N2Cl-+ N2H3PO2/H2O+522) How to synthesize 1,3,5-tribromobenzene

22、from benzene?Question: 1) How to synthesize 2-methyl benzoic acid from toluene?CH3CH3COOHBrBrBr53CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+051)CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2C

23、lKCN,CuCNCH3CNH2O/H+CH3HNO3/H2SO4CH3NO2CH3NO2+separateCH3NO2CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+CH3CH3COOHHNO3/H2SO4CH3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+CH3CH3COOHHNO3/H2SO4C

24、H3NO2Fe/HClCH3NH2NaNO2/HClCH3N2ClKCN,CuCNCH3CNH2O/H+54NHO3/H2SO4NO2Fe/HClNH2Br2/H2ONH2BrBrBrNaNO2/HClN2ClBrBrBrH2PO3/H2OBrBrBr2)NHO3/H2SO4NO2Fe/HClNH2Br2/H2ONH2BrBrBrNaNO2/HClN2ClBrBrBrH2PO3/H2OBrBrBrNHO3/H2SO4NO2Fe/HClNH2Br2/H2ONH2BrBrBrNaNO2/HClN2ClBrBrBrH2PO3/H2OBrBrBrNHO3/H2SO4NO2Fe/HClNH2Br2/H2

25、ONH2BrBrBrNaNO2/HClN2ClBrBrBrH2PO3/H2OBrBrBr05H3PO2/H2OBrBrBr552. Coupled Reaction (偶联反应偶联反应)OH+N2Cl-N NOHNaOHNaOH+N2Cl-OHCH3CH3OHN NN2ClN(CH3)2HOAcN(CH3)2NN56Azo compounds are endowed with color, can be used as dye. For example:N N(CH3)2NSO3Namethyl orange（甲基橙）（甲基橙）57NNHO（Sudan,苏丹红）苏丹红） 5859NNHOSud

26、an I, Solvent yellow 14NNHOH3CCH3Sudan IINNHONNSudan IIINNHONNCH3CH3Sudan IV60NNHOSudan INH2NH2OH+NNHOH3CCH3Sudan IINH2OH+NH2CH3CH361NNHONNSudan III+NH2+NNHOH2NNH2NN+NH2OHNH2H2N+62NNHONNCH3CH3Sudan IVNH2H3C+NNHOH2NCH3NH2OH+NH2NNCH3CH3+NH2H2NCH363Give the products of following reactions:NHNNO2NNO2N2C

27、ldilute NaOH2.OHCH3H3COHCH3NNCH3NHN2ClNO2O2NHOAc1.64Section 3 Amides. NomenclatureAmides, the nitrogen counterparts of esters, are systematically named by dropping the final “e” of the parent alkane and adding the suffix “amide.” As usual the smaller members of the class have retained their common n

28、ames, which are base on the common names for smaller carboxylic acids. Substitution on nitrogen is indicated with a prefix N, as in N-methyl, N,N-diethyl, and so on. Cyclic amides are known as lactams(内酰胺内酰胺).65ethanamide or acetamide3-methylbutanamidebenzamideOC NH2CH3OC NH2CH2CHCH3CH3OC NH2OCHN(CH

29、3)2NHO-propiolactamN,N-dimethylformamide (DMF)A all-purpose solvent66. Chemical Properties1. Acidity and BasicityAlmost amides are neutral. A classic exceptional example is phthalimide, which is very weak acid.NOOHKOHNOOKQuestion: why phthalimide is different form other amides?672. HydrolysisOC NHRR

30、H or OH+-OCROH + RNH268We know Penicillin G sodium or potassium are stored in solid form, and be dispensed to injection before be used. Why Penicillin G sodium or potassium can not be prepared to injection in laboratories?CH2CONHNSCH3CH3OCOONa(K)Penicillin G sodium or potassium693. React with Nitrou

31、s Acid+ N2RCONH2HNO2RCOOH70. Important Amides1. UreaOC NH2H2NChemical Properties of Urea:(1) Slightly baseHNO3OC NH2H2NOC NH2H2NHNO371(2) HydrolysisH or OH+-OC NH2H2NNH3 + H2CO3OC NH2H2NHCl/H2ONH4Cl + CO2OC NH2H2NNaOH/H2ONH3 + Na2CO372(3) React with Nitrous AcidHNO2OC NH2H2NN2CO2+73(4) Biuret Reacti

32、on (缩二脲反应)OC NH2H2N2OCH2NNHOC NH2 Biuret can dissolve in alkali solution. If a little cupric sulfate be added to the biuret alkali solution, the color of the solution will turn to violet color. This color reaction is called Biuret Reaction. Compounds contain two or more than two peptide linkages ( 肽

33、键 ) such as polypeptide, protein, etc. can take place biuret reaction.C NH C NHOOPeptide linkages（肽键）（肽键）74NNNNH2NH2H2NCOH2NNH2pressure, high temperature三聚氰胺（三聚氰胺（Melamine ）NNNNH2NH2H2NH+, H2ONNNOHOHHO三聚氰酸（三聚氰酸（Cyanuric acid） 752. Sulfonamides (Sulfa Drugs, 磺胺药物磺胺药物)SO2NH2H2Np-sulfanilamide, the par

34、ent compound of sulfa drugsSulfonamides are antimicrobial.76H2NNNSO2NH2NH2Prontosil, 百浪多息百浪多息Domagk, 1932The Nobel Prize in Physiology or Medicine 1939 77H2NSO2NHRThe general structure of sulfonamides.78H2NSO2NHNOCH3sulfamethoxazole (SMZ), or Sinomin, 磺胺甲噁唑磺胺甲噁唑, 新诺明新诺明 CH3OCH3OCH3OCH2NNNH2H2Ntrimet

35、hyoprim (TMP),三甲氧苄氨嘧啶三甲氧苄氨嘧啶 a excellent synergist for sulfa drugsChemitrim(百炎净百炎净): 400mg SMZ + 80mg TMP793. Guanidine 胍胍C NH2H2NNHCH2NNHNHCH2NNHguanidino胍基胍基guanyl脒基脒基Guanidine is a strong organic base, its basicity is similar to potassium hydroxide (KOH.)80Some important medicines contain guanidi

36、no or guanyl.NNCH2S(CH2)2NH C NHCH3NCNCH3HCimetidine, 西咪替丁西咪替丁, 甲腈咪胍甲腈咪胍, 泰胃美泰胃美CH2S(CH2)2NH C NHCH3OC NO2(CH3)2NCH2 Ranitidine, 雷尼替丁，呋喃硝胺雷尼替丁，呋喃硝胺81NCH2S(CH2)2NH CSNCNH2NH2NSO2NH2NH2Famotidine, 法莫替丁法莫替丁,高舒达高舒达Cimetidine, Ranitidine and Famotidine are Histamine H2-Receptor Antagonists, used as anti-

37、gastric ulcer medicines. Cimetidine is the first generation histamine H2-receptor antagonist; Ranitidine and Famotidine respectively belong to second and third generation. 824.Malonyl Urea (丙二酰脲丙二酰脲, 巴比妥酸巴比妥酸)barbituric acidNNOHHOHONNOOOHHureadiethyl malonateC2H5ONaOCH2NH2N+OC OC2H5CH2OC2H5CO83The b

38、arbituric acid does not possess biological activities. But when the two hydrogens of the methylene be substituted by alkyl groups, the derivatives will possess activities. For example, Barbital and Phenobarbital are classic sedative hypnotic.NNOOOC2H5C2H5HHBarbital巴比妥巴比妥NNOOOC2H5C6H5HHPhenobarbital

39、or Luminal苯苯巴比妥巴比妥，鲁米诺，鲁米诺84sodium pentothal, 喷妥撒钠，硫喷妥钠喷妥撒钠，硫喷妥钠NNCH2CH3CH3CH2CH2CHCH3SNaHOO85 Execution by lethal injection involves the continuous intravenous administration of three drugs. In executions conducted by the U.S. Bureau of Prisons, the first drug, sodium pentothal（喷妥撒钠）（喷妥撒钠）, is a ba

40、rbiturate that renders the condemned person unconscious. Executioners then administer pancuronium bromide（巴夫龙）（巴夫龙）, a muscle relaxant that paralyzes the lungs and diaphragm and stops breathing. A third drug, usually potassium chloride（氯化钾）（氯化钾）, , causes cardiac arrest and stops the heart. The drug

41、s, administered at levels that exceed clinical use, should cause death within five minutes. Executioners flush the IV lines with saline solution after each drug to prevent the lines from clogging. However, blocked lines and collapsed veins are common problems in the lethal injection process. Some st

42、ates allow the administering of a sedative before execution to relax the inmate and make locating a suitable vein easier. Timothy McVeigh will be executed.86McVeigh is executed at 7:14 June 11, 2001April 23, 1968 June 11, 2001 87April 19, 1995, Oklahoma City bombing 88CH3COONCH3OCOCH3NCH32Brsodium p

43、entothal, 喷妥撒钠，喷妥撒钠，硫喷妥钠硫喷妥钠pancuronium bromide, Pavulon, 泮库溴铵，巴夫龙泮库溴铵，巴夫龙KCl Potassium chlorideNNCH2CH3CH3CH2CH2CHCH3SNaHOO89药家鑫药家鑫糯康糯康90As sedative hypnotics, the derivatives of barbituric acid are not very safe. Now the derivatives of benzodiazepine （苯并二氮卓）（苯并二氮卓）are widely use as more effective

44、and more safe sedative hypnotics, such as DiazepamDiazepam地西泮地西泮 安定安定ClNNOCH391NNO2NOFH氟硝安定，氟硝安定，Flunitrazepam92NNO2NOFH氟硝安定，氟硝安定，FlunitrazepamFM2，十字架，十字架，“date-rape drug” Rohypnol, 氟硝西泮氟硝西泮罗氏罗氏(Hoffman LaRoche )药厂制造药厂制造93ClNHCH3O氯胺酮，氯胺酮，Ketamine，K仔，仔，K粉粉94Ketamine crystals 95Lysergide，LSD (Lysergsu

45、re-dithylamid ) D-麦角酸二乙胺麦角酸二乙胺，麦角二乙酰胺麦角二乙酰胺 LSD is the most potent mood- and perception-altering drug known: doses as small as 30 micrograms can produce effects lasting six to 12 hours. NHNNO96Albert Hofmann (艾伯特霍夫曼 )January 11, 1906 April 29, 2008 “LSD, My Problem Child”97OH2NHNCOOC2H5COH3CCOOHHOHO

46、HOover 10 stepsTamiflu (Oseltamivir) 特敏福，奥司他韦 ，达菲 shikimic acid莽草酸Shikimic acid is exracted from spice Chinese star aniseTamiflu (Oseltamivir) is one of a handful of drugs believed to be effective in treating H5N1 bird flu. swine flu H1N1982009年05月01日广州日报作者: 谢绮珊、赵琳琳 “中午我在食堂吃的其中两个菜就有猪肉，所以卫生部的同志们都在吃猪肉

47、。”卫生部部长陈竺支招说：“达菲的原料莽草酸主要就在八角茴香里面，我们可以把猪肉和八角茴香煮在一起，肯定是一剂良方。”99 Zanamivir, 扎那米韦,乐感清 Peramivir ,帕拉米韦帕拉米韦1001.(a)CH3CH2NH2(b)(CH3CH2)2NH(c)NH3(d)(CH3CH2)3N (e)NH(f)NH2(g)3N2.(a)CH3CH2CH2NH2(b)CH3CH2CH2SH(c)CH3CH2CH2OH比较化合物的碱性：比较化合物的碱性：1234567123101Section 4 AlkaloidAlkaloid: A nitrogen-containing compou

48、nd, often polycyclic and generally of the plant origin. The term is more loosely applied to other naturally occurring amines.102Lethal dose: 5070 mg (direct injection)Recently, some reports said, nicotine can cure senile dementia.NNCH3Nicotine. NicotineContent of Nicotine:2030 mg / a cigarette 120 m

49、g / a cigar Some important alkaloids:103NNCH3KMnO4 / H+NCOOHNicotinic acid 烟酸烟酸, 尼克酸尼克酸104. Opium alkaloidsMorphine, a member of the class of opium alkaloids constitutes about 10% of crude opium, and is an extraordinarily effective painkiller.NOCH3OHHOMorphine105Poppy，罂粟 106107Opium，鸦片 108Codeine is

50、 another member of this family and is a less addictive and less powerful analgesic than morphine. But codeine is a extraordinarily effective antitussive.NOCH3OHCH3OCodeine109联邦止咳露110NOCH3OHCH3OCodeineNCOOCH3CH3O COCocaine111Coca, 古柯古柯112Heroin, a synthetic derivative of morphine not found in nature

51、is also a close relative. The ester structures make it a strong fatsoluble material. Heroin can easily get across blood brain barrier, which make it become strong addictive narcotics.NOCH3OOCCOOCH3CH3Heroin113Question: How to synthesize heroin from codeine?NOCH3OOCCOOCH3CH3NOCH3OHCH3O114NOCH3OHCH3OH

52、INOCH3OHHONOCH3OOCCOOCH3CH3(CH3CO)2O115NOCH3OOCCOOCH3CH3NOCH3OHCH3OHow to synthesize codeine from heroin?116NOCH3OOCCOOCH3CH3H2O/OH-NOCH3OHHONaOHNOCH3OHNaO117NOCH3OHCH3OCH3I118NCH3COOC2H5NOCH3OHHOWe have know that morphine is a effective analgetic. Can we synthesize a simple molecule to instead of m

53、orphine? Yes, if we can find the pharmacophore group of morphine. The fragment contained by red line is the pharmacophore group of morphine. We can accord to that to synthesize analgetic, for example, dolantin.Dolantin, Pethidine119NCH3COOC2H5N(CH3)2CH3COCH2CH3Dolantin, PethidineMethadone, 美沙酮美沙酮120

54、盐酸美沙酮盐酸美沙酮121. CocaineNCOOCH3CH3O COThe synthesize of procaine is related to cocaine, can you find the relation between them?H2NOC OCH2CH2N(C2H5)2local anesthetic:122. Strychnine NNOOStrychnine used as tool reagent in pharmacological experiment. Also be used as exhilarant in athletic sports. Strychn

55、ine is a powerful convulsant and a lethal agent. The lethal dosage is about 30mg.士的宁，马钱子士的宁，马钱子碱，番木鳖碱碱，番木鳖碱123巫丹巫丹124NNNNOOH3CCH3CH3NNNNHOOH3CCH3HNNNNOOCH3CH3Caffeine咖啡因咖啡因Theophylline茶碱茶碱Theobromine可可碱可可碱V. Purine alkaloids125ClNOCH3OCH3OOBerberine Chloride盐酸黄连素盐酸黄连素 (氯化小檗碱氯化小檗碱)VI. Others126NCH3OC

56、CHCH2OHOAtropine（阿托品），（阿托品），A typical M receptor antagonist127OOCOOHNO2OCH3AristoIohic Acid, 马兜铃酸马兜铃酸龙胆泻肝丸龙胆泻肝丸 毒性较大的毒性较大的“关木通关木通”现已改为毒性较小的现已改为毒性较小的“木木通通” 关木通、马兜铃、广防己、青木香、天仙藤、寻关木通、马兜铃、广防己、青木香、天仙藤、寻骨风、朱砂莲等骨风、朱砂莲等 128Preparation of Aromatic AmineAr NO2HAr NH2NO2CHCH2H2,cat.CH2CH3NH2NO2CH CH2NH2CH CH2Fe/HClFe/HCl can reduce nitro group but can not reduce carbon-carbon double bond.Ni, Pd, Pt1291. Se