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AMINES Basic nitrogene compounds Single bonds

Amines are highly reactive basic nitrogen compounds that are commonly used as synthetic intermediates in organic chemistry. This text provides an overview of their nomenclature and important reactions, along with other functional groups consisting of nitrogen. It also covers hydrazine derivatives, imines, nitriles, azo compounds, nitro compounds, nitroso compounds, nitric acid esters, nitrous acid esters, nitrones, urea and its derivatives, carbamates, thiourea, thiosemicarbazides, thiosemicarbazones, and other important sulfur-containing functional groups.

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AMINES Basic nitrogene compounds Single bonds

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  1. AMINES Basic nitrogenecompounds Singlebonds Ammoniaprimary amine secondary amine tertiary amine querternary amine 2H 1H no H excessbondwith R R could be an aliphatic, alicyclic, aromaticorheterocycliccarbonmoiety

  2. -NH2 (amino) group a polar andbasicgroup -Aminesarehighlyreactive -Nomenclature: Simplyindicatethehydrocarbonemoietyfirstandthen amine ending: CH3-NH2methylamine C6H5-NH2 aniline N-methylethylamine (smallgroup as a substituent) N,N-dimethylethylamine N-ethyl-N-methylaniline

  3. Aminesaresyntheticintermediates but theyarerathertoxicchemicals. • Theirimportantreactions: Alkylation:

  4. Acylation: (withacylchloridestogiveamides): Salt formation (withacids): Imineformation: (withaldehydesorketones):

  5. Oxidation:

  6. Otherfunctionalgroupsconsisting of nitrogene Oximes R-CH=N-OH CH3-CH=N-OH C6H5-CH=N-OH acetaldehydeoximebenzaldehydeoxime (CH3)2C=N-OH acetoneoxime Nitrates (nitricacidesters) R-O-NO2 CH3-O-NO2methylnitrate C6H5-O-NO2phenylnitrate

  7. Nitrites(nitrousacidesters) R-O-NO CH3-O-NO methylnitrite C6H5-O-NO phenylnitrite HydroxamicacidsR-CO-NH-OH Verytoxiccompounds These can be considered as N-hydroxiyamidesoracyl/aroylhydroxylamines C6H5-CO-NH-OH benzohydroxamicacidor N-hydroxybenzamide C6H5-CO-NH-OHbenzohydroxamicacidor N-hydroxybenzamide

  8. Oxidation of amidesaredifficultcomparedtoamines but in case it is possible, hydroxamicacids can be obtained. Generallyaliphaticamidesaremuchmoreeasilyoxidized: HYDRAZINE DERIVATIVES Hydrazine is a verybasic, smallcompound H2N-NH2 Hydrazine can be alkylated, acylated as in thecase of aminestoormsomederivatives: NH2-NH-CH3 N-methylhydrazine

  9. N-acylhydrazinesareknown as hydrazidesandtheseareimportantantimicrobialagents in medicinalchemistry: NH-NH-CO-CH3aceticacidhydrazide oracetichydrazide oracetohydrazide ISONIAZID (isonicotinicacidhydrazide) p-aminobenzoichydrazide

  10. Ring hydrazide is alsoimportant: IMINES -C=N- is iminogroup N-nonsubstituted imine N-substituted imine Stabilityorder: N-aromaticsubstituted > N-aliphaticsubstituted > N-nonsubstitutedimines N-aromaticsubstitutediminesarecalled «SchiffBases»

  11. CH3-CH=N-H 1-etanimine (CH3)2C=N-H 2-propanimine N-substitutediminesarenamed as N-alkylideneor N-arylidenesubstitutedamines: C6H5-N=CH-C6H5 N-benzylideneaniline CH3-N=CH-CH3 N-ethylidenemethylamine Imines can be easilyhydrolyzedbackto amine plusthecorrespondingcarbonylcompound (aldehydeorketone): R-N=CH-R + H2O -> R-NH2 + O=CH-R

  12. HYDRAZONES Theseareproducts of hydrazineswithaldehydesandketones: R-CHO + H2N-NH2 -> R-CH=NH-NH2 (hydrazones) (R) (R) Thesecompoundshavegenerallyantimicrobialproperty. Nomenclature: CH3-CH=N-NH2acetalhydrazone (acetaldehydehydrazone) C6H5-CH=N-NH2benzalhydrazone (benzaldehydehydrazone)

  13. NITRILE (CYANIDE) • Toxicmoiety • -CN cyanomoiety Theirnamescomefromthe name of thecorrespondingacids: CH3-CN acetonitrile (fromaceticacid) C6H5CN benzonitrile (frombenzoicacid) Alternatively, nitriles can be named as cyanides (namesaremethylcyanideorphenylcyanideforthecompoundsabove) Nitriles can be hydrolysedtocarboxylicacidsviaamides: RCN + H2O -> R-CONH2 R-CONH2 + H2O -> R-COOH

  14. AZO COMPOUNDS R-N=N-R symmetrical R-N=N-R1asymmetrical CH3-N=N-CH3azomethane C3H7-N=N-C3H7azopropane CH3-CH2-N=N-CH3methylazoethane C6H5-N=N-CH3methylazobenzene (in assymetricones, thesmallercarbon is considered as a substituent)

  15. AZOXY COMPOUNDS azoxybenzene N-NITROSAMINES N-nitrosoaniline C6H5-NH-NO NITRO COMPOUNDS R-NO2 CH3-NO2nitromethane C6H5-NO2nitrobenzene

  16. NITROSO COMPOUNDS R-NO CH3-NO nitrosomethane C6H5-NO nitrosobenzene

  17. NITRIC ACID ESTERS (NITRATES) R-O-NO2 CH3-O-NO2methylnitrate C6H5-O-NO2phenylnitrate NITROUS ACID ESTERS (NITRITES)R-O-NO CH3-O-NOmethylnitrite C6H5-O-NOphenylnitrite

  18. NITRONES (Thisgroup can be considered as N-oxide of imines) N-ethyl-alpha-methyl-alpha-propylnitrone N,alpha-diphenylnitrone

  19. UREA and DERIVATIVES HO-CO-OH carbonicacid NH2-CO-OH carbamicacid NH2-CO-NH2carbamide (urea) Urea is a monoamide of carbamicacidand a diamide of carbonicacid Differentnitrogenes can be namedeither N, N’ or N1, N3 andthese can be substitutedwithalkyl, arylorotherfunctonalgroups. NH2-CO-NH-CH3 (N-methylurea) Cl-NH-CO-NH-C2H5 (N-chloro-N’-ethylurea)

  20. UREIDES (N-acylurea) NH2-CO-NH-CO-R NH2-CO-NH-CO-CH3 (N-acetylurea) Cyclicureide is alsoimportant in pharmaceuticalchemistry: Malonylurea (BARBITURIC ACID)

  21. CARBAMATES (URETANE) NH2-CO-OR Carbamicacidestersarecalled as carbamatesoruretanes NH2-CO-OC2H5 is ethyluretaneorethylcarbamate

  22. THIOUREA SEMICARBAZIDE (N-aminourea) NH2-CO-NH-NH2 1 2 3 4 SEMICARBAZONE (N-aminourea) NH2-CO-NH-NH=CH(R)-R NH2-CO-NH-NH=CH-CH3 (acetaldehydesemicarbazone)

  23. THIOSEMICARBAZIDES (N-aminourea) NH2-CS-NH-NH2 1 2 3 4 THIOSEMICARBAZONES (N-aminourea) NH2-CS-NH-NH=CH(R)-R NH2-CO-NH-NH=CH-C6H5 (benzaldehydethiosemicarbazone)

  24. IMPORTANT SULPHUR CONTAINING FUNCTIONAL GROUPS THIOALCOHOLS R-SH CH3-SH methanethiol THIOPHENOLS C6H5-SH THIOETHERS (SULFIDES) R-S-R CH3-S-CH3 (dimethylsulfide) C2H5-S-C6H5 (ethylphenylsulfide)

  25. SULFOXIDES R-SO-R CH3-SO-CH3dimethylsulfoxide SULFONES R-SO2-R CH3-SO2-CH3dimethylsulfone

  26. SULFONIC ACIDS R-SO3H CH3-SO3H methanesulfonicacid C6H5-SO3H benzenesulfonicacid

  27. SULFONAMIDES R-SO2-NH2 Arylsulfonamidesareimportantantimicrobialagents. p-aminobenzenesulfonamide

  28. SULFONYL CHLORIDE R-SO2-Cl Sulfonylchloridesareimportant SIM forproducingsulfonamides C2H5-SO2-Cl ethanesulfonylchloride C6H5-SO2-Cl benzenesulfonylchloride SULFONYLUREA R-SO2-NH-CO-NH2 Sulfonylureasareimportantantihyperglycemiccompounds: 1-butyl-3-p-(tolylsulfonyl)urea

  29. THIONES Thionesare ring ketoneswith S (withthereplacement of O in ketones): Thiocyclohexanone (cyclohexanethione)

  30. POLIFUNCTIONAL GROUPS Polyfunctionalgroupsmaycontainmorethanonefunctionalgroup in a molecule. One of them is selected as a main functionalgroupandthe rest is considered as substitents. Theorder of theirpriority is as follows: carboxylicacid > carboxylicacidderivatives > aldehydesandketones > alcohol > amine > doublebond Forexample: H2N-CH2-CH2-CH2-CH2-OH 4-amino-1-butanol (not 1-amino-4-butanol)

  31. Unsaturatedacids CH2=CH-COOH 2-propenoic acid (acrylicacid) CH3-CH=CH-COOH 2-butenoic acid(crotonicacid) b. Unsaturatedaldehydes CH2=CH-COOH acrylicacid CH2=CH-CHO acrolein CH3-CH=CH-COOH crotonicacid CH3-CH=CH-COOH crotonaldehyde

  32. c. Hydroxyacids CH3-CH(OH)-COOH lacticacid d. Amino acids NH2-CH2-COOH glycine CH3-CH(NH2)-COOH alpha-alanine H2N-CH2-CH2-COOH beta-alanine

  33. e. Hydroxyaldehydes f. Polyoles (dioles, trioles) CH2OH CH2OH Ethylenglycol (GLYCOL) or 1,2-ethanediol CH2OH CHOH CH2OH Glycerol (GLYCERIN) or 1,2,3-propanetriol glucose

  34. g. Diacids COOH COOH oxalicacid COOH CH2 COOH malonicacid COOH CH2 CH2 COOH succinicacid

  35. IMPORTANT REACTIONS IN MEDICINAL CHEMISTRY • Alkylation (amines) • Acylation (amines) • Halogenation (aromaticsubstitution) • Esterification (carboxylicacid, alcohol) • Sulphonation (aromaticsubstitution) • Nitration(aromaticsubstitution) • Schiffbaseformation (imines, amines, aldehydes, ketones) • Oxidation (Aldehyde, ketone, alcohol, amine) • Reduction (aldehyde, ketone, nitro, azo,doublebond) • Hydrolysis (ester, amide, imine) • Decarboxylation (carboxylicacid) • Dealkylation (prandsec amine, ether, thioether)

  36. AROMATIC SUBSTITION OF BENZENE RING

  37. 1st groupsubstituents Theseareorthoand para directinggroupsie OH, NH2, X and CH3 Reactionsareeasiercomparedto 2nd groupsubstituents: 2,4,6-trichlorotoluene 2st groupsubstituents ThesearemetadirectinggroupsieCOOH, and NO2 groups Reactionsaremoredifficultcomparedto1st groupsubstituents: 3,5-dichloronitrobenzene

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